JP2008111175A - Composite metal powder, its production method, and electrically conductive paste - Google Patents
Composite metal powder, its production method, and electrically conductive paste Download PDFInfo
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- JP2008111175A JP2008111175A JP2006296014A JP2006296014A JP2008111175A JP 2008111175 A JP2008111175 A JP 2008111175A JP 2006296014 A JP2006296014 A JP 2006296014A JP 2006296014 A JP2006296014 A JP 2006296014A JP 2008111175 A JP2008111175 A JP 2008111175A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 154
- 239000002184 metal Substances 0.000 title claims abstract description 154
- 239000000843 powder Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 238000007747 plating Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- -1 ammonium carbonate-sodium ethylenediaminetetraacetate Chemical compound 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IZHWHGBOIBTTII-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[N+](=O)([O-])[O-].[Ag+2] Chemical compound C([O-])([O-])=O.[NH4+].[N+](=O)([O-])[O-].[Ag+2] IZHWHGBOIBTTII-UHFFFAOYSA-M 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- FSEPMQBEESWQEX-UHFFFAOYSA-N silver;ethane-1,2-diamine;nitrate Chemical compound [Ag+].NCCN.[O-][N+]([O-])=O FSEPMQBEESWQEX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Abstract
Description
本発明は、複合金属粉とその製造方法および、複合金属粉を用いた導電性ペーストに関する。 The present invention relates to a composite metal powder, a method for producing the same, and a conductive paste using the composite metal powder.
導電性ペーストは、導電性接着剤、導電性塗料として、各種電子機器、電子部品、電子回路など幅広く使用されている。このような導電性ペーストに含まれる導電性フィラーとしては、銀フレークや銅フレークが代表的なものである。しかし、銀フレークは高価であり、銅フレークは酸化しやすいという問題があった。 Conductive pastes are widely used as conductive adhesives and conductive paints such as various electronic devices, electronic components, and electronic circuits. Typical conductive fillers contained in such a conductive paste are silver flakes and copper flakes. However, silver flakes are expensive and copper flakes are easily oxidized.
このような問題を解決するために、種々の導電性フィラーが検討されている。例えば、導電性フィラーとして、樹脂粒子の表面を銀メッキした銀メッキ樹脂粒子が知られている。しかし、銀メッキ樹脂粒子は、銀メッキが不十分なことがあった。
そこで、金属粉の表面に、該金属とは異なる金属を被覆した金属メッキ粉体が提案されている。例えば、特許文献１には、銅粉の表面に銀を被覆した銀メッキ銅粉が開示されている。銀メッキ銅粉は、銅粉の表面を銀層で覆うことにより銅粉の酸化を防ぐので、このような銀メッキ銅粉を用いた導電性ペーストは、導電性が良好であった。
Therefore, a metal plating powder in which the surface of the metal powder is coated with a metal different from the metal has been proposed. For example, Patent Document 1 discloses silver-plated copper powder in which the surface of copper powder is coated with silver. Since the silver-plated copper powder prevents the copper powder from being oxidized by covering the surface of the copper powder with a silver layer, the conductive paste using such a silver-plated copper powder has good conductivity.
しかしながら、銀メッキ銅粉などの金属メッキ粉体を用いた導電性ペーストは、より優れた導電性能が求められている。 However, a conductive paste using a metal plating powder such as silver plating copper powder is required to have better conductive performance.
本発明は上記事情を鑑みてなされたもので、導電性により優れた導電性ペーストおよび、該導電性ペーストに用いる複合金属粉とその製造方法の提供を課題とする。 This invention is made | formed in view of the said situation, and makes it a subject to provide the electroconductive paste excellent in electroconductivity, the composite metal powder used for this electroconductive paste, and its manufacturing method.
本発明者らは鋭意検討した結果、例えば、銅粉の表面に銀を被覆した金属メッキ粉体を熱処理した複合金属粉は、銀の表面に***物が形成されることに注目した。そのような複合金属粉を用いた導電性ペーストは、熱処理を施さない金属メッキ粉体を用いた導電性ペーストに比べて、導電性が高くなることを見出し、本発明を完成するに至った。
すなわち、本発明の複合金属粉は、第一の金属粉の表面に、該第一の金属粉とは異なる第二の金属が被覆した複合金属粉であって、前記第二の金属の表面に***物が形成されていることを特徴とする。
また、前記***物の高さが２００ｎｍ以上であることが好ましい。
さらに、前記第二の金属は、前記第一の金属粉よりも比抵抗が低く、かつ、酸化しにくい金属であることが好ましい。
また、前記第一の金属粉が銅粉であり、前記第二の金属が銀であることが好ましい。
さらに、本発明の導電性ペーストは、前記複合金属粉を含むことを特徴とする。
As a result of intensive studies, the inventors of the present invention, for example, focused on the fact that bumps are formed on the surface of silver in a composite metal powder obtained by heat-treating a metal plating powder in which the surface of copper powder is coated with silver. It has been found that a conductive paste using such a composite metal powder has higher conductivity than a conductive paste using a metal plating powder not subjected to heat treatment, and has completed the present invention.
That is, the composite metal powder of the present invention is a composite metal powder in which the surface of the first metal powder is coated with a second metal different from the first metal powder, and the surface of the second metal is A raised object is formed.
Moreover, it is preferable that the height of the said protrusion is 200 nm or more.
Further, it is preferable that the second metal is a metal having a specific resistance lower than that of the first metal powder and hardly oxidizing.
Moreover, it is preferable that said 1st metal powder is copper powder and said 2nd metal is silver.
Furthermore, the conductive paste of the present invention is characterized by containing the composite metal powder.
また、本発明の複合金属粉の製造方法は、第一の金属粉の表面に、該第一の金属粉とは異なる第二の金属を被覆した後、２００℃以上で熱処理を施すことを特徴とする。
ここで、前記熱処理が還元性気体中で行われることが好ましい。
また、前記第二の金属は、前記第一の金属粉よりも比抵抗が低く、かつ、酸化しにくい金属であることが好ましい。
さらに、前記第一の金属粉が銅粉であり、前記第二の金属が銀であることが好ましい。
The method for producing a composite metal powder of the present invention is characterized in that the surface of the first metal powder is coated with a second metal different from the first metal powder, and then subjected to a heat treatment at 200 ° C. or higher. And
Here, the heat treatment is preferably performed in a reducing gas.
The second metal is preferably a metal having a specific resistance lower than that of the first metal powder and hardly oxidizing.
Furthermore, it is preferable that the first metal powder is copper powder and the second metal is silver.
本発明によれば、導電性により優れた導電性ペーストおよび、該導電性ペーストに用いる複合金属粉とその製造方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the electroconductive paste excellent in electroconductivity, the composite metal powder used for this electroconductive paste, and its manufacturing method can be provided.
以下、本発明について詳細に説明する。
本発明の複合金属粉は、第一の金属粉の表面に、該第一の金属粉とは異なる第二の金属が被覆しており、かつ、第二の金属の表面に***物が形成されている。
本発明においては、第一の金属粉の表面の少なくとも一部が第二の金属で被覆され、第一の金属粉の表面の全部が第二の金属で被覆されていてもよい。なお、第二の金属による第一の金属粉の表面の被覆率は２５％以上が好ましく、より好ましくは５０％以上である。被覆率が上記範囲より少なくと、第一の金属粉が酸化されやすくなる。
Hereinafter, the present invention will be described in detail.
In the composite metal powder of the present invention, the surface of the first metal powder is coated with a second metal different from the first metal powder, and a ridge is formed on the surface of the second metal. ing.
In the present invention, at least a part of the surface of the first metal powder may be coated with the second metal, and the entire surface of the first metal powder may be coated with the second metal. The coverage of the surface of the first metal powder with the second metal is preferably 25% or more, and more preferably 50% or more. When the coverage is less than the above range, the first metal powder is easily oxidized.
第一の金属粉としては、例えば、銅粒子、ニッケル粒子、アルミニウム粒子などが挙げられ、中でも、銅粒子が好ましい。また、形状は、略球形であっても、フレーク状であってもよいが、フレーク状が好ましい。第一の金属粉の含有量は、複合金属粉１００質量％中７０〜９９．５質量％が好ましく、８０〜９９質量％がより好ましい。 Examples of the first metal powder include copper particles, nickel particles, and aluminum particles. Among these, copper particles are preferable. The shape may be a substantially spherical shape or a flake shape, but a flake shape is preferred. 70-99.5 mass% is preferable in 100 mass% of composite metal powder, and, as for content of 1st metal powder, 80-99 mass% is more preferable.
第二の金属は、前記第一の金属粉とは異なる金属であり、また、第一の金属粉よりも比抵抗が低く、かつ、酸化しにくい金属が好ましい。第二の金属としては、第一の金属粉の表面をメッキできるものであればとくに限定されないが、例えば、銀、金などが挙げられ、中でも、銀が好ましい。第二の金属の含有量は、複合金属粉１００質量％中０．５〜３０質量％が好ましく、１〜２０質量％がより好ましい。第二の金属の含有量の下限値が上記値より小さくなると、第二の金属の表面での***物の形成が不十分となる。一方、含有量の上限値が上記値より大きくなると、メッキによる被覆が困難になり、コストアップになる。 The second metal is a metal different from the first metal powder, and is preferably a metal having a lower specific resistance than the first metal powder and hardly oxidizing. The second metal is not particularly limited as long as the surface of the first metal powder can be plated. Examples thereof include silver and gold. Among these, silver is preferable. 0.5-30 mass% is preferable in 100 mass% of composite metal powder, and, as for content of a 2nd metal, 1-20 mass% is more preferable. When the lower limit value of the content of the second metal is smaller than the above value, the formation of the raised matter on the surface of the second metal becomes insufficient. On the other hand, when the upper limit value of the content is larger than the above value, coating by plating becomes difficult and the cost increases.
ここで、本発明の複合金属粉の製造方法について説明する。
まず、第一の金属粉の表面に第二の金属を被覆して、金属メッキ粉体を製造する。被覆の方法としては、特に制限されないが、化学メッキが好ましく、その中でも特に置換メッキが好ましい。
例えば、銅粉に銀を被覆して銀メッキ銅粉を製造する場合は、水、炭酸アンモニウム水溶液、炭酸アンモニウム―エチレンジアミンテトラ酢酸ナトリウム（ＥＤＴＡ）水溶液に銅粉を分散させ銅分散液を調整し、該銅分散液に銀化合物の水溶液を添加しながら置換反応処理を行い、銀メッキ銅粉を製造する。銀化合物の水溶液としては、塩、錯体などの水溶液が用いられ、具体的には、硝酸銀水溶液、硝酸銀―炭酸アンモニウム水溶液、硝酸銀―エチレンジアミン水溶液、硝酸銀と各種水溶性のアミンとを含む水溶液、硝酸銀―炭酸アンモニウム―クエン酸塩水溶液、硝酸銀―炭酸アンモニウム―エチレンジアミンテトラ酢酸ナトリウム（ＥＤＴＡ）水溶液、シアン化銀アルカリ性水溶液などの銀イオンまたは銀錯イオンを含む水溶液が挙げられる。
なお、上述したようなメッキの処理によれば、第一の金属粉の表面の全部が第二の金属で被覆される。
Here, the manufacturing method of the composite metal powder of this invention is demonstrated.
First, the surface of the first metal powder is coated with the second metal to produce a metal plating powder. The coating method is not particularly limited, but chemical plating is preferable, and displacement plating is particularly preferable among them.
For example, when producing silver-plated copper powder by coating silver on copper powder, the copper dispersion is prepared by dispersing the copper powder in water, an aqueous solution of ammonium carbonate, or an aqueous solution of ammonium carbonate-sodium ethylenediaminetetraacetate (EDTA), A substitution reaction treatment is performed while adding an aqueous solution of a silver compound to the copper dispersion to produce silver-plated copper powder. As the aqueous solution of the silver compound, an aqueous solution of a salt, a complex or the like is used. Specifically, an aqueous solution of silver nitrate, an aqueous solution of silver nitrate-ammonium carbonate, an aqueous solution of silver nitrate-ethylenediamine, an aqueous solution containing silver nitrate and various water-soluble amines, silver nitrate— Examples of the aqueous solution include silver ions or silver complex ions such as an aqueous solution of ammonium carbonate-citrate, an aqueous solution of silver nitrate-ammonium carbonate-sodium ethylenediaminetetraacetate (EDTA), and an aqueous alkaline solution of silver cyanide.
In addition, according to the plating process as described above, the entire surface of the first metal powder is covered with the second metal.
次いで、金属メッキ粉体に２００℃以上で熱処理を施して、複合金属粉を得る。好ましい熱処理の温度は２００〜６００℃であり、より好ましくは２５０〜５００℃である。熱処理の温度の下限値が上記値より小さくなると、第二の金属の表面での***物の形成が不十分となる。なお、***物は熱処理の温度が高くなるに連れて大きく成長する傾向にあるが、温度の上限値が上記値を超えると***物の成長は止まるため、温度の上限値は上記値とすることが好ましい。 Next, the metal plating powder is heat-treated at 200 ° C. or higher to obtain a composite metal powder. A preferable heat treatment temperature is 200 to 600 ° C, more preferably 250 to 500 ° C. When the lower limit value of the temperature of the heat treatment is smaller than the above value, the formation of the raised matter on the surface of the second metal becomes insufficient. Note that the protuberance tends to grow greatly as the temperature of the heat treatment increases, but when the upper limit of the temperature exceeds the above value, the growth of the protuberance stops, so the upper limit of the temperature should be the above value. Is preferred.
前記熱処理は還元性気体中で行われるのが好ましい。還元性気体中で熱処理を行うことにより、通常の熱処理に伴う金属の酸化が防げる。また、複合金属粉の表面に金属の酸化膜が生じても、取り除くことができる。
前記還元性気体としては、水素、ホルムアルデヒドなどが挙げられ、中でも、水素が好ましい。
前記熱処理の処理時間は３０〜１８０分が好ましく、熱処理の温度に応じて、適宜変更してよい。
なお、上述したような熱処理を施すと、第一の金属粉が露出する場合もある。
The heat treatment is preferably performed in a reducing gas. By performing the heat treatment in a reducing gas, the oxidation of the metal accompanying the normal heat treatment can be prevented. Even if a metal oxide film is formed on the surface of the composite metal powder, it can be removed.
Examples of the reducing gas include hydrogen and formaldehyde. Among them, hydrogen is preferable.
The treatment time for the heat treatment is preferably 30 to 180 minutes, and may be appropriately changed according to the temperature of the heat treatment.
In addition, when the heat treatment as described above is performed, the first metal powder may be exposed.
このようにして得られる複合金属粉は、第一の金属粉の表面に第二の金属が被覆し、かつ、第二の金属の表面に***物が形成される。***物が形成されることにより、第二の金属の表面積が増え、隣接する複合金属粉同士が接触しやすくなる。なお、***物は、第二の金属の表面の少なくとも一部に形成されてもよく、表面全体に形成されてもよいが、表面積が増えることを考慮した場合、表面全体に形成されるのが望ましい。
前記***物の高さは、２００ｎｍ以上であることが好ましく、より好ましい高さは ２００〜５００ｎｍである。高さの下限値が上記値より小さくなると、表面積の増加が不十分で、導電性の向上が得られにくくなる。なお、***物の高さは上記値より高くなりにくい。
In the composite metal powder obtained in this manner, the surface of the first metal powder is coated with the second metal, and a ridge is formed on the surface of the second metal. By forming the protuberance, the surface area of the second metal is increased, and adjacent composite metal powders are easily brought into contact with each other. The raised object may be formed on at least a part of the surface of the second metal, or may be formed on the entire surface. However, when the surface area is increased, it is formed on the entire surface. desirable.
The height of the raised object is preferably 200 nm or more, and more preferably 200 to 500 nm. When the lower limit of the height is smaller than the above value, the surface area is not increased sufficiently, and it becomes difficult to obtain an improvement in conductivity. In addition, the height of the raised object is unlikely to be higher than the above value.
複合金属粉の平均粒子径は、０．５〜５０μｍが好ましく、より好ましくは１〜３０μｍである。平均粒子径の下限値が上記値より小さくなると、製造が困難となる。一方、平均粒子径の上限値が上記値より大きくなると、導電性ペーストの塗工が困難となる。 The average particle size of the composite metal powder is preferably 0.5 to 50 μm, more preferably 1 to 30 μm. If the lower limit value of the average particle diameter is smaller than the above value, production becomes difficult. On the other hand, when the upper limit value of the average particle diameter is larger than the above value, it becomes difficult to apply the conductive paste.
上述したように、本発明の複合金属粉は、第二の金属の表面に***物が形成されているため、複合金属粉の表面積が増え、隣接する複合金属粉同士が接触しやすくなる。その結果、複合金属粉を用いた本発明の導電性ペーストは、熱処理を施さない金属メッキ粉体を用いた導電性ペーストに比べて導電性が向上する。 As described above, in the composite metal powder of the present invention, since the raised material is formed on the surface of the second metal, the surface area of the composite metal powder is increased, and adjacent composite metal powders are easily in contact with each other. As a result, the conductive paste of the present invention using the composite metal powder has improved conductivity as compared with the conductive paste using the metal plating powder not subjected to heat treatment.
前記導電性ペーストに含まれる成分としては、公知の成分が適用できるが、例えば、バインダー、硬化剤、溶剤、無機フィラーなどが挙げられる。また、任意の添加剤を含んでもよい。
バインダーとしては、例えば、エポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、フェノール樹脂、アクリル樹脂、塩化ビニル酢酸ビニル共重合樹脂、ブチラール樹脂などが挙げられる。
硬化剤としては、バインダーを硬化できるものであれば特に限定されないが、例えばイミダゾール化合物、イソシアネート化合物、酸無水物、アミン化合物、アミド化合物などが挙げられる。
As the component contained in the conductive paste, known components can be applied, and examples thereof include a binder, a curing agent, a solvent, and an inorganic filler. Moreover, you may include arbitrary additives.
Examples of the binder include an epoxy resin, a polyester resin, a polyurethane resin, a phenol resin, an acrylic resin, a vinyl chloride vinyl acetate copolymer resin, and a butyral resin.
The curing agent is not particularly limited as long as it can cure the binder, and examples thereof include imidazole compounds, isocyanate compounds, acid anhydrides, amine compounds, and amide compounds.
導電性ペースト中の複合金属粉の含有量は、２０〜９５質量％が好ましく、３０〜９０質量％がより好ましい。複合金属粉の含有量の下限値が上記値より小さくなると、十分な導電性が得られにくくなる。一方、含有量の上限値が上記値より大きくなると、ペースト状にすることが困難となる。
なお、導電性ペーストにおける複合金属粉とバインダー固形分比（質量％）は、複合金属粉／バインダー＝６０／４０〜９７／３が好ましく、７５／２５〜９０／１０が好ましい。
The content of the composite metal powder in the conductive paste is preferably 20 to 95% by mass, and more preferably 30 to 90% by mass. When the lower limit value of the content of the composite metal powder is smaller than the above value, it is difficult to obtain sufficient conductivity. On the other hand, when the upper limit of the content is larger than the above value, it becomes difficult to form a paste.
In addition, composite metal powder / binder solid content ratio (mass%) in the conductive paste is preferably composite metal powder / binder = 60/40 to 97/3, and more preferably 75/25 to 90/10.
導電性ペーストは、以上説明した複合金属粉とバインダーと硬化剤とをプラネタリーミキサーやロールミルなどで混合することにより得られる。
このような導電性ペーストは、種々の用途に使用できるが、特に各種電子部品などへの使用に適している。
The conductive paste can be obtained by mixing the above-described composite metal powder, a binder, and a curing agent with a planetary mixer or a roll mill.
Such a conductive paste can be used for various applications, but is particularly suitable for use in various electronic components.
このように、本発明の複合金属粉の製造方法により得られる複合金属粉は、第一の金属粉の表面を被覆する、第二の金属の表面に***物が形成されるため、本発明の複合金属粉を用いた導電性ペーストは、同じ金属比率の金属メッキ粉体を用いた導電性ペーストに比べて、より高い導電性能を示すことができる。
なお、本発明は、銀メッキ銅粉の導電性を向上させるのに、特に有用である。
As described above, the composite metal powder obtained by the method for producing a composite metal powder of the present invention covers the surface of the first metal powder, and the ridges are formed on the surface of the second metal. The conductive paste using the composite metal powder can exhibit higher conductive performance than the conductive paste using the metal plating powder having the same metal ratio.
The present invention is particularly useful for improving the conductivity of silver-plated copper powder.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.
＜実施例１＞
（複合金属粉の製造）
メタノール滑剤洗浄したフレーク銅（三井金属社製、「ＭＡ−ＤＦ（Ｅ）」、粒径１０μｍ）６０ｇを約５％の希硫酸水溶液１００ｍＬに添加し、１０分間撹拌して酸洗浄した後、中性になるまで洗浄を繰り返し、前処理銅粉とした。実施例１においては、洗浄回数を６回行い、洗浄水を約３Ｌ使用した。
先の前処理銅粉を１Ｌのビーカーに移し、炭酸アンモニウム３１．５ｇ、ＥＤＴＡ６３ｇ、水２５０ｇからなる水溶液を加えて銅分散液を調整した。硝酸銀１０．５ｇ、水３２．４ｇからなる水溶液を、前記銅分散液に撹拌しながら添加し、銀置換メッキを行った。その後、ろ過、洗浄、乾燥し、銀含有量が１０質量％の銀メッキ銅粉を得た。
次いで、銀メッキ銅粉を水素雰囲気下中、３００℃で１時間熱処理し、複合金属粉を製造した。
得られた複合金属粉の表面状態を走査型電子顕微鏡（ＳＥＭ、３０００倍）にて観察した。ＳＥＭ写真（観察画像）を図１に示す。
<Example 1>
(Manufacture of composite metal powder)
After adding 60 g of flake copper (Mitsui Kinzoku Co., Ltd., “MA-DF (E)”, particle size 10 μm) washed with methanol lubricant to 100 mL of about 5% dilute sulfuric acid aqueous solution, the mixture was stirred for 10 minutes and washed with acid. Washing was repeated until it became a pre-treated copper powder. In Example 1, washing was performed 6 times and about 3 L of washing water was used.
The pretreated copper powder was transferred to a 1 L beaker, and an aqueous solution composed of 31.5 g of ammonium carbonate, 63 g of EDTA, and 250 g of water was added to prepare a copper dispersion. An aqueous solution composed of 10.5 g of silver nitrate and 32.4 g of water was added to the copper dispersion with stirring, and silver substitution plating was performed. Thereafter, filtration, washing and drying were performed to obtain a silver-plated copper powder having a silver content of 10% by mass.
Next, the silver-plated copper powder was heat-treated at 300 ° C. for 1 hour in a hydrogen atmosphere to produce a composite metal powder.
The surface state of the obtained composite metal powder was observed with a scanning electron microscope (SEM, 3000 times). An SEM photograph (observed image) is shown in FIG.
（評価：導電性測定）
得られた複合金属粉を、３００ＭＰａの圧力にて圧縮成形し、直径１０ｍｍ、厚さ１ｍｍのタブレットを作成した。
得られたタブレットの導電性を、Ｈａｌｌ測定装置（Bio-Red Microscience社製、「ＨＬ５５００」）にて測定し、Van der Pauw法により比抵抗値（Ωｃｍ）を求めた。導電性の測定を計４回行い、比抵抗値の平均値を求めた。結果を表１と図４に示す。
(Evaluation: Conductivity measurement)
The obtained composite metal powder was compression molded at a pressure of 300 MPa to produce a tablet having a diameter of 10 mm and a thickness of 1 mm.
The conductivity of the obtained tablet was measured with a Hall measuring device (manufactured by Bio-Red Microscience, “HL5500”), and the specific resistance value (Ωcm) was determined by the Van der Pauw method. Conductivity was measured four times in total, and an average value of specific resistance values was obtained. The results are shown in Table 1 and FIG.
＜実施例２＞
（複合金属粉の製造と評価）
銀メッキ銅粉を水素雰囲気下中、４００℃で１時間熱処理した以外は実施例１と同様にして複合金属粉を製造し、導電性の評価を行った。結果を表１と図４に示す。
また、得られた複合金属粉の表面状態をＳＥＭ（３０００倍）にて観察した。ＳＥＭ写真（観察画像）を図２に示す。
<Example 2>
(Production and evaluation of composite metal powder)
A composite metal powder was produced in the same manner as in Example 1 except that the silver-plated copper powder was heat-treated at 400 ° C. for 1 hour in a hydrogen atmosphere, and conductivity was evaluated. The results are shown in Table 1 and FIG.
Moreover, the surface state of the obtained composite metal powder was observed with SEM (3000 times). An SEM photograph (observed image) is shown in FIG.
＜比較例＞
（銀メッキ銅粉の製造）
実施例１と同様にして、銀メッキ銅粉を製造した。
得られた銀メッキ銅粉の表面状態をＳＥＭ（３０００倍）にて観察した。ＳＥＭ写真（観察画像）を図３に示す。
<Comparative example>
(Manufacture of silver-plated copper powder)
In the same manner as in Example 1, silver-plated copper powder was produced.
The surface state of the obtained silver plating copper powder was observed with SEM (3000 times). An SEM photograph (observed image) is shown in FIG.
（評価：導電性測定）
得られた銀メッキ銅粉の導電性を、実施例１と同様にして評価した。結果を表１と図４に示す。
(Evaluation: Conductivity measurement)
The conductivity of the obtained silver-plated copper powder was evaluated in the same manner as in Example 1. The results are shown in Table 1 and FIG.
図１〜３より明らかなように、実施例で得られた複合金属粉の表面には***物が形成されていた。特に４００℃で熱処理を行った実施例２の複合金属粉は、３００℃で熱処理を行った実施例１の複合金属粉に比べて、***物が大きくなっていた。
一方、比較例で得られた銀メッキ銅粉の表面は鱗片状であり、平滑な表面であった。
As is clear from FIGS. 1 to 3, a ridge was formed on the surface of the composite metal powder obtained in the example. In particular, the composite metal powder of Example 2 that had been heat-treated at 400 ° C. had larger protrusions than the composite metal powder of Example 1 that had been heat-treated at 300 ° C.
On the other hand, the surface of the silver-plated copper powder obtained in the comparative example was scaly and smooth.
また、表１と図４から明らかなように、実施例１および２で得られた複合金属粉より作成した各タブレットは、同じ金属比率である比較例の銀メッキ銅粉より作成したタブレットに比べて平均比抵抗値が低く、導電性能に優れていた。特に実施例２の複合金属粉より作成したタブレットは、実施例１の複合金属粉より作成したタブレットに比べて、さらに平均比抵抗値が低かった。 Moreover, as is clear from Table 1 and FIG. 4, each tablet made from the composite metal powder obtained in Examples 1 and 2 is compared with the tablet made from the silver-plated copper powder of the comparative example having the same metal ratio. The average specific resistance value was low and the conductive performance was excellent. In particular, the tablet prepared from the composite metal powder of Example 2 had a lower average specific resistance value than the tablet prepared from the composite metal powder of Example 1.
Claims (9)
前記第二の金属の表面に***物が形成されていることを特徴とする複合金属粉。 The surface of the first metal powder is a composite metal powder coated with a second metal different from the first metal powder,
A composite metal powder, wherein a protuberance is formed on the surface of the second metal.
The method for producing a composite metal powder according to claim 8, wherein the first metal powder is copper powder and the second metal is silver.
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| JP2011044509A (en) * | 2009-08-20 | 2011-03-03 | Mitsubishi Materials Corp | Conductive ink composition, and solar cell module formed using the composition |
| WO2013141425A1 (en) * | 2012-03-23 | 2013-09-26 | (주)창성 | Electrode paste composition for solar cell |
| WO2014156978A1 (en) | 2013-03-28 | 2014-10-02 | 東洋アルミニウム株式会社 | Conductive particles, method for producing same, conductive resin composition containing same, and conductive coated material |
| WO2015107996A1 (en) | 2014-01-14 | 2015-07-23 | 東洋アルミニウム株式会社 | Composite conductive particles, conductive resin composition containing same and conductive coated article |
| WO2016080544A1 (en) * | 2014-11-20 | 2016-05-26 | 国立大学法人山形大学 | Method for treating metal surface, silver-coated copper treated by said method, and composite metal body |
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| WO2013141425A1 (en) * | 2012-03-23 | 2013-09-26 | (주)창성 | Electrode paste composition for solar cell |
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| KR20180132176A (en) | 2013-03-28 | 2018-12-11 | 도요 알루미늄 가부시키가이샤 | Conductive particles, method for producing same, conductive resin composition containing same, and conductive coated material |
| US10020090B2 (en) | 2013-03-28 | 2018-07-10 | Toyo Aluminium Kabushiki Kaisha | Conductive particles, method of manufacturing the same, conductive resin composition containing the same, and conductive coated object |
| WO2014156978A1 (en) | 2013-03-28 | 2014-10-02 | 東洋アルミニウム株式会社 | Conductive particles, method for producing same, conductive resin composition containing same, and conductive coated material |
| KR20210027541A (en) | 2013-03-28 | 2021-03-10 | 도요 알루미늄 가부시키가이샤 | Conductive particles, method for producing same, conductive resin composition containing same, and conductive coated material |
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| WO2016080544A1 (en) * | 2014-11-20 | 2016-05-26 | 国立大学法人山形大学 | Method for treating metal surface, silver-coated copper treated by said method, and composite metal body |
| JP2016098398A (en) * | 2014-11-20 | 2016-05-30 | 国立大学法人山形大学 | Metal surface treatment method, and silver clad copper and composite metal body treated by the method |
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