JP2015092017A - Silver coated copper powder and manufacturing method therefor, and conductive paste - Google Patents
Silver coated copper powder and manufacturing method therefor, and conductive paste Download PDFInfo
- Publication number
- JP2015092017A JP2015092017A JP2014197068A JP2014197068A JP2015092017A JP 2015092017 A JP2015092017 A JP 2015092017A JP 2014197068 A JP2014197068 A JP 2014197068A JP 2014197068 A JP2014197068 A JP 2014197068A JP 2015092017 A JP2015092017 A JP 2015092017A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- copper powder
- coated copper
- coated
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 242
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 221
- 239000004332 silver Substances 0.000 title claims abstract description 221
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 52
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 50
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 50
- 239000000467 phytic acid Substances 0.000 claims abstract description 50
- 229940068041 phytic acid Drugs 0.000 claims abstract description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 32
- 239000011574 phosphorus Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims description 49
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
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- 150000004665 fatty acids Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
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- 230000008859 change Effects 0.000 abstract description 5
- 230000002123 temporal effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 42
- 238000000034 method Methods 0.000 description 41
- 229910052802 copper Inorganic materials 0.000 description 24
- 239000010949 copper Substances 0.000 description 24
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- 239000002245 particle Substances 0.000 description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
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Abstract
Description
本発明は、銀被覆銅粉及びその製造方法、並びに導電性ペーストに関する。 The present invention relates to a silver-coated copper powder, a method for producing the same, and a conductive paste.
従来から、電子部品等の電極や回路、電磁波シールドフィルム、電磁波シールド材等を形成するために、銀粉を有機成分中に分散させた導電性ペーストが使用されている。前記導電性ペーストの中でも、樹脂硬化型の導電性ペースト（特許文献１参照）は、樹脂の体積収縮により銀粉同士が接触して導通が取られる。前記樹脂硬化型の導電性ペーストに配合される銀粉としては、接触面積が大きいフレーク状銀粉が使用されている（特許文献２参照）。
しかし、フレーク状銀粉を配合した「銀系ペースト」は、フレーク状銅粉を配合した「銅系ペースト」と比べて、地金価格が高いため高価でマイグレーションが起こりやすい。また、「銅系ペースト」はマイグレーションが起こりにくいが酸化しやすく導電性が悪化するという欠点がある。これら欠点を克服する手法の一つとして、銅粉を扁平化処理し、銀を被覆した銀被覆フレーク状銅粉が提案されている。
前記銀被覆フレーク状銅粉に用いられる銅粉は、アトマイズ法、湿式還元法、電気分解法により製造されている。これらの中でも、価格的にも大量生産性にも有利な点から、アトマイズ法が好ましく、アトマイズ法による球状の銅粉を扁平化処理した銀被覆フレーク状銅粉が提案されている（特許文献３参照）。
しかしながら、前記アトマイズ法による銀被覆フレーク状銅粉は、特に低フィラー含量ペーストでは導電性の点で十分満足できる性能を有しておらず、更なる改善が望まれている。
Conventionally, a conductive paste in which silver powder is dispersed in an organic component has been used to form electrodes and circuits such as electronic components, electromagnetic wave shielding films, electromagnetic wave shielding materials, and the like. Among the conductive pastes, resin-cured conductive pastes (see Patent Document 1) are brought into conduction by silver powders contacting each other due to volumetric shrinkage of the resin. As silver powder blended in the resin curable conductive paste, flaky silver powder having a large contact area is used (see Patent Document 2).
However, the “silver paste” blended with flaky silver powder is expensive and prone to migration because the metal price is higher than the “copper paste” blended with flaky copper powder. Further, “copper paste” has a drawback that migration is difficult to occur but it is easily oxidized and conductivity is deteriorated. As one method for overcoming these drawbacks, a silver-coated flaky copper powder in which copper powder is flattened and coated with silver has been proposed.
The copper powder used for the silver-coated flaky copper powder is manufactured by an atomizing method, a wet reduction method, or an electrolysis method. Among these, the atomization method is preferable from the viewpoint of cost and mass productivity, and silver-coated flaky copper powder obtained by flattening spherical copper powder by the atomization method has been proposed (Patent Document 3). reference).
However, the silver-coated flaky copper powder by the atomizing method does not have a sufficiently satisfactory performance in terms of electrical conductivity, particularly in a low filler content paste, and further improvement is desired.
銀被覆銅粉の欠点として、経時変化による銅の酸化があり、酸化しにくい銀で覆われていても、銀粉と比較すると導電性ペーストの劣化が起きやすい。特に銀被覆銅粉の表面積が大きいほど劣化しやすい。その解決策として銀被覆銅粉の銀の割合を高めるという手法が知られていたが、銀の割合を高めることは、銅粉を使用する利点であるコスト低減の効果を減じてしまうため、好ましくない。
そこで、本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、銀の割合を高めることなく、優れた導電性を有し、かつ該導電性の経時変化が少ない導電膜を形成することができる銀被覆銅粉及び銀被覆銅粉の製造方法、並びに前記銀被覆銅粉を用いた導電性ペーストを提供することを目的とする。
The disadvantage of silver-coated copper powder is that copper is oxidized due to changes over time, and even if it is covered with silver that is difficult to oxidize, the conductive paste is more likely to deteriorate than silver powder. In particular, the larger the surface area of the silver-coated copper powder, the more likely it is to deteriorate. As a solution, a technique of increasing the silver ratio of the silver-coated copper powder has been known, but increasing the silver ratio is preferable because it reduces the cost reduction effect that is an advantage of using the copper powder. Absent.
Therefore, the present invention aims to solve the above-described problems and achieve the following object. That is, the present invention provides a silver-coated copper powder and a silver-coated copper powder capable of forming a conductive film having excellent conductivity and little change with time in the conductivity without increasing the proportion of silver. An object is to provide a method and a conductive paste using the silver-coated copper powder.
前記課題を解決するための手段としての本発明の銀被覆銅粉は、銅粉に銀を被覆してなる銀被覆銅粉の表面にリンを含有する化合物を少なくとも有する。 The silver-coated copper powder of the present invention as a means for solving the above problems has at least a compound containing phosphorus on the surface of a silver-coated copper powder obtained by coating silver on a copper powder.
本発明によると、従来における前記諸問題を解決することができ、銀の割合を高めることなく、優れた導電性を有し、かつ該導電性の経時変化が少ない導電膜を形成することができる銀被覆銅粉及び銀被覆銅粉の製造方法、並びに前記銀被覆銅粉を用いた導電性ペーストを提供することができる。 According to the present invention, the above-described problems can be solved, and a conductive film having excellent conductivity and little change with time in the conductivity can be formed without increasing the proportion of silver. Silver-coated copper powder, a method for producing silver-coated copper powder, and a conductive paste using the silver-coated copper powder can be provided.
（銀被覆銅粉）
本発明の銀被覆銅粉は、銅粉に銀を被覆してなる銀被覆銅粉の表面にリンを含有する化合物を少なくとも有する。
(Silver-coated copper powder)
The silver-coated copper powder of the present invention has at least a compound containing phosphorus on the surface of the silver-coated copper powder obtained by coating silver on the copper powder.
＜銀被覆銅粉＞
前記銀被覆銅粉は、銅粉の表面を銀で被覆したものであり、前記銅粉は、アトマイズ法、湿式還元法、又は電気分解法により製造され、いずれの銅粉を用いてもよいが、例えば、低フィラー濃度の導電性ペーストを用いた導電膜を作製する場合は、そのタップ密度の低さから電気分解法が特に好ましい。
<Silver-coated copper powder>
The silver-coated copper powder is obtained by coating the surface of a copper powder with silver, and the copper powder is manufactured by an atomization method, a wet reduction method, or an electrolysis method, and any copper powder may be used. For example, when a conductive film using a conductive paste having a low filler concentration is produced, an electrolysis method is particularly preferable because of its low tap density.
また、前記銅粉は、該銅粉を扁平化処理したフレーク状銅粉であることが、接触面積が大きく、導電性に優れている点で好ましい。目的によりフレーク化処理されていない球状粉、粒状粉を用いてもよいが、低フィラー濃度の導電性ペーストを用いた導電膜を作製する場合は、後述するＢＥＴ比表面積を有するものの方が導電性に優れている点から好ましい。前記扁平化処理については、後述する銀被覆銅粉の製造方法で説明する。 The copper powder is preferably a flaky copper powder obtained by flattening the copper powder from the viewpoint of a large contact area and excellent conductivity. Spherical powder and granular powder that have not been flaked may be used depending on the purpose, but when a conductive film using a conductive paste having a low filler concentration is produced, the one having a BET specific surface area described later is more conductive. From the point which is excellent in it. About the said flattening process, it demonstrates with the manufacturing method of the silver covering copper powder mentioned later.
＜リンを含有する化合物＞
前記リンを含有する化合物としては、フィチン酸が好ましい。
前記銀被覆銅粉は、表面に前記リンを含有する化合物としてフィチン酸を有することにより、電気抵抗を低減し、又は電気抵抗の上昇を起こさずに銅の酸化を防止することができる。
前記銀被覆銅粉におけるリンの含有量は、０．０１質量％（１００ｐｐｍ）以下であり、０．００３質量％（３０ｐｐｍ）以下が好ましい。酸化しやすい銅が露出している表面部分は少ないため、前記リンの含有量が０．００００１質量％（０．１ｐｐｍ）以上あれば耐酸化性は向上し、リンの含有量はできるだけ少ない方が抵抗値の上昇が抑えられるため好ましい。
前記リンの含有量が、０．０１質量％を超えると、前記リンの含有量の銀被覆銅粉を含む導電性ペーストからなる導電膜の体積抵抗率が悪化してしまうことがある。
前記銀被覆銅粉におけるリンの含有量は、例えば、銀被覆銅粉を塩酸抽出した液を、エスアイアイ・ナノテクノロジー株式会社製プラズマ発光分光装置 ＳＰＳ５１００により測定することができる。
<Compound containing phosphorus>
As the compound containing phosphorus, phytic acid is preferable.
By having phytic acid as a compound containing the phosphorus on the surface, the silver-coated copper powder can reduce electrical resistance or prevent oxidation of copper without causing an increase in electrical resistance.
The phosphorus content in the silver-coated copper powder is 0.01% by mass (100 ppm) or less, and preferably 0.003% by mass (30 ppm) or less. Since there are few exposed surface parts of copper that is easily oxidized, oxidation resistance is improved if the phosphorus content is 0.00001 mass% (0.1 ppm) or more, and the phosphorus content should be as low as possible. This is preferable because an increase in resistance value can be suppressed.
If the phosphorus content exceeds 0.01% by mass, the volume resistivity of the conductive film made of a conductive paste containing silver-coated copper powder having the phosphorus content may be deteriorated.
The phosphorus content in the silver-coated copper powder can be measured, for example, by using a plasma emission spectrometer SPS5100 manufactured by SII NanoTechnology Co., Ltd., as a solution obtained by extracting the silver-coated copper powder with hydrochloric acid.
前記フィチン酸は、イノシトールの６リン酸エステルであり、組成式はＣ６Ｈ１８Ｏ２４Ｐ６であり、以下の構造式で表される。
ここで、前記「銀被覆銅粉の表面にフィチン酸を有する」とは、銀被覆銅粉の表面に吸着、被覆などの何らかの方法によってフィチン酸が付着している状態を含む意味であり、銀被覆銅粉の表面の少なくとも一部にフィチン酸を有していればよく、銀被覆銅粉の表面全体がフィチン酸を有していてもよいし、銀被覆銅粉の表面の一部がフィチン酸を有していてもよい。なお、銀被覆銅粉の内部にフィチン酸を有していても構わない。好ましくは、銀被覆銅粉において酸化しやすい銅が露出している表面部分にフィチン酸が付着していればよい。フィチン酸のリン酸基は銀よりも銅と反応性が高いと考えられることから、銀被覆銅粉の表面全体を覆う量よりも少ない量で、銅が露出している部分にフィチン酸による耐酸化性を付与できる。 Here, “having phytic acid on the surface of the silver-coated copper powder” means that the surface of the silver-coated copper powder includes a state in which phytic acid is attached by some method such as adsorption or coating, It is only necessary that at least a part of the surface of the coated copper powder has phytic acid, the entire surface of the silver-coated copper powder may have phytic acid, or a part of the surface of the silver-coated copper powder is phytin. You may have an acid. In addition, you may have a phytic acid in the inside of silver covering copper powder. Preferably, phytic acid should just adhere to the surface part in which the copper which is easy to oxidize is exposed in silver covering copper powder. Since the phosphate group of phytic acid is considered to be more reactive with copper than silver, it is less than the amount covering the entire surface of the silver-coated copper powder. Can be imparted.
前記銀被覆銅粉の表面には、更に脂肪酸を含有することが好ましい。前記脂肪酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、例えば、プロピオン酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、アクリル酸、オレイン酸、リノール酸、アラキドン酸などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ステアリン酸が好ましい。
前記銀被覆銅粉を脂肪酸で表面処理する場合には、前記フィチン酸で表面処理してから、脂肪酸での表面処理を行うことが好ましい。前記フィチン酸は親水性であるため、疎水性であるステアリン酸などの脂肪酸で先に処理するとフィチン酸の付着が抑制される可能性があるからである。
The surface of the silver-coated copper powder preferably further contains a fatty acid. The fatty acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, for example, propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, olein Examples include acids, linoleic acid, and arachidonic acid. These may be used individually by 1 type and may use 2 or more types together. Of these, stearic acid is preferred.
When surface-treating the silver-coated copper powder with a fatty acid, it is preferable to surface-treat with the fatty acid after the surface treatment with the phytic acid. This is because, since the phytic acid is hydrophilic, if it is first treated with a fatty acid such as stearic acid which is hydrophobic, adhesion of phytic acid may be suppressed.
前記銀被覆銅粉の表面にフィチン酸を有することは、一般的には硝酸により前記銀被覆銅粉を溶解、あるいは塩酸で抽出した後に、ＩＣＰ−ＯＥＳ（誘導結合プラズマ発光分光装置）又はＨＰＬＣ（液体クロマトグラフィー）により分析することができる。例えば、銀被覆銅粉を１質量％トリクロロ酢酸又はＨＣｌ／ＭｅＯＨにて抽出した溶液について、イオンクロマトグラフ（ダイオネクス社製ＤＣ−５００、カラムはダイオネクス社製ＩｏｎｐａｃＡＳ１７−Ｃ）を用いて測定することにより、フィチン酸を示すピークを検出することにより、銀被覆銅粉表面のフィチン酸を定性分析できる。 Having phytic acid on the surface of the silver-coated copper powder generally means that after the silver-coated copper powder is dissolved with nitric acid or extracted with hydrochloric acid, ICP-OES (Inductively Coupled Plasma Emission Spectrometer) or HPLC ( (Liquid chromatography). For example, by measuring a solution obtained by extracting silver-coated copper powder with 1% by mass of trichloroacetic acid or HCl / MeOH using an ion chromatograph (DC-500 manufactured by Dionex, the column is Ionpac AS17-C manufactured by Dionex). The phytic acid on the surface of the silver-coated copper powder can be qualitatively analyzed by detecting a peak indicating phytic acid.
本発明の銀被覆銅粉は、銅粉に銀を被覆してなる銀被覆銅粉を表面処理剤で表面処理してなり、
銀の被覆量は２０質量％以下が好ましく、
熱重量測定（ＴＧ）による４００℃での重量増加率は１３重量％以下が好ましく、
ＢＥＴ比表面積は０．７ｍ２／ｇ以上が好ましい。
The silver-coated copper powder of the present invention is obtained by surface-treating a silver-coated copper powder obtained by coating silver on a copper powder with a surface treatment agent,
The silver coating amount is preferably 20% by mass or less,
The weight increase rate at 400 ° C. by thermogravimetry (TG) is preferably 13% by weight or less,
The BET specific surface area is preferably 0.7 m 2 / g or more.
前記銀の被覆量は、２０質量％以下が好ましく、０．３質量％〜２０質量％がより好ましく、０．５質量％〜１５質量％が更に好ましい。前記銀の被覆量が、２０質量％を超えると、コスト高となって銀単体に対するメリットが大きく減少することがある。
前記銀の被覆量は、例えば、硝酸により銀被覆銅粉を溶解後、塩酸を加え生じた塩化銀の沈殿の重量を測定することにより測定することができる。
なお、銅粉に銀を被覆する方法については、後述する銀被覆銅粉の製造方法において説明する。
The silver coating amount is preferably 20% by mass or less, more preferably 0.3% by mass to 20% by mass, and further preferably 0.5% by mass to 15% by mass. If the silver coating amount exceeds 20% by mass, the cost may increase and the merit for the silver element may be greatly reduced.
The silver coating amount can be measured, for example, by dissolving silver-coated copper powder with nitric acid and then adding hydrochloric acid to measure the weight of the resulting silver chloride precipitate.
In addition, about the method of coat | covering silver to copper powder, it demonstrates in the manufacturing method of the silver covering copper powder mentioned later.
ここで、図３に示すように、フィチン酸及びステアリン酸で表面処理した実施例１の銀被覆銅粉は、図５に示すように、ステアリン酸のみで表面処理した比較例１の銀被覆銅粉に比べて、熱重量測定（ＴＧ）による４００℃での重量増加率が有意に低くなっており、フィチン酸の添加による大気中での銀被覆銅粉の酸化抑制効果が認められる。図８に実施例１と比較例１の重量増加率の差をグラフに示す。
前記熱重量測定（ＴＧ）による温度に対する重量増加率の測定は、例えば、株式会社リガク製ＴｈｅｒｍｏＰｌｕｓ ＴＧ−８１２０を用いて、試料２０ｍｇを室温から１０℃／分の速度で昇温させ、２秒間ごとに各温度における試料増加重量を測定し、試料増加重量÷試料重量×１００により測定し、算出することができる。
また、図９に示すように、フィチン酸のみで表面処理した実施例２の銀被覆銅は、ステアリ酸のみで表面処理した比較例１、ステアリアン酸及びベンゾトリアゾールで表面処理した比較例２、ベンゾトリアゾールのみで表面処理した比較例３に比べて、導電膜の体積抵抗率が有意に低くなっており、優れた導電性を持たせる効果が認められる。
Here, as shown in FIG. 3, the silver-coated copper powder of Example 1 surface-treated with phytic acid and stearic acid was the silver-coated copper of Comparative Example 1 surface-treated only with stearic acid, as shown in FIG. Compared to the powder, the weight increase rate at 400 ° C. by thermogravimetry (TG) is significantly lower, and the effect of suppressing the oxidation of the silver-coated copper powder in the air by adding phytic acid is observed. FIG. 8 is a graph showing the difference in weight increase rate between Example 1 and Comparative Example 1.
The measurement of the rate of weight increase with respect to temperature by thermogravimetry (TG) is performed by, for example, using a ThermoPlus TG-8120 manufactured by Rigaku Corporation to raise the temperature of a sample 20 mg from room temperature at a rate of 10 ° C./minute every 2 seconds. The sample increased weight at each temperature is measured, and the sample increased weight / sample weight × 100 can be measured and calculated.
Moreover, as shown in FIG. 9, the silver-coated copper of Example 2 surface-treated only with phytic acid was Comparative Example 1 surface-treated with only stearic acid, Comparative Example 2 surface-treated with stearic acid and benzotriazole, The volume resistivity of the conductive film is significantly lower than that of Comparative Example 3 that is surface-treated with only benzotriazole, and an effect of imparting excellent conductivity is recognized.
前記銀被覆銅粉のＢＥＴ比表面積は、０．７ｍ２／ｇ以上が好ましく、０．７ｍ２／ｇ〜４ｍ２／ｇがより好ましく、０．７ｍ２／ｇ〜１．５ｍ２／ｇが更に好ましい。
前記ＢＥＴ比表面積が０．７ｍ２／ｇ未満であると、低フィラー濃度の導電性ペーストを用いた導電膜を作製する場合は、前記導電膜の体積抵抗率が不十分になることがある。
前記ＢＥＴ比表面積は、例えば、ＭＯＮＯＳＯＲＢ装置（湯浅アイオニクス株式会社製）で、Ｈｅ：７０％、Ｎ２：３０％のキャリアガスを用い、銅粉３ｇをセルに入れて脱気を６０℃で１０分間行った後、ＢＥＴ１点法により測定することができる。
BET specific surface area of the silver-coated copper powder is preferably at least 0.7 m 2 / g, more preferably 0.7m 2 / g~4m 2 / g, is 0.7m 2 /g~1.5m 2 / g Further preferred.
When the BET specific surface area is less than 0.7 m 2 / g, when producing a conductive film using a conductive paste having a low filler concentration, the volume resistivity of the conductive film may be insufficient.
The BET specific surface area is, for example, a MONOSORB apparatus (manufactured by Yuasa Ionics Co., Ltd.) using He: 70%, N 2 : 30% carrier gas, putting 3 g of copper powder into the cell, and degassing at 60 ° C. After 10 minutes, it can be measured by the BET 1 point method.
前記銀被覆銅粉のレーザー回折式粒度分布測定法による体積基準の粒子径分布における累積５０％粒子径（Ｄ５０）は、０．１μｍ〜２０μｍが好ましく、０．５μｍ〜１５μｍがより好ましい。
前記累積５０％粒子径（Ｄ５０）は、例えば、マイクロトラック粒度分布測定装置（ハネウエル（Ｈｏｎｅｙｗｅｌｌ）−日機装株式会社製、９３２０ＨＲＡ（Ｘ−１００））などを用いて測定することができる。
The cumulative 50% particle size (D 50 ) in the volume-based particle size distribution by the laser diffraction particle size distribution measurement method of the silver-coated copper powder is preferably 0.1 μm to 20 μm, more preferably 0.5 μm to 15 μm.
The cumulative 50% particle diameter (D 50 ) can be measured using, for example, a microtrack particle size distribution measuring apparatus (Honeywell-Nikkiso Co., Ltd., 9320HRA (X-100)).
前記表面処理剤としては、脂肪酸と、リンを含有する化合物とを併用することが好ましく、前記リンを含有する化合物としては、銀被覆銅粉に対する酸化防止効果の点から、フィチン酸が特に好ましい。フィチン酸を用いることで、酸化防止剤のデメリットとして予想される電気抵抗の上昇を抑えることができ、結果として導電膜の体積抵抗率の上昇を抑えることができる。リンを含有する化合物により粉体表面を被覆してから、脂肪酸を用いて被覆する順番が好ましい。前記脂肪酸としては、上述したものを用いることができ、これらの中でも、ステアリン酸が好ましい。
前記表面処理剤による銀被覆銅粉の表面処理方法については、後述する銀被覆銅粉の製造方法で説明する。
As the surface treatment agent, it is preferable to use a fatty acid and a compound containing phosphorus, and as the compound containing phosphorus, phytic acid is particularly preferable from the viewpoint of an antioxidant effect on the silver-coated copper powder. By using phytic acid, it is possible to suppress an increase in electrical resistance that is expected as a disadvantage of the antioxidant, and as a result, it is possible to suppress an increase in the volume resistivity of the conductive film. The order in which the powder surface is coated with a phosphorus-containing compound and then coated with a fatty acid is preferred. As the fatty acid, those described above can be used, and among these, stearic acid is preferable.
The surface treatment method of the silver-coated copper powder with the surface treatment agent will be described in the method for producing the silver-coated copper powder described later.
（銀被覆銅粉の製造方法）
本発明の銀被覆銅粉の製造方法は、第１の表面処理工程を少なくとも含み、第２の表面処理工程、銀粉作製工程、扁平化工程、及び銀被覆工程を含むことが好ましく、更に必要に応じてその他の工程を含んでなる。
(Method for producing silver-coated copper powder)
The method for producing a silver-coated copper powder according to the present invention preferably includes at least a first surface treatment step, and preferably includes a second surface treatment step, a silver powder preparation step, a flattening step, and a silver coating step. According to other steps.
＜第１の表面処理工程＞
前記第１の表面処理工程は、銅粉の表面に銀を被覆してなる銀被覆銅粉をフィチン酸で表面処理する工程である。
前記フィチン酸の表面処理は、前記銀被覆銅粉を含むスラリーにフィチン酸を添加（湿式添加）して行うことが好ましい。
前記湿式添加は、例えば、銅粉に銀を被覆する湿式反応の直後に、撹拌中の当該粉を含むスラリーにフィチン酸を水又はアルコール等で溶解させたものを滴下することにより行うことができる。前記第１の表面処理工程（フィチン酸の添加）を銅粉に銀を被覆する湿式反応の直後、即ち、銀被覆銅粉の固液分離の前に行うことで、被覆時の反応により液中に遊離した銅イオンの再析出の抑制も同時に行うことができる。
前記フィチン酸の添加量は、前記銀被覆銅粉に対して、０．００１質量％〜１０質量％が好ましい。そして、濾過、水洗、乾燥後に銀被覆銅粉に付着しているフィチン酸は、リンの含有量として０．０１質量％（１００ｐｐｍ）以下であり、０．００３質量％（３０ｐｐｍ）以下が好ましい。酸化しやすい銅が露出している表面部分は少ないため、フィチン酸の付着量はリンの含有量として０．００００１質量％（０．１ｐｐｍ）以上あれば耐酸化性は向上し、リンの含有量はできるだけ少ない方が抵抗値の上昇が抑えられるため好ましい。
<First surface treatment step>
The first surface treatment step is a step of surface-treating silver-coated copper powder obtained by coating silver on the surface of copper powder with phytic acid.
The surface treatment of the phytic acid is preferably performed by adding (wet addition) phytic acid to the slurry containing the silver-coated copper powder.
The wet addition can be performed, for example, by dropping a solution of phytic acid dissolved in water or alcohol or the like into a slurry containing the powder being stirred immediately after the wet reaction in which copper powder is coated with silver. . By performing the first surface treatment step (addition of phytic acid) immediately after the wet reaction for coating the copper powder with silver, that is, before solid-liquid separation of the silver-coated copper powder, In addition, the reprecipitation of copper ions liberated at the same time can be suppressed at the same time.
As for the addition amount of the said phytic acid, 0.001 mass%-10 mass% are preferable with respect to the said silver covering copper powder. And the phytic acid adhering to silver-coated copper powder after filtration, water washing, and drying is 0.01 mass% (100 ppm) or less as content of phosphorus, and 0.003 mass% (30 ppm) or less is preferable. Since there are few exposed surface parts of copper that are susceptible to oxidation, oxidation resistance is improved if the amount of phytic acid deposited is 0.00001 mass% (0.1 ppm) or more as the phosphorus content, and the phosphorus content Is preferably as small as possible because an increase in resistance value can be suppressed.
＜第２の表面処理工程＞
前記第２の表面処理工程は、フィチン酸で表面処理した銀被覆銅粉を脂肪酸で表面処理する工程である。
前記脂肪酸の表面処理は、前記フィチン酸で表面処理した銀被覆銅粉に脂肪酸を湿式添加して行うことが好ましい。
前記脂肪酸としては、例えば、プロピオン酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、アクリル酸、オレイン酸、リノール酸、アラキドン酸などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ステアリン酸が好ましい。
前記湿式添加は、前記第１の表面処理工程と同様であるが、脂肪酸をアルコール等の有機溶剤で希釈したものを添加する、又は脂肪酸のエマルジョンを直接あるいは水で希釈したものを投入することが好ましい。
前記脂肪酸の添加量は、前記銀被覆銅に対して、０．００１質量％〜１０質量％が好ましい。
以下、銀被覆銅粉が銀被覆フレーク状銅粉である場合を例にして、各工程を説明する。
<Second surface treatment step>
The second surface treatment step is a step of surface-treating the silver-coated copper powder surface-treated with phytic acid with a fatty acid.
The surface treatment of the fatty acid is preferably performed by wet addition of a fatty acid to the silver-coated copper powder surface-treated with the phytic acid.
Examples of the fatty acid include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linoleic acid, arachidonic acid, and the like. These may be used individually by 1 type and may use 2 or more types together. Of these, stearic acid is preferred.
The wet addition is the same as the first surface treatment step, but adding a fatty acid diluted with an organic solvent such as alcohol, or adding a fatty acid emulsion directly or diluted with water. preferable.
The addition amount of the fatty acid is preferably 0.001% by mass to 10% by mass with respect to the silver-coated copper.
Hereinafter, each process will be described by taking as an example the case where the silver-coated copper powder is a silver-coated flaky copper powder.
＜銅粉作製工程＞
前記銅粉作製工程は、銅粉を作製する工程であり、通常、銅粉は、アトマイズ法、湿式還元法、又は電気分解法により製造されているが、特に制限はなく、いずれの方法を用いてもよい。例えば、低フィラー濃度の導電膜を形成する場合においては、そのタップ密度の低さの点から、電気分解法が特に好ましい。
前記電気分解法としては、例えば、銅イオンを含む硫酸酸性の電解液に陽極と陰極を浸漬し、これに直流電流を流して電気分解を行い、陰極表面に粉末状に銅を析出させ、機械的又は電気的方法により掻き落として回収し、洗浄し、乾燥し、必要に応じて篩別工程などを経て電解銅粉を製造する方法などが挙げられる。
前記電気分解法で銅粉を製造する場合、銅の析出に伴って電解液中の銅イオンが消費されるため、電極板付近の電解液の銅イオン濃度は薄くなり、そのままでは電解効率が低下してしまう。そのため、通常は電解効率を高めるために、電解槽内の電解液の循環を行って電極間の電解液の銅イオン濃度が薄くならないようにする。
<Copper powder production process>
The copper powder production step is a step of producing copper powder, and the copper powder is usually produced by an atomization method, a wet reduction method, or an electrolysis method, but there is no particular limitation, and any method is used. May be. For example, in the case of forming a conductive film having a low filler concentration, an electrolysis method is particularly preferable because of its low tap density.
As the electrolysis method, for example, an anode and a cathode are immersed in a sulfuric acid acidic electrolyte solution containing copper ions, a direct current is passed through the electrolysis, and copper is deposited in a powder form on the cathode surface. And a method of producing electrolytic copper powder through a sieving step and the like, if necessary.
When copper powder is produced by the electrolysis method, the copper ions in the electrolyte solution are consumed as the copper deposits, so the copper ion concentration in the electrolyte solution near the electrode plate becomes thin, and the electrolysis efficiency decreases as it is. Resulting in. Therefore, normally, in order to increase the electrolysis efficiency, the electrolytic solution in the electrolytic cell is circulated so that the copper ion concentration of the electrolytic solution between the electrodes does not decrease.
＜扁平化工程＞
前記扁平化工程は、前記銅粉を扁平化処理する工程である。
前記扁平化処理を行う装置としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、転動ボールミル、アトライター、ＳＣミル等のメディア式ミル（ボール、ビーズによる粉砕ミル）などが挙げられる。前記装置としては、市販されているものをそのまま使用可能である。
<Flatening process>
The flattening step is a step of flattening the copper powder.
There is no restriction | limiting in particular as an apparatus which performs the said flattening process, According to the objective, it can select suitably, For example, media-type mills, such as a rolling ball mill, an attritor, and SC mill (Pulverizing mill with a ball and beads) Etc. A commercially available device can be used as it is.
前記扁平化処理は溶媒を添加して行うことが好ましい。前記溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水、有機溶媒などが挙げられる。
前記有機溶媒としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、分子量２００以下の有機溶媒が好ましく、分子量２００以下のアルコール（例えば、メタノール、エタノール、プロパノール、又はこれらの混合物）がより好ましい。
前記溶媒の添加量としては、特に制限はなく、目的に応じて適宜選択することができるが、扁平化処理する銅粉に対し、質量で０．１倍〜３倍が好ましい。前記添加量が、０．１倍未満であると、溶媒添加の効果が不十分であることがあり、３倍を超えると、十分なアスペクト比が得られないことがある。
The flattening treatment is preferably performed by adding a solvent. There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, water, an organic solvent, etc. are mentioned.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an organic solvent having a molecular weight of 200 or less is preferable, and an alcohol having a molecular weight of 200 or less (for example, methanol, ethanol, propanol, or these) More preferred).
There is no restriction | limiting in particular as addition amount of the said solvent, Although it can select suitably according to the objective, 0.1 times-3 times are preferable by mass with respect to the copper powder to flatten. If the addition amount is less than 0.1 times, the effect of solvent addition may be insufficient, and if it exceeds 3 times, a sufficient aspect ratio may not be obtained.
前記ボール（メディア）としては、直径が０．１ｍｍ〜３ｍｍで形状が球状のボール（メディア）である限り、特に制限はなく、目的に応じて適宜選択することができる。前記ボール（メディア）の直径が、０．１ｍｍ未満であると、扁平化処理後のフレーク状銅粉とメディアを分離する際、メディアの目詰まり等により、分離の効率が低下し、３ｍｍを超えると、得られるフレーク状銅粉の粒径が過大になることがある。
前記ボール（メディア）の材質としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ステンレス（ＳＵＳ）等の金属、アルミナ、ジルコニア等のセラミックスなどが挙げられる。これらの中でも、製品へのコンタミネーションを考えると、ステンレス（ＳＵＳ）が特に好ましい。
前記ボール（メディア）の扁平化処理時における添加量としては、特に制限はなく、目的に応じて適宜選択することができるが、扁平化処理する銅粉に対し、質量で１倍〜５０倍が好ましい。前記添加量が、１倍未満であると、十分なアスペクト比が得られないことがあり、５０倍を超えると、１回に扁平化処理できる銅粉の量が少なくなり、処理コストが高くなることがある。
The ball (media) is not particularly limited as long as it is a ball (media) having a diameter of 0.1 mm to 3 mm and a spherical shape, and can be appropriately selected according to the purpose. When the diameter of the ball (media) is less than 0.1 mm, when separating the flaky copper powder after the flattening treatment and the media, the efficiency of the separation decreases due to clogging of the media, and exceeds 3 mm. And the particle size of the obtained flaky copper powder may become excessive.
There is no restriction | limiting in particular as a material of the said ball | bowl (media), According to the objective, it can select suitably, For example, metals, such as stainless steel (SUS), ceramics, such as an alumina and a zirconia, etc. are mentioned. Among these, stainless steel (SUS) is particularly preferable in view of product contamination.
There is no restriction | limiting in particular as addition amount at the time of the flattening process of the said ball | bowl (media), Although it can select suitably according to the objective, 1-50 times by mass with respect to the copper powder to flatten a process. preferable. When the addition amount is less than 1 time, a sufficient aspect ratio may not be obtained, and when it exceeds 50 times, the amount of copper powder that can be flattened at one time decreases, and the processing cost increases. Sometimes.
前記扁平化処理の処理時間は、特に制限はなく、フレーク装置やボール・銅粉の添加量に応じて適宜選択することができるが、例えば、アトライターを用いるなら、１０分間〜１８０分間が好ましく、６０分間〜１５０分間がより好ましい。前記処理時間が、１０分間未満であると、扁平化が不十分になりやすく、１８０分間を超えると、扁平化が進みすぎてＢＥＴ比表面積が大きくなり、また凝結が起きやすく導電性ペーストとした場合の電気抵抗が上がりやすくなる。
なお、前記扁平化処理は、投入した全ての銅粉が扁平化される必要はなく、扁平化処理後に扁平化が進んでいない銅粉が混在していてもよい。扁平化処理の前後で、投入した銅粉に対して上記のフレーク状銅粉が一つでも形成されていれば扁平化処理されたということができる。
The treatment time of the flattening treatment is not particularly limited and can be appropriately selected according to the addition amount of the flake device and the ball / copper powder. For example, when an attritor is used, it is preferably 10 minutes to 180 minutes. 60 minutes to 150 minutes is more preferable. If the treatment time is less than 10 minutes, flattening tends to be insufficient, and if it exceeds 180 minutes, flattening proceeds excessively, resulting in a large BET specific surface area, and condensing is likely to occur. In this case, the electrical resistance is likely to increase.
In the flattening process, it is not necessary to flatten all of the input copper powder, and copper powder that has not been flattened after the flattening process may be mixed. If at least one of the above flaky copper powders is formed on the supplied copper powder before and after the flattening process, it can be said that the flattening process has been performed.
得られるフレーク状銅粉の分散性を向上させるためには、公知の分散剤を扁平化処理する銅粉に対して、０．１質量％〜５質量％添加することができる。なお、前記扁平化工程前の銅粉に分散剤を添加する代わりに、溶媒とともに前記分散剤を添加することもできる。前記分散剤を扁平化工程前の銅粉に添加し、かつ前記分散剤を扁平化工程で溶媒とともに添加してもよい。 In order to improve the dispersibility of the obtained flaky copper powder, a known dispersant can be added in an amount of 0.1% by mass to 5% by mass with respect to the copper powder to be flattened. In addition, the said dispersing agent can also be added with a solvent instead of adding a dispersing agent to the copper powder before the said flattening process. The dispersant may be added to the copper powder before the flattening step, and the dispersant may be added together with the solvent in the flattening step.
＜銀被覆工程＞
前記銀被覆工程は、銅粉又は扁平化処理後のフレーク状銅粉表面に銀を被覆する工程である。
前記銅粉又はフレーク状銅粉表面に銀を被覆させる方法としては、例えば、還元法と置換法の２種類を挙げることができる。
前記還元法は、銅粉粒子の表面に、還元剤で還元された銀の微粒子を緻密に被覆させていく方法である（例えば、特開２０００−２４８３０３号公報等参照）。
前記置換法は、銅粉粒子の界面で、銀イオンが金属の銅と電子の授受を行い、銀イオンが金属の銀に還元され、代わりに金属の銅が酸化され銅イオンになることで、銅粉粒子の表面層を銀層とする方法である（例えば、特開２００６−１６１０８１号公報等参照）。
これらの中でも、銀被覆の均一性、銅表面への銀層の密着の点から、置換法が好ましい。
<Silver coating process>
The silver coating step is a step of coating silver on the surface of the copper powder or the flaky copper powder after the flattening treatment.
As a method for coating the surface of the copper powder or flaky copper powder with silver, for example, there are two kinds of methods, a reduction method and a substitution method.
The reduction method is a method in which fine particles of silver reduced with a reducing agent are densely coated on the surface of copper powder particles (see, for example, JP-A-2000-248303).
In the substitution method, at the interface of the copper powder particles, silver ions exchange electrons with metallic copper, silver ions are reduced to metallic silver, and instead metallic copper is oxidized into copper ions, In this method, the surface layer of the copper powder particles is a silver layer (see, for example, JP-A-2006-161081).
Among these, the substitution method is preferable in terms of uniformity of silver coating and adhesion of the silver layer to the copper surface.
前記置換法において、銀被覆反応を行わせる際には、まず、銀塩を添加する前の液中に銅粉原料を入れて攪拌し、銅粉が液中に十分分散している状態で銀塩を含んだ液を添加することが好ましい。反応温度は、反応液が凝固したり蒸発したりしなければ特に規定されるものではないが、概ね２０℃〜８０℃で設定可能である。反応時間は、銀の被覆量・反応温度によって異なるが、概ね１分間〜５時間の範囲で設定可能である。 In the substitution method, when the silver coating reaction is performed, first, the copper powder raw material is put in the liquid before adding the silver salt and stirred, and then the silver powder is sufficiently dispersed in the liquid. It is preferable to add a liquid containing a salt. The reaction temperature is not particularly defined as long as the reaction solution does not solidify or evaporate, but it can be set at about 20 ° C to 80 ° C. The reaction time varies depending on the silver coating amount and reaction temperature, but can be set within a range of approximately 1 minute to 5 hours.
前記銀被覆反応を行う反応液としては、有機溶媒を含む溶液、又は有機溶媒相と水溶媒相からなるエマルジョンを用いる。水に対する溶解度が大きい有機溶媒を使用する場合は均一な混合溶液となるが、溶解度が低い有機溶媒の場合は、静止状態では水相と有機溶媒相が分離するため、液を攪拌することによりエマルジョンを形成させた状態で銀被覆反応を行う。これらの反応液を使用することにより、扁平化の際に添加した助剤を除去することなく、フレーク状銅粉をそのままの銀被覆反応に供することができる。 As a reaction solution for performing the silver coating reaction, a solution containing an organic solvent or an emulsion composed of an organic solvent phase and an aqueous solvent phase is used. When using an organic solvent with a high solubility in water, a uniform mixed solution is obtained. However, in the case of an organic solvent with a low solubility, the aqueous phase and the organic solvent phase are separated in a stationary state. The silver coating reaction is carried out in the state where is formed. By using these reaction solutions, the flaky copper powder can be subjected to the silver coating reaction as it is without removing the auxiliary added during flattening.
前記有機溶媒としては、水との相溶性、銀塩（主として硝酸銀）の溶解度を有する、アルコール、ケトン、アルデヒド、エーテルを使用することができる。具体的には、メタノール、エタノール、１−プロパノール、イソプロピルアルコール、１−ブタノール、２−メチルプロパノール、３−メチルプロパノール、１，１−ジメチルエタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、グリセリン、カルビトール、メチルカルビトール、ブチルカルビトール、セロソルブ、メチルセロソルブ、ブチルセロソルブ、テルピネオール、ホルムアルデヒド、アセトアルデヒド、アセトン、メチルエチルケトン、メチルエーテル、エチルエーテル、メチルエチルエーテルなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
これらの中でも、水を含有せず有機溶媒を単独の反応液として使用する場合は、銀塩を直接溶解することが可能な多価アルコールが好ましく、具体的には、エチレングリコール、ジエチレングリコール、グリセリンなどが挙げられる。
As the organic solvent, alcohols, ketones, aldehydes, and ethers having compatibility with water and solubility of silver salts (mainly silver nitrate) can be used. Specifically, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-methylpropanol, 3-methylpropanol, 1,1-dimethylethanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, carbitol , Methyl carbitol, butyl carbitol, cellosolve, methyl cellosolve, butyl cellosolve, terpineol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methyl ether, ethyl ether, methyl ethyl ether and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, when using an organic solvent as a single reaction solution without containing water, a polyhydric alcohol capable of directly dissolving a silver salt is preferable, specifically, ethylene glycol, diethylene glycol, glycerin, etc. Is mentioned.
有機溶媒と水との混合溶液、又はエマルジョン中にて銀被覆を行う場合は、有機溶媒として室温（２０℃〜３０℃）において液体となるものを用いる必要がある。前記水と前記有機溶媒との混合比率は、使用する有機溶媒により適宜調整することができる。また、有機溶媒と混合する水としては、不純物が混入する恐れがなければ、蒸留水、イオン交換水、工業用水等のいずれを用いてもよい。 When silver coating is performed in a mixed solution of an organic solvent and water or in an emulsion, it is necessary to use an organic solvent that is liquid at room temperature (20 ° C. to 30 ° C.). The mixing ratio of the water and the organic solvent can be appropriately adjusted depending on the organic solvent used. As the water mixed with the organic solvent, any of distilled water, ion-exchanged water, industrial water and the like may be used as long as there is no fear that impurities are mixed therein.
銀被覆反応に使用する銀原料としては、銀イオンを液中に存在させる必要があるため、水あるいは多くの有機溶媒に対して溶解度を有する硝酸銀を用いることが好ましい。できるだけ均一な被覆反応を実現するために、硝酸銀を固体状で添加せず、水溶液、有機溶媒、又は水−有機溶媒混合液に硝酸銀を溶解した硝酸銀溶液として使用することが好ましい。目的とする銀被覆量に応じて、使用する硝酸銀溶液の濃度、有機溶媒量、及び使用する硝酸銀溶液量を決める。 As a silver raw material used for the silver coating reaction, it is preferable to use silver nitrate having solubility in water or many organic solvents because silver ions need to be present in the liquid. In order to realize as uniform a covering reaction as possible, it is preferable to use silver nitrate solution in which silver nitrate is dissolved in an aqueous solution, an organic solvent, or a water-organic solvent mixed solution without adding silver nitrate in a solid state. The concentration of silver nitrate solution to be used, the amount of organic solvent, and the amount of silver nitrate solution to be used are determined according to the target silver coating amount.
銀被覆層をより均一に形成させるために、有機溶媒を含有する反応液（混合溶液又はエマルジョン）中にキレート化剤を添加してもよい。前記キレート化剤としては、銀イオンと金属銅との置換反応により副生成する銅イオンが再析出しないよう、銅イオンとの錯安定度定数の高いものが好ましい。具体的には、エチレンジアミン四酢酸（ＥＤＴＡ）、イミノジ酢酸、ジエチレントリアミン、トリエチレンジアミン、又はこれらの塩を使用することができる。
銀被覆反応を安定かつ安全に行うにあたり、ｐＨ緩衝剤を添加してもよい。具体的には、炭酸アンモニウム、炭酸水素アンモニウム、アンモニア水、炭酸水素ナトリウムをｐＨ緩衝剤として使用することができる。
なお、銀被覆層の形成時にフィチン酸などの表面処理剤があると銀被覆反応自体を阻害するおそれがあるため、表面処理剤の添加は銀被覆層の形成後が好ましい。
In order to form the silver coating layer more uniformly, a chelating agent may be added to a reaction liquid (mixed solution or emulsion) containing an organic solvent. As the chelating agent, those having a high complex stability constant with copper ions are preferred so that copper ions by-produced by substitution reaction between silver ions and metallic copper do not reprecipitate. Specifically, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriamine, triethylenediamine, or a salt thereof can be used.
In performing the silver coating reaction stably and safely, a pH buffer may be added. Specifically, ammonium carbonate, ammonium hydrogen carbonate, aqueous ammonia, and sodium hydrogen carbonate can be used as a pH buffering agent.
In addition, since there exists a possibility that silver coating reaction itself may be inhibited if there exists surface treating agents, such as phytic acid, at the time of formation of a silver coating layer, addition of a surface treatment agent is preferable after formation of a silver coating layer.
前記フレーク状銅粉を被覆する銀の銅に対する割合（銀の被覆量）は、２０質量％以下が好ましく、０.３質量％〜２０質量％がより好ましく、０.５質量％〜１５質量％が更に好ましい。前記銀の被覆量が、０.３質量％未満であると、前記銀被覆銅粉を含む導電性ペーストからなる導電膜の体積抵抗率を十分に低減することができないことがあり、２０質量％を超えると、前記導電膜の体積抵抗率の低減効果に大きな差は見られず、銀の割合が増えることでコストが増大してしまう。 20 mass% or less is preferable, as for the ratio (silver coating amount) with respect to the copper which coat | covers the said flaky copper powder, 0.3 mass%-20 mass% are more preferable, 0.5 mass%-15 mass% Is more preferable. If the silver coating amount is less than 0.3% by mass, the volume resistivity of the conductive film made of a conductive paste containing the silver-coated copper powder may not be sufficiently reduced. If it exceeds 1, no significant difference is seen in the effect of reducing the volume resistivity of the conductive film, and the cost increases due to an increase in the proportion of silver.
＜その他の工程＞
前記その他の工程としては、例えば、洗浄及び乾燥工程などが挙げられる。
−洗浄及び乾燥工程−
前記洗浄及び乾燥工程は、得られた銀被覆銅粉を固液分離し、必要に応じて、洗浄を行い、乾燥する工程である。
前記洗浄及び乾燥としては、特に制限はなく、銅粉に対する公知の方法を適宜使用することができ、乾燥後において解砕を行ってもよい。
<Other processes>
As said other process, a washing | cleaning, a drying process, etc. are mentioned, for example.
-Cleaning and drying process-
The said washing | cleaning and drying process is a process of solid-liquid-separating the obtained silver covering copper powder, and washing | cleaning and drying as needed.
There is no restriction | limiting in particular as said washing | cleaning and drying, The well-known method with respect to copper powder can be used suitably, You may disintegrate after drying.
得られた本発明の前記銀被覆銅粉は、以下に説明する導電性ペーストに配合して用いることが好ましい。 The obtained silver-coated copper powder of the present invention is preferably used by blending into the conductive paste described below.
（導電性ペースト）
本発明の導電性ペーストは、本発明の前記銀被覆銅粉と、樹脂とを含み、更に必要に応じてその他の成分を含有してなる。
前記導電性ペーストとしては、例えば、樹脂硬化型ペーストなどが挙げられる。
前記導電性ペーストにおける前記銀被覆銅粉の含有量は、特に制限はなく、目的に応じて適宜選択することができる。
(Conductive paste)
The conductive paste of the present invention contains the silver-coated copper powder of the present invention and a resin, and further contains other components as necessary.
Examples of the conductive paste include a resin curable paste.
There is no restriction | limiting in particular in content of the said silver covering copper powder in the said electrically conductive paste, According to the objective, it can select suitably.
＜樹脂＞
前記樹脂としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリウレタン樹脂、フェノキシ樹脂、シリコーン樹脂、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
<Resin>
There is no restriction | limiting in particular as said resin, According to the objective, it can select suitably, For example, an epoxy resin, an acrylic resin, a polyester resin, a polyimide resin, a polyurethane resin, a phenoxy resin, a silicone resin etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
＜溶剤＞
前記溶剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、トルエン、メチルエチルケトン、メチルイソブチルケトン、テトラデカン、テトラリン、プロピルアルコール、イソプロピルアルコール、テルピネオール、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、ブチルカルビトールアセテート、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、酢酸ジエチレングリコールモノ−ｎ−エチルエーテルなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
<Solvent>
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, tetradecane, tetralin, propyl alcohol, isopropyl alcohol, terpineol, ethyl carbitol, butyl carbitol Ethyl carbitol acetate, butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, diethylene glycol acetate mono-n-ethyl ether, and the like. These may be used individually by 1 type and may use 2 or more types together.
＜その他の成分＞
前記その他の成分としては、例えば、界面活性剤、ガラスフリット、分散剤、粘度調整剤などが挙げられる。
<Other ingredients>
Examples of the other components include surfactants, glass frit, dispersants, viscosity modifiers, and the like.
前記導電性ペーストの作製方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、本発明の前記銀被覆銅粉を、前記樹脂、前記溶剤、及び必要に応じて前記その他の成分を、例えば、超音波分散、ディスパー、三本ロールミル、ボールミル、ビーズミル、二軸ニーダー、自公転式攪拌機などを用い、混合することにより作製することができる。 There is no restriction | limiting in particular as a preparation method of the said electrically conductive paste, According to the objective, it can select suitably, For example, the said silver covering copper powder of this invention is the said resin, the said solvent, and the said as needed. Other components can be prepared by mixing using, for example, ultrasonic dispersion, a disper, a three-roll mill, a ball mill, a bead mill, a twin-screw kneader, a self-revolving stirrer, and the like.
前記導電性ペーストの粘度としては、特に制限はなく、目的に応じて適宜選択することができるが、２５℃で、５Ｐａ・ｓ〜１００Ｐａ・ｓが好ましい。前記導電性ペーストの粘度が、５Ｐａ・ｓ未満であると、印刷時に「にじみ」が発生することがあり、１００Ｐａ・ｓを超えると、印刷むらが発生することがある。
前記導電性ペーストを用いた導電膜の体積抵抗率は、特に制限はなく、目的に応じて適宜選択することができるが、１×１０−２Ω・ｃｍ以下が好ましく、１×１０−３Ω・ｃｍ以下がより好ましく、５×１０−４Ω・ｃｍ以下が更に好ましい。前記体積抵抗率が、１×１０−２Ω・ｃｍ以下であると、極めて低い体積抵抗率の導電膜が実現可能である。前記体積抵抗率が、１×１０−２Ω・ｃｍを超えると、導電膜の導電性が不十分となることがある。
前記導電膜の体積抵抗率は、例えば、デジタルマルチメーター（ＡＤＶＡＮＴＥＳＴ社製、Ｒ６５５１）を用いて、導電膜の長手方向の２点間の抵抗値を測定し、体積抵抗率＝抵抗値×導電膜の厚み×導電膜の幅÷導電膜の長さを算出することにより測定することができる。
There is no restriction | limiting in particular as a viscosity of the said electrically conductive paste, Although it can select suitably according to the objective, 5 Pa * s-100 Pa * s are preferable at 25 degreeC. When the viscosity of the conductive paste is less than 5 Pa · s, “bleeding” may occur during printing, and when it exceeds 100 Pa · s, uneven printing may occur.
The volume resistivity of the conductive film using the conductive paste is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1 × 10 −2 Ω · cm or less, and preferably 1 × 10 −3 Ω. -More preferably, it is cm or less, and more preferably 5 x 10-4 Ω-cm or less. When the volume resistivity is 1 × 10 −2 Ω · cm or less, a conductive film having an extremely low volume resistivity can be realized. When the volume resistivity exceeds 1 × 10 −2 Ω · cm, the conductivity of the conductive film may be insufficient.
For the volume resistivity of the conductive film, for example, a resistance value between two points in the longitudinal direction of the conductive film is measured using a digital multimeter (manufactured by ADVANTEST, R6551), and volume resistivity = resistance value × conductive film. The thickness can be measured by calculating the thickness of the conductive film × the width of the conductive film ÷ the length of the conductive film.
本発明の前記銀被覆銅粉を含む本発明の前記導電性ペーストは、例えば、太陽電池用のシリコンウエハー、タッチパネル用フィルム、ＥＬ素子用ガラス等の各種基体上に直接、あるいは必要に応じて前記基体上に更に透明導電膜を設けたその膜上に、塗布又は印刷して導電膜の形成に好適に用いることができる。
本発明の導電性ペーストを用いて得られた導電膜は、例えば、太陽電池セルの集電電極、チップ型電子部品の外部電極、ＲＦＩＤ、電磁波シールド、振動子接着、メンブレンスイッチ、エレクトロルミネセンス等の電極又は電気配線用途に好適に用いられる。
The conductive paste of the present invention containing the silver-coated copper powder of the present invention is directly on a variety of substrates such as a silicon wafer for a solar cell, a film for a touch panel, and glass for an EL element, or as necessary. It can be suitably used for forming a conductive film by coating or printing on the film in which a transparent conductive film is further provided on the substrate.
The conductive film obtained using the conductive paste of the present invention is, for example, a collector electrode of a solar battery cell, an external electrode of a chip-type electronic component, an RFID, an electromagnetic wave shield, a vibrator adhesive, a membrane switch, electroluminescence, etc. It is suitably used for electrode or electrical wiring applications.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
以下のようにして、銀被覆銅粉を製造した。また、得られた銀被覆銅粉を用い、導電性ペーストを作製した。また、前記導電性ペーストを塗布し、加熱処理することにより導電膜を形成した。
前記銀被覆銅粉のＢＥＴ比表面積、粒度分布（Ｄ１０、Ｄ５０、及びＤ９０）、タップ密度、及び銀被覆量の測定方法は、以下に示す通りである。
Silver-coated copper powder was produced as follows. Moreover, the electrically conductive paste was produced using the obtained silver covering copper powder. Moreover, the said electrically conductive paste was apply | coated and the electrically conductive film was formed by heat-processing.
The methods for measuring the BET specific surface area, the particle size distribution (D 10 , D 50 , and D 90 ), the tap density, and the silver coating amount of the silver-coated copper powder are as follows.
＜ＢＥＴ比表面積の測定方法＞
銀被覆銅粉のＢＥＴ比表面積は、ＭＯＮＯＳＯＲＢ装置（湯浅アイオニクス株式会社製）で、Ｈｅ：７０％、Ｎ２：３０％のキャリアガスを用い、銀被覆銅粉３ｇをセルに入れて脱気を６０℃で１０分間行った後、ＢＥＴ１点法により測定を行った。
<Measurement method of BET specific surface area>
The BET specific surface area of the silver-coated copper powder was degassed with a MONOSORB apparatus (manufactured by Yuasa Ionics Co., Ltd.) using He: 70%, N 2 : 30% carrier gas, and 3 g of the silver-coated copper powder in the cell. Was carried out at 60 ° C. for 10 minutes and then measured by the BET one-point method.
＜粒度分布（Ｄ１０、Ｄ５０、及びＤ９０）の測定方法＞
銀被覆銅粉の粒度分布は、レーザー回折散乱式粒度分布測定装置（日機装株式会社製、ＭＩＣＲＯＴＯＲＡＣ ＨＲＡ）を用いて、銀被覆銅粉０．３ｇをイソプロパノール３０ｍＬに加え、超音波分散処理を５分間行って試料を準備し、全反射モードで粒径の測定を行った。測定により得た質量累積分布により、累積１０質量％粒径（Ｄ１０）、累積５０質量％粒径（Ｄ５０）、及び累積９０質量％粒径（Ｄ９０）の値を求めた。
<Measurement method of particle size distribution (D 10, D 50, and D 90)>
The particle size distribution of the silver-coated copper powder is determined by adding 0.3 g of silver-coated copper powder to 30 mL of isopropanol using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., MICROTORAC HRA), and subjecting it to ultrasonic dispersion treatment for 5 minutes. A sample was prepared and the particle size was measured in total reflection mode. Mass cumulative distribution obtained by the measurement, the cumulative 10% particle size (D 10), the cumulative 50% particle size (D 50), and determine the value of the cumulative 90% particle size (D 90).
＜タップ密度の測定＞
タップ密度は、タップ密度測定装置（柴山科学株式会社製、カサ比重測定装置ＳＳ−ＤＡ−２）を使用し、銀被覆銅粉１５ｇを計量して、容器（２０ｍＬ試験管）に入れ、落差２０ｍｍで１，０００回タッピングし、タップ密度＝試料重量（１５ｇ）／タッピング後の試料体積から算出した。
<Measurement of tap density>
The tap density is measured using a tap density measuring device (Shibayama Kagaku Co., Ltd., Casa specific gravity measuring device SS-DA-2), 15 g of silver-coated copper powder is weighed, put into a container (20 mL test tube), and a drop of 20 mm. And tapped 1,000 times, and calculated from tap density = sample weight (15 g) / sample volume after tapping.
＜銀被覆量の実測値＞
前記銀の被覆量は、銀被覆銅粉を硝酸で溶解後に塩酸を添加し、生じた塩化銀の沈殿を乾燥し、重量を測定することにより求めた。
<Measured value of silver coating amount>
The silver coating amount was determined by dissolving silver-coated copper powder with nitric acid, adding hydrochloric acid, drying the resulting silver chloride precipitate, and measuring the weight.
＜銀被覆銅粉におけるリンの含有量（実測値）＞
銀被覆銅粉を塩酸抽出した液を、エスアイアイ・ナノテクノロジー株式会社製プラズマ発光分光装置 ＳＰＳ５１００により、銀被覆銅粉におけるリンの含有量を測定した。
<Phosphorus content in silver-coated copper powder (measured value)>
The liquid in which the silver-coated copper powder was extracted with hydrochloric acid was measured for the phosphorus content in the silver-coated copper powder with a plasma emission spectrometer SPS5100 manufactured by SII Nano Technology.
（実施例１）
＜銀被覆フレーク状銅粉の作製＞
−電解銅粉−
電解銅粉として、ＪＸ日鉱日石金属株式会社製 ＃５１−Ｒ（Ａ）を用意した。
電解銅粉について、走査型電子顕微鏡（ＳＥＭ、日本電子工業株式会社製、ＪＳＭ−６１００）を使用し、２，０００倍にて観察を行った。得られたＳＥＭ写真を図１に示した。
Example 1
<Preparation of silver-coated flaky copper powder>
-Electrolytic copper powder-
As electrolytic copper powder, JX Nippon Mining & Metals Co., Ltd. # 51-R (A) was prepared.
The electrolytic copper powder was observed at a magnification of 2,000 using a scanning electron microscope (SEM, manufactured by JEOL Ltd., JSM-6100). The obtained SEM photograph is shown in FIG.
−扁平化工程−
前記電解銅粉１，２５４ｇとネオエタノールＰ−７（大伸化学株式会社製）６２４ｇをＳＵＳボール（直径１．６ｍｍ）１０．５ｋｇとともにアトライター（日本コークス工業株式会社製、ＭＡ−１ＳＥ−Ｘ）に入れて、回転数３６０ｒｐｍ、処理時間１２０分間の条件で扁平化処理を実施し、フレーク状銅粉スラリーを得た。得られたフレーク状銅粉スラリーとＳＵＳボールの分離後、濾過して得られたウェットケーキを７０℃で真空乾燥を行い、フレーク状銅粉を得た。
-Flattening process-
The electrolytic copper powder 1,254 g and neoethanol P-7 (manufactured by Daishin Chemical Co., Ltd.) 624 g together with 10.5 kg of SUS balls (diameter 1.6 mm), attritor (manufactured by Nippon Coke Industries, Ltd., MA-1SE-X ), And a flattening treatment was performed under the conditions of a rotation speed of 360 rpm and a treatment time of 120 minutes to obtain a flaky copper powder slurry. After separating the obtained flaky copper powder slurry and SUS balls, the wet cake obtained by filtration was vacuum dried at 70 ° C. to obtain flaky copper powder.
−銀被覆工程及び表面処理工程−
炭酸アンモニウム１７５ｇとエチレンジアミン四酢酸四ナトリウム塩溶液（ＥＤＴＡ・４Ｎａ）７３５ｇを純水１，１３６ｇに溶解し、液温を３５℃に調整した。この溶液と銀３８．９ｇ含有の硝酸銀水溶液を混合して、銀錯塩溶液を調整した。また、炭酸アンモニウム９．１ｇとＥＤＴＡ・４Ｎａ １１３ｇを純水１，４０４ｇに溶解させた後、前記フレーク銅粉３５０ｇを加え攪拌してフレーク状銅粉分散液を準備した。このフレーク状銅粉分散液を乾燥窒素ガス雰囲気にて液温を３５℃に調整し、前記銀錯塩溶液を添加し銀被覆反応を実施し、３０分間攪拌しながら保持した。
-Silver coating process and surface treatment process-
175 g of ammonium carbonate and 735 g of ethylenediaminetetraacetic acid tetrasodium salt solution (EDTA · 4Na) were dissolved in 1,136 g of pure water, and the liquid temperature was adjusted to 35 ° C. This solution and a silver nitrate aqueous solution containing 38.9 g of silver were mixed to prepare a silver complex salt solution. Moreover, after 9.1 g of ammonium carbonate and 113 g of EDTA · 4Na were dissolved in 1,404 g of pure water, 350 g of the flake copper powder was added and stirred to prepare a flaky copper powder dispersion. The liquid temperature of this flaky copper powder dispersion was adjusted to 35 ° C. in a dry nitrogen gas atmosphere, the silver complex salt solution was added to carry out the silver coating reaction, and the mixture was held for 30 minutes with stirring.
−表面処理工程−
前記銀被覆後のスラリーを撹拌しながら、表面処理剤１として純正化学株式会社製フィチン酸５０％水溶液（フィチン酸含有率５０質量％）１．６１ｇを純水８．０５ｇで希釈した後、この希釈液を添加し５分間撹拌を継続した。
次いで、表面処理剤２としてのステアリン酸１５質量％のステアリン酸エマルジョン５．７ｇを添加し、５分間攪拌を継続して、銀被覆銅粉への表面処理を行った。
得られた銀被覆フレーク銅粉を濾過して、イオン交換水で洗浄し、更にイソプロパノールで洗浄し、得られたウェットケーキを７０℃で真空乾燥を行い、実施例１の銀被覆フレーク状銅粉を得た。
得られた実施例１の銀被覆フレーク状銅粉の走査型電子顕微鏡（ＳＥＭ、日本電子工業株式会社製、ＪＳＭ−６１００）によるＳＥＭ写真を図２に示した。
-Surface treatment process-
While stirring the slurry after the silver coating, 1.61 g of 50% aqueous phytic acid (manufactured by phytic acid content: 50% by mass) as a surface treatment agent 1 was diluted with 8.05 g of pure water. Dilution was added and stirring was continued for 5 minutes.
Next, 5.7 g of a stearic acid emulsion containing 15% by mass of stearic acid as the surface treatment agent 2 was added, and stirring was continued for 5 minutes to perform surface treatment on the silver-coated copper powder.
The obtained silver-coated flake copper powder is filtered, washed with ion-exchanged water, further washed with isopropanol, and the resulting wet cake is vacuum-dried at 70 ° C. to obtain the silver-coated flake-like copper powder of Example 1 Got.
The SEM photograph by the scanning electron microscope (SEM, the JEOL Ltd. make, JSM-6100) of the obtained silver covering flaky copper powder of Example 1 was shown in FIG.
（実施例２）
実施例１において、表面処理工程においてステアリン酸を用いなかった以外は、実施例１と同様にして、実施例２の銀被覆フレーク状銅粉を得た。
(Example 2)
In Example 1, a silver-coated flaky copper powder of Example 2 was obtained in the same manner as in Example 1 except that stearic acid was not used in the surface treatment step.
（比較例１）
実施例１において、表面処理工程においてフィチン酸を添加しなかった以外は、実施例１と同様にして、比較例１の銀被覆フレーク状銅粉を得た。
(Comparative Example 1)
In Example 1, a silver-coated flaky copper powder of Comparative Example 1 was obtained in the same manner as in Example 1 except that phytic acid was not added in the surface treatment step.
（比較例２）
比較例１において、表面処理工程においてフィチン酸をベンゾトリアゾール（ＢＴＡ）に代えた以外は、比較例１と同様にして、比較例２の銀被覆フレーク状銅粉を得た。
(Comparative Example 2)
In Comparative Example 1, a silver-coated flaky copper powder of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that phytic acid was replaced with benzotriazole (BTA) in the surface treatment step.
（比較例３）
比較例１において、表面処理工程においてフィチン酸をベンゾトリアゾール（ＢＴＡ）に代え、ステアリン酸を用いなかった以外は、比較例１と同様にして、比較例３の銀被覆フレーク状銅粉を得た。
(Comparative Example 3)
In Comparative Example 1, the silver-coated flaky copper powder of Comparative Example 3 was obtained in the same manner as in Comparative Example 1, except that phytic acid was replaced with benzotriazole (BTA) in the surface treatment step and stearic acid was not used. .
（比較例４）
実施例１において、銀被覆反応の直後には表面処理剤１及び表面処理剤２を添加せず、銀被覆フレーク銅粉を濾過して固液分離し、イオン交換水で洗浄した後に再度純水３，８００ｇを添加して攪拌したところに表面処理剤１及び表面処理剤２を添加し、再度、銀被覆フレーク銅粉を濾過して、イオン交換水で洗浄し、更にイソプロパノールで洗浄し、得られたウェットケーキを７０℃で真空乾燥を行った以外は、実施例１と同様にして、比較例４の銀被覆フレーク状銅粉を得た。
(Comparative Example 4)
In Example 1, immediately after the silver coating reaction, the surface treatment agent 1 and the surface treatment agent 2 were not added, the silver-coated flake copper powder was filtered and solid-liquid separated, washed with ion-exchanged water, and then pure water again. When 3,800 g was added and stirred, surface treatment agent 1 and surface treatment agent 2 were added, and the silver-coated flake copper powder was filtered again, washed with ion-exchanged water, and further washed with isopropanol. A silver-coated flaky copper powder of Comparative Example 4 was obtained in the same manner as in Example 1 except that the obtained wet cake was vacuum-dried at 70 ° C.
（比較例５）
比較例４において、表面処理剤１のフィチン酸をリン酸（和光純薬工業株式会社製）１．００ｇに変えた以外は、比較例４と同様にして、比較例５の銀被覆フレーク状銅粉を得た。
(Comparative Example 5)
In Comparative Example 4, the silver-coated flaky copper of Comparative Example 5 was the same as Comparative Example 4 except that the phytic acid of the surface treatment agent 1 was changed to 1.00 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.). I got a powder.
次に、実施例１〜２及び比較例１〜５の条件などについて表１にまとめて示した。得られた実施例１〜２及び比較例１〜５の銀被覆フレーク状銅粉の諸特性を評価した。結果を表２に示した。 Next, Table 1 collectively shows the conditions of Examples 1-2 and Comparative Examples 1-5. Various characteristics of the obtained silver-coated flaky copper powders of Examples 1-2 and Comparative Examples 1-5 were evaluated. The results are shown in Table 2.
＜ＴＧ−ＤＴＡ測定＞
作製した実施例１〜２及び比較例１〜５について、以下の装置及び条件でＴＧ−ＤＴＡ測定を行った。４００℃での重量増加率の結果を表３に示した。実施例１の結果を図３、実施例２の結果を図４、比較例１の結果を図５、比較例２の結果を図６、比較例３の結果を図７、比較例４の結果を図１０、比較例５の結果を図１１にそれぞれ示した。
＜＜ＴＧ−ＤＴＡ装置及び条件＞＞
株式会社リガク製ＴｈｅｒｍｏＰｌｕｓ ＴＧ−８１２０を用い、試料２０ｍｇを１０℃／分の速度で昇温し、重量の変化を測定した。（重量増加値÷試料重量）×１００＝重量増加率（重量％）を算出した。
<TG-DTA measurement>
About the produced Examples 1-2 and Comparative Examples 1-5, TG-DTA measurement was performed on the following apparatuses and conditions. The results of the weight increase rate at 400 ° C. are shown in Table 3. FIG. 3 shows the result of Example 1, FIG. 4 shows the result of Example 2, FIG. 5 shows the result of Comparative Example 1, FIG. 6 shows the result of Comparative Example 2, FIG. 7 shows the result of Comparative Example 3, and FIG. FIG. 10 shows the results of Comparative Example 5, and FIG. 11 shows the results.
<< TG-DTA apparatus and conditions >>
Using ThermoPlus TG-8120 manufactured by Rigaku Corporation, a sample 20 mg was heated at a rate of 10 ° C./min, and the change in weight was measured. (Weight increase value ÷ sample weight) × 100 = weight increase rate (% by weight) was calculated.
＜導電性ペーストの作製＞
次に、作製した実施例１〜２及び比較例１〜５の各銀被覆銅粉、ポリエステル樹脂、及び溶剤を下記の組成で混合し、３本ロール（オットハーマン社製、ＥＸＡＫＴ８０Ｓ）を用いて、ロールギャップを１００μｍ〜２０μｍまで通過させて混練処理を行い、更に適宜溶剤を追加し粘度を約８Ｐａ・ｓ（ブルックフィールド社製粘度計ＤＶ−ＩＩＩ ＵＲＴＲＡにて回転数１ｒｐｍ時の値）に調整を行うことにより、実施例及び比較例の各導電性ペーストを得た。
・各銀被覆銅粉・・・６０質量部
・ポリエステル樹脂（東洋紡績株式会社製、バイロン２００）・・・１２質量部
・溶剤〔ＥＣＡ（酢酸ジエチレングリコールモノ−ｎ−エチルエーテル）、和光純薬工業株式会社製〕・・・２８質量部
<Preparation of conductive paste>
Next, each silver covering copper powder, polyester resin, and solvent of the produced Examples 1-2 and Comparative Examples 1-5 were mixed by the following composition, and 3 rolls (EXOTT80S made by Otto Herman) were used. , Kneading by passing the roll gap from 100 μm to 20 μm, and adding a solvent as appropriate to adjust the viscosity to about 8 Pa · s (value at 1 rpm with Brookfield viscometer DV-III URTRA). As a result, the conductive pastes of Examples and Comparative Examples were obtained.
Each silver-coated copper powder: 60 parts by mass Polyester resin (byron 200, manufactured by Toyobo Co., Ltd.): 12 parts by mass Solvent [ECA (acetic acid diethylene glycol mono-n-ethyl ether), Wako Pure Chemical Industries, Ltd. Made by Co., Ltd.] 28 parts by mass
次に、アルミナ基板上にスクリーン印刷で、作製した導電性ペーストの膜を形成した。スクリーン印刷条件は、下記のとおりであった。
・印刷装置：マイクロテック社製 ＭＴ−３２０Ｔ
・印刷条件：スキージ圧０．１８ＭＰａ、膜は、幅５００μｍ、長さ３７．５ｍｍの回路形成をした。
得られた膜を、大気循環式乾燥機を用い、１３０℃、３０分間の条件で加熱処理し、導電膜を形成した。
得られた各導電膜について、以下のようにして、平均厚み、及び体積抵抗率を測定した。結果を表４及び図９に示した。
Next, a film of the produced conductive paste was formed on the alumina substrate by screen printing. Screen printing conditions were as follows.
-Printing device: MT-320T manufactured by Microtech
-Printing conditions: A squeegee pressure of 0.18 MPa, a film having a width of 500 μm and a length of 37.5 mm was formed.
The obtained film was heat-treated at 130 ° C. for 30 minutes using an air circulation dryer to form a conductive film.
About each obtained electrically conductive film, average thickness and volume resistivity were measured as follows. The results are shown in Table 4 and FIG.
＜導電膜の平均厚み＞
得られた各導電膜を、表面粗さ計（株式会社小坂研究所製、ＳＥ−３０Ｄ）を用いて、
アルミナ基板上で膜を印刷していない部分と導電膜の部分との段差を測定することにより、導電膜の平均厚みを測定した。
<Average thickness of conductive film>
Each obtained conductive film was measured using a surface roughness meter (SE-30D, manufactured by Kosaka Laboratory Ltd.)
The average thickness of the conductive film was measured by measuring the level difference between the portion where the film was not printed on the alumina substrate and the conductive film portion.
＜導電膜の体積抵抗率＞
デジタルマルチメーター（ＡＤＶＡＮＴＥＳＴ社製、Ｒ６５５１）を用いて、各導電膜の長さ(間隔）の位置の抵抗値を測定した。各導電膜のサイズ（膜厚、幅、長さ）より、導電膜の体積を求め、この体積と測定した抵抗値から、体積抵抗率を求めた。
<Volume resistivity of conductive film>
The resistance value at the position of the length (interval) of each conductive film was measured using a digital multimeter (manufactured by ADVANTEST, R6551). The volume of the conductive film was determined from the size (film thickness, width, length) of each conductive film, and the volume resistivity was determined from this volume and the measured resistance value.
以上の実施例１、２及び比較例１〜３の体積抵抗率の結果から、フィチン酸を用いて表面処理を行うと、導電膜の体積抵抗率を低減できることが分かった。また、体積抵抗率の結果及びＴＧの重量増加率の結果から、フィチン酸と脂肪酸を用いて表面処理を行うと、銀の割合を高めることなく、導電膜の体積抵抗率が低減し、かつ優れた酸化防止効果が得られることがわかった。
ただし、比較例４のように表面処理後の銀被覆銅粉に含まれるリンの含有量が０．０１質量％を超えて多いと、導電膜の体積抵抗率は逆に悪化することが分かった。そして、体積抵抗率はリン酸を用いた比較例５の方が悪化しやすく、リンを含有する化合物の中でもフィチン酸が優れた導電性を有し、かつ該導電性の経時変化を少なくするのに有効であることが分かった。
From the results of the volume resistivity of Examples 1 and 2 and Comparative Examples 1 to 3 described above, it was found that when the surface treatment was performed using phytic acid, the volume resistivity of the conductive film could be reduced. Further, from the results of the volume resistivity and the result of the weight increase rate of TG, when surface treatment is performed using phytic acid and a fatty acid, the volume resistivity of the conductive film is reduced without increasing the proportion of silver, and excellent. It was found that an antioxidant effect was obtained.
However, when the content of phosphorus contained in the silver-coated copper powder after the surface treatment was larger than 0.01% by mass as in Comparative Example 4, it was found that the volume resistivity of the conductive film deteriorated conversely. . And, the volume resistivity is more likely to be worse in Comparative Example 5 using phosphoric acid, and among the compounds containing phosphorus, phytic acid has excellent conductivity, and reduces the temporal change of the conductivity. It was found to be effective.
本発明の態様としては、例えば、以下のものなどが挙げられる。
＜１＞ 銅粉に銀を被覆してなる銀被覆銅粉の表面にリンを含有する化合物を少なくとも有し、リンの含有量が０．０１質量％以下であることを特徴とする銀被覆銅粉である。
＜２＞ 前記リンを含有する化合物が、フィチン酸である前記＜１＞に記載の銀被覆銅粉である。
＜３＞ 前記銀被覆銅粉の表面に、脂肪酸を更に含有する前記＜１＞から＜２＞のいずれかに記載の銀被覆銅粉である。
＜４＞ 前記脂肪酸が、ステアリン酸である前記＜３＞に記載の銀被覆銅粉である。
＜５＞ 前記銅粉に銀を被覆してなる銀被覆銅粉を表面処理剤で表面処理してなり、
銀の被覆量が２０質量％以下であり、
熱重量測定（ＴＧ）による４００℃での重量増加率が１３重量％以下であり、
ＢＥＴ比表面積が０．７ｍ２／ｇ以上である前記＜３＞から＜４＞のいずれかに記載の銀被覆銅粉である。
＜６＞ 前記銅粉が、該銅粉をフレーク化処理したフレーク状銅粉である前記＜１＞から＜５＞のいずれかに記載の銀被覆銅粉である。
＜７＞ 前記銅粉が、電気分解法により得られた電解銅粉である前記＜６＞に記載の銀被覆銅粉である。
＜８＞ 銅粉の表面に銀を被覆してなる銀被覆銅粉をフィチン酸で表面処理する第１の表面処理工程を少なくとも含み、前記第１の表面処理工程後の銀被覆銅粉におけるリンの含有量が０．０１質量％以下であることを特徴とする銀被覆銅粉の製造方法である。
＜９＞ 前記フィチン酸で表面処理した銀被覆銅粉を脂肪酸で表面処理する第２の表面処理工程を更に含み、
前記脂肪酸が、ステアリン酸である前記＜８＞に記載の銀被覆銅粉の製造方法である。
＜１０＞ 前記表面処理工程を銅粉に銀を被覆する湿式反応の後で固液分離の前に行う前記＜８＞から＜９＞のいずれかに記載の銀被覆銅粉の製造方法。
＜１１＞ 前記＜１＞から＜７＞のいずれかに記載の銀被覆銅粉を含有することを特徴とする導電性ペーストである。
Examples of the aspect of the present invention include the following.
<1> Silver-coated copper characterized in that it has at least a compound containing phosphorus on the surface of silver-coated copper powder obtained by coating silver on copper powder, and the phosphorus content is 0.01% by mass or less. It is powder.
<2> The silver-coated copper powder according to <1>, wherein the phosphorus-containing compound is phytic acid.
<3> The silver-coated copper powder according to any one of <1> to <2>, further containing a fatty acid on a surface of the silver-coated copper powder.
<4> The silver-coated copper powder according to <3>, wherein the fatty acid is stearic acid.
<5> Surface treatment of a silver-coated copper powder obtained by coating silver on the copper powder with a surface treatment agent,
The silver coating amount is 20% by mass or less,
The weight increase rate at 400 ° C. by thermogravimetry (TG) is 13% by weight or less,
The silver-coated copper powder according to any one of <3> to <4>, wherein the BET specific surface area is 0.7 m 2 / g or more.
<6> The silver-coated copper powder according to any one of <1> to <5>, wherein the copper powder is a flaky copper powder obtained by flaking the copper powder.
<7> The silver-coated copper powder according to <6>, wherein the copper powder is an electrolytic copper powder obtained by an electrolysis method.
<8> At least a first surface treatment step of surface-treating silver-coated copper powder obtained by coating silver on the surface of copper powder with phytic acid, and phosphorus in the silver-coated copper powder after the first surface treatment step Is a method for producing silver-coated copper powder, characterized in that the content of is 0.01% by mass or less.
<9> A second surface treatment step of surface-treating the silver-coated copper powder surface-treated with phytic acid with a fatty acid,
It is a manufacturing method of the silver covering copper powder as described in said <8> whose said fatty acid is stearic acid.
<10> The method for producing a silver-coated copper powder according to any one of <8> to <9>, wherein the surface treatment step is performed after a wet reaction for coating copper powder with silver and before solid-liquid separation.
<11> A conductive paste comprising the silver-coated copper powder according to any one of <1> to <7>.
本発明の前記銀被覆銅粉を含む本発明の前記導電性ペーストは、例えば、太陽電池用のシリコンウエハー、タッチパネル用フィルム、ＥＬ素子用ガラス等の各種基体上に直接、あるいは必要に応じて前記基体上に更に透明導電膜を設けたその膜上に、塗布又は印刷して導電膜の形成に好適に用いることができる。
本発明の導電性ペーストを用いて得られた導電膜は、例えば、太陽電池セルの集電電極、チップ型電子部品の外部電極、ＲＦＩＤ、電磁波シールド、振動子接着、メンブレンスイッチ、エレクトロルミネセンス等の電極又は電気配線用途に好適に用いられる。
The conductive paste of the present invention containing the silver-coated copper powder of the present invention is directly on a variety of substrates such as a silicon wafer for a solar cell, a film for a touch panel, and glass for an EL element, or as necessary. It can be suitably used for forming a conductive film by coating or printing on the film in which a transparent conductive film is further provided on the substrate.
The conductive film obtained using the conductive paste of the present invention is, for example, a collector electrode of a solar battery cell, an external electrode of a chip-type electronic component, an RFID, an electromagnetic wave shield, a vibrator adhesive, a membrane switch, electroluminescence, etc. It is suitably used for electrode or electrical wiring applications.
Claims (11)
銀の被覆量が２０質量％以下であり、
熱重量測定（ＴＧ）による４００℃での重量増加率が１３重量％以下であり、
ＢＥＴ比表面積が０．７ｍ２／ｇ以上である請求項３から４のいずれかに記載の銀被覆銅粉。 The surface of the silver-coated copper powder formed by coating silver on the copper powder is treated with a surface treatment agent,
The silver coating amount is 20% by mass or less,
The weight increase rate at 400 ° C. by thermogravimetry (TG) is 13% by weight or less,
The silver-coated copper powder according to claim 3, wherein the BET specific surface area is 0.7 m 2 / g or more.
前記脂肪酸が、ステアリン酸である請求項８に記載の銀被覆銅粉の製造方法。 A second surface treatment step of surface-treating the silver-coated copper powder surface-treated with the phytic acid with a fatty acid;
The method for producing a silver-coated copper powder according to claim 8, wherein the fatty acid is stearic acid.
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