JP2017066501A - Method for producing coated silver particle, liquid composition, coated silver particle, coated silver particle-containing composition, conductive member, method for producing conductive member, electric/electronic component and electric/electronic equipment - Google Patents
Method for producing coated silver particle, liquid composition, coated silver particle, coated silver particle-containing composition, conductive member, method for producing conductive member, electric/electronic component and electric/electronic equipment Download PDFInfo
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- JP2017066501A JP2017066501A JP2015196648A JP2015196648A JP2017066501A JP 2017066501 A JP2017066501 A JP 2017066501A JP 2015196648 A JP2015196648 A JP 2015196648A JP 2015196648 A JP2015196648 A JP 2015196648A JP 2017066501 A JP2017066501 A JP 2017066501A
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- Prior art keywords
- coated silver
- conductive member
- silver
- particle
- silver particle
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- 239000002245 particle Substances 0.000 title claims abstract description 283
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 276
- 239000004332 silver Substances 0.000 title claims abstract description 275
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- 239000000203 mixture Substances 0.000 title claims abstract description 182
- 239000007788 liquid Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
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- 150000003379 silver compounds Chemical class 0.000 claims abstract description 21
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 33
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Abstract
Description
本発明は、被覆銀粒子の製造方法、当該製造方法に使用されうる液状組成物、上記の製造方法により製造される被覆銀粒子、当該被覆銀粒子を含有する被覆銀粒子含有組成物、当該被覆銀粒子含有組成物から製造される導電部材、上記の被覆銀粒子含有組成物を用いる導電部材の製造方法、上記の導電部材または上記の製造方法により製造される導電部材を備える電気・電子部品、および当該電気・電子部品を備える電気・電子機器に関する。 The present invention relates to a method for producing coated silver particles, a liquid composition that can be used in the production method, a coated silver particle produced by the above production method, a coated silver particle-containing composition containing the coated silver particle, and the coating A conductive member produced from a silver particle-containing composition, a method for producing a conductive member using the coated silver particle-containing composition, an electric / electronic component comprising the conductive member or the conductive member produced by the production method, The present invention also relates to an electric / electronic device including the electric / electronic component.
特許文献１には、有機酸架橋銀アルキルアミン錯体熱分解法により、数ｎｍから１００ｎｍの大きさの被覆銀粒子を合成する方法が記載されている。特許文献１に記載される被覆銀粒子は、良好な分散性、焼結性、導電性を示し、特許文献１に記載される被覆銀粒子の製造方法は、大量合成が容易な製造方法である。 Patent Document 1 describes a method of synthesizing coated silver particles having a size of several nm to 100 nm by an organic acid crosslinked silver alkylamine complex thermal decomposition method. The coated silver particles described in Patent Document 1 exhibit good dispersibility, sinterability, and conductivity, and the method for producing coated silver particles described in Patent Document 1 is a method that facilitates mass synthesis. .
特許文献１に記載される製造方法で製造される銀被覆粒子とバインダーと含む組成物を焼成して導電性の部材を得ようとすると、被覆銀粒子の粒径が小さいため、焼成して得られる部材は粒子同士の接点が多くなり、バインダーによる抵抗増加の影響を受けやすかった。上記の問題を解決する手段の一つに、被覆銀粒子の大型化が挙げられる。しかしながら、特許文献１に記載される製造方法は、上記のとおり、数ｎｍから１００ｎｍの大きさの被覆銀粒子を製造する方法としては適しているものの、０．２μｍから数μｍの大きさ、いわゆる、サブミクロンからミクロンサイズの大きさの被覆銀粒子を安定的に製造することは困難であった。 When a composition containing silver-coated particles and a binder produced by the production method described in Patent Document 1 is baked to obtain a conductive member, the particle size of the coated silver particles is small, and thus obtained by calcination. The resulting member has many contact points between particles, and is easily affected by an increase in resistance due to the binder. One of the means for solving the above problem is an increase in the size of the coated silver particles. However, as described above, the production method described in Patent Document 1 is suitable as a method for producing coated silver particles having a size of several nm to 100 nm, but a size of 0.2 μm to several μm, so-called It has been difficult to stably produce coated silver particles having a size of submicron to micron size.
本発明は、特許文献１に記載される製造方法により製造される被覆銀粒子よりも大きな粒径を有する被覆銀粒子を製造することが可能な製造方法、当該製造方法に使用されうる液状組成物、上記の製造方法により製造される銀含有粒子（本明細書において、本発明に係る銀含有粒子を「被覆銀粒子」と称する場合もある。）、当該被覆銀粒子を含有する被覆銀粒子含有組成物、当該被覆銀粒子含有組成物から製造される導電部材、上記の被覆銀粒子含有組成物を用いる導電部材の製造方法、上記の導電部材または上記の製造方法により製造される導電部材を備える電気・電子部品、および当該電気・電子部品を備える電気・電子機器を提供することを目的とする。 The present invention relates to a production method capable of producing coated silver particles having a particle size larger than the coated silver particles produced by the production method described in Patent Document 1, and a liquid composition that can be used in the production method. Silver-containing particles produced by the above production method (in the present specification, the silver-containing particles according to the present invention may be referred to as “coated silver particles”), containing coated silver particles A conductive member produced from the composition, the coated silver particle-containing composition, a method for producing a conductive member using the coated silver particle-containing composition, the conductive member or the conductive member produced by the production method An object is to provide an electric / electronic component and an electric / electronic device including the electric / electronic component.
上記の課題を解決するために提供される本発明の一態様は、加熱により 分解して金属銀を生成しうる銀化合物とアルキルアミンとを混合することを含んで、前記銀化合物と前記アルキルアミンとを含む錯化合物を含有する液状組成物を得る第１工程と、前記液状組成物に含有される前記錯化合物を加熱分解して被覆銀粒子を生成する第２工程と、を含み、前記第１工程で得られる前記液状組成物は、全組成物に対して、１質量％以上８質量％以下で水を含有することを特徴とする被覆銀粒子の製造方法である。 One embodiment of the present invention provided to solve the above problem includes mixing a silver compound capable of being decomposed by heating to form metallic silver and an alkylamine, and the silver compound and the alkylamine. A first step of obtaining a liquid composition containing a complex compound comprising: a second step of thermally decomposing the complex compound contained in the liquid composition to produce coated silver particles, The liquid composition obtained in one step contains 1% by mass to 8% by mass of water based on the total composition, and is a method for producing coated silver particles.
本発明に係る被覆銀粒子の製造方法は、特許文献１に記載される銀ナノ粒子の製造方法と同様に、有機酸架橋銀アルキルアミン錯体熱分解法により、銀含有物質の粒子化を行う。この方法では、水のような金属と相互作用しやすい物質が錯化合物を含有する組成物中に存在すれば、粒子化プロセスが大きくダメージを受け、銀含有粒子を形成すること自体が困難になると考えられていた。ところが、本発明において明らかになったように、被覆銀粒子を形成するために調製される、錯化合物を含有する液状組成物に所定量の水分を存在させることにより、生成される被覆銀粒子の粒径を大型化することができることが明らかになった。具体的には、液状組成物における水の含有量を、全組成物に対して、１質量％以上５質量％以下とすることにより、長軸方向の長さが０．２μｍ以上の被覆銀粒子が製造されやすくなる。しかも、本発明に係る製造方法によれば、上記のように長い長軸長さを有しながら、被覆銀粒子の短軸長さを数ｎｍから１００ｎｍの範囲内とすることできる場合もある。このように短軸長が短い場合には、被覆銀粒子の全体形状はフレーク状となって、被覆銀粒子を含有する組成物を焼成して得られる部材は良好な導電性を有しやすい。 In the method for producing coated silver particles according to the present invention, a silver-containing substance is formed into particles by an organic acid-crosslinked silver alkylamine complex thermal decomposition method, similarly to the method for producing silver nanoparticles described in Patent Document 1. In this method, if a substance that easily interacts with a metal such as water is present in a composition containing a complex compound, the granulation process is greatly damaged and it becomes difficult to form silver-containing particles. It was thought. However, as has been clarified in the present invention, the presence of a predetermined amount of water in the liquid composition containing a complex compound prepared to form the coated silver particles allows the coated silver particles to be produced. It became clear that the particle size can be increased. Specifically, the content of water in the liquid composition is 1% by mass or more and 5% by mass or less with respect to the total composition, so that the length of the major axis direction is 0.2 μm or more. Becomes easier to manufacture. Moreover, according to the production method of the present invention, there are cases where the minor axis length of the coated silver particles can be in the range of several nm to 100 nm while having a long major axis length as described above. When the minor axis length is short as described above, the entire shape of the coated silver particles becomes flakes, and the member obtained by firing the composition containing the coated silver particles tends to have good conductivity.
上記の本発明に係る被覆銀粒子の製造方法において、前記銀化合物はシュウ酸銀を主成分とすることが好ましい。 In the method for producing coated silver particles according to the present invention, the silver compound preferably contains silver oxalate as a main component.
本発明の他の一態様は、加熱により分解して金属銀を生成しうる銀化合物とアルキルアミンとの錯化合物と、前記アルキルアミンと、水と、を含有し、水の含有量は、全組成物に対して、１質量％以上８質量％以下であることを特徴とする液状組成物である。上記の液状組成物を使用することにより、前述の長軸の長さが０．２μｍ以上の大きさの被覆銀粒子を製造することが容易となる。 Another embodiment of the present invention includes a complex compound of a silver compound and an alkylamine that can be decomposed by heating to form metallic silver, the alkylamine, and water. It is a liquid composition characterized by being 1 mass% or more and 8 mass% or less with respect to a composition. By using the above liquid composition, it becomes easy to produce coated silver particles having a major axis length of 0.2 μm or more.
本発明の別の一態様は、前述の本発明に係る製造方法により製造されることを特徴とする被覆銀粒子である。かかる被覆銀粒子は、前述のとおり、長軸の長さが０．２μｍ以上の大きさを有するものを含みやすく、好ましい一形態では、短軸の長さが、数ｎｍから１００ｎｍ程度の範囲内、具体的には、４０ｎｍ以上９０ｎｍ以下であるものを含みやすい。 Another aspect of the present invention is a coated silver particle produced by the production method according to the present invention described above. Such coated silver particles are likely to include those having a major axis length of 0.2 μm or more as described above, and in a preferred embodiment, the minor axis length is in the range of several nm to 100 nm. Specifically, it is easy to include those that are 40 nm or more and 90 nm or less.
前記被覆銀粒子の一群を電子顕微鏡で観察して円換算粒径の度数分布を得たときに、最頻出粒径が０．２μｍ以上０．６μｍ以下であることが好ましい。上記の最頻出粒径を用いることにより、被覆銀粒子の長軸の長さの程度を評価することができる。被覆銀粒子がかかる形状を有する場合には、被覆銀粒子を含有する組成物を焼成して得られる部材の体積抵抗率を１００μΩ・ｃｍ以下にすることが容易となる。 When a group of the coated silver particles is observed with an electron microscope to obtain a frequency distribution with a circular equivalent particle diameter, the most frequent particle diameter is preferably 0.2 μm or more and 0.6 μm or less. By using the most frequent particle diameter, the degree of the length of the long axis of the coated silver particle can be evaluated. When the coated silver particles have such a shape, it becomes easy to make the volume resistivity of the member obtained by firing the composition containing the coated silver particles 100 μΩ · cm or less.
本発明のさらに別の一態様は、上記の本発明に係る被覆銀粒子と、熱可塑性ポリウレタン樹脂とを含有する被覆銀粒子含有組成物である。かかる被覆銀粒子含有組成物は、これを焼成してなる部材の体積抵抗率が低下しやすく、好ましい一形態において、被覆銀粒子含有組成物を焼成して得られる部材の体積抵抗率を１００μΩ・ｃｍ以下にすることができる。 Yet another embodiment of the present invention is a coated silver particle-containing composition containing the coated silver particles according to the present invention and a thermoplastic polyurethane resin. Such a coated silver particle-containing composition is likely to have a reduced volume resistivity of a member obtained by firing the composition. In a preferred embodiment, the volume resistivity of a member obtained by firing the coated silver particle-containing composition is 100 μΩ · cm or less.
上記の本発明に係る被覆銀粒子含有組成物に含有される前記熱可塑性ポリウレタン樹脂の含有量は、前記被覆銀粒子の銀換算含有量に対する質量割合が１％超１０％未満となる量であることが好ましい。このように被覆銀粒子含有組成物が熱可塑性ポリウレタン樹脂を適量含有する場合には、被覆銀粒子含有組成物を焼成して得られる部材の体積抵抗率が１００μΩ・ｃｍ以下となりやすいこともある。 The content of the thermoplastic polyurethane resin contained in the coated silver particle-containing composition according to the present invention is such that the mass ratio of the coated silver particles to the silver equivalent content is more than 1% and less than 10%. It is preferable. As described above, when the coated silver particle-containing composition contains an appropriate amount of the thermoplastic polyurethane resin, the volume resistivity of the member obtained by firing the coated silver particle-containing composition is likely to be 100 μΩ · cm or less.
本発明のさらにまた別の一態様は、上記の本発明に係る被覆銀粒子含有組成物から製造されることを特徴とする導電部材である。前述のとおり、本発明に係る被覆銀粒子含有組成物を焼成して得られる部材は体積抵抗率が低いため、本発明に係る被覆銀粒子含有組成物から製造される導電部材は、導電性に優れる。 Yet another embodiment of the present invention is a conductive member manufactured from the above-described coated silver particle-containing composition according to the present invention. As described above, since the member obtained by firing the coated silver particle-containing composition according to the present invention has a low volume resistivity, the conductive member produced from the coated silver particle-containing composition according to the present invention is electrically conductive. Excellent.
上記の本発明に係る導電部材は、体積抵抗率が５０μΩ・ｃｍ以下であってもよい。 The conductive member according to the present invention may have a volume resistivity of 50 μΩ · cm or less.
本発明のさらにまた別の一態様は、上記の本発明に係る導電部材からなる電気配線を備えることを特徴とする電気・電子部品である。 Yet another embodiment of the present invention is an electrical / electronic component comprising an electrical wiring comprising the conductive member according to the present invention.
本発明のさらにまた別の一態様は、上記の本発明に係る電気・電子部品を備えることを特徴とする電気・電子機器である。 Yet another embodiment of the present invention is an electrical / electronic apparatus comprising the electrical / electronic component according to the present invention.
本発明のさらにまた別の一態様は、上記の本発明に係る被覆銀粒子含有組成物を基体上に配置する配置工程；および前記基体上に配置された前記被覆銀粒子含有組成物を加熱することにより前記被覆銀粒子含有組成物に含まれる前記被覆銀粒子を焼成して、前記基体上に導電部材を形成する焼成工程を備えることを特徴とする導電部材の製造方法である。かかる導電部材の製造方法により得られた導電部材は、体積抵抗率が低下しやすい。 Still another embodiment of the present invention is an arrangement step of disposing the coated silver particle-containing composition according to the present invention on a substrate; and heating the coated silver particle-containing composition disposed on the substrate. By this, the said covering silver particle contained in the said covering silver particle containing composition is baked, It is a manufacturing method of the electrically-conductive member characterized by including the baking process which forms an electrically-conductive member on the said base | substrate. The conductive member obtained by such a method for manufacturing a conductive member tends to have a low volume resistivity.
上記の本発明に係る製造方法は、かつ前記配置工程の後、前記焼成工程の前に、前記基体上に配置された前記被覆銀粒子含有組成物を部分的に除去するパターニング工程を備えていてもよい。焼成工程前の被覆銀粒子含有組成物は、被覆銀粒子がバインダー成分で保持された構造を有するため、基体上に配置された被覆銀粒子含有組成物は部分除去が容易である。これに対し、焼成加工を経て得られた導電部材は、被覆銀粒子が焼結しているため、部分除去は容易でない。したがって、配置工程の後、かつ焼成工程の前にパターニング工程を行うことを含んで導電部材を製造することにより、パターニングされた導電部材を得ることが容易になる。 The manufacturing method according to the present invention includes a patterning step of partially removing the coated silver particle-containing composition disposed on the substrate after the placing step and before the firing step. Also good. Since the coated silver particle-containing composition before the firing step has a structure in which the coated silver particles are held by a binder component, partial removal of the coated silver particle-containing composition disposed on the substrate is easy. On the other hand, the conductive member obtained through the firing process is not easily removed because the coated silver particles are sintered. Therefore, it becomes easy to obtain the patterned conductive member by manufacturing the conductive member including performing the patterning step after the arranging step and before the firing step.
上記の本発明に係る製造方法において、前記焼成工程における前記基体上に配置された前記被覆銀粒子含有組成物の加熱温度は１１０℃以下であってもよい。前述のとおり、本発明に係る被覆銀粒子含有組成物に含有される被覆銀粒子は、好ましい一形態において短軸の長さが数ｎｍから１００ｎｍの範囲であるものを含みやすい。したがって、加熱温度が１１０℃以下であっても、本発明に係る被覆銀粒子含有組成物に含有される被覆銀粒子同士の焼結が生じやすい。 In the manufacturing method according to the present invention, the heating temperature of the coated silver particle-containing composition disposed on the substrate in the baking step may be 110 ° C. or less. As described above, the coated silver particles contained in the coated silver particle-containing composition according to the present invention are likely to include those having a minor axis length in the range of several nm to 100 nm in a preferred embodiment. Therefore, even when the heating temperature is 110 ° C. or lower, the coated silver particles contained in the coated silver particle-containing composition according to the present invention are likely to be sintered.
上記の本発明に係る製造方法において、前記焼成工程における前記基体上に配置された前記被覆銀粒子含有組成物の加熱時間は３時間以下であってもよい。上記のとおり、本発明の一実施形態に係る被覆銀粒子含有組成物に含有される被覆銀粒子は、好ましい一形態において被覆銀粒子同士の焼結が生じやすい。したがって、加熱時間が３時間以下であっても、被覆銀粒子含有組成物から導電部材を得ることが可能である。 In the production method according to the present invention, the heating time of the coated silver particle-containing composition disposed on the substrate in the baking step may be 3 hours or less. As described above, the coated silver particles contained in the coated silver particle-containing composition according to an embodiment of the present invention are likely to sinter the coated silver particles in a preferred embodiment. Therefore, even when the heating time is 3 hours or less, it is possible to obtain a conductive member from the coated silver particle-containing composition.
上記の本発明に係る製造方法において、前記導電部材の体積抵抗率は５０μΩ・ｃｍ以下であることが好ましい。導電部材の体積抵抗率が５０μΩ・ｃｍ以下である場合には、その導電部材を薄膜の電気配線として好適に使用することができる。 In the manufacturing method according to the present invention, the volume resistivity of the conductive member is preferably 50 μΩ · cm or less. When the volume resistivity of the conductive member is 50 μΩ · cm or less, the conductive member can be suitably used as a thin-film electrical wiring.
本発明のさらにまた別の一態様は、上記の本発明に係る製造方法により製造された導電部材からなる電気配線を備えることを特徴とする電気・電子部品である。 Yet another aspect of the present invention is an electrical / electronic component comprising an electrical wiring made of a conductive member manufactured by the manufacturing method according to the present invention.
本発明のさらにまた別の一態様は、上記の本発明に係る電気・電子部品を備えることを特徴とする電気・電子機器である。 Yet another embodiment of the present invention is an electrical / electronic apparatus comprising the electrical / electronic component according to the present invention.
本発明によれば、被覆銀粒子を製造する際に使用される液状組成物に水を含有させることにより、形成される被覆銀粒子の形状を制御することが可能である。そして、当該液状組成物内の水分量を適切に制御して被覆銀粒子を製造すれば、当該被覆銀粒子を含有する組成物を焼成して得られる部材の導電性を高めることが可能となる。かかる部材からなる導電部材は体積抵抗率が低いため、電気配線などに好適に使用することができる。 According to the present invention, it is possible to control the shape of the formed coated silver particles by adding water to the liquid composition used in producing the coated silver particles. If the coated silver particles are produced by appropriately controlling the amount of water in the liquid composition, the conductivity of the member obtained by firing the composition containing the coated silver particles can be increased. . Since the conductive member made of such a member has a low volume resistivity, it can be suitably used for electrical wiring and the like.
以下、本発明の実施形態に係る、被覆銀粒子の製造方法、当該製造方法に使用されうる液状組成物、上記の製造方法により製造される被覆銀粒子、当該被覆銀粒子を含有する被覆銀粒子含有組成物、当該被覆銀粒子含有組成物から製造される導電部材、上記の被覆銀粒子含有組成物を用いる導電部材の製造方法、上記の導電部材または上記の製造方法により製造される導電部材を備える電気・電子部品、および当該電気・電子部品を備える電気・電子機器について説明する。 Hereinafter, a method for producing coated silver particles, a liquid composition that can be used in the production method, a coated silver particle produced by the above production method, and a coated silver particle containing the coated silver particle according to an embodiment of the present invention A conductive member produced from the containing composition, the conductive member produced from the coated silver particle-containing composition, the conductive member production method using the coated silver particle-containing composition, the conductive member or the conductive member produced by the production method The electric / electronic component provided and the electric / electronic device provided with the electric / electronic component will be described.
１．被覆銀粒子の製造方法
本発明の一実施形態に係る被覆銀粒子の製造方法は、次に説明する第１工程および第２工程を備える。
1. The manufacturing method of a covering silver particle The manufacturing method of the covering silver particle which concerns on one Embodiment of this invention is equipped with the 1st process and 2nd process which are demonstrated below.
（１）第１工程
第１工程では、加熱により分解して金属銀を生成しうる銀化合物とアルキルアミンとを混合することを含んで、銀化合物と前記アルキルアミンとを含む錯化合物を含有する液状組成物を得る。本明細書において「液状」とは、組成物が液体である場合および液体と同等の物理的振る舞いをする場合を含む。したがって、組成物がスラリーやエマルジョンである場合も「液状」の概念に含まれる。
(1) 1st process 1st process contains the complex compound containing a silver compound and the said alkylamine including mixing the silver compound and alkylamine which can be decomposed | disassembled by heating and produce | generate metal silver. A liquid composition is obtained. In the present specification, the “liquid” includes a case where the composition is a liquid and a case where the composition behaves similarly to the liquid. Therefore, the case where the composition is a slurry or an emulsion is also included in the concept of “liquid”.
（１−１）加熱により分解して金属銀を生成しうる銀化合物
被覆銀粒子を製造するために用いる銀の原料としては、銀を含む化合物の中で、加熱により容易に分解して原子状の銀を生成する銀化合物が好ましく使用される。このような銀化合物として、ギ酸、酢酸、シュウ酸、マロン酸、安息香酸、フタル酸などのカルボン酸と銀原子が化合したカルボン酸銀の他、塩化銀、硝酸銀、炭酸銀等がある。これらの中で、分解により容易に金属銀を生成し、かつ銀以外の不純物を生じにくい等の観点からシュウ酸銀が好ましく用いられる。シュウ酸銀は、銀含量が高く、また通常２００℃以下の低温で分解しやすく、分解の際にシュウ酸イオンが二酸化炭素として除去され金属銀が得られるため、不純物が残留しにくい点で有利である。本発明の一実施形態に係る液状組成物に含有されるシュウ酸銀は、例えば、市販のシュウ酸銀を用いることができる。また、シュウ酸銀のシュウ酸イオンを、２０モル％以下の炭酸イオン、硝酸イオン、酸化物イオンの１種以上で置換した銀化合物を使用してもよい。特に、シュウ酸イオンの２０モル％以下が炭酸イオンで置換されたシュウ酸銀は熱安定性が高まるが、置換量が２０モル％を超えると、これを用いて生成した錯化合物が熱分解しにくくなる場合がある。
(1-1) Silver compound that can be decomposed by heating to produce metallic silver As a raw material of silver used for producing coated silver particles, it is easily decomposed by heating in an atomic form among compounds containing silver. A silver compound that forms silver is preferably used. Examples of such a silver compound include silver chloride, silver nitrate, silver carbonate, and the like in addition to silver carboxylate in which a silver atom is combined with a carboxylic acid such as formic acid, acetic acid, oxalic acid, malonic acid, benzoic acid, and phthalic acid. Among these, silver oxalate is preferably used from the viewpoints of easily producing metallic silver by decomposition and hardly generating impurities other than silver. Silver oxalate is advantageous in that it has a high silver content and is usually easily decomposed at a low temperature of 200 ° C. or lower, and oxalate ions are removed as carbon dioxide during the decomposition, so that metallic silver is obtained, so that impurities hardly remain. It is. As the silver oxalate contained in the liquid composition according to one embodiment of the present invention, for example, commercially available silver oxalate can be used. Moreover, you may use the silver compound which substituted the oxalate ion of silver oxalate by 1 or more types of 20 mol% or less of carbonate ion, nitrate ion, and oxide ion. In particular, silver oxalate in which 20 mol% or less of the oxalate ions are substituted with carbonate ions has improved thermal stability. However, when the substitution amount exceeds 20 mol%, the complex compound formed using the oxalate ions is thermally decomposed. It may be difficult.
（１−２）アルキルアミン
第１工程において使用するアミンとして、アルキル基の一部にアミノ基が結合したアルキルモノアミン、アルキルジアミン等が例示される。アルキルモノアミンとして、アミルアミン（沸点１０４℃）、２−エトキシエチルアミン（１０５℃）、４−メトキシブチルアミン、ブチルアミン（７８℃）、ジエチルアミン（５５℃）、プロピルアミン（４８℃）、イソプロピルアミン（３４℃）、エチルアミン（１７℃）、ジメチルアミン（７℃）、ジプロピルアミン（１０７℃）、ジブチルアミン（１５９℃）、ヘキシルアミン（１３１℃）、シクロヘキシルアミン（１３４℃）、ヘプチルアミン（１５５℃）、３−ブトキシプロピルアミン（１７０℃）、オクチルアミン（１７６℃）、ノニルアミン（２０１℃）、デシルアミン（２１７℃）、３−アミノプロピルトリエトキシシラン（２１７℃）、ドデシルアミン（２４８℃）、ヘキサデシルアミン（３３０℃）、オレイルアミン（３４９℃）、オクタデシルアミン（２３２℃（３２ｍｍＨｇ））などが例示される。アルキルジアミンとして、エチレンジアミン（１１８℃）、Ｎ，Ｎ−ジメチルエチレンジアミン（１０５℃）、Ｎ，Ｎ’−ジメチルエチレンジアミン（１１９℃）、Ｎ，Ｎ-ジエチルエチレンジアミン（１４６℃）、Ｎ，Ｎ’−ジエチルエチレンジアミン（１５３℃）、１，３−プロパンジアミン（１４０℃）、２，２-ジメチル−１，３−プロパンジアミン（１５３℃）、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン（１３６℃）、Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパン（１４５℃）、Ｎ，Ｎ−ジエチル−１，３−ジアミノプロパン（１７１℃）、１，４−ジアミノブタン（１５９℃）、１，５−ジアミノ−２−メチルペンタン（１９３℃）、１，６−ジアミノヘキサン（２０４℃）、Ｎ，Ｎ’−ジメチル−１，６−ジアミノヘキサン（２２８℃）、１，７−ジアミノヘプタン（２２４℃）、１，８−ジアミノオクタン（２２５℃）などが例示される。
(1-2) Alkylamine Examples of the amine used in the first step include alkyl monoamines and alkyldiamines in which an amino group is bonded to a part of the alkyl group. As alkyl monoamines, amylamine (boiling point 104 ° C), 2-ethoxyethylamine (105 ° C), 4-methoxybutylamine, butylamine (78 ° C), diethylamine (55 ° C), propylamine (48 ° C), isopropylamine (34 ° C) Ethylamine (17 ° C), dimethylamine (7 ° C), dipropylamine (107 ° C), dibutylamine (159 ° C), hexylamine (131 ° C), cyclohexylamine (134 ° C), heptylamine (155 ° C), 3-butoxypropylamine (170 ° C), octylamine (176 ° C), nonylamine (201 ° C), decylamine (217 ° C), 3-aminopropyltriethoxysilane (217 ° C), dodecylamine (248 ° C), hexadecyl Amine (330 ° C), oleylamine 349 ° C.), octadecylamine (232 ℃ (32mmHg)) and the like are exemplified. As the alkyl diamine, ethylenediamine (118 ° C), N, N-dimethylethylenediamine (105 ° C), N, N'-dimethylethylenediamine (119 ° C), N, N-diethylethylenediamine (146 ° C), N, N'-diethyl Ethylenediamine (153 ° C), 1,3-propanediamine (140 ° C), 2,2-dimethyl-1,3-propanediamine (153 ° C), N, N-dimethyl-1,3-diaminopropane (136 ° C) N, N′-dimethyl-1,3-diaminopropane (145 ° C.), N, N-diethyl-1,3-diaminopropane (171 ° C.), 1,4-diaminobutane (159 ° C.), 1,5 -Diamino-2-methylpentane (193 ° C.), 1,6-diaminohexane (204 ° C.), N, N′-dimethyl-1,6-diaminohexane 228 ° C.), 1,7-diamino heptane (224 ℃), 1,8- diamino-octane (225 ° C.) and the like are exemplified.
上記の錯化合物の熱分解温度を考慮すれば、アルキルアミンは１００℃以上の沸点であることが好ましい。得られた被覆銀粒子の低温焼結性を考慮すれば、アルキルアミンは２５０℃以下の沸点であることが好ましい。 Considering the thermal decomposition temperature of the complex compound, the alkylamine preferably has a boiling point of 100 ° C. or higher. Considering the low-temperature sinterability of the obtained coated silver particles, the alkylamine preferably has a boiling point of 250 ° C. or lower.
第１工程において使用されるアルキルアミンは、一種類の化合物から構成されていてもよいし、複数種類の化合物から構成されていてもよい。銀化合物とアルキルアミンとから錯化合物を適切に生成できる限り、アルキルアミンの使用量は限定されない。 The alkylamine used in the first step may be composed of one type of compound or may be composed of a plurality of types of compounds. The amount of alkylamine used is not limited as long as a complex compound can be appropriately formed from a silver compound and an alkylamine.
（１−３）水
本発明の一実施形態に係る液状組成物は、全組成物に対して、１質量％以上８質量％以下で水を含有する。液状組成物が水分を含有することによって、液状組成物を用いて製造される被覆銀粒子の形状を変化させることができる。
(1-3) Water The liquid composition according to an embodiment of the present invention contains water at 1% by mass or more and 8% by mass or less with respect to the total composition. When the liquid composition contains moisture, the shape of the coated silver particles produced using the liquid composition can be changed.
図１は、本発明の一実施形態に係る液状組成物を用いて製造された被覆銀粒子の電子顕微鏡による観察画像である。図２は、従来技術に係る、水を実質的に含有しない液状組成物を用いて製造された被覆銀粒子の電子顕微鏡による観察画像である。 FIG. 1 is an electron microscope observation image of coated silver particles produced using a liquid composition according to an embodiment of the present invention. FIG. 2 is an electron microscope observation image of coated silver particles produced using a liquid composition containing substantially no water according to the prior art.
図１に示されるように、液状組成物の水の含有量（水分量）を１質量％以上とすることにより、被覆銀粒子は大型化し、長軸の長さが０．２μｍ以上のものを含みやすくなる。好ましい一形態において、長軸の長さが０．２μｍ以上でありながら、短軸の長さは、水分を実質的に含有しない液状組成物から形成された被覆銀粒子の一般的な粒径である数ｎｍから１００ｎｍの範囲を維持しやすくなる。このため、本発明の一実施形態に係る液状組成物を用いて製造された被覆銀粒子はフレーク状の形状を有しやすい。 As shown in FIG. 1, by setting the water content (moisture content) of the liquid composition to 1% by mass or more, the coated silver particles are enlarged and the major axis has a length of 0.2 μm or more. It becomes easy to include. In a preferred embodiment, the length of the short axis is the general particle size of the coated silver particles formed from a liquid composition substantially free of moisture, while the length of the long axis is 0.2 μm or more. It becomes easy to maintain a certain range of several nm to 100 nm. For this reason, the covering silver particle manufactured using the liquid composition concerning one embodiment of the present invention tends to have a flake shape.
液状組成物が水を含有することにより被覆銀粒子が大型化（フレーク状化）する理由は定かでない。液状組成物から被覆銀粒子が形成される際に、アルキルアミンが銀粒子を被覆することを水が阻害することによって、銀粒子の成長が促進されている可能性がある。 The reason why the coated silver particles increase in size (flakes) when the liquid composition contains water is not clear. When coated silver particles are formed from a liquid composition, the growth of silver particles may be promoted by water inhibiting the alkylamine from coating the silver particles.
液状組成物における水分量は、全組成物に対して、１．５質量％以上であることが好ましく、２質量％以上であることがより好ましく、２．５質量％以上であることが特に好ましい。 The amount of water in the liquid composition is preferably 1.5% by mass or more, more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more with respect to the total composition. .
液状組成物における水分量が過度に多い場合には、液状組成物から形成される銀を含む固体物質はフレーク状の被覆銀粒子からさらに大型化して、銀を含有する物質からなる膜状体となる。したがって、粒子としての性質を有する物質を安定的に得る観点から、液状組成物における水分量は、全組成物に対して、８質量％以下とされる。粒子としての性質を有する物質をより安定的に得る観点から、液状組成物における水分量は、全組成物に対して、７．５質量％以下であることが好ましく、７質量％以下であることがより好ましく、６．５質量％以下であることがさらに好ましく、４質量％以下であることが特に好ましい。 When the water content in the liquid composition is excessively large, the solid substance containing silver formed from the liquid composition is further enlarged from the flaky coated silver particles, and a film-like body made of a substance containing silver Become. Therefore, from the viewpoint of stably obtaining a substance having properties as particles, the water content in the liquid composition is 8% by mass or less with respect to the total composition. From the viewpoint of more stably obtaining a substance having properties as particles, the amount of water in the liquid composition is preferably 7.5% by mass or less, and 7% by mass or less with respect to the total composition. Is more preferably 6.5% by mass or less, and particularly preferably 4% by mass or less.
（１−４）液状組成物の調製条件等
液状組成物は、上記の成分以外の成分を含有してもよい。そのような成分として、アルコール類が例示される。
銀化合物およびアルキルアミンから錯化合物を生成する方法は、両者を混合させることができれば、限定されない。液状組成物を調製するに当たり、水分を存在させるタイミングと錯化合物の生成が開始するタイミングとの関係は限定されない。錯化合物の生成が開始する前の段階から水分が存在していてもよいし、錯化合物の生成が開始した後に水分を添加してもよい。
(1-4) Preparation conditions of liquid composition, etc. The liquid composition may contain components other than the above components. Examples of such components include alcohols.
The method for producing a complex compound from a silver compound and an alkylamine is not limited as long as both can be mixed. In preparing the liquid composition, there is no limitation on the relationship between the timing at which moisture is present and the timing at which the formation of complex compounds starts. Water may be present from the stage before the formation of the complex compound is started, or moisture may be added after the formation of the complex compound is started.
次に説明する第２工程において錯化合物の熱分解の加熱を行う前に、必ずしも錯化合物の生成が完了する必要はなく、錯化合物の生成過程においても適宜加熱を行うことで、被覆銀粒子の生成を行うことができる。すなわち、第１工程と第２工程とは一連の作業において行われてもよく、この場合には、液状組成物に含有されるべき成分を添加する段階で加熱を行い、全成分の添加、そのまま調製された液状組成物を加熱撹拌すればよい。 It is not always necessary to complete the formation of the complex compound before heating the thermal decomposition of the complex compound in the second step to be described below. Generation can be performed. That is, the first step and the second step may be performed in a series of operations. In this case, heating is performed at the stage of adding the components to be contained in the liquid composition, and all components are added as they are. What is necessary is just to heat and stir the prepared liquid composition.
（２）第２工程
第２工程では、第１工程を実施することにより得られた液状組成物に含有される錯化合物を加熱分解して被覆銀粒子を生成する。
(2) Second Step In the second step, the complex compound contained in the liquid composition obtained by performing the first step is thermally decomposed to produce coated silver particles.
加熱温度は、液状組成物に含有される錯化合物から原子状の銀が遊離する温度の直上の温度域とすることが好ましい。この温度域は、錯化合物を構成する銀化合物およびアルキルアミンの種類に応じて適宜設定される。通常、７０〜１５０℃の温度範囲とされ、更に典型的には８０〜１２０℃の温度範囲とされる。加熱時間は限定されない。被覆銀粒子の生成が適切に完了するように、通常は設定される。 The heating temperature is preferably a temperature range immediately above the temperature at which atomic silver is liberated from the complex compound contained in the liquid composition. This temperature range is appropriately set according to the types of silver compound and alkylamine constituting the complex compound. Usually, it is set as the temperature range of 70-150 degreeC, More typically, it is set as the temperature range of 80-120 degreeC. The heating time is not limited. It is usually set so that the production of coated silver particles is properly completed.
第２工程が終了したら、濾過、遠心分離などの手段により、生成した被覆銀粒子を反応媒から分離して、回収すればよい。その際、必要に応じて、アルコール類などを用いて洗浄してもよい。 When the second step is completed, the produced coated silver particles may be separated from the reaction medium and collected by means such as filtration and centrifugation. In that case, you may wash | clean using alcohol etc. as needed.
２．被覆銀粒子
本発明の一実施形態に係る被覆銀粒子は、上記の本発明の一実施形態に係る製造方法により製造された被覆銀粒子である。被覆銀粒子の具体的な構造は明らかでないが、銀粒子の周囲に、第１工程において使用したアルキルアミンが、銀粒子を被覆するように存在している可能性がある。銀粒子の周囲に水が存在している可能性もある。
2. Coated silver particles Coated silver particles according to one embodiment of the present invention are coated silver particles produced by the production method according to one embodiment of the present invention. The specific structure of the coated silver particles is not clear, but the alkylamine used in the first step may be present around the silver particles so as to cover the silver particles. There may also be water around the silver particles.
本発明の一実施形態に係る被覆銀粒子は、前述のように、液状組成物に含有される水分量を変化させることにより、その形状が制御されたものである。具体的には、本発明の一実施形態に係る被覆銀粒子は、長軸の長さが０．２μｍ以上であって、短軸の長さが数ｎｍから１００ｎｍの範囲内、具体的には、４０ｎｍ以上９０ｎｍ以下である、フレーク状の形状を有する粒子が得られやすい（図１）。 As described above, the shape of the coated silver particles according to the embodiment of the present invention is controlled by changing the amount of water contained in the liquid composition. Specifically, the coated silver particles according to an embodiment of the present invention have a major axis length of 0.2 μm or more and a minor axis length in the range of several nm to 100 nm, specifically , Particles having a flake shape of 40 nm or more and 90 nm or less are easily obtained (FIG. 1).
本発明の一実施形態に係る被覆銀粒子の一群を電子顕微鏡で観察して円換算粒径の度数分布を得たときに、最頻出粒径が０．２μｍ以上０．６μｍ以下であることが好ましい。上記の最頻出粒径を用いることにより、被覆銀粒子の長軸の長さの程度を評価することができる。一群の被覆銀粒子を電子顕微鏡で観察した場合には、観察視線方向と粒子の長軸方向とが垂直にならないこと、すなわち、フレーク状の被覆銀粒子が基体に対して斜めに配置されていることがある。また、大径の粒子上に小径の粒子が載っていたり、粒子同士が重なっていたりすることがある。したがって、一群の被覆銀粒子を電子顕微鏡で観察した場合に被覆銀粒子に対応するものとして円換算粒径の測定対象となる閉曲線の面積は、通常、本来の被覆銀粒子における長軸方向を面内方向とする表面の面積よりも小さくなる。したがって、上記の最頻出粒径が０．２μｍ以上である場合には、測定対象となった一群の被覆銀粒子において、長径長さが０．２μｍ以上であるものが相当量存在すると判断することは妥当である。 When a group of coated silver particles according to an embodiment of the present invention is observed with an electron microscope to obtain a frequency distribution of a circular equivalent particle size, the most frequent particle size may be 0.2 μm or more and 0.6 μm or less. preferable. By using the most frequent particle diameter, the degree of the length of the long axis of the coated silver particle can be evaluated. When a group of coated silver particles is observed with an electron microscope, the observation line-of-sight direction and the major axis direction of the particles are not perpendicular to each other, that is, the flaky coated silver particles are arranged obliquely with respect to the substrate. Sometimes. In addition, small particles may be placed on large particles, or the particles may overlap each other. Therefore, when a group of coated silver particles is observed with an electron microscope, the area of the closed curve that is the subject of measurement of the circle-equivalent particle diameter as corresponding to the coated silver particles is usually the major axis direction of the original coated silver particles. It becomes smaller than the area of the surface in the inward direction. Therefore, when the above-mentioned most frequent particle diameter is 0.2 μm or more, it is determined that there is a considerable amount of the major axis length of 0.2 μm or more in the group of coated silver particles to be measured. Is reasonable.
そして、上記の最頻出粒径が０．２μｍ以上である場合には、後述するように、測定対象となった一群の被覆銀粒子を含む組成物（被覆銀粒子含有組成物）を焼成して得られる部材（本明細書において、被覆銀粒子含有組成物を焼成して得られる部材を「焼結部材」ともいう。）の体積抵抗率を１００Ω・ｃｍ以下にすることが可能となる。 And when said most frequent particle diameter is 0.2 micrometer or more, as mentioned later, the composition (coating silver particle containing composition) containing the group of covering silver particles used as a measuring object was baked. The volume resistivity of the obtained member (in this specification, the member obtained by firing the coated silver particle-containing composition is also referred to as “sintered member”) can be set to 100 Ω · cm or less.
焼結部材の導電性を高める観点から、上記の最頻出粒径は、０．２５μｍ以上であることが好ましく、０．３μｍ以上であることがより好ましく、０．３５μｍ以上であることが特に好ましい。 From the viewpoint of enhancing the conductivity of the sintered member, the most frequent particle size is preferably 0.25 μm or more, more preferably 0.3 μm or more, and particularly preferably 0.35 μm or more. .
上記の被覆銀粒子の長軸長さが過度に大きい場合には、被覆銀粒子が粒子としての機能、特に流動性を失いやすくなる。その結果、被覆銀粒子含有組成物を焼成して得られた焼結部材は、銀を含有する物質が緻密に配置されず、すなわち、パッキング性が低下して、焼結部材の導電性が低下しやすくなる。このような、粒子としての機能を適切に有しない被覆銀粒子が含まれる可能性を低減させる観点から、上記の最頻出粒径は、０．６μｍ以下であることが好ましく、０．５５μｍ以下であることがより好ましい。 When the major axis length of the coated silver particles is excessively large, the coated silver particles tend to lose their function as particles, particularly fluidity. As a result, the sintered member obtained by firing the composition containing coated silver particles is not densely arranged with a substance containing silver, that is, the packing property is lowered, and the conductivity of the sintered member is lowered. It becomes easy to do. From the viewpoint of reducing the possibility that such coated silver particles that do not appropriately have the function as particles are included, the most frequent particle size is preferably 0.6 μm or less, preferably 0.55 μm or less. More preferably.
３．被覆銀粒子含有組成物
本発明の一実施形態に係る被覆銀粒子含有組成物は、上記の本発明の一実施形態に係る被覆銀粒子と熱可塑性ポリウレタン樹脂とを含有する。かかる被覆銀粒子含有組成物は、これを焼成してなる部材（焼結部材）の導電性が向上しやすい。具体的には、焼結部材の体積抵抗率が低下しやすい。被覆銀粒子含有組成物が熱可塑性ポリウレタン樹脂を含有することにより、焼結部材の導電性が向上する理由は定かでない。断面観察によれば、図３に示されるように、本発明の一実施形態に係る被覆銀粒子含有組成物を焼成して得られた焼結部材は、銀を含有する物質が密に配置された状態で焼結している。熱可塑性ポリウレタン樹脂は、焼結部材における銀を含有する物質のパッキング性に影響を与えて、焼結部材の導電性を向上させている可能性がある。
3. Coated silver particle containing composition The coated silver particle containing composition which concerns on one Embodiment of this invention contains the covering silver particle and thermoplastic polyurethane resin which concern on one Embodiment of said this invention. Such a coated silver particle-containing composition is likely to improve the conductivity of a member (sintered member) obtained by firing the composition. Specifically, the volume resistivity of the sintered member tends to decrease. The reason why the conductivity of the sintered member is improved by the inclusion of the thermoplastic polyurethane resin in the coated silver particle-containing composition is not clear. According to the cross-sectional observation, as shown in FIG. 3, the sintered member obtained by firing the coated silver particle-containing composition according to one embodiment of the present invention is densely arranged with silver-containing substances. Sintered in a heated state. The thermoplastic polyurethane resin may affect the packing property of the silver-containing substance in the sintered member and improve the conductivity of the sintered member.
熱可塑性ポリウレタン樹脂の種類は、ウレタン結合を有する重合体であれば、限定されない。ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールなどのポリオールと、脂肪族ポリイソシアネート、脂環式ポリイソシアネート、芳香族ポリイソシアネートなどのイソシアネート化合物との重合物などが挙げられる。熱可塑性ポリウレタン樹脂は一種類の樹脂から構成されていてもよいし、複数種類の樹脂から構成されていてもよい。 The type of the thermoplastic polyurethane resin is not limited as long as it is a polymer having a urethane bond. Polymers of polyols such as polyether polyols, polyester polyols, and polycarbonate polyols and isocyanate compounds such as aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates can be used. The thermoplastic polyurethane resin may be composed of one type of resin, or may be composed of a plurality of types of resins.
熱可塑性ポリウレタン樹脂の分子量（重量平均分子量Ｍｗ、数平均分子量Ｍｎ）は限定されない。これらは、被覆銀粒子含有組成物が有するべき特性、例えば粘度に応じて適宜設定される。 The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) of the thermoplastic polyurethane resin is not limited. These are appropriately set according to the characteristics that the coated silver particle-containing composition should have, for example, the viscosity.
熱可塑性ポリウレタン樹脂の被覆銀粒子含有組成物における含有量は限定されない。被覆銀粒子含有組成物に含有される熱可塑性ポリウレタン樹脂の含有量は、被覆銀粒子の銀換算含有量に対する質量割合が１％超１０％未満となる量であることが好ましい場合がある。当該質量割合を１％超とすることにより、焼結部材の基体に対する密着性が向上しやすくなる場合がある。焼結部材の基体に対する密着性が向上しやすくなることをより安定的に実現させる観点から、上記の質量割合は、２％以上であることが好ましい場合があり、３％以上であることがより好ましい場合がある。焼結部材に残存する熱可塑性ポリウレタン樹脂は絶縁性であるから、上記の質量割合を１０％未満とすることにより焼結部材の導電性の低下が生じにくくなる場合がある。焼結部材が良好な導電性を有することを容易にする観点から、上記の質量割合は、７％以下であることが好ましい場合があり、５％以下であることがより好ましい場合がある。 The content of the thermoplastic polyurethane resin in the coated silver particle-containing composition is not limited. In some cases, the content of the thermoplastic polyurethane resin contained in the coated silver particle-containing composition is preferably such that the mass ratio of the coated silver particles to the silver equivalent content is more than 1% and less than 10%. By setting the mass ratio to more than 1%, the adhesion of the sintered member to the base may be easily improved. From the viewpoint of more stably realizing that the adhesion of the sintered member to the substrate is more stable, the above mass ratio may be preferably 2% or more, and more preferably 3% or more. It may be preferable. Since the thermoplastic polyurethane resin remaining in the sintered member is insulative, when the mass ratio is less than 10%, the conductivity of the sintered member may not easily decrease. From the viewpoint of facilitating that the sintered member has good conductivity, the mass ratio may be preferably 7% or less, and more preferably 5% or less.
本発明の一実施形態に係る被覆銀粒子含有組成物は、被覆銀粒子および熱可塑性ポリウレタン樹脂以外の成分として、溶剤や分散剤を含有していてもよい。 The coated silver particle-containing composition according to an embodiment of the present invention may contain a solvent or a dispersant as a component other than the coated silver particles and the thermoplastic polyurethane resin.
溶剤として、ブタノール等のアルコール溶剤や、オクタン等の非極性溶剤、またはそれらの混合溶剤等の適宜の有機溶媒が挙げられる。使用する有機溶媒は、被覆銀粒子の保護膜に含まれるアルキルアミン等の脱離を生じさせず、かつ、被覆銀粒子含有組成物が基体上に配置された後、比較的速やかに蒸発するものが好ましく用いられる。被覆銀粒子含有組成物における溶剤の含有量は限定されない。溶剤の種類、被覆銀粒子含有組成物の粘度などを考慮して適宜設定される。 Examples of the solvent include alcohol solvents such as butanol, nonpolar solvents such as octane, and appropriate organic solvents such as a mixed solvent thereof. The organic solvent used does not cause detachment of alkylamine or the like contained in the protective film of the coated silver particles, and evaporates relatively quickly after the coated silver particle-containing composition is placed on the substrate. Is preferably used. The content of the solvent in the coated silver particle-containing composition is not limited. It is appropriately set in consideration of the type of solvent, the viscosity of the coated silver particle-containing composition, and the like.
分散剤として、例えばオレイン酸などの脂肪酸をアミン混合物に混合して用いてもよい。特に、短鎖のアルキルアミンを大きな割合で含有するなどにより、アルキルアミンの平均の分子量が小さいアミン混合物を用いる場合に適宜の脂肪酸を加えることは効果的である。ただし、過剰な量の脂肪酸を使用した場合には、被覆銀粒子からの保護被膜の脱離温度が上昇する傾向が見られるため、分散剤の添加量は反応系に含まれる金属銀原子に対して５モル％以下とすることが望ましい。被覆銀粒子含有組成物における分散剤の含有量は限定されない。分散剤の種類、被覆銀粒子含有組成物の粘度、被覆銀粒子含有組成物を焼成して得られる部材（焼結部材）の導電性などを考慮して適宜設定される。 As the dispersant, for example, a fatty acid such as oleic acid may be mixed with the amine mixture and used. In particular, it is effective to add an appropriate fatty acid when an amine mixture having a small average molecular weight of alkylamine is used, for example, by containing a large proportion of short-chain alkylamine. However, if an excessive amount of fatty acid is used, the desorption temperature of the protective film from the coated silver particles tends to increase, so the amount of dispersant added is relative to the metallic silver atoms contained in the reaction system. It is desirable to make it 5 mol% or less. The content of the dispersant in the coated silver particle-containing composition is not limited. It is appropriately set in consideration of the type of dispersant, the viscosity of the coated silver particle-containing composition, the conductivity of a member (sintered member) obtained by firing the coated silver particle-containing composition.
４．導電部材
本発明の一実施形態に係る導電部材は、上記の本発明の一実施形態に係る被覆銀粒子含有組成物から製造されたものである。具体的には、本発明の一実施形態に係る被覆銀粒子含有組成物の焼結部材である。
4). Conductive Member The conductive member according to one embodiment of the present invention is manufactured from the coated silver particle-containing composition according to one embodiment of the present invention. Specifically, it is a sintered member of a coated silver particle-containing composition according to an embodiment of the present invention.
前述のように、本発明の一実施形態に係る被覆銀粒子含有組成物は、長軸の長さが０．２μｍ以上の被覆銀粒子を含みやすく、しかも、熱可塑性ポリウレタン樹脂を含有するため、当該被覆銀粒子含有組成物から製造された焼結部材からなる導電部材は、導電性に優れる。具体的には、１００μΩ・ｃｍ以下の体積抵抗率を有することができる。被覆銀粒子の形状を制御したり、熱可塑性ポリウレタン樹脂の含有量を調整したりすることにより、本発明の一実施形態に係る導電部材は、好ましい一例において５０μΩ・ｃｍ以下の体積抵抗率を有することができ、より好ましい一例において３０μΩ・ｃｍ以下の体積抵抗率を有することができ、特に好ましい一例において１０μΩ・ｃｍ以下の体積抵抗率を有することができる。 As described above, the coated silver particle-containing composition according to one embodiment of the present invention is likely to contain coated silver particles having a major axis length of 0.2 μm or more, and contains a thermoplastic polyurethane resin. A conductive member made of a sintered member produced from the coated silver particle-containing composition is excellent in conductivity. Specifically, it can have a volume resistivity of 100 μΩ · cm or less. By controlling the shape of the coated silver particles or adjusting the content of the thermoplastic polyurethane resin, the conductive member according to one embodiment of the present invention has a volume resistivity of 50 μΩ · cm or less in a preferred example. In a more preferred example, it can have a volume resistivity of 30 μΩ · cm or less, and in a particularly preferred example, it can have a volume resistivity of 10 μΩ · cm or less.
５．導電部材の製造方法
上記の本発明の一実施形態に係る導電部材は、例えば、次に説明する配置工程および焼成工程を備え、必要に応じさらにパターニング工程を備える方法により製造することができる。
5. Manufacturing Method of Conductive Member The conductive member according to one embodiment of the present invention described above can be manufactured, for example, by a method including a disposing step and a firing step described below, and further including a patterning step as necessary.
（１）配置工程
配置工程では、上記の本発明の一実施形態に係る被覆銀粒子含有組成物を基体上に配置する。基体の形状および材質は限定されない。基体の形状は、板状であってもよいし、筒状などより立体的な形状を有していてもよい。さらに、凹凸を有した複雑な形状を有していてもよい。
(1) Arrangement Step In the arrangement step, the coated silver particle-containing composition according to one embodiment of the present invention is arranged on a substrate. The shape and material of the substrate are not limited. The shape of the substrate may be a plate shape or a three-dimensional shape such as a cylindrical shape. Furthermore, you may have a complicated shape with an unevenness | corrugation.
基体の材質として、例えば、熱可塑性樹脂、熱硬化性樹脂、ガラス、紙、金属、シリコン、無機系材料および金属系材料ならびにこれらの材料の複合材料（かかる複合材料を用いた基体の具体例としてガラスエポキシ基板が挙げられる。）を用いることができる。熱可塑性樹脂としては、例えば、ポリエチレン、ポリエチレンテレフタレート、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、アクリロニトリル−ブタジエン−スチレン共重合樹脂、アクリロニトリル−スチレン共重合樹脂、ポリカーボネート、ポリアセタール、ポリブチレンテレフタレート、ポリフェニレンオキシド、ポリアミド、ポリフェニレンサルファイド、ポリスルホン、ポリエーテルスルホン、ポリエーテル−エーテルケトン、ポリアリレート、アロマティックポリエステル、アロマティックポリアミド、フッ素樹脂、ポリビニリデンクロライド、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルホルマール、ポリビニルブチラール、ポリメタクリル酸メチル、酢酸セルロース等が挙げられる。 As the material of the substrate, for example, thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, inorganic material and metal material, and composite materials of these materials (as specific examples of the substrate using such a composite material) A glass epoxy substrate can be used). Examples of the thermoplastic resin include polyethylene, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polycarbonate, polyacetal, polybutylene terephthalate, polyphenylene oxide, polyamide, Polyphenylene sulfide, polysulfone, polyethersulfone, polyether-etherketone, polyarylate, aromatic polyester, aromatic polyamide, fluororesin, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polymethyl methacrylate And cellulose acetate.
熱硬化性樹脂としては、例えば、フェノール樹脂、尿素樹脂、キシレン樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、ケイ素樹脂、ジアリルフタレート樹脂、フラン樹脂、アニリン樹脂、アセトン−ホルムアルデヒド樹脂、アルキド樹脂等が挙げられる。 Examples of the thermosetting resin include phenol resin, urea resin, xylene resin, urea resin, melamine resin, epoxy resin, silicon resin, diallyl phthalate resin, furan resin, aniline resin, acetone-formaldehyde resin, alkyd resin, and the like. It is done.
無機系材料としては、酸化物、炭化物、窒化物、ホウ化物などの無機化合物を意味し、例えばアルミナ（Ａｌ２Ｏ３）、シリコンナイトライド（ＳｉＮ）、シリコンカーバイド（ＳｉＣ）、アルミナイトライド（ＡｌＮ）、ホウ化ジルコニウム（ＺｒＢ２）等が挙げられる。 Inorganic materials mean inorganic compounds such as oxides, carbides, nitrides and borides. For example, alumina (Al 2 O 3 ), silicon nitride (SiN), silicon carbide (SiC), aluminum nitride ( AlN), zirconium boride (ZrB 2 ) and the like.
被覆銀粒子含有組成物を基体上に配置する方法は限定されない。オフセット印刷、グラビア印刷、グラビアオフセット印刷、凸版印刷、フレキソ印刷、スクリーン印刷、インクジェット印刷等の印刷；スピンコート、浸漬、バーコート、ロールコート等の塗布；スプレーなどが例示される。 The method for disposing the coated silver particle-containing composition on the substrate is not limited. Examples include offset printing, gravure printing, gravure offset printing, relief printing, flexographic printing, screen printing, inkjet printing, and the like; spin coating, dipping, bar coating, roll coating, and the like; spraying and the like.
前述のように、被覆銀粒子含有組成物の粘度を調整することにより、被覆銀粒子含有組成物を基体上に配置することが容易になったり、基体上の被覆銀粒子含有組成物の厚さの制御性が向上したりする場合もある。 As described above, by adjusting the viscosity of the coated silver particle-containing composition, it becomes easy to dispose the coated silver particle-containing composition on the substrate, or the thickness of the coated silver particle-containing composition on the substrate. In some cases, the controllability is improved.
（２）焼成工程
焼成工程では、基体上に配置された被覆銀粒子含有組成物を加熱する。この加熱により被覆銀粒子含有組成物に含まれる被覆銀粒子を焼成して、基体上に導電部材を形成する。焼成温度は適宜設定されるが、１１０℃またはそれ以下の温度でもよい。被覆銀粒子において保護膜を形成する材料の一種である可能性があるアルキルアミンは、そのアミノ基を介した配位結合により銀粒子の表面に対して弱く結合しており、加熱によって比較的容易に脱離可能であると考えられる。それゆえ、例えば、基体上に配置された被覆銀粒子含有組成物の焼成温度が１１０℃程度以下であっても、被覆銀粒子からアルキルアミンが容易に脱離して、銀粒子同士が直接接触する（結合する）ことが実現されていると考えられる。基体を構成する材料が樹脂系材料からなる場合には、焼成温度は可能な限り低いことが好ましく、この場合には、１００℃以下であることが好ましい場合があり、９０℃以下であることが好ましい場合がある。
(2) Firing step In the firing step, the coated silver particle-containing composition disposed on the substrate is heated. By this heating, the coated silver particles contained in the coated silver particle-containing composition are fired to form a conductive member on the substrate. The firing temperature is appropriately set, but may be 110 ° C. or lower. Alkylamine, which may be a kind of material that forms a protective film in coated silver particles, is weakly bonded to the surface of silver particles due to coordination bonds via the amino group, and is relatively easy to heat. It is thought that it can be detached. Therefore, for example, even when the firing temperature of the coated silver particle-containing composition disposed on the substrate is about 110 ° C. or less, the alkylamine is easily detached from the coated silver particles, and the silver particles are in direct contact with each other. (Joining) is considered to be realized. When the material constituting the substrate is made of a resin material, the firing temperature is preferably as low as possible. In this case, it may be preferably 100 ° C. or lower, and may be 90 ° C. or lower. It may be preferable.
焼成時間は限定されない。加熱温度が上記の温度であれば、通常、焼成時間を１時間程度以上とすることで、被覆銀粒子含有組成物に含有される被覆銀粒子の焼成が可能である。焼成時間を延長することにより、焼成により得られた導電部材の導電性を高めることが可能であるが、焼成時間の延長により導電部材の導電性を高めることには限界があり、通常、焼成時間を５時間程度とすれば、それ以上焼成時間を延長しても、導電部材の導電性の向上の程度はわずかである。導電部材について導電率の向上と生産性の向上とのバランスを良好にする観点から、焼成時間は、５時間以下とすることが好ましい場合があり、３時間以下とすることがより好ましい場合がある。本発明の一実施形態に係る被覆銀粒子含有組成物を用いることにより、この程度の焼成時間であっても、得られた導電部材は１００μΩ・ｃｍ以下の体積抵抗率を有することが可能であり、好ましい一例では５０μΩ・ｃｍ以下の体積抵抗率を有することが可能であり、より好ましい一例では１０μΩ・ｃｍ以下の体積抵抗率を有することが可能である。 The firing time is not limited. If the heating temperature is the above temperature, the coated silver particles contained in the coated silver particle-containing composition can usually be fired by setting the firing time to about 1 hour or longer. By extending the firing time, it is possible to increase the conductivity of the conductive member obtained by firing, but there is a limit to increasing the conductivity of the conductive member by extending the firing time, usually the firing time Is about 5 hours, the degree of improvement of the conductivity of the conductive member is slight even if the firing time is extended further. From the viewpoint of improving the balance between the improvement in conductivity and the improvement in productivity for the conductive member, the firing time may be preferably 5 hours or less, and more preferably 3 hours or less. . By using the coated silver particle-containing composition according to one embodiment of the present invention, the obtained conductive member can have a volume resistivity of 100 μΩ · cm or less even with such a firing time. In a preferred example, it is possible to have a volume resistivity of 50 μΩ · cm or less, and in a more preferred example it is possible to have a volume resistivity of 10 μΩ · cm or less.
（３）パターニング工程
パターニング工程は、配置工程の後、かつ焼成工程の前に通常設定され、基体上に配置された被覆銀粒子含有組成物を部分的に除去する作業が行われる。除去方法は限定されない。被覆銀粒子含有組成物のうち、除去しない部分をレジストなどにより覆うことによりマスキングして、露出した被覆銀粒子含有組成物を物理的・化学的に除去してもよい。被覆銀粒子含有組成物のうち除去すべき部分にエネルギー線、例えばレーザー光やイオンビームを照射して、当該部分を選択的に除去してもよい。配置工程において印刷などの手段を用いて被覆銀粒子含有組成物を基体上の選択された部分に配置する場合には、本工程を実施することなく、所定の形状（パターン）を有する被覆銀粒子含有組成物を基体上に配置することができる。
(3) Patterning step The patterning step is usually set after the placing step and before the firing step, and an operation of partially removing the coated silver particle-containing composition placed on the substrate is performed. The removal method is not limited. A portion of the coated silver particle-containing composition that is not removed may be masked by covering it with a resist, and the exposed coated silver particle-containing composition may be physically and chemically removed. You may selectively remove the said part by irradiating the part which should be removed among coating silver particle containing compositions to an energy ray, for example, a laser beam, or an ion beam. When the coated silver particle-containing composition is disposed on a selected portion on the substrate using printing or the like in the arranging step, the coated silver particles having a predetermined shape (pattern) without performing this step The containing composition can be disposed on a substrate.
６．電気・電子部品および電気・電子機器
本発明の一実施形態に係る電気・電子部品は、前述の本発明の一実施形態に係る導電部材からなる電気配線を備える。本発明の一実施形態に係る導電部材は、前述のように、１００μΩ・ｃｍ以下の体積抵抗率を有することが可能であり、１０μΩ・ｃｍ以下の体積抵抗率を有することが可能となる場合もある。それゆえ、本発明の一実施形態に係る導電部材からなる電気配線は、厚さが２μｍ程度の薄膜からなる場合であっても導電性が高く、かかる電気配線を備える電気・電子部品は、配線幅が狭い場合であっても、配線抵抗が高くなる不具合が生じにくい。したがって、電気・電子部品を小型化することが可能である。
6). Electric / Electronic Component and Electric / Electronic Device An electric / electronic component according to an embodiment of the present invention includes an electric wiring made of the conductive member according to the above-described embodiment of the present invention. As described above, the conductive member according to the embodiment of the present invention can have a volume resistivity of 100 μΩ · cm or less, and can have a volume resistivity of 10 μΩ · cm or less. is there. Therefore, the electrical wiring made of the conductive member according to an embodiment of the present invention has high conductivity even when it is made of a thin film having a thickness of about 2 μm. Even when the width is narrow, it is difficult to cause a problem that the wiring resistance increases. Therefore, it is possible to reduce the size of the electric / electronic component.
また、上記の本発明の一実施形態に係る製造方法により導電部材を製造すれば、微細形状（ファインパターン）の導電部材を様々な材質からなる基体上に低温で形成することが可能である。具体的には、例えば、樹脂系材料からなる基体の曲面に沿って、数十μｍの幅の電気配線を形成することができる。したがって、上記の本発明の一実施形態に係る製造方法により導電部材からなる電気配線を備える電気・電子部品は、材料および形状について高い設計自由度で製造された部品とすることができる。 Moreover, if a conductive member is manufactured by the manufacturing method according to the embodiment of the present invention, it is possible to form a conductive member having a fine shape (fine pattern) on a substrate made of various materials at a low temperature. Specifically, for example, an electrical wiring having a width of several tens of μm can be formed along the curved surface of the base made of a resin material. Therefore, the electrical / electronic component provided with the electrical wiring made of the conductive member by the manufacturing method according to the embodiment of the present invention can be a component manufactured with a high degree of design freedom in terms of material and shape.
そのような電気・電子部品の具体例として、タッチパネルが挙げられる。タッチパネルは表示デバイスの前面に配置される場合があり、この場合には全体の厚さが薄いことが求められる。また、検出領域を拡大することも求められている。このため、タッチパネルの配線は、さらに薄くかつ狭くすることが求められている。これらの要請に応える手段の一つとして、配線の体積抵抗率を低下させることが挙げられる。さらに、タッチパネルの曲面化が求められ始めており、そのためには、樹脂系材料上に体積抵抗率の低い配線を形成することが必要である。本発明の一実施形態に係る導電部材からなる電気配線は、こうした要請の全てに応えることが可能である。 A specific example of such an electric / electronic component is a touch panel. The touch panel may be disposed on the front surface of the display device. In this case, the entire thickness is required to be thin. There is also a need to expand the detection area. For this reason, the wiring of the touch panel is required to be thinner and narrower. One means for meeting these requirements is to reduce the volume resistivity of the wiring. Furthermore, the curved surface of the touch panel has begun to be demanded. For this purpose, it is necessary to form a wiring having a low volume resistivity on the resin material. The electrical wiring made of the conductive member according to the embodiment of the present invention can meet all of these requirements.
本発明の一実施形態に係る電気・電子機器は、上記の本発明の一実施形態に係る電気・電子部品を備える。上記のとおり、本発明の一実施形態に係る電気・電子部品は小型化が可能であり、かつ材料および形状についての設計自由度が高いため、かかる電気・電子機器は、携帯性に優れる、省電力性に優れる、といった利点を有することが期待される。本発明の一実施形態に係る電気・電子部品の具体例として、スマートフォン、タブレット端末、ノートＰＣなど従来型の情報端末に加えて、メガネ型の情報端末、時計型の情報端末など、いわゆるウェアラブル端末が挙げられる。 An electrical / electronic device according to an embodiment of the present invention includes the electrical / electronic component according to the embodiment of the present invention. As described above, since the electrical / electronic component according to an embodiment of the present invention can be miniaturized and has a high degree of design freedom for materials and shapes, the electrical / electronic device has excellent portability, savings. It is expected to have advantages such as excellent power performance. Specific examples of electrical / electronic components according to an embodiment of the present invention include so-called wearable terminals such as glasses-type information terminals and clock-type information terminals in addition to conventional information terminals such as smartphones, tablet terminals, and notebook PCs. Is mentioned.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
以下、以下に実施例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely below, this invention is not limited to these.
（実施例１）
銀化合物として、硝酸銀（関東化学社製、一級）とシュウ酸二水和物（関東化学社製、特級）とから合成したシュウ酸銀を使用した。水０．２０ｇ、Ｎ，Ｎ−ジエチルジアミノプロパンを１．６２５ｇおよび３ｍＬの１−ヘキサノールを５０ｍＬ遠沈管内に入れて、９０℃に加熱して２０分間撹拌した。その後、シュウ酸銀３ｇを添加して、９０℃に維持した状態で６０分間撹拌した。この撹拌の間に、シュウ酸銀は溶解して液状組成物が得られ、得られた液状組成物の加熱撹拌によって被覆銀粒子が生成して懸濁液が得られた。こうして得られた懸濁液にメタノールを５ｍＬ添加して遠心分離（２６００Ｇ）により銀粒子を沈殿させて反応媒から分離し、分離した銀粒子に対し、再度メタノール５ｍＬを加え、撹拌、遠心分離を行うことで、銀粒子を沈殿させて分離し、ペースト状の被覆銀粒子を２．０ｇ得た。
Example 1
As the silver compound, silver oxalate synthesized from silver nitrate (Kanto Chemical Co., Ltd., first grade) and oxalic acid dihydrate (Kanto Chemical Co., Ltd., special grade) was used. 0.20 g of water, 1.625 g of N, N-diethyldiaminopropane and 3 mL of 1-hexanol were placed in a 50 mL centrifuge tube, heated to 90 ° C. and stirred for 20 minutes. Thereafter, 3 g of silver oxalate was added and stirred for 60 minutes while maintaining the temperature at 90 ° C. During this stirring, the silver oxalate was dissolved to obtain a liquid composition, and the obtained liquid composition was heated and stirred to produce coated silver particles to obtain a suspension. 5 mL of methanol was added to the suspension obtained in this way, silver particles were precipitated by centrifugation (2600G) and separated from the reaction medium, and 5 mL of methanol was added again to the separated silver particles, followed by stirring and centrifugation. As a result, silver particles were precipitated and separated to obtain 2.0 g of paste-like coated silver particles.
得られた被覆銀粒子と熱可塑性ポリウレタン樹脂（荒川化学社製、ユリアーノ８００１）とを混合して、被覆銀粒子含有組成物を得た。熱可塑性ポリウレタン樹脂の添加量は、被覆銀粒子の銀換算の含有量に対する質量割合として、１質量％であった。 The obtained coated silver particles and thermoplastic polyurethane resin (Arakawa Chemical Co., Ltd., Juliano 8001) were mixed to obtain a coated silver particle-containing composition. The addition amount of the thermoplastic polyurethane resin was 1% by mass as a mass ratio with respect to the content in terms of silver of the coated silver particles.
得られた被覆銀粒子含有組成物を、バーコート（ＯＳＰ−１０）を用いて、ポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗布した。被覆銀粒子含有組成物が塗布されたＰＥＴフィルムを１００℃で１時間焼成して、ＰＥＴフィルム上に膜状の導電部材を得た。 The obtained coated silver particle-containing composition was applied onto a polyethylene terephthalate (PET) film using a bar coat (OSP-10). The PET film coated with the coated silver particle-containing composition was baked at 100 ° C. for 1 hour to obtain a film-like conductive member on the PET film.
（実施例２）
水分を添加しないこと以外は実施例１と同様の操作を行って、被覆銀粒子を製造した。得られた被覆銀粒子を用いて、実施例１と同様の操作を行って被覆銀粒子含有組成物を製造した。得られた被覆銀粒子含有組成物を用いて、実施例１と同様の操作を行って導電部材を製造した。
(Example 2)
Coated silver particles were produced in the same manner as in Example 1 except that no water was added. Using the obtained coated silver particles, the same operation as in Example 1 was performed to produce a coated silver particle-containing composition. Using the obtained coated silver particle-containing composition, the same operation as in Example 1 was performed to produce a conductive member.
（実施例３）
実施例１と同様の操作を行って製造した被覆銀粒子からなる被覆銀粒子含有組成物を用意した。この熱可塑性ポリウレタン樹脂を含有しない被覆銀粒子含有組成物を用いて、実施例１と同様の操作を行って導電部材を製造した。
(Example 3)
A coated silver particle-containing composition comprising coated silver particles produced by performing the same operation as in Example 1 was prepared. Using the coated silver particle-containing composition not containing the thermoplastic polyurethane resin, the same operation as in Example 1 was performed to produce a conductive member.
（実施例４）
被覆銀粒子を製造する際に添加させる水分量を変更して（表１参照。）、形状分布が異なる複数種類の被覆銀粒子を製造した。これらの被覆銀粒子のそれぞれを含有する被覆銀粒子含有組成物を、実施例１と同様の操作を実施することにより製造した。得られた被覆銀粒子含有組成物について実施例１と同様の作業を行って、印刷物が配置されたＰＥＴフィルムを得た。これらの印刷物の焼成時間を変更して、複数種類の導電部材を得た。
Example 4
A plurality of types of coated silver particles having different shape distributions were produced by changing the amount of water added when the coated silver particles were produced (see Table 1). A coated silver particle-containing composition containing each of these coated silver particles was produced by performing the same operation as in Example 1. The obtained coated silver particle-containing composition was subjected to the same operation as in Example 1 to obtain a PET film on which printed matter was arranged. Various types of conductive members were obtained by changing the firing time of these printed materials.
（試験例１）被覆銀粒子の観察
実施例において製造した被覆銀粒子を、電子顕微鏡を用いて観察した。観察結果を図に示した。各図と実施例および液状組成物に含有される水分量との関係は次のとおりである。
(Test Example 1) Observation of coated silver particles The coated silver particles produced in the examples were observed using an electron microscope. The observation results are shown in the figure. The relationship between each figure and the amount of water contained in the examples and the liquid composition is as follows.
図１ 実施例１ 水分量２．８質量％
図２ 実施例２ 水分無添加
図５ 実施例４−１ 水分量０．７質量％
図６ 実施例４−２ 水分量２．１質量％
図７ 実施例４−３ 水分量４．２質量％
図８ 実施例４−４ 水分量６．４質量％
図９ 実施例４−５ 水分量８．５質量％
図１０ 実施例４−６ 水分量１０．６質量％
図１１ 実施例４−７ 水分量１２．７質量％
図１２ 実施例４−８ 水分量２．３質量％
図１３ 実施例４−９ 水分量２．５質量％
図１４ 実施例４−１０ 水分量２．８質量％
図１５ 実施例４−１１ 水分量３．０質量％
図１６ 実施例４−１２ 水分量３．２質量％
FIG. 1 Example 1 Water content 2.8% by mass
Fig. 2 Example 2 No water addition Fig. 5 Example 4-1 Water content 0.7 mass%
FIG. 6 Example 4-2 Moisture content 2.1 mass%
FIG. 7 Example 4-3 Moisture content 4.2 mass%
FIG. 8 Example 4-4 Moisture content 6.4% by mass
Figure 9 Example 4-5 Moisture content 8.5% by mass
FIG. 10 Example 4-6 Moisture content 10.6 mass%
FIG. 11 Example 4-7 Water content 12.7 mass%
FIG. 12 Example 4-8 Moisture content 2.3 mass%
FIG. 13 Example 4-9 Moisture content 2.5 mass%
FIG. 14 Example 4-10 Moisture content 2.8% by mass
FIG. 15 Example 4-11 Water content 3.0% by mass
FIG. 16 Example 4-12 Moisture content 3.2 mass%
これらの図に示されるように、液状組成物の水分量を変化させることにより、液状組成物を用いて製造される被覆銀粒子の形状分布を制御しうることが、本試験例により確認された。具体的には、フレーク状であってその長軸長さの大きな被覆銀粒子を製造しうることが確認された。 As shown in these figures, it was confirmed by this test example that the shape distribution of the coated silver particles produced using the liquid composition can be controlled by changing the water content of the liquid composition. . Specifically, it was confirmed that coated silver particles having a flake shape and a long major axis can be produced.
（試験例２）被覆銀粒子の粒径分布の評価
実施例により製造した被覆銀粒子の粒径分布を、電子顕微鏡により観察した一群の被覆銀粒子の観察画像を用いて評価した。具体的には、画像解析式粒度分布ソフトウェア（マウンテック社製、Ｍａｃ−ＶＩＥＷ）による画像処理を、加速電圧を５ｋＶとして２００００倍で観察した画像に対して適用し、観察画像から認識された粒子の円換算粒径の度数分布を得た。この度数分布の最頻出値を用いて、評価対象となった被覆銀粒子の粒径の大小を評価した。測定結果を表１に示す。
(Test Example 2) Evaluation of particle size distribution of coated silver particles The particle size distribution of the coated silver particles produced according to the examples was evaluated using observation images of a group of coated silver particles observed with an electron microscope. Specifically, image processing using image analysis type particle size distribution software (Mac-VIEW, manufactured by Mountech Co., Ltd.) is applied to an image observed at 20000 times with an acceleration voltage of 5 kV, and particles recognized from the observed image are detected. A frequency distribution of the diameter in terms of a circle was obtained. Using the most frequent value of the frequency distribution, the size of the particle diameter of the coated silver particles to be evaluated was evaluated. The measurement results are shown in Table 1.
表１に示されるように、液状組成物の水分量を増加させることにより、液状組成物から製造された被覆銀粒子の最頻出粒径を増加させうることが、本試験例により確認された。 As shown in Table 1, it was confirmed by this test example that the most frequent particle diameter of the coated silver particles produced from the liquid composition can be increased by increasing the water content of the liquid composition.
（試験例３）導電部材の体積抵抗率の測定
実施例および比較例により製造した導電部材の体積抵抗率（単位：μΩ・ｃｍ）を測定した。測定結果を表２に示す。表２において、長時間加熱の列には、体積抵抗率の値とともに加熱時間を記した。
(Test Example 3) Measurement of Volume Resistivity of Conductive Member The volume resistivity (unit: μΩ · cm) of the conductive member manufactured according to the example and the comparative example was measured. The measurement results are shown in Table 2. In Table 2, in the long-time heating column, the heating time was written together with the value of volume resistivity.
被覆銀粒子の形状分布を変化させることにより、当該被覆銀粒子を含有する組成物を用いて製造された導電部材の体積抵抗率を変化させうることが、本試験例により確認された。本試験例によれば、表２に示されるように、水分量が３．２質量％程度の場合に、最も導電部材の体積抵抗率が低下した。また、焼成工程における焼成時間を延ばすことにより、導電部材の体積抵抗率を低下させることが可能であるが、焼成時間の延長により体積抵抗率を低下させることには限界があり、焼成時間は３時間程度またはそれ以下で十分であることも、本試験例により確認された。 It was confirmed by this test example that the volume resistivity of the conductive member manufactured using the composition containing the coated silver particles can be changed by changing the shape distribution of the coated silver particles. According to this test example, as shown in Table 2, when the water content was about 3.2% by mass, the volume resistivity of the conductive member was reduced most. Further, it is possible to reduce the volume resistivity of the conductive member by extending the firing time in the firing step, but there is a limit to reducing the volume resistivity by extending the firing time, and the firing time is 3 It was also confirmed by this test example that a time of about or less was sufficient.
以上のように、本発明に係る被覆銀粒子を用いて製造される導電部材は導電性に優れるため、電気・電子部品の電気配線などに好適に使用することができる。 As described above, since the conductive member produced using the coated silver particles according to the present invention is excellent in conductivity, it can be suitably used for electric wiring of electric / electronic parts.
Claims (18)
前記液状組成物に含有される前記錯化合物を加熱分解して被覆銀粒子を生成する第２工程と、を含み、
前記第１工程で得られる前記液状組成物は、全組成物に対して、１質量％以上８質量％以下で水を含有すること
を特徴とする被覆銀粒子の製造方法。 A first step of obtaining a liquid composition containing a complex compound containing the silver compound and the alkylamine, comprising mixing a silver compound capable of being decomposed by heating to form metallic silver and an alkylamine;
A second step of thermally decomposing the complex compound contained in the liquid composition to produce coated silver particles,
The said liquid composition obtained at the said 1st process contains 1 to 8 mass% of water with respect to all the compositions, The manufacturing method of the covering silver particle characterized by the above-mentioned.
前記アルキルアミンと、
水と、を含有し、
水の含有量は、全組成物に対して、１質量％以上８質量％以下であること
を特徴とする液状組成物。 A complex compound of a silver compound and an alkylamine that can be decomposed by heating to form metallic silver;
The alkylamine;
Containing water,
Content of water is 1 to 8 mass% with respect to the whole composition, The liquid composition characterized by the above-mentioned.
前記基体上に配置された前記被覆銀粒子含有組成物を加熱することにより前記被覆銀粒子含有組成物に含まれる前記被覆銀粒子を焼成して、前記基体上に導電部材を形成する焼成工程
を備えることを特徴とする導電部材の製造方法。 An arrangement step of arranging the coated silver particle-containing composition according to claim 6 or 7 on a substrate; and the coated silver particle-containing composition by heating the coated silver particle-containing composition disposed on the substrate. A method for producing a conductive member, comprising a firing step of firing the coated silver particles contained in a product to form a conductive member on the substrate.
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