JP2013117047A - Fine silver particle dispersion - Google Patents

Fine silver particle dispersion Download PDF

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JP2013117047A
JP2013117047A JP2011265376A JP2011265376A JP2013117047A JP 2013117047 A JP2013117047 A JP 2013117047A JP 2011265376 A JP2011265376 A JP 2011265376A JP 2011265376 A JP2011265376 A JP 2011265376A JP 2013117047 A JP2013117047 A JP 2013117047A
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silver fine
particle dispersion
silver
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JP5775438B2 (en
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Hidefumi Fujita
英史 藤田
Yoshi Murano
由 村野
Kimitaka Sato
王高 佐藤
Shinichi Konno
慎一 紺野
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Dowa Electronics Materials Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a fine silver particle dispersion that can be printed on a substrate by a flexographic press, and also can form a favorable wiring or conductive circuit by sintering the fine silver particles even by short heat treatment at a lower temperature than the prior art.SOLUTION: The fine silver particle dispersion in which fine silver particles having an average diameter of 1 to 100 nm are dispersed in an aqueous dispersion medium that is a solvent mainly containing water, contains 30 to 70 mass%, or preferably 40 to 65 mass% of the fine silver particles. One or more chlorine compounds selected from a group of sodium chloride, ammonium chloride, potassium chloride, and a calcium chloride are added to the fine silver dispersion so that the mass ratio of Cl to Ag (Cl/Ag) falls within the range of 0.05 to 0.3 mass%.

Description

本発明は、銀微粒子分散液に関し、特に、RFIDアンテナなどの電子部品の導電回路などの形成に使用する銀微粒子分散液に関する。   The present invention relates to a silver fine particle dispersion, and more particularly, to a silver fine particle dispersion used for forming a conductive circuit of an electronic component such as an RFID antenna.

従来、RFIDアンテナなどの高信頼性が要求される電子部品の配線や導電回路は、マスクした基板上に高価な貴金属のスパッタリングにより形成されている。しかし、スパッタリングにより配線や導電回路を形成する方法では、様々な工程が必要となるため、生産性が高いとはいえず、また、原料として投入される高価な貴金属のすべてが配線や導電回路の形成に使用されるのではないため、資源の有効活用の観点から、他の方法により配線や導電回路を形成することが検討されている。   Conventionally, wiring and conductive circuits of electronic components such as RFID antennas that require high reliability are formed on a masked substrate by sputtering of expensive noble metal. However, the method of forming a wiring or a conductive circuit by sputtering requires various steps, so it cannot be said that the productivity is high, and all of the expensive noble metal that is input as a raw material is not the wiring or conductive circuit. Since it is not used for formation, from the viewpoint of effective utilization of resources, formation of wirings and conductive circuits by other methods has been studied.

近年、電子部品の配線や導電回路などを大量に且つ容易に形成する方法として、印刷技術を応用して配線や導電回路などを形成するプリンテッド・エレクトロニクスが注目されており、金属粒子を分散媒中に分散させた導電性インクを、フレキソ印刷やスクリーン印刷などの様々な印刷技術により基材上に印刷した後に、金属粒子同士を焼結させて配線や導電回路などを形成することが検討されている。   In recent years, as a method for easily forming a large amount of wiring and conductive circuits of electronic components, printed electronics that forms wiring and conductive circuits by applying printing technology has attracted attention. After the conductive ink dispersed in the substrate is printed on the substrate by various printing techniques such as flexographic printing and screen printing, it is considered to sinter metal particles to form wiring, conductive circuits, etc. ing.

一方、金属粒子の粒径が数nm〜数十nm程度になると、比表面積が非常に大きくなって、融点が劇的に低下するため、数μm程度の粒径の金属粒子を分散媒中に分散させた導電性インクを使用して配線や導電回路を形成する場合と比べて、微細な配線や導電回路の形成が可能になるだけでなく、200℃以下の低温で焼成しても金属粒子同士を焼結させることができるようになるので、耐熱性の低い基板などの様々な基板を使用することができるようになる。そのため、粒径が数十nm以下の金属微粒子(金属ナノ粒子)を分散媒中に分散させた導電性インク(金属微粒子分散液)をプリンテッド・エレクトロニクスに応用して電子部品の微細な配線や導電回路を形成することが期待されている。   On the other hand, when the particle size of the metal particles is several nanometers to several tens of nanometers, the specific surface area becomes very large and the melting point decreases dramatically. Compared to the case where wiring or conductive circuit is formed using dispersed conductive ink, not only fine wiring and conductive circuit can be formed, but also metal particles even when fired at a low temperature of 200 ° C. or lower. Since it becomes possible to sinter each other, various substrates such as a substrate having low heat resistance can be used. For this reason, conductive ink (metal fine particle dispersion) in which metal fine particles (metal nanoparticles) with a particle size of several tens of nanometers or less are dispersed in a dispersion medium is applied to printed electronics to make fine wiring and It is expected to form a conductive circuit.

また、粒径が数十nm以下の金属微粒子は、活性が非常に高く、そのままでは粒子として不安定であるので、金属微粒子同士の焼結や凝集を防止して、金属微粒子の独立性や保存安定性を確保するために、長鎖の界面活性剤などの有機物で被覆した金属微粒子をデカンやターピネオールなどの有機溶媒中に分散させた導電性インク(金属微粒子分散液)が提案されている。しかし、金属微粒子を高分子量の長鎖の界面活性剤で被覆すると、その沸点や分解点が高いことから、金属微粒子同士を焼結させて配線や導電回路など形成する際に、金属微粒子の表面の界面活性剤を除去や分解するために、高温で処理する必要があり、耐熱性の低い基板を使用することができなくなるだけでなく、30分〜1時間程度の比較的長時間にわたって熱処理する必要があり、生産性が悪くなる。また、導電性インクの分散媒として有機溶媒を使用すると、廃棄の際に注意を払わなければ環境汚染の原因になり得るし、また、加熱の際や開放系で放置した場合に蒸発した有機成分が周囲に拡散するため、大量に処理する場合に局所排気装置の設置などが必要になるので、有機溶媒を主成分としない分散媒を使用することができれば、環境面および作業面において望ましい。   In addition, metal fine particles having a particle size of several tens of nanometers or less have very high activity and are unstable as particles as they are, so that sintering and aggregation of metal fine particles are prevented, and the independence and storage of metal fine particles In order to ensure stability, a conductive ink (metal fine particle dispersion) is proposed in which metal fine particles coated with an organic substance such as a long-chain surfactant are dispersed in an organic solvent such as decane or terpineol. However, when metal fine particles are coated with a high-molecular-weight long-chain surfactant, the boiling point and decomposition point thereof are high, so when the metal fine particles are sintered together to form wiring, conductive circuits, etc., the surface of the metal fine particles In order to remove or decompose the surface active agent, it is necessary to perform the treatment at a high temperature, which makes it impossible to use a substrate having low heat resistance, and heat treatment is performed for a relatively long time of about 30 minutes to 1 hour. It is necessary and productivity is deteriorated. In addition, if an organic solvent is used as a dispersion medium for the conductive ink, it may cause environmental pollution if care is not taken during disposal, and organic components that have evaporated when heated or left in an open system. Since it diffuses to the surroundings, it is necessary to install a local exhaust device in the case of processing in large quantities. Therefore, if a dispersion medium that does not contain an organic solvent as a main component can be used, it is desirable in terms of environment and work.

そのため、炭素数3〜8の直鎖脂肪酸またはその誘導体で被覆された金属ナノ粒子が水を主体とする媒体中に分散した金属ナノ粒子組成物が提案されている(例えば、特許文献1参照)。この金属ナノ粒子組成物を使用すれば、低温で短時間の熱処理、例えば、140℃以下で90秒未満の熱処理でも金属ナノ粒子同士を焼結させて基材上に良好な配線や導電回路など形成することができる。   Therefore, a metal nanoparticle composition is proposed in which metal nanoparticles coated with a linear fatty acid having 3 to 8 carbon atoms or a derivative thereof are dispersed in a medium mainly composed of water (for example, see Patent Document 1). . If this metal nanoparticle composition is used, heat treatment at a low temperature for a short time, for example, heat treatment of 140 ° C. or less and less than 90 seconds, the metal nanoparticles are sintered to each other so that a good wiring or conductive circuit is formed on the substrate. Can be formed.

また、水性媒体中に、0.1μm以下の銀超微粒子と、ポリマーラテックスと、水溶性ハロゲン化物とを含有する銀超微粒子含有組成物が提案されている(例えば、特許文献2参照)。この銀超微粒子含有組成物を使用すれば、焼成工程を必要とせずに、基材上に配線や導電回路など形成することができる。   In addition, a composition containing ultrafine silver particles containing ultrafine silver particles of 0.1 μm or less, a polymer latex, and a water-soluble halide in an aqueous medium has been proposed (see, for example, Patent Document 2). If this silver ultrafine particle containing composition is used, a wiring, a conductive circuit, etc. can be formed on a base material, without requiring a baking process.

特開2011−202265号公報(段落番号0027−0045)Japanese Patent Laying-Open No. 2011-202265 (paragraph numbers 0027-0045) 特開2011−159392号公報(段落番号0020)JP2011-159392A (paragraph number 0020)

しかし、工業的に通常用いられているロール・ツー・ロールの連続式のフレキソ印刷機により、特許文献1の金属ナノ粒子組成物をPETフィルムや紙などの安価で且つ耐熱性の低い基板上に印刷して熱処理すると、金属ナノ粒子同士を十分に焼結させることができず、良好な導電性を得るのは困難である。すなわち、ロール・ツー・ロールの連続式のフレキソ印刷機では、生産性を高めるために、印刷速度を30m/分以上に設定することが望まれているが、このように印刷速度を高速にすると、フレキソ印刷機に付属する熱処理炉内を仮に(特許文献1の金属ナノ粒子組成物の金属ナノ粒子同士を焼結させるために)140℃に設定しても、基材がその温度まで加熱される前に熱処理炉から送出されてしまう。一方、設定温度を高くすると、金属ナノ粒子同士を焼成することができても、熱により基板が変形したり焦げてしまうなどの問題がある。そのため、金属ナノ粒子同士を十分に焼結させることができず、良好な導電性を得るのは困難である。   However, the metal nanoparticle composition of Patent Document 1 is applied to an inexpensive and low heat resistant substrate such as PET film or paper by a roll-to-roll continuous flexo printing machine that is usually used industrially. When printed and heat-treated, the metal nanoparticles cannot be sufficiently sintered, and it is difficult to obtain good conductivity. In other words, in a roll-to-roll continuous flexo printing machine, in order to increase productivity, it is desired to set the printing speed to 30 m / min or more. Even if the heat treatment furnace attached to the flexographic printing machine is set to 140 ° C. (to sinter the metal nanoparticles of the metal nanoparticle composition of Patent Document 1), the substrate is heated to that temperature. Before the heat treatment furnace. On the other hand, when the set temperature is increased, there is a problem that even if the metal nanoparticles can be fired, the substrate is deformed or burnt by heat. For this reason, the metal nanoparticles cannot be sufficiently sintered, and it is difficult to obtain good conductivity.

また、特許文献2の銀超微粒子含有組成物は、焼成工程を必要とせずに、基材上に塗布して乾燥させることにより導電性パターンを形成しているので、ロール・ツー・ロールの連続式のフレキソ印刷機により、基材上に印刷して良好な導電性を得るのは困難である。   Moreover, since the silver ultrafine particle containing composition of patent document 2 forms the electroconductive pattern by apply | coating on a base material and making it dry without requiring a baking process, it is a roll-to-roll continuous It is difficult to obtain good conductivity by printing on a substrate with a flexographic press of the type.

したがって、本発明は、このような従来の問題点に鑑み、フレキソ印刷機により基材上に印刷することができるとともに、従来よりさらに低温で短時間の熱処理でも銀微粒子同士を焼結させて良好な配線や導電回路を形成することができる、銀微粒子分散液を提供することを目的とする。   Therefore, in view of such a conventional problem, the present invention can be printed on a substrate by a flexographic printing machine, and can sinter silver fine particles even by heat treatment at a lower temperature and in a shorter time than before. An object of the present invention is to provide a silver fine particle dispersion capable of forming simple wirings and conductive circuits.

本発明者らは、上記課題を解決するために鋭意研究した結果、水系分散媒中に銀微粒子が分散した銀微粒子分散液において、30〜70質量%の銀微粒子を含み、Agに対するClの質量の割合(Cl/Ag)が0.05〜0.3質量%になるように塩素化合物を添加することにより、フレキソ印刷機により基材上に印刷することができるとともに、従来よりさらに低温で短時間の熱処理でも銀微粒子同士を焼結させて良好な配線や導電回路を形成することができる、銀微粒子分散液を提供することができることを見出し、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present inventors have found that a silver fine particle dispersion in which silver fine particles are dispersed in an aqueous dispersion medium contains 30 to 70% by mass of silver fine particles, and the mass of Cl relative to Ag. By adding a chlorine compound so that the ratio (Cl / Ag) is 0.05 to 0.3% by mass, it is possible to print on a substrate with a flexographic printing machine, and at a lower temperature and at a lower temperature than before. The inventors have found that a silver fine particle dispersion that can sinter silver fine particles to form good wirings and conductive circuits by heat treatment for a long time can be provided, and the present invention has been completed.

すなわち、本発明による銀微粒子分散液は、水系分散媒中に銀微粒子が分散した銀微粒子分散液において、30〜70質量%の銀微粒子を含み、Agに対するClの質量の割合(Cl/Ag)が0.05〜0.3質量%になるように塩素化合物が添加されていることを特徴とする。   That is, the silver fine particle dispersion according to the present invention contains 30 to 70% by mass of silver fine particles in a silver fine particle dispersion in which silver fine particles are dispersed in an aqueous dispersion medium, and the ratio of the mass of Cl to Ag (Cl / Ag). Is characterized in that a chlorine compound is added so as to be 0.05 to 0.3% by mass.

この銀微粒子分散液において、塩素化合物が、塩化ナトリウム、塩化アンモニウム、塩化カリウムおよび塩化カルシウムからなる群から選ばれる1種以上であるのが好ましい。また、銀微粒子分散液中の銀微粒子の含有量が40〜65質量%であるのが好ましい。また、水系分散媒が50質量%以上の水を含む溶媒であるのが好ましい。さらに、銀微粒子の平均粒径が1〜100nmであるのが好ましい。   In this silver fine particle dispersion, the chlorine compound is preferably at least one selected from the group consisting of sodium chloride, ammonium chloride, potassium chloride and calcium chloride. Moreover, it is preferable that content of the silver fine particle in a silver fine particle dispersion is 40-65 mass%. The aqueous dispersion medium is preferably a solvent containing 50% by mass or more of water. Furthermore, the average particle diameter of the silver fine particles is preferably 1 to 100 nm.

なお、本明細書中において、「銀微粒子の平均粒径」とは、銀微粒子の透過型電子顕微鏡写真(TEM像)による一次粒子径の平均値である一次粒子平均径(平均一次粒径)をいう。   In the present specification, “average particle diameter of silver fine particles” refers to an average primary particle diameter (average primary particle diameter) that is an average value of primary particle diameters according to a transmission electron micrograph (TEM image) of silver fine particles. Say.

本発明によれば、フレキソ印刷機により基材上に印刷することができるとともに、従来よりさらに低温で短時間の熱処理でも銀微粒子同士を焼結させて良好な配線や導電回路を形成することができる、銀微粒子分散液を提供することができる。   According to the present invention, it is possible to print on a substrate by a flexographic printing machine, and to form a good wiring or conductive circuit by sintering silver fine particles with each other even in a heat treatment at a lower temperature and in a shorter time than conventional. A silver fine particle dispersion that can be provided can be provided.

実施例および比較例で作製した銀微粒子分散液を基材に塗布するために使用したフレキソプルーフを概略的に示す斜視図である。It is a perspective view which shows schematically the flexoproof used in order to apply | coat to a base material the silver fine particle dispersion liquid produced in the Example and the comparative example. 図1Aのフレキソプルーフの側面図である。1B is a side view of the flexoproof of FIG. 1A. FIG. 実施例および比較例で作製したRFIDアンテナの形状を示す平面図である。It is a top view which shows the shape of the RFID antenna produced by the Example and the comparative example. 実施例および比較例で作製したICチップ実装RFIDアンテナの斜視図である。It is a perspective view of the IC chip mounting RFID antenna produced by the Example and the comparative example. 図3AのICチップ実装RFIDアンテナの側面図である。3B is a side view of the IC chip mounted RFID antenna of FIG. 3A. FIG.

本発明による銀微粒子分散液の実施の形態は、水系分散媒中に銀微粒子が分散した銀微粒子分散液において、30〜70質量%の銀微粒子を含み、Agに対するClの質量の割合(Cl/Ag)が0.05〜0.3質量%になるように塩素化合物が添加されている。   An embodiment of the silver fine particle dispersion according to the present invention is a silver fine particle dispersion in which silver fine particles are dispersed in an aqueous dispersion medium. The silver fine particle dispersion contains 30 to 70% by mass of silver fine particles, and the ratio of the mass of Cl to Ag (Cl / A chlorine compound is added so that Ag) is 0.05 to 0.3% by mass.

水系分散媒は、水を主成分とする溶媒であり、好ましくは50質量%以上、さらに好ましくは75質量%以上の水を含む溶媒である。この水系分散媒の粘度を調整するために、銀微粒子分散液に対して10質量%以下のポリウレタンシックナーなどのシックナー(増粘剤)を添加してもよく、湿潤のために10質量%以下のプロピレングリコールなどの有機溶媒を添加してもよい。また、水系分散媒と基材との密着性をより強固にするために、水中に高分子が安定して懸濁および分散した水性分散樹脂を添加してもよい。この水性分散樹脂として、塩化ビニルなどの水性ラテックスなどを使用することができる。水性分散樹脂の添加量は、0.5〜8質量%であるのが好ましく、1〜7質量%であるのがさらに好ましい。0.5質量%未満では基材との密着性をより強固にするには十分ではなく、8質量%よりも多いと、銀微粒子分散液中に凝集塊が発生するなど、分散性が悪化するととともに、塗膜化する際の導電性に悪影響を及ぼすため好ましくない。   The aqueous dispersion medium is a solvent containing water as a main component, and is preferably a solvent containing 50% by mass or more, more preferably 75% by mass or more. In order to adjust the viscosity of the aqueous dispersion medium, a thickener (thickener) such as polyurethane thickener of 10% by mass or less may be added to the silver fine particle dispersion, and 10% by mass or less for wetting. An organic solvent such as propylene glycol may be added. In order to further strengthen the adhesion between the aqueous dispersion medium and the substrate, an aqueous dispersion resin in which a polymer is stably suspended and dispersed in water may be added. As this aqueous dispersion resin, aqueous latex such as vinyl chloride can be used. The addition amount of the aqueous dispersion resin is preferably 0.5 to 8% by mass, and more preferably 1 to 7% by mass. If it is less than 0.5% by mass, it is not sufficient to further strengthen the adhesion to the substrate, and if it exceeds 8% by mass, the dispersibility deteriorates, for example, aggregates are generated in the silver fine particle dispersion. At the same time, it adversely affects the conductivity when forming a coating film, which is not preferable.

塩素化合物として、次亜塩素酸などのオキソ酸、亜塩素酸ナトリウム、亜塩素酸カリウム、次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウムなどのオキソ酸塩、塩酸などの水素化物、リチウム塩、ナトリウム塩、カリウム塩、バリウム塩、ストロンチウム塩、アンモニウム塩、ジルコニウム塩、アルミニウム塩、マグネシウム塩、カルシウム塩などの無機塩などを使用することができる。これらのうち、塩化ナトリウム、塩化アンモニウム、塩化カリウムおよび塩化カルシウムからなる群から選ばれる1種以上の塩素化合物を使用するのが好ましい。このような塩素化合物を添加して、Agに対するClの質量の割合(Cl/Ag)を0.05〜0.3質量%にするのが好ましい。   As chlorine compounds, oxoacids such as hypochlorous acid, sodium chlorite, potassium chlorite, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc., hydrogen such as hydrochloric acid Inorganic salts such as chemical compounds, lithium salts, sodium salts, potassium salts, barium salts, strontium salts, ammonium salts, zirconium salts, aluminum salts, magnesium salts, calcium salts, and the like can be used. Among these, it is preferable to use one or more chlorine compounds selected from the group consisting of sodium chloride, ammonium chloride, potassium chloride, and calcium chloride. It is preferable to add such a chlorine compound so that the mass ratio of Cl to Ag (Cl / Ag) is 0.05 to 0.3 mass%.

銀微粒子は、平均粒径が1〜100nmであり、1〜50nmであるのが好ましく、1〜30nmであるのがさらに好ましく、1〜20nmであるのが最も好ましい。平均粒径が100nmよりも大きいと、銀微粒子として期待される低温焼結性が得られ難くなる。また、銀微粒子分散液中の銀微粒子の含有量は、30〜70質量%であり、40〜65質量%であるのが好ましい。また、銀微粒子は、表面が炭素数3〜8の直鎖脂肪酸またはその誘導体で被覆されているのが好ましい。このような被覆により銀微粒子間の焼結を防ぎ、銀微粒子間の距離を適度に保つことができる。炭素数が8よりも大きくなると、熱分解時に高い熱エネルギーが必要となり、一方、炭素数が3より小さくなると、銀微粒子間の距離を適度に保つことができなくなる。   The silver fine particles have an average particle diameter of 1 to 100 nm, preferably 1 to 50 nm, more preferably 1 to 30 nm, and most preferably 1 to 20 nm. When the average particle size is larger than 100 nm, it is difficult to obtain the low-temperature sinterability expected as silver fine particles. Further, the content of the silver fine particles in the silver fine particle dispersion is 30 to 70% by mass, and preferably 40 to 65% by mass. Moreover, it is preferable that the surface of the silver fine particles is coated with a linear fatty acid having 3 to 8 carbon atoms or a derivative thereof. Such a coating prevents sintering between the silver fine particles and keeps the distance between the silver fine particles moderate. If the carbon number is greater than 8, high thermal energy is required during pyrolysis. On the other hand, if the carbon number is smaller than 3, the distance between the silver fine particles cannot be maintained appropriately.

なお、銀微粒子の平均粒径(一次粒子平均径)は、例えば、60質量%のAg粒子と3.0質量%の塩化ビニルコポリマーラテックスと2.0質量%のポリウレタンシックナーと2.5質量%のプロピレングリコールとを含む水系Agインクなどの銀微粒子を含む水系Agインク2質量部をシクロヘキサン96質量部とオレイン酸2質量部の混合溶液に添加し、超音波によって分散させた後、得られた分散溶液を支持膜付きCuマイクログリッドに滴下して乾燥させ、このマイクログリッド上の銀微粒子を透過型電子顕微鏡(日本電子株式会社製のJEM−100CXMark−II型)により加速電圧100kVとして明視野で観察した像を倍率300,000倍で撮影し、得られたTEM像から算出することができる。この銀微粒子の一次粒子平均径の算出は、例えば、画像解析ソフト(旭化成エンジニアリング株式会社製のA像くん(登録商標))を使用して行うことができる。この画像解析ソフトは、色の濃淡で個々の粒子を識別して解析するものであり、例えば、300,000倍のTEM像に対して「粒子の明度」を「暗」、「雑音除去フィルタ」を「有」、「円形しきい値」を「20」、「重なり度」を「50」とする条件で円形粒子解析を行って、200個以上の粒子について一次粒子径を測定し、その数平均径を求めて一次粒子平均径とすることができる。なお、TEM像中に凝結粒子や異形粒子が多数ある場合には、測定不能とすればよい。   The average particle diameter (primary particle average diameter) of the silver fine particles is, for example, 60% by mass of Ag particles, 3.0% by mass of vinyl chloride copolymer latex, 2.0% by mass of polyurethane thickener, and 2.5% by mass. Obtained by adding 2 parts by mass of an aqueous Ag ink containing silver fine particles such as an aqueous Ag ink containing propylene glycol to a mixed solution of 96 parts by mass of cyclohexane and 2 parts by mass of oleic acid and dispersing by ultrasonic waves. The dispersion solution is dropped onto a Cu microgrid with a support film and dried, and the silver fine particles on the microgrid are brightened at an accelerating voltage of 100 kV with a transmission electron microscope (JEM-100CXMark-II type manufactured by JEOL Ltd.) in a bright field. The observed image can be taken at a magnification of 300,000 and calculated from the obtained TEM image. The primary particle average diameter of the silver fine particles can be calculated using, for example, image analysis software (A Image-kun (registered trademark) manufactured by Asahi Kasei Engineering Co., Ltd.). This image analysis software discriminates and analyzes individual particles based on color shading. For example, for a 300,000-fold TEM image, the “particle brightness” is “dark” and “noise removal filter”. Is “Yes”, “Circular threshold” is “20”, and “Overlapping degree” is “50”, and circular particle analysis is performed to measure the primary particle diameter of 200 or more particles. An average diameter can be calculated | required and it can be set as an average primary particle diameter. In addition, what is necessary is just to make measurement impossible when there are many condensed particles and irregular-shaped particles in a TEM image.

以下、本発明による銀微粒子分散液の実施例について詳細に説明する。   Hereinafter, examples of the silver fine particle dispersion according to the present invention will be described in detail.

[実施例1〜4]
まず、60質量%のAg粒子(平均粒径10nmの銀粒子)と、3.0質量%の塩化ビニルコポリマーラテックスと、2.0質量%のポリウレタンシックナーと、2.5質量%のプロピレングリコールとを含む水系Agインク(ピーケム・アソシエイツ・インク社製のPFI−700型)を、(3000rpmで10分間の)遠心分離により、上澄み液とAg粒子に分離した後、沈降したAg粒子を巻き込まない程度に上澄み液を分取して、Ag濃度71.49質量%の濃縮Agインクを用意した。
[Examples 1 to 4]
First, 60% by mass of Ag particles (silver particles having an average particle size of 10 nm), 3.0% by mass of vinyl chloride copolymer latex, 2.0% by mass of polyurethane thickener, 2.5% by mass of propylene glycol, Aqueous Ag ink (PFI-700, manufactured by P-Chem Associates, Inc.) containing water is separated into a supernatant and Ag particles by centrifugation (at 3000 rpm for 10 minutes), and then the precipitated Ag particles are not entrained The supernatant liquid was separated into a concentrated Ag ink having an Ag concentration of 71.49% by mass.

また、塩化ナトリウム(和光純薬工業株式会社製)25gを純水75gに溶解して、25質量%の塩化ナトリウム水溶液を用意した。   Moreover, 25 g of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 75 g of pure water to prepare a 25% by mass sodium chloride aqueous solution.

次に、上記の濃縮Agインク19.5gに上記の塩化ナトリウム溶液をそれぞれ0.28g(実施例1)、0.18g(実施例2)、0.09g(実施例3)、0.05g(実施例4)添加した後、Ag濃度が65質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が65質量%でAgに対するClの質量の割合(Cl/Ag)がそれぞれ0.30質量%(実施例1)、0.20質量%(実施例2)、0.10質量%(実施例3)、0.05質量%(実施例4)の銀微粒子分散液を作製した。   Next, 0.25 g (Example 1), 0.18 g (Example 2), 0.09 g (Example 3), and 0.05 g (Example 3) of the above sodium chloride solution were added to 19.5 g of the concentrated Ag ink. Example 4) After the addition, the above supernatant (sorted supernatant) was added so that the Ag concentration was 65% by mass, and the Ag concentration was 65% by mass and the ratio of the mass of Cl to Ag ( Cl / Ag) of 0.30% by mass (Example 1), 0.20% by mass (Example 2), 0.10% by mass (Example 3) and 0.05% by mass (Example 4), respectively. A silver fine particle dispersion was prepared.

このようにして作製した各実施例の銀微粒子分散液を、図1Aおよび図1Bに概略的に示すフレキソプルーフ(RKプリント・コート・インスツルメンツ社製の型式ESI12、アニロックス、200線)を用いて、ポリエチレンテレフタレート(PET)フィルム(デュポンテイジンフィルム社製のMelinex(登録商標)545)からなる基材Aと、塗工紙(三菱製紙株式会社製のDF−110GN)からなる基材Bと、キャストコート紙(王子製紙株式会社製のミラコート)からなる基材Cの3種類の基材にそれぞれ塗布した。   The silver fine particle dispersion liquid of each Example produced in this manner was used with a flexo-proof (model ESI12, anilox, 200 line, manufactured by RK Print Court Instruments) schematically shown in FIGS. 1A and 1B. Base material A made of polyethylene terephthalate (PET) film (Melinex (registered trademark) 545 manufactured by Dupontidine Film Co.), base material B made of coated paper (DF-110GN manufactured by Mitsubishi Paper Industries Co., Ltd.), and cast coat Each of the three substrates was coated on a substrate C made of paper (Miracoat manufactured by Oji Paper Co., Ltd.).

図1Aおよび図1Bに示すように、フレキソプルーフ1は、円筒状のゴム版2と、このゴム版2の上方に配設された円筒状のアニロックスローラ3と、このアニロックスローラ3に対向して取り付けられたドクターブレード4とを備えている。ゴム版2とアニロックスローラ3の間隔とドクターブレード4とアニロックスローラ3の間隔はそれぞれ調整可能になっており、ゴム版2を基材7上に押し当てて矢印Aの方向に引くと、ゴム版2が矢印B方向に回転し、その回転に伴ってアニロックスローラ3が矢印C方向に逆回転するようになっている。このフレキソプルーフ1では、ドクターブレード4とアニロックスローラ3の間に滴下された塗料(銀微粒子分散液)5が、回転するアニロックスローラ3とドクターブレード4の間からが一定の膜厚でアニロックスローラ3の表面に付着し、ゴム版2との接触面においてゴム版2に転写された後、ゴム版2の回転により基材7まで運ばれて基材7上に転写されることにより、基材7上に塗膜6が形成される。このようなフレキソプルーフの両端の調整用つまみを操作して、ゴム版とアニロックスローラが接触する位置からさらに0.05〜0.10mmだけ押し込んだ後、ドクターブレードとアニロックスローラの間に約1mLの銀微粒子分散液を滴下し、約1秒間で銀微粒子分散液を基材上に塗布した。   As shown in FIGS. 1A and 1B, the flexoproof 1 includes a cylindrical rubber plate 2, a cylindrical anilox roller 3 disposed above the rubber plate 2, and the anilox roller 3. And a doctor blade 4 attached thereto. The distance between the rubber plate 2 and the anilox roller 3 and the distance between the doctor blade 4 and the anilox roller 3 can be adjusted. When the rubber plate 2 is pressed onto the substrate 7 and pulled in the direction of arrow A, the rubber plate 2 rotates in the direction of arrow B, and the anilox roller 3 rotates reversely in the direction of arrow C along with the rotation. In this flexoproof 1, the paint (silver fine particle dispersion) 5 dripped between the doctor blade 4 and the anilox roller 3 has a constant film thickness between the rotating anilox roller 3 and the doctor blade 4. After being transferred to the rubber plate 2 at the contact surface with the rubber plate 2, the rubber plate 2 is conveyed to the base material 7 by the rotation of the rubber plate 2 and transferred onto the base material 7. A coating film 6 is formed thereon. By operating the adjustment knobs at both ends of such a flexoproof and pushing it further from the position where the rubber plate and the anilox roller contact each other by 0.05 to 0.10 mm, about 1 mL is inserted between the doctor blade and the anilox roller. The silver fine particle dispersion was dropped, and the silver fine particle dispersion was applied onto the substrate in about 1 second.

このように銀微粒子分散液を塗布した直後に、ホットプレート上において60℃で15秒間焼成して銀導電膜を作製した。なお、焼成中に基材とホットプレートの良好な接触を保つために、最初に、印刷されていない基材の部分をホットプレートに押さえ付け、焼成が進んで銀微粒子分散液がベンコットに転写されなくなった後、ベンコットにより基材全体をホットプレートに押さえ付けるように焼成を行った。   Immediately after applying the silver fine particle dispersion in this way, a silver conductive film was produced by baking at 60 ° C. for 15 seconds on a hot plate. In order to maintain good contact between the base material and the hot plate during firing, the unprinted portion of the base material is first pressed against the hot plate, and the firing proceeds and the silver fine particle dispersion is transferred to Bencot. After the disappearance, firing was performed so that the entire base material was pressed against the hot plate by Bencott.

次に、作製した銀導電膜を3cm×3cmの大きさにカットし、表面抵抗率測定器(三菱化学アナリティック株式会社製のロレスターGP)を用いて、四端子法により銀導電膜の表面抵抗率(シート抵抗率)を測定した。その結果、銀導電膜の表面抵抗率は、実施例1ではそれぞれ0.12Ω/□(基材A)、0.14Ω/□(基材B)、0.21Ω/□(基材C)、実施例2ではそれぞれ0.07Ω/□(基材A)、0.11Ω/□(基材B)、0.10Ω/□(基材C)、実施例3ではそれぞれ0.07Ω/□(基材A)、0.13Ω/□(基材B)、0.11Ω/□(基材C)、実施例4ではそれぞれ0.06Ω/□(基材A)、0.31Ω/□(基材B)、0.25Ω/□(基材C)であった。   Next, the produced silver conductive film was cut into a size of 3 cm × 3 cm, and the surface resistance of the silver conductive film was measured by a four-terminal method using a surface resistivity meter (Lorestar GP manufactured by Mitsubishi Chemical Analytic Co., Ltd.). The rate (sheet resistivity) was measured. As a result, the surface resistivity of the silver conductive film was 0.12 Ω / □ (base material A), 0.14 Ω / □ (base material B), 0.21 Ω / □ (base material C) in Example 1, respectively. In Example 2, 0.07Ω / □ (base material A), 0.11Ω / □ (base material B), 0.10Ω / □ (base material C), and in Example 3, 0.07Ω / □ (base), respectively. Material A), 0.13Ω / □ (base material B), 0.11Ω / □ (base material C), and in Example 4, 0.06Ω / □ (base material A) and 0.31Ω / □ (base material), respectively. B), 0.25Ω / □ (base material C).

[比較例1]
実施例1で用意した濃縮Agインク19.5gに、Ag濃度が65質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が65質量%でAgに対するClの質量の割合(Cl/Ag)が0.00質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、それぞれ0.30Ω/□(基材A)、1.50Ω/□(基材B)、0.61Ω/□(基材C)であった。
[Comparative Example 1]
The above supernatant (sorted supernatant) was added to 19.5 g of the concentrated Ag ink prepared in Example 1 so that the Ag concentration was 65% by mass, and the Ag concentration was 65% by mass with respect to Ag. A silver fine particle dispersion having a mass ratio of Cl (Cl / Ag) of 0.00 mass% was produced, and a silver conductive film was produced in the same manner as in Example 1. Thus, when the surface resistivity of the produced silver electrically conductive film was measured by the method similar to Example 1, 0.30 ohm / square (base material A), 1.50 ohm / square (base material B), It was 0.61Ω / □ (base material C).

[比較例2]
実施例1で用意した濃縮Agインク19.5gに、実施例1で用意した塩化ナトリウム溶液0.46gを添加した後、Ag濃度が65質量%になるように、実施例1で分取した上澄み液を添加して、Ag濃度が65質量%でAgに対するClの質量の割合(Cl/Ag)が0.50質量%の銀微粒子分散液を作製した。この比較例では、濃縮Agインクに塩化ナトリウム溶液を添加した数分後に、Ag粒子の焼結と思われる現象が起こり、流動性を伴わない固形物となったため、銀導電膜を作製することができなかった。
[Comparative Example 2]
After adding 0.46 g of the sodium chloride solution prepared in Example 1 to 19.5 g of the concentrated Ag ink prepared in Example 1, the supernatant collected in Example 1 so that the Ag concentration is 65% by mass. The solution was added to prepare a silver fine particle dispersion having an Ag concentration of 65% by mass and a ratio of Cl to Ag (Cl / Ag) of 0.50% by mass. In this comparative example, a phenomenon that seems to be sintering of Ag particles occurred a few minutes after the sodium chloride solution was added to the concentrated Ag ink, and a solid material without fluidity was formed. could not.

[実施例5〜8]
実施例1で用意した濃縮Agインク18.0gに、実施例1で用意した塩化ナトリウム溶液をそれぞれ0.25g(実施例5)、0.17g(実施例6)、0.08g(実施例7)、0.04g(実施例8)添加した後、Ag濃度が60質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が60質量%でAgに対するClの質量の割合(Cl/Ag)がそれぞれ0.30質量%(実施例5)、0.20質量%(実施例6)、0.10質量%(実施例7)、0.05質量%(実施例8)の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。
[Examples 5 to 8]
The sodium chloride solution prepared in Example 1 was added to 18.0 g of the concentrated Ag ink prepared in Example 1 and 0.25 g (Example 5), 0.17 g (Example 6), and 0.08 g (Example 7), respectively. ), 0.04 g (Example 8) was added, and then the above supernatant (sorted supernatant) was added so that the Ag concentration was 60% by mass, and the Ag concentration was 60% by mass relative to Ag. The mass ratio of Cl (Cl / Ag) was 0.30 mass% (Example 5), 0.20 mass% (Example 6), 0.10 mass% (Example 7), and 0.05 mass%, respectively. A silver fine particle dispersion of (Example 8) was prepared, and a silver conductive film was prepared by the same method as in Example 1.

このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、実施例5ではそれぞれ0.18Ω/□(基材A)、0.21Ω/□(基材B)、0.22Ω/□(基材C)、実施例6ではそれぞれ0.11Ω/□(基材A)、0.27Ω/□(基材B)、0.19Ω/□(基材C)、実施例7ではそれぞれ0.12Ω/□(基材A)、0.25Ω/□(基材B)、0.25Ω/□(基材C)、実施例8ではそれぞれ0.12Ω/□(基材A)、0.32Ω/□(基材B)、0.28Ω/□(基材C)であった。   The surface resistivity of the silver conductive film thus prepared was measured by the same method as in Example 1. In Example 5, 0.18 Ω / □ (base material A) and 0.21 Ω / □ (base), respectively. Material B), 0.22 Ω / □ (base material C), and in Example 6, 0.11 Ω / □ (base material A), 0.27 Ω / □ (base material B), 0.19 Ω / □ (base material) C), in Example 7, 0.12 Ω / □ (base material A), 0.25 Ω / □ (base material B), 0.25 Ω / □ (base material C), and in Example 8, 0.12 Ω / □, respectively. □ (base material A), 0.32 Ω / □ (base material B), and 0.28 Ω / □ (base material C).

また、フレキソ印刷機(日本電子精機株式会社製の多目的微細印刷機JEM Flex)と、フレキソ印刷版(株式会社渡辺護三堂製、印刷版の材質は旭化成株式会社製の板状感光性樹脂AWP グレードDEF、表面加工150ライン、96DOT%)を使用し、アニロックス容量20cc/m(150線/インチ)、印刷速度20m/分、印刷回数を1回とし、ポリエチレンテレフタレート(PET)フィルム(デュポンテイジンフィルム社製のMelinex(登録商標)545)からなる基材Aと、塗工紙(三菱製紙株式会社製のDF−110GN)からなる基材Bの2種類の基材(図3Aおよび図3Bにおいて参照符号13で示す)の各々に、実施例5および7で得られた銀微粒子分散液を図2に示す形状(全長32.0mm、全幅18.5mm、線幅0.7mmのRFIDアンテナ10の形状)に印刷した後、ホットプレート上において140℃で30秒間熱処理して焼成することによって、銀導電膜からなるRFIDアンテナを作製した。 In addition, flexographic printing machines (JEM Flex, a multi-purpose fine printing machine manufactured by JEOL Seiki Co., Ltd.) and flexographic printing plates (manufactured by Gosando Watanabe, printing plate made of Asahi Kasei's plate-like photosensitive resin AWP) Grade DEF, surface treatment 150 lines, 96 DOT%), anilox capacity 20 cc / m 2 (150 lines / inch), printing speed 20 m / min, printing frequency 1 time, polyethylene terephthalate (PET) film (Dupontidine) Two types of base materials (in FIGS. 3A and 3B), a base material A composed of Melinex (registered trademark) 545 manufactured by Film Co., Ltd. and a base material B composed of coated paper (DF-110GN manufactured by Mitsubishi Paper Industries Co., Ltd.) Each of the silver fine particle dispersions obtained in Examples 5 and 7 was formed in each of the shapes shown in FIG. After printing on the shape of the RFID antenna 10 having a width of 18.5 mm and a line width of 0.7 mm, an RFID antenna made of a silver conductive film was manufactured by heat treatment on a hot plate at 140 ° C. for 30 seconds and firing.

この銀導電膜のライン抵抗(図2に示すDとEの間の電気抵抗)をテスター(CUSTOM社製の型式CDM−03D)により測定したところ、実施例5ではそれぞれ43.7Ω(基材A)、33.2Ω(基材B)であり、実施例7ではそれぞれ31.0Ω(基材A)、28.7Ω(基材B)であった。   When the line resistance (electric resistance between D and E shown in FIG. 2) of this silver conductive film was measured by a tester (model CDM-03D manufactured by CUSTOM), in Example 5, 43.7Ω (base material A ), 33.2Ω (base material B), and in Example 7, they were 31.0Ω (base material A) and 28.7Ω (base material B), respectively.

また、これらのRFIDアンテナ10のICチップ実装部11に異方性導電接着剤(ACP)(京セラケミカル株式会社製のTAP0604C(Au/Niコートポリマー粒子))を薄く塗布し、このACP上にICチップ(Impinj社製のMonza2)12を配置した後、熱圧着装置(ミュールバウワー社製のTTS300)により160℃の温度で1.0Nの圧力を加えて10秒間密着させ、RFIDアンテナ10にICチップ12を固定して接続することによって、図3Aおよび図3Bに示すように、RFIDアンテナ10にICチップ12を実装した。   Further, an anisotropic conductive adhesive (ACP) (TAP0604C (Au / Ni coated polymer particles) manufactured by Kyocera Chemical Co., Ltd.) is thinly applied to the IC chip mounting portion 11 of these RFID antennas 10, and an IC is formed on the ACP. After placing the chip (Monza 2 manufactured by Impinj) 12 and applying pressure of 1.0 N at a temperature of 160 ° C. for 10 seconds with a thermocompression bonding apparatus (TTS300 manufactured by Mühlbauer), the IC chip is attached to the RFID antenna 10. By fixing and connecting 12, the IC chip 12 was mounted on the RFID antenna 10 as shown in FIGS. 3A and 3B.

このようにして作製したICチップ実装RFIDアンテナについて、電波暗箱(マイクロニクス社製のMY1530)中において、通信距離測定器(Voyantic社製のtagformance)を用いて、800MHz〜1100MHzの周波数領域(ISO/IEC 18000−6C規格に準拠)の通信距離(Theoretical read range forward)を測定した。なお、この測定に先立って、この条件における環境設定(tagformance付属のリファレンスタグによる設定)を行った。その結果、周波数955MHzの通信距離は、実施例5ではそれぞれ1.6m(基材A)、1.4m(基材B)であり、実施例7ではそれぞれ1.6m(基材A)、1.6m(基材B)であった。   With respect to the IC chip mounted RFID antenna thus manufactured, in a anechoic box (MY1530 made by Micronics), a communication distance measuring device (tagformance made by Voyantic) was used, and a frequency region (ISO / ISO) of 800 MHz to 1100 MHz was used. The communication distance (theoretical read range forward) of the IEC 18000-6C standard was measured. Prior to this measurement, the environment was set under these conditions (setting using a reference tag attached to tagformance). As a result, the communication distance at a frequency of 955 MHz is 1.6 m (base material A) and 1.4 m (base material B) in Example 5, and 1.6 m (base material A) and 1 in Example 7, respectively. .6 m (Base B).

また、耐候性試験として、実施例5および7で得られた銀導電膜からなるRFIDアンテナとICチップ実装RFIDアンテナをそれぞれ温度85℃、湿度85%に設定した恒温恒湿機中に500時間放置(保持)した後、銀導電膜のライン抵抗とICチップ実装RFIDアンテナの通信距離を測定した。その結果、銀導電膜のライン抵抗は、実施例5ではそれぞれ46.4Ω(基材A)、35.1Ω(基材B)であり、実施例7ではそれぞれ30.1Ω(基材A)、32.7Ω(基材B)であった。また、ICチップ実装RFIDアンテナの周波数955MHzの通信距離は、実施例5ではそれぞれ1.5m(基材A)、1.4m(基材B)であり、実施例7ではそれぞれ1.6m(基材A)、1.5m(基材B)であった。   In addition, as a weather resistance test, the RFID antenna made of the silver conductive film obtained in Examples 5 and 7 and the IC chip mounted RFID antenna were left in a constant temperature and humidity chamber set at a temperature of 85 ° C. and a humidity of 85%, respectively, for 500 hours. After (holding), the line resistance of the silver conductive film and the communication distance of the IC chip mounted RFID antenna were measured. As a result, the line resistances of the silver conductive film were 46.4Ω (base material A) and 35.1Ω (base material B) in Example 5, respectively, and 30.1Ω (base material A) in Example 7 respectively. It was 32.7Ω (base material B). Further, the communication distance of the frequency 955 MHz of the IC chip mounted RFID antenna is 1.5 m (base material A) and 1.4 m (base material B) in Example 5, respectively, and 1.6 m (base material) in Example 7. Material A) and 1.5 m (base material B).

[比較例3]
実施例1で用意した濃縮Agインク18.0gに、Ag濃度が60質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が60質量%でAgに対するClの質量の割合(Cl/Ag)が0.00質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、それぞれ0.36Ω/□(基材A)、2.20Ω/□(基材B)、0.83Ω/□(基材C)であった。
[Comparative Example 3]
The above supernatant (sorted supernatant) is added to 18.0 g of the concentrated Ag ink prepared in Example 1 so that the Ag concentration is 60% by mass, and the Ag concentration is 60% by mass with respect to Ag. A silver fine particle dispersion having a mass ratio of Cl (Cl / Ag) of 0.00 mass% was produced, and a silver conductive film was produced in the same manner as in Example 1. Thus, when the surface resistivity of the produced silver electrically conductive film was measured by the method similar to Example 1, 0.36 ohm / square (base material A), 2.20 ohm / square (base material B), It was 0.83Ω / □ (base material C).

また、実施例5および7と同様の方法により、銀導電膜からなるRFIDアンテナとICチップ実装RFIDアンテナを作製し、銀導電膜のライン抵抗とICチップ実装RFIDアンテナの通信距離を測定した。その結果、銀導電膜のライン抵抗は、それぞれ30.8Ω(基材A)、28.5Ω(基材B)であり、ICチップ実装RFIDアンテナの周波数955MHzの通信距離は、それぞれ1.6m(基材A)、1.5m(基材B)であった。   Further, an RFID antenna made of a silver conductive film and an IC chip-mounted RFID antenna were prepared by the same method as in Examples 5 and 7, and the line resistance of the silver conductive film and the communication distance of the IC chip-mounted RFID antenna were measured. As a result, the line resistance of the silver conductive film is 30.8Ω (base material A) and 28.5Ω (base material B), respectively, and the communication distance of the frequency 955 MHz of the IC chip mounted RFID antenna is 1.6 m (each Base material A) and 1.5 m (base material B).

また、作製した銀導電膜からなるRFIDアンテナとICチップ実装RFIDアンテナをそれぞれ恒温恒湿機中に500時間放置(保持)した後、銀導電膜のライン抵抗とICチップ実装RFIDアンテナの通信距離を測定した。その結果、銀導電膜のライン抵抗は、それぞれ29.2Ω(基材A)、29.5Ω(基材B)であり、ICチップ実装RFIDアンテナの周波数955MHzの通信距離は、それぞれ1.5m(基材A)、1.5m(基材B)であった。   In addition, after the RFID antenna made of the silver conductive film and the IC chip mounted RFID antenna are left (held) in a thermo-hygrostat for 500 hours, the line resistance of the silver conductive film and the communication distance of the IC chip mounted RFID antenna are set. It was measured. As a result, the line resistance of the silver conductive film is 29.2Ω (base material A) and 29.5Ω (base material B), respectively, and the communication distance of the frequency 955 MHz of the IC chip mounted RFID antenna is 1.5 m (each Base material A) and 1.5 m (base material B).

[比較例4]
実施例1で用意した濃縮Agインク18.0gに、実施例1で用意した塩化ナトリウム溶液0.42gを添加した後、Ag濃度が60質量%になるように、実施例1で分取した上澄み液を添加して、Ag濃度が60質量%でAgに対するClの質量の割合(Cl/Ag)が0.50質量%の銀微粒子分散液を作製した。この比較例では、濃縮Agインクに塩化ナトリウム溶液を添加した数分後に、Ag粒子の焼結と思われる現象が起こり、流動性を伴わない固形物となったため、銀導電膜を作製することができなかった。
[Comparative Example 4]
After adding 0.42 g of the sodium chloride solution prepared in Example 1 to 18.0 g of the concentrated Ag ink prepared in Example 1, the supernatant fractionated in Example 1 so that the Ag concentration is 60% by mass. The solution was added to prepare a silver fine particle dispersion having an Ag concentration of 60% by mass and a ratio of Cl to Ag (Cl / Ag) of 0.50% by mass. In this comparative example, a phenomenon that seems to be sintering of Ag particles occurred a few minutes after the sodium chloride solution was added to the concentrated Ag ink, and a solid material without fluidity was formed. could not.

[実施例9〜11]
塩化アンモニウム(NHCl)(和光純薬工業株式会社製)25gを純水75gに溶解して25質量%の塩化アンモニウム水溶液(実施例9)、塩化カリウム(KCl)(和光純薬工業株式会社製)25gを純水75gに溶解して25質量%の塩化カリウム水溶液(実施例10)、塩化カルシウム(CaCl)(和光純薬工業株式会社製)25gを純水75gに溶解して25質量%の塩化カルシウム水溶液(実施例11)を用意した。
[Examples 9 to 11]
25 g of ammonium chloride (NH 4 Cl) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 75 g of pure water to prepare a 25 mass% ammonium chloride aqueous solution (Example 9), potassium chloride (KCl) (Wako Pure Chemical Industries, Ltd.) 25 g of 25% by weight potassium chloride aqueous solution (Example 10) and calcium chloride (CaCl 2 ) (manufactured by Wako Pure Chemical Industries, Ltd.) 25 g are dissolved in 75 g of pure water. % Calcium chloride aqueous solution (Example 11) was prepared.

次に、実施例1で用意した濃縮Agインク18.0gに、上記の塩化アンモニウム溶液0.16g(実施例9)、塩化カリウム溶液0.22g(実施例10)、塩化カルシウム溶液0.16g(実施例11)をそれぞれ添加した後、Ag濃度が60質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が60質量%でAgに対するClの質量の割合(Cl/Ag)が0.20質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。   Next, 18.0 g of the concentrated Ag ink prepared in Example 1 was added to the above ammonium chloride solution 0.16 g (Example 9), potassium chloride solution 0.22 g (Example 10), and calcium chloride solution 0.16 g ( After each of Example 11) was added, the above supernatant (sorted supernatant) was added so that the Ag concentration was 60% by mass, and the Ag concentration was 60% by mass and the mass of Cl relative to Ag. A silver fine particle dispersion having a ratio (Cl / Ag) of 0.20% by mass was produced, and a silver conductive film was produced in the same manner as in Example 1.

このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、実施例9ではそれぞれ0.11Ω/□(基材A)、0.26Ω/□(基材B)、0.19Ω/□(基材C)、実施例10ではそれぞれ0.12Ω/□(基材A)、0.28Ω/□(基材B)、0.21Ω/□(基材C)、実施例11ではそれぞれ0.12Ω/□(基材A)、0.37Ω/□(基材B)、0.21Ω/□(基材C)であった。   When the surface resistivity of the silver conductive film thus produced was measured by the same method as in Example 1, in Example 9, 0.11Ω / □ (base material A) and 0.26Ω / □ (base), respectively. Material B), 0.19Ω / □ (base material C), and in Example 10, 0.12Ω / □ (base material A), 0.28Ω / □ (base material B), 0.21Ω / □ (base material), respectively. C) and Example 11 were 0.12 Ω / □ (base material A), 0.37 Ω / □ (base material B), and 0.21 Ω / □ (base material C), respectively.

[実施例12〜15]
実施例1で用意した濃縮Agインク15.0gに、実施例1で用意した塩化ナトリウム溶液をそれぞれ0.21g(実施例12)、0.14g(実施例13)、0.07g(実施例14)、0.04g(実施例15)添加した後、Ag濃度が50質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が50質量%でAgに対するClの質量の割合(Cl/Ag)がそれぞれ0.30質量%(実施例12)、0.20質量%(実施例13)、0.10質量%(実施例14)、0.05質量%(実施例15)の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。
[Examples 12 to 15]
0.21 g (Example 12), 0.14 g (Example 13), and 0.07 g (Example 14) of the sodium chloride solution prepared in Example 1 were added to 15.0 g of the concentrated Ag ink prepared in Example 1. ), 0.04 g (Example 15) was added, and then the above supernatant (sorted supernatant) was added so that the Ag concentration was 50% by mass, and the Ag concentration was 50% by mass relative to Ag. The mass ratio of Cl (Cl / Ag) was 0.30 mass% (Example 12), 0.20 mass% (Example 13), 0.10 mass% (Example 14), and 0.05 mass%, respectively. A silver fine particle dispersion of (Example 15) was prepared, and a silver conductive film was prepared by the same method as in Example 1.

このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、実施例12ではそれぞれ0.30Ω/□(基材A)、0.43Ω/□(基材B)、0.47Ω/□(基材C)、実施例13ではそれぞれ0.21Ω/□(基材A)、0.29Ω/□(基材B)、0.33Ω/□(基材C)、実施例14ではそれぞれ0.21Ω/□(基材A)、0.44Ω/□(基材B)、0.40Ω/□(基材C)、実施例15ではそれぞれ0.24Ω/□(基材A)、0.65Ω/□(基材B)、0.52Ω/□(基材C)であった。   When the surface resistivity of the silver conductive film thus produced was measured by the same method as in Example 1, in Example 12, 0.30Ω / □ (base material A) and 0.43Ω / □ (base), respectively. Material B), 0.47Ω / □ (base material C), and in Example 13, 0.21Ω / □ (base material A), 0.29Ω / □ (base material B), 0.33Ω / □ (base material) C), Example 14 is 0.21 Ω / □ (base material A), 0.44 Ω / □ (base material B), 0.40 Ω / □ (base material C), and Example 15 is 0.24 Ω / □. □ (base material A), 0.65 Ω / □ (base material B), and 0.52 Ω / □ (base material C).

[比較例5]
実施例1で用意した濃縮Agインク15.0gに、Ag濃度が50質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が50質量%でAgに対するClの質量の割合(Cl/Ag)が0.00質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、それぞれ0.56Ω/□(基材A)、8.60Ω/□(基材B)、1.70Ω/□(基材C)であった。
[Comparative Example 5]
The above supernatant liquid (prepared supernatant liquid) is added to 15.0 g of the concentrated Ag ink prepared in Example 1 so that the Ag concentration is 50% by mass, and the Ag concentration is 50% by mass with respect to Ag. A silver fine particle dispersion having a mass ratio of Cl (Cl / Ag) of 0.00 mass% was produced, and a silver conductive film was produced in the same manner as in Example 1. When the surface resistivity of the silver conductive film thus produced was measured by the same method as in Example 1, 0.56Ω / □ (base material A), 8.60Ω / □ (base material B), It was 1.70Ω / □ (base material C).

[比較例6]
実施例1で用意した濃縮Agインク15.0gに、実施例1で用意した塩化ナトリウム溶液0.35gを添加した後、Ag濃度が50質量%になるように、実施例1で分取した上澄み液を添加して、Ag濃度が50質量%でAgに対するClの質量の割合(Cl/Ag)が0.50質量%の銀微粒子分散液を作製した。この比較例では、濃縮Agインクに塩化ナトリウム溶液を添加した数分後に、Ag粒子の焼結と思われる現象が起こり、流動性を伴わない固形物となったため、銀導電膜を作製することができなかった。
[Comparative Example 6]
After adding 0.35 g of the sodium chloride solution prepared in Example 1 to 15.0 g of the concentrated Ag ink prepared in Example 1, the supernatant collected in Example 1 so that the Ag concentration is 50% by mass. The solution was added to prepare a silver fine particle dispersion having an Ag concentration of 50 mass% and a mass ratio of Cl to Ag (Cl / Ag) of 0.50 mass%. In this comparative example, a phenomenon that seems to be sintering of Ag particles occurred a few minutes after the sodium chloride solution was added to the concentrated Ag ink, and a solid material without fluidity was formed. could not.

[実施例16〜19]
実施例1で用意した濃縮Agインク12.0gに、実施例1で用意した塩化ナトリウム溶液をそれぞれ0.17g(実施例16)、0.11g(実施例17)、0.06g(実施例18)、0.03g(実施例19)添加した後、Ag濃度が40質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が40質量%でAgに対するClの質量の割合(Cl/Ag)がそれぞれ0.30質量%(実施例16)、0.20質量%(実施例17)、0.10質量%(実施例18)、0.05質量%(実施例19)の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。
[Examples 16 to 19]
0.17 g (Example 16), 0.11 g (Example 17), and 0.06 g (Example 18) of the sodium chloride solution prepared in Example 1 were added to 12.0 g of the concentrated Ag ink prepared in Example 1, respectively. ), 0.03 g (Example 19) was added, and then the above supernatant (sorted supernatant) was added so that the Ag concentration was 40% by mass, and the Ag concentration was 40% by mass relative to Ag. The mass ratio of Cl (Cl / Ag) was 0.30 mass% (Example 16), 0.20 mass% (Example 17), 0.10 mass% (Example 18), and 0.05 mass%, respectively. A silver fine particle dispersion of (Example 19) was prepared, and a silver conductive film was prepared by the same method as in Example 1.

このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、実施例16ではそれぞれ0.75Ω/□(基材A)、0.70Ω/□(基材B)、0.74Ω/□(基材C)、実施例17ではそれぞれ0.80Ω/□(基材A)、0.62Ω/□(基材B)、0.40Ω/□(基材C)、実施例18ではそれぞれ0.78Ω/□(基材A)、0.60Ω/□(基材B)、0.50Ω/□(基材C)、実施例19ではそれぞれ0.86Ω/□(基材A)、0.96Ω/□(基材B)、0.73Ω/□(基材C)であった。   When the surface resistivity of the silver conductive film thus produced was measured by the same method as in Example 1, in Example 16, 0.75Ω / □ (base material A) and 0.70Ω / □ (base), respectively. Material B), 0.74Ω / □ (base material C), and in Example 17, 0.80Ω / □ (base material A), 0.62Ω / □ (base material B), 0.40Ω / □ (base material), respectively. C), Example 18 is 0.78 Ω / □ (base material A), 0.60 Ω / □ (base material B), 0.50 Ω / □ (base material C), and Example 19 is 0.86 Ω / □. □ (base material A), 0.96 Ω / □ (base material B), and 0.73 Ω / □ (base material C).

[比較例7]
実施例1で用意した濃縮Agインク12.0gに、Ag濃度が40質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が40質量%でAgに対するClの質量の割合(Cl/Ag)が0.00質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、それぞれ13.00Ω/□(基材A)、14.00Ω/□(基材B)、2.00Ω/□(基材C)であった。
[Comparative Example 7]
The above supernatant liquid (prepared supernatant liquid) is added to 12.0 g of the concentrated Ag ink prepared in Example 1 so that the Ag concentration is 40% by mass, and the Ag concentration is 40% by mass with respect to Ag. A silver fine particle dispersion having a mass ratio of Cl (Cl / Ag) of 0.00 mass% was produced, and a silver conductive film was produced in the same manner as in Example 1. Thus, when the surface resistivity of the produced silver electrically conductive film was measured by the method similar to Example 1, it was 13.00 ohm / square (base material A), 14.00 ohm / square (base material B), respectively. It was 2.00Ω / □ (base material C).

[比較例8]
実施例1で用意した濃縮Agインク12.0gに、実施例1で用意した塩化ナトリウム溶液0.28gを添加した後、Ag濃度が40質量%になるように、実施例1で分取した上澄み液を添加して、Ag濃度が40質量%でAgに対するClの質量の割合(Cl/Ag)が0.50質量%の銀微粒子分散液を作製した。この比較例では、濃縮Agインクに塩化ナトリウム溶液を添加した数分後に、Ag粒子の焼結と思われる現象が起こり、流動性を伴わない固形物となったため、銀導電膜を作製することができなかった。
[Comparative Example 8]
After adding 0.28 g of the sodium chloride solution prepared in Example 1 to 12.0 g of the concentrated Ag ink prepared in Example 1, the supernatant collected in Example 1 so that the Ag concentration is 40% by mass. The solution was added to prepare a silver fine particle dispersion having an Ag concentration of 40% by mass and a ratio of Cl to Ag (Cl / Ag) of 0.50% by mass. In this comparative example, a phenomenon that seems to be sintering of Ag particles occurred a few minutes after the sodium chloride solution was added to the concentrated Ag ink, and a solid material without fluidity was formed. could not.

[比較例9〜12]
実施例1で用意した濃縮Agインク6.0gに、実施例1で用意した塩化ナトリウム溶液をそれぞれ0.08g(比較例9)、0.06g(比較例10)、0.03g(比較例11)、0.01g(比較例12)添加した後、Ag濃度が20質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が20質量%でAgに対するClの質量の割合(Cl/Ag)がそれぞれ0.30質量%(比較例9)、0.20質量%(比較例10)、0.10質量%(比較例11)、0.05質量%(比較例12)の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。
[Comparative Examples 9-12]
0.08 g (Comparative Example 9), 0.06 g (Comparative Example 10), and 0.03 g (Comparative Example 11) of the sodium chloride solution prepared in Example 1 were added to 6.0 g of the concentrated Ag ink prepared in Example 1. ), 0.01 g (Comparative Example 12) was added, and then the above supernatant (sorted supernatant) was added so that the Ag concentration was 20% by mass, and the Ag concentration was 20% by mass relative to Ag. The mass ratio of Cl (Cl / Ag) was 0.30 mass% (Comparative Example 9), 0.20 mass% (Comparative Example 10), 0.10 mass% (Comparative Example 11), and 0.05 mass%, respectively. A silver fine particle dispersion of (Comparative Example 12) was prepared, and a silver conductive film was prepared by the same method as in Example 1.

このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、比較例9ではそれぞれオーバーロード(OL)で測定不能(基材A)、30.0Ω/□(基材B)、13.0Ω/□(基材C)、比較例10ではそれぞれオーバーロード(OL)で測定不能(基材A)、30.0Ω/□(基材B)、9.4Ω/□(基材C)、比較例11ではそれぞれオーバーロード(OL)で測定不能(基材A)、20.0Ω/□(基材B)、21.0Ω/□(基材C)、比較例12ではそれぞれオーバーロード(OL)で測定不能(基材A)、720.0Ω/□(基材B)、47.0Ω/□(基材C)であった。   The surface resistivity of the silver conductive film thus produced was measured by the same method as in Example 1. As a result, in Comparative Example 9, measurement was impossible due to overload (OL) (base material A), 30.0Ω / □ (base material B), 13.0Ω / □ (base material C), and in Comparative Example 10, measurement is not possible due to overload (OL) (base material A), 30.0Ω / □ (base material B), 9. In 4Ω / □ (base material C), in Comparative Example 11, measurement is not possible due to overload (OL) (base material A), 20.0Ω / □ (base material B), 21.0Ω / □ (base material C), In Comparative Example 12, the measurement was impossible due to overload (OL) (base material A), 720.0Ω / □ (base material B), and 47.0Ω / □ (base material C).

[比較例13]
実施例1で用意した濃縮Agインク6.0gに、Ag濃度が20質量%になるように、上記の上澄み液(分取した上澄み液)を添加して、Ag濃度が20質量%でAgに対するClの質量の割合(Cl/Ag)が0.00質量%の銀微粒子分散液を作製し、実施例1と同様の方法により、銀導電膜を作製した。このようにして作製した銀導電膜の表面抵抗率を、実施例1と同様の方法により測定したところ、それぞれオーバーロード(OL)で測定不能(基材A)、オーバーロード(OL)で測定不能(基材B)、150.0Ω/□(基材C)であった。
[Comparative Example 13]
The above supernatant (sorted supernatant) is added to 6.0 g of concentrated Ag ink prepared in Example 1 so that the Ag concentration is 20% by mass, and the Ag concentration is 20% by mass with respect to Ag. A silver fine particle dispersion having a mass ratio of Cl (Cl / Ag) of 0.00 mass% was produced, and a silver conductive film was produced in the same manner as in Example 1. When the surface resistivity of the silver conductive film thus prepared was measured by the same method as in Example 1, it was impossible to measure with the overload (OL) (base material A) and impossible to measure with the overload (OL). (Base material B) and 150.0Ω / □ (Base material C).

実施例および比較例の銀導電膜の製造条件および表面抵抗率の測定結果を表1に示し、実施例5、7および比較例3の銀導電膜からなるRFIDアンテナのライン抵抗とICチップ実装RFIDアンテナの通信距離の測定結果を表2に示す。   Table 1 shows the manufacturing conditions and surface resistivity measurement results of the silver conductive films of the examples and comparative examples. The line resistance of the RFID antenna made of the silver conductive films of Examples 5 and 7 and Comparative Example 3 and the IC chip mounted RFID Table 2 shows the measurement results of the communication distance of the antenna.

Figure 2013117047
Figure 2013117047

Figure 2013117047
Figure 2013117047

表1からわかるように、銀微粒子分散液に少量のClを添加すれば、低温で短時間の熱処理でも、十分な導電性を示す銀導電膜を得ることができる。また、表2からわかるように、銀微粒子分散液に少量のClを添加して、銀導電膜からなるRFIDアンテナやICチップ実装RFIDアンテナを作製しても、導電性や通信距離には影響がない。   As can be seen from Table 1, when a small amount of Cl is added to the silver fine particle dispersion, a silver conductive film exhibiting sufficient conductivity can be obtained even at a low temperature for a short time. As can be seen from Table 2, even if a small amount of Cl is added to the silver fine particle dispersion to produce an RFID antenna made of a silver conductive film or an IC chip mounted RFID antenna, the conductivity and communication distance are affected. Absent.

本発明による銀微粒子分散液は、プリンテッド・エレクトロニクスに適用することができ、例えば、印刷CPU、印刷照明、印刷タグ、オール印刷ディスプレイ、センサ、プリント配線板、有機太陽電池、電子ブック、ナノインプリントLED、液晶ディスプレイパネル、プラズマディスプレイパネル、印刷メモリなどの製造に使用することができる。   The silver fine particle dispersion according to the present invention can be applied to printed electronics, for example, printing CPU, printing illumination, printing tag, all printing display, sensor, printed wiring board, organic solar cell, electronic book, nanoimprint LED. It can be used for manufacturing liquid crystal display panels, plasma display panels, print memories, and the like.

1 フレキソプルーフ
2 ゴム版
3 アニロックスローラ
4 ドクターブレード
5 塗料(銀微粒子分散液)
6 塗膜
7 基材
10 RFIDアンテナ
11 ICチップ実装部
12 ICチップ
13 基材
1 Flexoproof 2 Rubber plate 3 Anilox roller 4 Doctor blade 5 Paint (silver fine particle dispersion)
6 Coating 7 Base material 10 RFID antenna 11 IC chip mounting part 12 IC chip 13 Base material

Claims (5)

水系分散媒中に銀微粒子が分散した銀微粒子分散液において、30〜70質量%の銀微粒子を含み、Agに対するClの質量の割合(Cl/Ag)が0.05〜0.3質量%になるように塩素化合物が添加されていることを特徴とする、銀微粒子分散液。 In a silver fine particle dispersion in which silver fine particles are dispersed in an aqueous dispersion medium, 30 to 70% by mass of silver fine particles are contained, and the ratio of Cl to Ag (Cl / Ag) is 0.05 to 0.3% by mass. A silver fine particle dispersion having a chlorine compound added thereto. 前記塩素化合物が、塩化ナトリウム、塩化アンモニウム、塩化カリウムおよび塩化カルシウムからなる群から選ばれる1種以上であることを特徴とする、請求項1に記載の銀微粒子分散液。 The silver fine particle dispersion according to claim 1, wherein the chlorine compound is at least one selected from the group consisting of sodium chloride, ammonium chloride, potassium chloride, and calcium chloride. 前記銀微粒子分散液中の銀微粒子の含有量が40〜65質量%であることを特徴とする、請求項1または2に記載の銀微粒子分散液。 The silver fine particle dispersion according to claim 1 or 2, wherein a content of silver fine particles in the silver fine particle dispersion is 40 to 65 mass%. 前記水系分散媒が、50質量%以上の水を含む溶媒であることを特徴とする、請求項1乃至3のいずれかに記載の銀微粒子分散液。 The silver fine particle dispersion liquid according to any one of claims 1 to 3, wherein the aqueous dispersion medium is a solvent containing 50% by mass or more of water. 前記銀微粒子の平均粒径が1〜100nmであることを特徴とする、請求項1乃至4のいずれかに記載の銀微粒子分散液。 The silver fine particle dispersion according to any one of claims 1 to 4, wherein the silver fine particles have an average particle diameter of 1 to 100 nm.
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