JP5332186B2 - Method for producing transparent conductive film using metal nanowire and transparent conductive film produced using the same - Google Patents
Method for producing transparent conductive film using metal nanowire and transparent conductive film produced using the same Download PDFInfo
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- JP5332186B2 JP5332186B2 JP2007304206A JP2007304206A JP5332186B2 JP 5332186 B2 JP5332186 B2 JP 5332186B2 JP 2007304206 A JP2007304206 A JP 2007304206A JP 2007304206 A JP2007304206 A JP 2007304206A JP 5332186 B2 JP5332186 B2 JP 5332186B2
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- conductive film
- control agent
- transparent conductive
- nanowires
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Description
本発明は、金属ナノワイヤを用いた透明導電膜の製造方法及びそれを用いて製造された透明導電膜に関する。詳しくは、金属ナノワイヤを含む導電層を有する導電性と透明性に優れた透明導電膜の製造方法等に関するものである。 The present invention relates to a method for producing a transparent conductive film using metal nanowires and a transparent conductive film produced using the method. Specifically, the present invention relates to a method for producing a transparent conductive film having a conductive layer including a metal nanowire and excellent in conductivity and transparency.
近年、薄型ＴＶ需要の高まりに伴い、液晶・プラズマ・有機エレクトロルミネッセンス・フィールドエミッション等、各種方式のディスプレイ技術が開発されている。これら表示方式の異なる何れのディスプレイにおいても、透明導電膜を用いた透明電極は必須の構成技術となっている。また、テレビ以外でも、タッチパネルや携帯電話、電子ペーパ、各種太陽電池、各種エレクトロルミネッセンス調光素子においても、透明導電膜は欠くことのできない技術要素となっている。また、液晶ディスプレイやタッチディスプレイに代表されるように、透明導電膜の大面積化が指向されており、それに伴い透明導電材料の軽量化や柔軟性に対する要請が高まっている。 In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays having different display methods, a transparent electrode using a transparent conductive film is an essential constituent technology. In addition to televisions, transparent conductive films are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescent light control elements. Further, as represented by liquid crystal displays and touch displays, an increase in the area of the transparent conductive film is directed, and accordingly, demands for weight reduction and flexibility of the transparent conductive material are increasing.
このような要請に対して、特許文献１〜３ではＣＮＴ（カーボンナノチューブ）や金属ナノワイヤのような導電性繊維を含む分散液を、フィルム支持体上に塗布して透明導電膜を形成する方法が開示されている。また、バルク状態での導電率が１×１０7Ｓ／ｍ以上の金属元素のナノワイヤを、液相法や気相法などの色々な方法で作製できることも報告されている。例えば、Ａｇナノワイヤの製造方法としては非特許文献１等、Ａｕナノワイヤの製造方法としては特許文献４等、Ｃｕナノワイヤの製造方法としては特許文献５等、Ｃｏナノワイヤの製造方法としては特許文献６等を参考にできる。特に、銀は金属中で最大の導電率を有し、かつ非特許文献１によれば、液相で簡便に銀ナノワイヤを製造することができるため、導電性繊維を用いる透明導電膜において、銀ナノワイヤは最も好ましい導電材料として位置付けることができる。 In response to such a request, Patent Documents 1 to 3 describe a method of forming a transparent conductive film by applying a dispersion containing conductive fibers such as CNT (carbon nanotube) and metal nanowire on a film support. It is disclosed. It has also been reported that nanowires of metal elements having a bulk conductivity of 1 × 10 7 S / m or more can be produced by various methods such as a liquid phase method and a gas phase method. For example, Non-Patent Document 1 and the like as a manufacturing method of Ag nanowires, Patent Document 4 and the like as a manufacturing method of Au nanowires, Patent Document 5 and the like as a manufacturing method of Cu nanowires, and Patent Document 6 and the like as a manufacturing method of Co nanowires Can be referred to. In particular, silver has the highest conductivity among metals, and according to Non-Patent Document 1, since silver nanowires can be easily produced in a liquid phase, in a transparent conductive film using conductive fibers, silver Nanowires can be positioned as the most preferred conductive material.
金属ナノワイヤを導体として用いる透明導電膜においては、金属ナノワイヤ間の電気的なネットワーク形成によって導電性が発現する。一つの金属ナノワイヤによって数μｍ〜数十μｍの導電パスを形成できるため、金属ナノワイヤを含む材料が導電性を発現するためのパーコレーション閾値が非常に小さく、それ故、導電性と透明性の両立が可能となる。導電性の観点では、金属ナノワイヤ間の電気的なネットワーク形成の障害となる金属ナノワイヤ間の接触抵抗を低減する技術が重要であり、透明性の観点では、金属ナノワイヤの凝集を防止し光散乱の影響を軽減する技術が重要である。 In a transparent conductive film using metal nanowires as a conductor, conductivity is exhibited by forming an electrical network between metal nanowires. Since a conductive path of several μm to several tens of μm can be formed by one metal nanowire, the percolation threshold for the material containing the metal nanowire to exhibit conductivity is extremely small, and therefore both conductivity and transparency can be achieved. It becomes possible. From the viewpoint of conductivity, it is important to reduce the contact resistance between metal nanowires, which is an obstacle to the formation of an electrical network between metal nanowires. From the viewpoint of transparency, aggregation of metal nanowires is prevented and light scattering is prevented. Technology that reduces the impact is important.
前記特許文献１〜３では、ＣＮＴや銀ナノワイヤなどの導電性繊維間の接触抵抗を低減する方法として、まず導電性繊維だけを支持体上に堆積させ、その後バインダー材料を塗布して導電性繊維を支持体に固定化する方法が開示されている。このような方法は、バインダー材料に導電性繊維を分散した分散液を支持体に塗布する方法に較べて、導電性繊維間にバインダー材料が介在する可能性が低くなるため、導電性繊維間の接触抵抗を軽減する方法の一つとして有効ではあるが、得られる抵抗値としてはＩＴＯに比較して満足できるレベルには無かった。また、前記特許文献５の実施例では、銀ナノワイヤだけを支持体上に堆積させた後、該銀ナノワイヤ層を加圧処理することによって銀ナノワイヤ間の接触性を高めることも試みられている。但し、この方法では抵抗値の改良は認められるが、光透過率とヘイズの劣化を伴う。おそらく、加圧処理によって銀ナノワイヤが潰れ、投影面積が大きくなったことが原因の一つとして考えられる。
以上のように、従来技術においては、金属ナノワイヤ間の接触抵抗を低減する技術や、金属ナノワイヤの凝集を防止する技術が不十分であり、金属ナノワイヤを用いた透明導電膜において、導電性と透明性を十分満足できるレベルに両立することができなかった。 As described above, in the prior art, the technology for reducing the contact resistance between the metal nanowires and the technology for preventing the aggregation of the metal nanowires are insufficient. In the transparent conductive film using the metal nanowires, It was not possible to achieve a level that sufficiently satisfies the sex.
従って、本発明の第一の課題は、導電性と透明性が改良された金属ナノワイヤを用いた透明導電膜の製造方法を提供することであり、第二の課題は、各種方式のディスプレイやタッチパネル、携帯電話、電子ペーパ、各種太陽電池、各種エレクトロルミネッセンス調光素子の透明電極に好適に用いることができる、導電性と透明性に優れた透明導電膜を提供することである。 Therefore, the first problem of the present invention is to provide a method for producing a transparent conductive film using metal nanowires with improved conductivity and transparency, and the second problem is to display various types of displays and touch panels. It is to provide a transparent conductive film excellent in conductivity and transparency, which can be suitably used for a transparent electrode of a mobile phone, electronic paper, various solar cells, and various electroluminescence light control devices.
本発明者は前記課題を解決すべく鋭意研究を重ねた結果、粒子形成工程において金属ナノワイヤ表面に吸着した形態制御剤が金属ナノワイヤ間に介在して導電ネットワークの形成、即ち導電性を阻害していること、また、粒子形成工程以降に粒子が凝集状態や乾燥状態を経ることが金属ナノワイヤを用いた透明導電膜の透明性を劣化させることを発見し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventor has inhibited the formation of a conductive network, that is, conductivity, by interposing the shape control agent adsorbed on the surface of the metal nanowire in the particle formation process between the metal nanowires. In addition, the inventors have discovered that the fact that particles pass through an agglomerated state or a dried state after the particle forming step deteriorates the transparency of the transparent conductive film using metal nanowires, and have led to the present invention.
本発明における前記課題の解決手段は以下の通りである。 The means for solving the problems in the present invention are as follows.
１．透明支持体上に金属ナノワイヤを含む導電層を有する透明導電膜の製造方法において、該製造方法が、親水性高分子または両親媒性分子である形態制御剤を含む溶液中で該金属ナノワイヤを形成する工程（粒子形成工程）を有し、かつ該粒子形成工程の後に限外濾過膜を用いた膜分離法によって前記形態制御剤を除去する工程（形態制御剤除去工程）を有し、
前記粒子形成工程は、
還元剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、金属の微粒子からなる核粒子を形成する核形成工程と、
還元剤、前記核粒子、および前記形態制御剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、前記核形成工程において形成した前記核粒子をワイヤ状の形態を有する金属粒子に成長させる粒子成長工程と、
を含むことを特徴とする透明導電膜の製造方法。
２．前記金属ナノワイヤの長軸方向の平均粒径が３〜５００μｍである、前記１に記載の透明導電膜の製造方法。
３．前記核形成工程においては前記形態制御剤を用いない、前記１または２に記載の透明導電膜の製造方法。
1. In a method for producing a transparent conductive film having a conductive layer containing metal nanowires on a transparent support, the production method forms the metal nanowires in a solution containing a form control agent which is a hydrophilic polymer or an amphiphilic molecule. to include a step (particle forming step), and have a step (form control agent removing step) of removing the morphology control agent by diafiltration using an ultrafiltration membrane after the particle formation process,
The particle forming step includes
A nucleation step in which at least one metal salt solution is added to a solution containing a reducing agent to reduce metal ions to form core particles composed of metal fine particles;
At least one metal salt solution is added to a solution containing a reducing agent, the core particles, and the shape control agent to reduce metal ions, and the core particles formed in the nucleation step are formed into wire-like shapes. A particle growth step for growing metal particles having a shape;
The manufacturing method of the transparent conductive film characterized by including .
2. 2. The method for producing a transparent conductive film according to 1 above, wherein the metal nanowire has an average particle size in the major axis direction of 3 to 500 μm.
3. 3. The method for producing a transparent conductive film according to 1 or 2, wherein the form control agent is not used in the nucleation step.
４．前記形態制御剤除去工程終了後の、形態制御剤の含有率（＝形態制御剤質量／金属ナノワイヤ質量）が３％以下であることを特徴とする前記１〜３のいずれか一項に記載の透明導電膜の製造方法。 4 . The content rate of the form control agent (= form control agent mass / metal nanowire mass) after completion of the form control agent removal step is 3% or less, according to any one of 1 to 3 above, A method for producing a transparent conductive film.
５．前記形態制御剤除去工程の後に、分散剤の存在下に分散機を用いて金属ナノワイヤを分散する工程（分散工程）を有することを特徴とする前記１〜４のいずれか一項に記載の透明導電膜の製造方法。 5 . The transparent according to any one of 1 to 4, further comprising a step (dispersing step) of dispersing the metal nanowires using a disperser in the presence of a dispersing agent after the shape control agent removing step. Manufacturing method of electrically conductive film.
６．透明支持体上に金属ナノワイヤを含む導電層を有する透明導電膜であって、前記１〜５のいずれか一項に記載の製造方法を用いて製造されたことを特徴とする透明導電膜。 6 . A transparent conductive film having a conductive layer containing metal nanowires on a transparent support, wherein the transparent conductive film is manufactured using the manufacturing method according to any one of 1 to 5 above.
本発明によって、金属ナノワイヤ間の接触抵抗が低減された金属ナノワイヤの製造方法、また、金属ナノワイヤの凝集性が改良された金属ナノワイヤの製造方法を提供することができ、さらに、金属ナノワイヤを用いた導電性と透明性に優れた透明導電膜を提供することができる。 According to the present invention, it is possible to provide a method for producing a metal nanowire with reduced contact resistance between metal nanowires, a method for producing a metal nanowire with improved cohesiveness of the metal nanowire, and further using the metal nanowire. A transparent conductive film excellent in conductivity and transparency can be provided.
本発明の透明導電膜の製造方法は、透明支持体上に金属ナノワイヤを含む導電層を有する透明導電膜の製造方法において、形態制御剤を含む溶液中で該金属ナノワイヤを形成する工程（粒子形成工程）を有し、かつ該粒子形成工程の後に限外濾過膜を用いた膜分離法によって前記形態制御剤を除去する工程（形態制御剤除去工程）を有することを特徴とする。この特徴は、請求項１〜４に係る発明に共通する技術的特徴である。 The method for producing a transparent conductive film of the present invention is a method for producing a transparent conductive film having a conductive layer containing a metal nanowire on a transparent support, wherein the metal nanowire is formed in a solution containing a shape control agent (particle formation). And a step of removing the shape control agent by a membrane separation method using an ultrafiltration membrane (a shape control agent removal step) after the particle formation step. This feature is a technical feature common to the inventions according to claims 1 to 4.
本発明の実施態様としては、前記形態制御剤除去工程終了後の、形態制御剤の含有率（＝形態制御剤質量／金属ナノワイヤ質量）が３％以下であることが好ましい。また、前記形態制御剤除去工程の後に、分散剤の存在下に分散機を用いて金属ナノワイヤを分散する工程（分散工程）を有する態様であることが好ましい。 As an embodiment of the present invention, it is preferable that the content of the form control agent (= form control agent mass / metal nanowire mass) after the form control agent removal step is 3% or less. Moreover, it is preferable that it is an aspect which has the process (dispersion process) of disperse | distributing a metal nanowire using a disperser in presence of a dispersing agent after the said form control agent removal process.
なお、本発明の透明導電膜の製造方法は、特に透明支持体上に金属ナノワイヤを含む導電層を有する透明導電膜の製造方法として好適である。 In addition, the manufacturing method of the transparent conductive film of this invention is especially suitable as a manufacturing method of the transparent conductive film which has a conductive layer containing a metal nanowire on a transparent support body.
以下、本発明とその構成要素、及び本発明を実施するための最良の形態・態様等について詳細な説明をする。 Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.
〔金属ナノワイヤ〕
一般に、「金属ナノワイヤ」とは、金属元素を主要な構成要素とする線状構造体のことをいう。特に、本発明における金属ナノワイヤとは、原子スケールからｎｍサイズの直径を有する線状構造体を意味する。
[Metal nanowires]
In general, a “metal nanowire” refers to a linear structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a linear structure having a diameter from the atomic scale to the nm size.
本発明の透明導電膜に適用される金属ナノワイヤを含む導電層は、金属ナノワイヤが互いに接触し合い三次元的な導電ネットワーク構造を形成することにより導電性を発現する。従って、ワイヤ長が長い方が導電ネットワーク形成に有利であり好ましいが、ワイヤ長が長すぎると金属ナノワイヤ同士が絡み合って凝集体を生じ、光散乱を劣化させる場合がある。導電ネットワーク形成や凝集体生成には、金属ナノワイヤの剛性や直径等も影響するため、使用する金属ナノワイヤの材質に応じて最適なワイヤ長を選択することが好ましい。本発明の透明導電膜の導電層に用いられる金属ナノワイヤとしては、長軸方向の平均粒径として（以下、長軸方向の粒径を長さと称する場合もある）、３μｍ以上であることが好ましく、更には３〜５００μｍが好ましく、特に、３〜３００μｍであることが好ましい。併せて、長軸方向の粒径分布は４０％以下であることが好ましい。 The conductive layer including metal nanowires applied to the transparent conductive film of the present invention exhibits conductivity when the metal nanowires are in contact with each other to form a three-dimensional conductive network structure. Accordingly, a longer wire length is advantageous and preferable for forming a conductive network. However, if the wire length is too long, metal nanowires are entangled with each other to form aggregates, which may deteriorate light scattering. Since the formation of the conductive network and the formation of aggregates are affected by the rigidity and diameter of the metal nanowires, it is preferable to select an optimal wire length according to the material of the metal nanowires to be used. The metal nanowire used for the conductive layer of the transparent conductive film of the present invention preferably has an average particle size in the major axis direction (hereinafter, the particle size in the major axis direction may be referred to as a length) of 3 μm or more. Furthermore, 3-500 micrometers is preferable, and it is especially preferable that it is 3-300 micrometers. In addition, the particle size distribution in the major axis direction is preferably 40% or less.
本発明の透明導電膜においては、金属ナノワイヤを含む導電層における光散乱の影響を軽減し透明性を高めるために、金属ナノワイヤの短軸方向の平均粒径は（以下、短軸方向の粒径を直径と称する場合もある。）３００ｎｍより小さいことが好ましく、一方で、導電性を高めるためには短軸方向の平均粒径が大きい方が好ましい。本発明においては、金属ナノワイヤの短軸方向の平均粒径として１０〜２００ｎｍが好ましく、３０〜１８０ｎｍであることがより好ましい。併せて、短軸方向の粒径分布は２０％以下であることが好ましい。 In the transparent conductive film of the present invention, in order to reduce the influence of light scattering in the conductive layer containing metal nanowires and increase transparency, the average particle size in the short axis direction of the metal nanowires (hereinafter referred to as the particle size in the short axis direction). ) Is preferably smaller than 300 nm. On the other hand, it is preferable that the average particle size in the minor axis direction is larger in order to increase conductivity. In the present invention, the average particle size in the minor axis direction of the metal nanowire is preferably 10 to 200 nm, and more preferably 30 to 180 nm. In addition, the particle size distribution in the minor axis direction is preferably 20% or less.
本発明において、金属ナノワイヤの長さや直径、アスペクト比（＝長さ／直径）の平均値は、十分な数の金属ナノワイヤについて電子顕微鏡写真を撮影し、個々の金属ナノワイヤ像の計測値の算術平均から求めることができる。金属ナノワイヤの長さは、本来直線状に伸ばした状態で測定するべきであるが、現実には屈曲している場合もあるため、電子顕微鏡写真から画像解析装置を用いて金属ナノワイヤの投影直径及び投影面積を算出し、円柱体を仮定して算出してもよい（長さ＝投影面積／投影直径）。また、長軸方向や短軸方向の粒径分布は、測定粒径の標準偏差を平均粒径で除した値に１００を乗じた値で表す。
粒径分布［％］＝粒径の標準偏差／平均粒径×１００
計測対象の金属ナノワイヤ数は、少なくとも１００個以上が好ましく、３００個以上の金属ナノワイヤを計測することが更に好ましい。
In the present invention, the average value of the length, diameter, and aspect ratio (= length / diameter) of the metal nanowire is obtained by taking an electron micrograph of a sufficient number of metal nanowires and calculating the arithmetic average of the measured values of the individual metal nanowire images. Can be obtained from The length of the metal nanowire should be measured in a linearly stretched state, but in reality it may be bent, so from the electron micrograph, the projected diameter and The projected area may be calculated and calculated assuming a cylindrical body (length = projected area / projected diameter). The particle size distribution in the major axis direction or minor axis direction is represented by a value obtained by multiplying the value obtained by dividing the standard deviation of the measured particle size by the average particle size by 100.
Particle size distribution [%] = standard deviation of particle size / average particle size × 100
The number of metal nanowires to be measured is preferably at least 100 or more, more preferably 300 or more metal nanowires.
本発明に係る金属ナノワイヤの金属組成としては、特に制限は無く、貴金属元素や卑金属元素の１種または複数の金属から構成されることができるが、貴金属（例えば、金、白金、銀、パラジウム、ロジウム、イリジウム、ルテニウム、オスミウム等）及び鉄、コバルト、銅、錫からなる群に属する少なくとも１種の金属を含むことが好ましく、導電性の観点から少なくとも銀を含むことがより好ましい。さらには、導電性と安定性（金属ナノワイヤの硫化や酸化耐性、およびマグレーション耐性）を両立するために、銀と銀を除く貴金属に属する少なくとも１種の金属を含むことがより好ましい。本発明に係る金属ナノワイヤが２種類以上の金属元素を含む場合には、例えば、金属ナノワイヤの表面と内部で金属組成が異なっていてもよいし、金属ナノワイヤ全体が同一の金属組成を有していてもよい。 The metal composition of the metal nanowire according to the present invention is not particularly limited, and can be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, Rhodium, iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. Furthermore, in order to achieve both electrical conductivity and stability (sulfurization and oxidation resistance of metal nanowires, and resistance to magnesium), it is more preferable to include at least one metal belonging to noble metal other than silver and silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.
〔導電層〕
本発明の透明導電膜に適用される導電層には、金属ナノワイヤ以外に、透明なバインダー材料や添加剤を含んでいてもよい。透明なバインダー材料としては、天然高分子樹脂または合成高分子樹脂から広く選択して使用することができる。例えば、透明な熱可塑性樹脂（例えば、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリメチルメタクリレート、ニトロセルロース、塩素化ポリエチレン、塩素化ポリプロピレン、フッ化ビニリデン）や、熱・光・電子線・放射線で硬化する透明硬化性樹脂（例えば、メラミンアクリレート、ウレタンアクリレート、エポキシ樹脂、ポリイミド樹脂、アクリル変性シリケート等のシリコーン樹脂）を使用することができる。添加剤としては、可塑剤、酸化防止剤や硫化防止剤などの安定剤、界面活性剤、溶解促進剤、重合禁止剤、染料や顔料などの着色剤などが挙げられる。更に、塗布性などの作業性を高める観点から、溶媒（例えば、水や、アルコール類、グリコール類、セロソルブ類、ケトン類、エステル類、エーテル類、アミド類、炭化水素類等の有機溶媒）を含んでいてもよい。
[Conductive layer]
In addition to metal nanowires, the conductive layer applied to the transparent conductive film of the present invention may contain a transparent binder material or additive. The transparent binder material can be selected from a wide range of natural polymer resins or synthetic polymer resins. For example, transparent thermoplastic resin (eg, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride), heat, light, electron beam A transparent curable resin that is cured by radiation (for example, melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, silicone resin such as acrylic-modified silicate) can be used. Examples of the additive include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments. Furthermore, from the viewpoint of improving workability such as coating properties, solvents (for example, water, organic solvents such as alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.
金属ナノワイヤを含む導電層の厚さは、使用する金属ナノワイヤの平均直径や含有量によって異なるが、大凡の目安として、金属ナノワイヤの平均直径以上、５００ｎｍ以下が好ましい。本発明に係る金属ナノワイヤを含む導電層の厚さを薄くすると、厚さ方向の金属ナノワイヤ間のネットワーク形成を密にすることができるため好ましい。 The thickness of the conductive layer containing the metal nanowires varies depending on the average diameter and content of the metal nanowires to be used, but as a rough guide, it is preferably not less than the average diameter of the metal nanowires and not more than 500 nm. It is preferable to reduce the thickness of the conductive layer including the metal nanowire according to the present invention because the network formation between the metal nanowires in the thickness direction can be made dense.
〔透明導電膜〕
本発明の透明導電膜の厚さには特に制限はなく、目的に応じて適宜選択することができるが、一般的に１０μｍ以下であることが好ましく、厚さが薄くなるほど透明性が向上するためより好ましい。
[Transparent conductive film]
There is no restriction | limiting in particular in the thickness of the transparent conductive film of this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and since transparency improves, so that thickness becomes thin. More preferred.
本発明の透明導電膜における全光線透過率は、６０％以上であることが好ましく、７０％以上であることがより好ましく、８０％以上であることが特に好ましい。全光透過率は、分光光度計等を用いた公知の方法に従って測定することができる。また、本発明に係る透明電極における電気抵抗値としては、電極としての機能性、電磁波シールド特性等の観点から、表面抵抗率として１０4Ω／□以下であることが好ましく、１０3Ω／□以下であることがより好ましく、１０2Ω／□以下であることが特に好ましい。 The total light transmittance in the transparent conductive film of the present invention is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. As the electric resistance of the transparent electrode according to the present invention, the functionality of an electrode, from the viewpoint of electromagnetic wave shielding properties, is preferably 10 4 Ω / □ or less as the surface resistivity, 10 3 Ω / □ More preferably, it is more preferably 10 2 Ω / □ or less.
前記表面抵抗率は、例えば、ＪＩＳ Ｋ７１９４、ＡＳＴＭ Ｄ２５７、などに準拠して測定することができ、また市販の表面抵抗率計を用いて簡便に測定することもできる。 The surface resistivity can be measured based on, for example, JIS K7194, ASTM D257, etc., and can also be easily measured using a commercially available surface resistivity meter.
本発明の透明導電膜には、必要に応じてハードコート層やノングレアコート層、バリアコート層、アンカーコート層、キャリア輸送層、キャリア蓄積層などの各種機能性層を付与することもできる。ハードコート層やノングレアコート層を付与する場合には、透明支持体を挟み本発明に係る導電層とは反対側に配置させることが好ましく、バリアコート層を付与する場合には、透明支持体と本発明に係る導電層の間に配置させることが好ましく、アンカーコート層やキャリア輸送層、キャリア蓄積層を付与する場合には、透明支持体に対して本発明に係る導電層と同じ側に配置させることが好ましい。 Various functional layers such as a hard coat layer, a non-glare coat layer, a barrier coat layer, an anchor coat layer, a carrier transport layer, and a carrier accumulation layer can be added to the transparent conductive film of the present invention as necessary. When providing a hard coat layer or a non-glare coat layer, it is preferable to place the transparent support on the side opposite to the conductive layer according to the present invention, and when providing a barrier coat layer, It is preferable to dispose between the conductive layers according to the present invention. When an anchor coat layer, a carrier transport layer, or a carrier accumulation layer is provided, the transparent support is disposed on the same side as the conductive layer according to the present invention. It is preferable to make it.
本発明の透明導電膜は、本発明に係る導電層やそれ以外の層に導電性高分子を含有してもよい。本発明の透明導電膜に用いることができる導電性高分子として、例えば、ポリピロール、ポリアニリン、ポリチオフェン、ポリチエニレンビニレン、ポリアズレン、ポリイソチアナフテン、ポリカルバゾール、ポリアセチレン、ポリフェニレン、ポリフェニレンビニレン、ポリアセン、ポリフェニルアセチレン、ポリジアセチレン及びポリナフタレンの各誘導体からなる群より選ばれる化合物等を挙ることができる。 The transparent conductive film of the present invention may contain a conductive polymer in the conductive layer according to the present invention or other layers. Examples of the conductive polymer that can be used in the transparent conductive film of the present invention include polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, poly Examples include compounds selected from the group consisting of phenylacetylene, polydiacetylene, and polynaphthalene derivatives.
本発明の透明導電膜は、１種類の導電性高分子を単独で含有してもよいし、２種類以上の導電性高分子を組み合わせて含有してもよいが、導電性及び透明性の観点から、下記一般式（Ｉ）または一般式（II）で示される繰り返し単位を有するポリアニリンまたはその誘導体や、下記一般式（III）で示される繰り返し単位を有するポリピロール誘導体、または下記一般式（IV）で示される繰り返し単位を有するポリチオフェン誘導体からなる群より選ばれる少なくとも１種の化合物を含むことがより好ましい。 The transparent conductive film of the present invention may contain one kind of conductive polymer alone or may contain two or more kinds of conductive polymers in combination, but from the viewpoint of conductivity and transparency. To polyaniline having a repeating unit represented by the following general formula (I) or general formula (II) or a derivative thereof, a polypyrrole derivative having a repeating unit represented by the following general formula (III), or the following general formula (IV) More preferably, it contains at least one compound selected from the group consisting of polythiophene derivatives having a repeating unit represented by the formula:
なお、上記一般式（III）及び一般式（IV）において、Ｒは主として線状有機置換基であり、アルキル基、アルコキシ基、アリル基又はこれらの基の組み合わせが好ましいが、可溶性導電性高分子としての性質を失わなければよく、さらにこれらにスルホネート基、エステル基、アミド基などが結合しても、組み合わされてもよい。なお、ｎは整数である。 In the above general formula (III) and general formula (IV), R is mainly a linear organic substituent, preferably an alkyl group, an alkoxy group, an allyl group, or a combination of these groups. As long as it does not lose its properties, a sulfonate group, an ester group, an amide group, or the like may be bonded to or combined with these. Note that n is an integer.
本発明の透明導電膜で用いられる導電性高分子には、導電性をより高めるためにドーピング処理を施すことができる。導電性高分子に対するドーパントとしては、例えば、炭素数が６〜３０の炭化水素基を有するスルホン酸（以下、長鎖スルホン酸ともいう。）あるいはその重合体（例えば、ポリスチレンスルホン酸）、ハロゲン原子、ルイス酸、プロトン酸、遷移金属ハロゲン化物、遷移金属化合物、アルカリ金属、アルカリ土類金属、ＭＣｌＯ4（Ｍ＝Ｌｉ+、Ｎａ+）、Ｒ4Ｎ+（Ｒ＝ＣＨ3、Ｃ4Ｈ9、Ｃ6Ｈ5）、またはＲ4Ｐ+（Ｒ＝ＣＨ3、Ｃ4Ｈ9、Ｃ6Ｈ5）からなる群から選ばれる少なくとも１種が挙げられる。なかでも、上記長鎖スルホン酸が好ましい。 The conductive polymer used in the transparent conductive film of the present invention can be subjected to a doping treatment in order to further increase the conductivity. As a dopant for the conductive polymer, for example, a sulfonic acid having a hydrocarbon group having 6 to 30 carbon atoms (hereinafter also referred to as a long-chain sulfonic acid) or a polymer thereof (for example, polystyrene sulfonic acid), a halogen atom Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, alkaline earth metal, MClO 4 (M = Li + , Na + ), R 4 N + (R = CH 3 , C 4 H 9 , C 6 H 5 ), or R 4 P + (R═CH 3 , C 4 H 9 , C 6 H 5 ). Of these, the long-chain sulfonic acid is preferable.
また、導電性高分子に対するドーパントは、水素化フラーレン、水酸化フラーレン、スルホン酸化フラーレンなどのフラーレン類に導入されていてもよい。透明導電膜において、上記ドーパントは、導電性高分子１００質量部に対して、０．００１質量部以上含まれていることが好ましい。さらには、０．５質量部以上含まれていることがより好ましい。 The dopant for the conductive polymer may be introduced into fullerenes such as hydrogenated fullerene, hydroxylated fullerene, and sulfonated fullerene. In the transparent conductive film, the dopant is preferably contained in an amount of 0.001 part by mass or more with respect to 100 parts by mass of the conductive polymer. Furthermore, it is more preferable that 0.5 mass part or more is contained.
尚、本発明の透明導電膜は、長鎖スルホン酸、長鎖スルホン酸の重合体（例えば、ポリスチレンスルホン酸）、ハロゲン、ルイス酸、プロトン酸、遷移金属ハロゲン化物、遷移金属化合物、アルカリ金属、アルカリ土類金属、ＭＣｌＯ4、Ｒ4Ｎ+、およびＲ4Ｐ+からなる群から選ばれる少なくとも１種のドーパントと、フラーレン類との双方を含んでいてもよい。 The transparent conductive film of the present invention includes a long-chain sulfonic acid, a polymer of long-chain sulfonic acid (for example, polystyrene sulfonic acid), halogen, Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, Both at least one dopant selected from the group consisting of alkaline earth metals, MClO 4 , R 4 N + , and R 4 P + and fullerenes may be included.
本発明の透明導電膜に用いられる導電性高分子として、特表２００１−５１１５８１号公報や特開２００４−９９６４０号公報、特開２００７−１６５１９９号公報などに開示される金属によって改質された導電性高分子を用いることもできる。 As the conductive polymer used in the transparent conductive film of the present invention, a conductive polymer modified by a metal disclosed in JP-T-2001-511581, JP-A-2004-99640, JP-A-2007-165199, or the like. Can also be used.
本発明の透明導電膜に係る導電性高分子を含む導電層には、水溶性有機化合物を含有してもよい。水溶性有機化合物の中で、導電性高分子材料に添加することによって導電性を向上させる効果を有する化合物が知られており、２ｎｄ．ドーパント（或いは増感剤）と称される場合がある。本発明の透明導電膜で用いることができる２ｎｄ．ドーパントには特に制限はなく、公知のものの中から適宜選択することができ、例えば、酸素含有化合物が好適に挙げられる。 The conductive layer containing the conductive polymer according to the transparent conductive film of the present invention may contain a water-soluble organic compound. Among water-soluble organic compounds, compounds having an effect of improving conductivity by adding to a conductive polymer material are known, and 2nd. Sometimes called a dopant (or sensitizer). 2nd. Can be used in the transparent conductive film of the present invention. There is no restriction | limiting in particular in a dopant, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably.
本発明の透明導電膜に係る導電性高分子を含む導電層において、導電性高分子１００質量部に対する上記２ｎｄ．ドーパントの含有量は、０．００１質量部以上が好ましく、０．０１〜５０質量部がより好ましく、０．０１〜１０質量部が特に好ましい。 In the conductive layer containing the conductive polymer according to the transparent conductive film of the present invention, the 2nd. 0.001 mass part or more is preferable, as for content of a dopant, 0.01-50 mass parts is more preferable, and 0.01-10 mass parts is especially preferable.
本発明の透明導電膜に係る導電性高分子を含む導電層は、成膜性や膜強度を確保するために、導電性高分子の他に透明な樹脂成分や添加剤を含んでいてもよい。透明な樹脂成分としては、導電性高分子と相溶又は混合分散可能であれば特に制限されず、熱硬化性樹脂であってもよいし、熱可塑性樹脂であってもよい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、ポリイミド、ポリアミドイミド等のポリイミド系樹脂、ポリアミド６、ポリアミド６，６、ポリアミド１２、ポリアミド１１等のポリアミド樹脂、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリテトラフルオロエチレン、エチレンテトラフルオロエチレンコポリマー、ポリクロロトリフルオロエチレン等のフッ素樹脂、ポリビニルアルコール、ポリビニルエーテル、ポリビニルブチラール、ポリ酢酸ビニル、ポリ塩化ビニル等のビニル樹脂、エポキシ樹脂、キシレン樹脂、アラミド樹脂、ポリウレタン系樹脂、ポリウレア系樹脂、メラミン樹脂、フェノール系樹脂、ポリエーテル、アクリル系樹脂及びこれらの共重合体等が挙げられる。 The conductive layer containing the conductive polymer according to the transparent conductive film of the present invention may contain a transparent resin component or additive in addition to the conductive polymer in order to ensure film formability and film strength. . The transparent resin component is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer, and may be a thermosetting resin or a thermoplastic resin. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like.
〔透明支持体〕
本発明の透明導電膜を構成する透明支持体としては、高い光透過性を有していればそれ以外に特に制限はなく、その材料、形状、構造、厚さ等については公知のものの中から適宜選択することができる。例えば、基材としての硬度に優れ、またその表面への導電層の形成のし易さ等の点で、ガラス基板、樹脂基板、樹脂フィルムなどが好適に挙げられるが、軽量性と柔軟性の観点から樹脂フィルムを用いることが好ましい。該樹脂には特に制限はなく、公知のものの中から適宜選択することができ、例えば、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリ塩化ビニル樹脂、ポリエーテルスルホン樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリ酢酸ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリフッ化ビニリデン樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルブチラール樹脂、ポリメタクリル酸メチル樹脂、ポリアクリロニトリル樹脂、ポリオレフィンポリスチレン樹脂、ポリアミド樹脂、ポリブタジエン樹脂、酢酸セルロース、硝酸セルロース、アクリロニトリル−ブタジエン−スチレン共重合樹脂などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を組み合わせて用いてもよい。これらの中でも、透明性及び可撓性に優れる点で、ポリエチレンテレフタレート樹脂が好ましい。
(Transparent support)
The transparent support constituting the transparent conductive film of the present invention is not particularly limited as long as it has high light transmittance, and its material, shape, structure, thickness, etc. are from known ones. It can be selected appropriately. For example, a glass substrate, a resin substrate, a resin film, and the like are preferable in terms of excellent hardness as a base material and ease of formation of a conductive layer on the surface. It is preferable to use a resin film from the viewpoint. The resin is not particularly limited and can be appropriately selected from known ones. For example, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, polyethersulfone resin, polycarbonate resin, Polystyrene resin, polyimide resin, polyetherimide resin, polyvinyl acetate resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyolefin polystyrene Examples thereof include resins, polyamide resins, polybutadiene resins, cellulose acetate, cellulose nitrate, and acrylonitrile-butadiene-styrene copolymer resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, polyethylene terephthalate resin is preferable in terms of excellent transparency and flexibility.
〔粒子形成工程〕
一般に、金属ナノワイヤの製造方法としては、金属イオンを還元して金属ナノ粒子を形成し、金属ナノ粒子間のオストワルド熟成によって金属ナノワイヤを形成する方法や、最初に核形成工程において金属イオンを還元して核となるナノ粒子を形成した後、粒子成長工程において該核粒子上に金属イオンを還元沈積させて核粒子を成長させて金属ナノワイヤを形成する方法などがある。
[Particle formation step]
In general, metal nanowires can be produced by reducing metal ions to form metal nanoparticles and forming metal nanowires by Ostwald ripening between metal nanoparticles, or by first reducing metal ions in the nucleation step. Then, after forming nanoparticles as nuclei, there is a method of forming metal nanowires by growing nuclear particles by reducing and depositing metal ions on the nuclei particles in a particle growth step.
本発明に係る粒子形成工程は、金属ナノワイヤの形態（直径や長さ）や金属組成の制御性向上の観点から、核形成工程と粒子成長工程を分離して実施することが好ましい。本発明において核形成工程とは、反応容器内の還元剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、粒子成長工程において成長の核となる金属の微粒子（核粒子）を形成するための工程を意味する。一方、本発明において粒子成長工程とは、反応容器内の還元剤と核粒子、および形態制御剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、核形成工程において形成した金属核粒子をワイヤ状の形態を有する金属粒子に成長させるための工程を意味する。 The particle formation step according to the present invention is preferably carried out separately from the nucleation step and the particle growth step from the viewpoint of improving the controllability of the form (diameter and length) of the metal nanowire and the metal composition. In the present invention, the nucleation step refers to the addition of at least one metal salt solution to a solution containing a reducing agent in a reaction vessel to reduce metal ions, and the metal that becomes the nucleus of growth in the particle growth step. It means a process for forming fine particles (nuclear particles). On the other hand, in the present invention, the particle growth step means that at least one metal salt solution is added to a solution containing the reducing agent, the core particles, and the shape control agent in the reaction vessel to reduce the metal ions, thereby It means a step for growing the metal core particles formed in the forming step into metal particles having a wire shape.
形成する金属ナノワイヤの形態（直径や長さ）の均一性を高める上で、粒子成長工程において新たな金属微粒子が生成しないように金属イオンの還元反応を制御することが重要である。そのためには、粒子成長工程における金属塩溶液の添加速度や金属イオンの還元速度の調整が必要である。本発明において、金属塩溶液の添加速度を制御するためには、シングルジェット法やマルチジェット法を用いることが有効である。還元反応速度を制御するためには、還元剤の種類や濃度、反応温度、ｐＨなどを好ましい条件に設定することが有効である。 In order to improve the uniformity of the form (diameter and length) of the metal nanowires to be formed, it is important to control the reduction reaction of metal ions so that new metal fine particles are not generated in the particle growth process. For this purpose, it is necessary to adjust the addition rate of the metal salt solution and the reduction rate of the metal ions in the particle growth step. In the present invention, in order to control the addition rate of the metal salt solution, it is effective to use a single jet method or a multi jet method. In order to control the reduction reaction rate, it is effective to set the kind and concentration of the reducing agent, the reaction temperature, pH, and the like to preferable conditions.
本発明に係るシングルジェット法やマルチジェット法とは、適当な送液装置等を用いて必要に応じて送液量を制御して、１種類または複数の添加液を各々反応容器内の液の液面上または液中に滴下または噴射、あるいは注入することによって該容器内の液中で反応させる方法であり、本発明においては、１種類または複数の金属塩溶液や形態制御剤を含む溶液、凝集防止剤を含む溶液、還元剤を含む溶液などを添加液として用いることにより実施できる。 In the single jet method and the multi jet method according to the present invention, the amount of liquid fed is controlled as necessary using an appropriate liquid feeding device or the like, and one or a plurality of additive liquids are respectively added to the liquid in the reaction vessel. It is a method of reacting in the liquid in the container by dropping or spraying or injecting on the liquid surface or in the liquid, and in the present invention, a solution containing one or more metal salt solutions and a form control agent, It can be carried out by using a solution containing an anti-aggregation agent, a solution containing a reducing agent, or the like as the additive solution.
本発明においては、核形成工程と粒子成長工程で使用する金属塩（金属イオン）のモル比を任意に変えることができる。また、モル比を調整することにより、粒径やアスペクト比の制御も可能である。例えば、平均アスペクト比の高い金属ナノワイヤを形成する場合には、粒子製造工程全体で使用する金属塩に対する核形成工程で使用する金属塩のモル比を小さくする方が有利である。これは、金属ナノワイヤの形成には粒子成長工程の寄与が大きいためである。従って、本発明では、核形成工程で使用する金属塩のモル比を１０モル％以下に設定することが好ましく、５モル％以下がより好ましく、０．００１〜１モル％であることがさらに好ましい。 In the present invention, the molar ratio of the metal salt (metal ion) used in the nucleation step and the particle growth step can be arbitrarily changed. In addition, the particle size and aspect ratio can be controlled by adjusting the molar ratio. For example, when forming metal nanowires having a high average aspect ratio, it is advantageous to reduce the molar ratio of the metal salt used in the nucleation step to the metal salt used in the entire particle production process. This is because the particle growth process greatly contributes to the formation of metal nanowires. Accordingly, in the present invention, the molar ratio of the metal salt used in the nucleation step is preferably set to 10 mol% or less, more preferably 5 mol% or less, and further preferably 0.001 to 1 mol%. .
本発明において、核形成工程および粒子成長工程で使用する金属塩の種類には特に制限は無く、金属のハロゲン化物、酢酸金属塩、過ハロゲン酸金属塩、硫酸金属塩、硝酸金属塩、炭酸金属塩、修酸金属塩などの各種酸の金属塩などを用いることができる。通常、これらの金属塩は、水などの溶媒に溶解して金属塩溶液として用いることができる。溶液中の金属イオンの濃度としては、適宜好ましい濃度に設定することができるが、濃度を薄くすると反応液中での金属イオンの還元反応や、金属ナノワイヤの形成反応を均一化する上で好ましく、一方、濃度を濃くすると金属ナノワイヤ収率を高めることができるため好ましい。従って、本発明において添加する金属塩溶液の体積モル濃度としては、０．００１〜１Ｍであることが好ましい。 In the present invention, the type of metal salt used in the nucleation step and the grain growth step is not particularly limited, and is a metal halide, metal acetate, metal perhalogenate, metal sulfate, metal nitrate, metal carbonate. Various metal salts such as salts and oxalic acid metal salts can be used. Usually, these metal salts can be dissolved in a solvent such as water and used as a metal salt solution. The concentration of the metal ions in the solution can be appropriately set to a preferred concentration, but reducing the concentration is preferable for uniforming the reduction reaction of the metal ions in the reaction solution and the formation reaction of the metal nanowires, On the other hand, increasing the concentration is preferable because the yield of metal nanowires can be increased. Therefore, the volume molar concentration of the metal salt solution added in the present invention is preferably 0.001 to 1M.
本発明においては、核形成工程と粒子成長工程を分離して金属ナノワイヤを形成する場合、核形成工程で使用する金属塩の種類と粒子成長工程で使用する金属塩の種類は、同じであってもよいし異なっていてもよい。 In the present invention, when forming the metal nanowire by separating the nucleation step and the particle growth step, the type of metal salt used in the nucleation step and the type of metal salt used in the particle growth step are the same. May be different.
〔形態制御剤〕
本発明に係る粒子形成工程で用いられる「形態制御剤」とは、金属粒子の成長方向を一次元様に規定する機能を有する化合物であり、形態制御剤を用いることによって、粒子形成工程において形成される金属ナノワイヤ粒子の比率を高めることができる。多くの場合、形態制御剤は、対象となる粒子の特定の結晶面に優先的あるいは選択的に吸着して、吸着面の成長を抑制することによって成長方位を制御する。
[Form control agent]
The “form control agent” used in the particle formation step according to the present invention is a compound having a function of defining the growth direction of metal particles in a one-dimensional manner, and is formed in the particle formation step by using the form control agent. The ratio of metal nanowire particles to be produced can be increased. In many cases, the shape control agent preferentially or selectively adsorbs on a specific crystal plane of a target particle to control the growth orientation by suppressing the growth of the adsorption plane.
本発明に係る粒子形成工程で用いられる形態制御剤としては、例えば、親水性高分子、両親媒性分子などを挙げることができる。 Examples of the shape control agent used in the particle forming step according to the present invention include hydrophilic polymers and amphiphilic molecules.
親水性高分子としては、ポリビニルピロリドン〔例えば、ポリ（Ｎ−ビニル−２−ピロリドン）〕、ポリビニルアルコール、ポリ（メタ）アクリル酸塩のように、アミド基、水酸基、カルボキシル基および／またはアミノ基を含有するポリマーあるいはこれら親水性ホモ重合体形成用モノマーの共重合体などのほか、シクロデキストリン、アミノペクチン、メチルセルロース、ゼラチンなどの天然物を挙げることができる。 Examples of hydrophilic polymers include amide groups, hydroxyl groups, carboxyl groups and / or amino groups such as polyvinylpyrrolidone [eg, poly (N-vinyl-2-pyrrolidone)], polyvinyl alcohol, and poly (meth) acrylate. In addition to polymers containing styrene or copolymers of monomers for forming these hydrophilic homopolymers, natural products such as cyclodextrin, aminopectin, methylcellulose, and gelatin can be used.
両親媒性分子としては、各種一官能性または多官能性界面活性剤（アニオン性、カチオン性、ノニオン性、両性いずれでも可）、例えば、ドデシル硫酸ナトリウム、ポリエチレングリコールモノラウレートなどを挙げることができる。 Examples of amphiphilic molecules include various monofunctional or polyfunctional surfactants (any of anionic, cationic, nonionic, and amphoteric), such as sodium dodecyl sulfate, polyethylene glycol monolaurate, and the like. it can.
形態制御剤の使用量は、金属１モルに対し、０．１モル以上存在することが好ましく、より好ましくは１〜５０モルである。なお、形態制御剤が高分子の場合には、前記モル量はそのモノマー単位のモル数に換算した値を意味する。 The amount of the form control agent used is preferably 0.1 mol or more, more preferably 1 to 50 mol, relative to 1 mol of the metal. When the form control agent is a polymer, the molar amount means a value converted to the number of moles of the monomer unit.
〔凝集防止剤〕
本発明においては、粒子形成工程において本発明に係る粒子形成工程で用いられる凝集防止剤としては、対象となる金属ナノワイヤに対して保護コロイド機能を有する化合物であれば特に制限はなく、例えば、親水性高分子、金属配位性分子、両親媒性分子、アニオン性化合物などを挙げることができる。
[Aggregation inhibitor]
In the present invention, the aggregation preventing agent used in the particle forming step according to the present invention in the particle forming step is not particularly limited as long as it is a compound having a protective colloid function with respect to the target metal nanowire. And a conductive polymer, a metal coordinating molecule, an amphiphilic molecule, and an anionic compound.
親水性高分子としては、ポリビニルピロリドン〔例えば、ポリ（Ｎ−ビニル−２−ピロリドン）〕、ポリビニルアルコール、ポリ（メタ）アクリル酸塩のように、アミド基、水酸基、カルボキシル基および／またはアミノ基を含有するポリマーあるいはこれら親水性ホモ重合体形成用モノマーの共重合体などのほか、シクロデキストリン、アミノペクチン、メチルセルロース、ゼラチンなどの天然物を挙げることができる。 Examples of hydrophilic polymers include amide groups, hydroxyl groups, carboxyl groups and / or amino groups such as polyvinylpyrrolidone [eg, poly (N-vinyl-2-pyrrolidone)], polyvinyl alcohol, and poly (meth) acrylate. In addition to polymers containing styrene or copolymers of monomers for forming these hydrophilic homopolymers, natural products such as cyclodextrin, aminopectin, methylcellulose, and gelatin can be used.
金属配位性分子としては、例えば、アミノ基、チオール基、ジスルフィド基、アミド基、カルボン酸基、ホスフィン基、スルホン酸基など金属に配位することのできる官能基を１つ以上持つ有機分子および一酸化炭素、一酸化窒素をあげることができる。 Examples of metal coordinating molecules include organic molecules having one or more functional groups capable of coordinating to metals such as amino groups, thiol groups, disulfide groups, amide groups, carboxylic acid groups, phosphine groups, and sulfonic acid groups. And carbon monoxide and nitric oxide.
両親媒性分子としては、各種一官能性または多官能性界面活性剤（アニオン性、カチオン性、ノニオン性、両性いずれでも可）、例えば、ドデシル硫酸ナトリウム、ポリエチレングリコールモノラウレートなどを挙げることができる。 Examples of amphiphilic molecules include various monofunctional or polyfunctional surfactants (any of anionic, cationic, nonionic, and amphoteric), such as sodium dodecyl sulfate, polyethylene glycol monolaurate, and the like. it can.
アニオン性化合物としては、例えば、塩化物などのハロゲン化物、過塩素酸塩、各種アルコキシドなどのほか修酸、酒石酸、クエン酸などのカルボン酸の塩を挙げることができ、その塩としてはアルカリ金属塩、アンモニウム塩、アミン塩などを挙げることができる。 Examples of the anionic compound include halides such as chlorides, perchlorates, various alkoxides, and salts of carboxylic acids such as oxalic acid, tartaric acid, citric acid, and the like. Examples thereof include salts, ammonium salts, and amine salts.
本発明係る粒子形成工程においては、上記化合物の中でもアミド基、水酸基、カルボキシル基および／またはアミノ基を含有する水溶性ポリマーを用いることが好ましい。 In the particle forming step according to the present invention, among the above compounds, it is preferable to use a water-soluble polymer containing an amide group, a hydroxyl group, a carboxyl group and / or an amino group.
前記形態制御剤の例示化合物に挙げたポリビニルピロリドンやポリビニルアルコール、ポリエチレングリコールなどは、金属ナノワイヤ形成の凝集防止剤としても機能するため、形態制御剤兼凝集防止剤として本発明において好ましく用いることができる。 Polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, and the like listed as exemplary compounds of the form control agent also function as an anti-aggregation agent for forming metal nanowires, and therefore can be preferably used in the present invention as an anti-coagulation agent. .
〔還元剤〕
本発明において、金属イオンを還元するための還元剤としては、対象となる金属を還元できる化合物であれば特に制限は無く、一般的な化学還元剤から少なくとも１種を選んで用いることができる。本発明で好ましく用いることができる還元剤としては、例えば、一級または二級アルコール類、グリコール類、酸素原子に隣接する炭素原子に水素原子が結合しているエーテル類、アタノールアミン類、水素化ホウ素類、ヒドラジン類よりなる群から選ばれた少なくとも１種を挙げることができる。
[Reducing agent]
In the present invention, the reducing agent for reducing the metal ion is not particularly limited as long as it is a compound capable of reducing the target metal, and at least one selected from general chemical reducing agents can be used. Examples of the reducing agent that can be preferably used in the present invention include primary or secondary alcohols, glycols, ethers in which a hydrogen atom is bonded to a carbon atom adjacent to an oxygen atom, ethanolamines, borohydride. And at least one selected from the group consisting of hydrazines.
〔形態制御剤除去工程〕
本発明の透明導電膜の製造方法は、粒子形成工程の後に粒子形成工程で使用した形態制御剤を、限外濾過膜を用いた膜分離法を用いて除去する工程（形態制御剤除去工程）を有する。前記粒子形成工程によって得られた金属ナノワイヤ分散液中には、残存原料や副生成物、各種添加剤など、本発明の透明導電膜に適用される導電層を形成したときの性能を劣化させる物質を含んでいる。特に、金属ナノワイヤ表面に吸着した前記形態制御剤は、金属ナノワイヤ間に介在して導電ネットワーク形成を阻害し、導電層の導電性を低下させるため、本発明においては形態制御剤除去工程においてそれらを取り除く。
[Form control agent removal step]
The method for producing a transparent conductive film of the present invention is a step of removing the morphology control agent used in the particle formation step after the particle formation step by using a membrane separation method using an ultrafiltration membrane (morphology control agent removal step). Have In the metal nanowire dispersion liquid obtained by the particle forming step, substances that deteriorate the performance when forming a conductive layer applied to the transparent conductive film of the present invention, such as residual raw materials, by-products, and various additives Is included. In particular, the shape control agent adsorbed on the surface of the metal nanowires intervenes between the metal nanowires to inhibit the formation of a conductive network and lower the conductivity of the conductive layer. remove.
形態制御剤の除去方法としては、遠心分離機などを用いて金属ナノワイヤを沈降させ、上澄みを捨てた後適当な溶媒を加えて再分散する処理を繰り返す方法（デカンテーション法）や、フィルターを用いて金属ナノワイヤを濾別した後、適当な溶媒に再分散する処理を繰り返す方法（フィルタリング法）などがある。これらの方法では、金属ナノワイヤ分散液中の過剰な形態制御剤を除去することはできるが、金属ナノワイヤ表面に吸着した形態制御剤は殆ど除去することができない。 As a method for removing the shape control agent, a method of decanting metal nanowires using a centrifuge, etc., discarding the supernatant, adding a suitable solvent and redispersing (decantation method), or using a filter For example, there is a method (filtering method) in which the metal nanowire is filtered and then redispersed in an appropriate solvent. With these methods, it is possible to remove the excess shape control agent in the metal nanowire dispersion liquid, but it is almost impossible to remove the shape control agent adsorbed on the surface of the metal nanowire.
また、デカンテーション法では遠心力による金属ナノワイヤ沈降時に沈降凝集が発生したり、フィルタリング法ではフィルター上での金属ナノワイヤの乾燥によって乾燥凝集が発生したりする。ナノサイズの粒子が一度凝集体を形成すると、それらは容易に解膠されないため、これらの方法を用いて処理した金属ナノワイヤを透明導電膜の導電層に適用すると、金属ナノワイヤの凝集体による光散乱によって透明性が損なわれてしまうという問題を生じてしまう。さらに、このような金属ナノワイヤの凝集体は、金属ナノワイヤによる導電ネットワーク構造を構築する上でロスとなるため、表面抵抗の増加をも招いてしまう。 In the decantation method, sedimentation aggregation occurs when the metal nanowires settle due to centrifugal force, and in the filtering method, dry aggregation occurs due to drying of the metal nanowires on the filter. Once nano-sized particles form aggregates, they are not easily peptized, so when metal nanowires treated using these methods are applied to the conductive layer of a transparent conductive film, light scattering by the aggregates of metal nanowires This causes a problem that transparency is impaired. Furthermore, such an aggregate of metal nanowires causes a loss in constructing a conductive network structure with the metal nanowires, and thus causes an increase in surface resistance.
本発明者が鋭意検討を重ねた結果、限外濾過膜を用いた膜分離法を形態制御剤の除去に適用することによって、金属ナノワイヤ分散液中の過剰な形態制御剤だけでなく、金属ナノワイヤ表面に吸着した形態制御剤も除去できることを見出した。限外濾過膜を用いた膜分離法で、金属ナノワイヤ表面に吸着した形態制御剤が除去できるメカニズムは明らかではないが、金属ナノワイヤ分散液を、送液ポンプなどを用いて限外濾過膜内部に高速循環させることによって、限外濾過膜内部の狭い流路で乱流が発生し、個々の金属ナノワイヤが強い剪断力を受け、その結果金属ナノワイヤ表面に吸着した形態制御剤が物理的に剥ぎ取られるためと推定している。 As a result of intensive studies by the present inventors, by applying a membrane separation method using an ultrafiltration membrane to the removal of the shape control agent, not only the excessive shape control agent in the metal nanowire dispersion liquid but also the metal nanowire It has been found that the shape control agent adsorbed on the surface can also be removed. Although the mechanism by which the form control agent adsorbed on the surface of the metal nanowires can be removed by the membrane separation method using an ultrafiltration membrane is not clear, the metal nanowire dispersion liquid is put inside the ultrafiltration membrane using a liquid feed pump or the like. By circulating at high speed, turbulent flow is generated in the narrow flow path inside the ultrafiltration membrane, and each metal nanowire is subjected to strong shearing force. As a result, the morphology control agent adsorbed on the surface of the metal nanowire is physically peeled off. It is estimated that
さらに、限外濾過膜を用いた膜分離法では、形態制御剤の除去プロセスにおいて凝集体を生成しないため、形態制御剤の除去処理を施した金属ナノワイヤを透明導電膜の導電層に適用した場合に、透明性を損ねたり表面抵抗が増加したりすることがなく、むしろ表面抵抗は低下する。これは、金属ナノワイヤ表面に吸着した形態制御剤が除去されたため、金属ナノワイヤ間の導電性が向上したためと考えられる。 Furthermore, in the membrane separation method using an ultrafiltration membrane, aggregates are not generated in the removal process of the shape control agent, and therefore, when metal nanowires that have been subjected to the removal process of the shape control agent are applied to the conductive layer of the transparent conductive film In addition, the transparency does not deteriorate and the surface resistance does not increase, but the surface resistance rather decreases. This is thought to be because the conductivity between the metal nanowires was improved because the shape control agent adsorbed on the surface of the metal nanowires was removed.
本発明において用いられる限外濾過膜は、金属ナノワイヤを分画し、かつ形態制御剤を透過できる分画分子量を有することが好ましい。また、限外濾過膜の材質には特に制限は無く、セルロース系、ポリエーテルスルホン系、ＰＴＦＥなどから選択できる。限外濾過膜を用いた形態制御剤の除去は、金属ナノワイヤ分散液を送液ポンプなどを用いて限外濾過膜に循環させ、形態制御剤を含むフラックスを金属ナノワイヤ分散液から除去しながら、適当な溶媒を断続的に或いは連続的に加えることにより実施できる。 The ultrafiltration membrane used in the present invention preferably has a molecular weight cut off to fractionate the metal nanowires and permeate the shape control agent. Moreover, there is no restriction | limiting in particular in the material of an ultrafiltration membrane, It can select from a cellulose type, a polyether sulfone type, PTFE, etc. The removal of the form control agent using the ultrafiltration membrane is performed by circulating the metal nanowire dispersion liquid to the ultrafiltration membrane using a liquid feed pump or the like, while removing the flux containing the form control agent from the metal nanowire dispersion liquid. It can be carried out by adding a suitable solvent intermittently or continuously.
本発明の製造方法において形態制御剤除去工程は、形態制御剤除去工程終了後の、形態制御剤の含有率（＝形態制御剤質量／金属ナノワイヤ質量）が３％以下になるよう実施することが好ましく、０〜２％であることがより好ましく、０〜１％であることが特に好ましい。上記形態制御剤の含有率は、金属ナノワイヤ単位質量当たりの形態制御剤質量を、ＴＧ（熱天秤）を用いて測定して求めることができる。 In the production method of the present invention, the form control agent removal step may be performed such that the content of the form control agent (= form control agent mass / metal nanowire mass) after the form control agent removal step is 3% or less. Preferably, it is 0 to 2%, more preferably 0 to 1%. The content rate of the said form control agent can be calculated | required by measuring the form control agent mass per metal nanowire unit mass using TG (thermobalance).
〔分散工程〕
本発明において分散工程は、金属ナノワイヤの凝集を防止することを目的として実施することができ、少なくとも塗布工程終了までの間に実施することが好ましく、形態制御剤除去工程から塗布工程までの間に実施することがより好ましく、形態制御剤除去工程の次工程として実施することがさらに好ましい。
[Dispersing process]
In the present invention, the dispersion step can be carried out for the purpose of preventing aggregation of the metal nanowires, and is preferably carried out at least until the end of the coating step, between the form control agent removing step and the coating step. More preferably, it is more preferable to implement as the next step of the form control agent removal step.
本発明の製造方法において、金属ナノワイヤ分散液中で金属ナノワイヤの凝集を抑制し高度に分散させる方法としては、高分子系の分散剤や極性部と非極性部を有する活性剤などを金属ナノワイヤ表面に吸着させ、その立体障害効果により凝集体の生成を抑制する方法が有効である。本発明において分散剤の構造は特に制限はなく、リン酸系、スルホン酸系、カルボン酸系、ノニオン系、カチオン系などから適宜選択して用いることができるが、アミノ基、チオール基、ジスルフィド基、アミド基、カルボン酸基、ホスフィン基、スルホン酸基などの金属に配位することのできる官能基を１つ以上有する分散剤を少なくとも１種用いることが好ましい。また、分散剤の分子量は、５０，０００以下が好ましく、更に好ましくは１００〜２０，０００、最も好ましいのは５００〜１０，０００である。あまり分子量が大きすぎると、分散剤が金属ナノワイヤ間で橋架け凝集を形成したり、金属ナノワイヤ間の導電性を阻害するため好ましくない。また、あまり分子量が小さすぎると、分子鎖が短く充分な立体障害効果が得られない。 In the production method of the present invention, as a method for highly suppressing the dispersion of metal nanowires in the metal nanowire dispersion liquid, a polymer-based dispersant or an active agent having a polar part and a nonpolar part can be used. An effective method is to adsorb to the surface and suppress the formation of aggregates by the steric hindrance effect. In the present invention, the structure of the dispersant is not particularly limited, and can be appropriately selected from phosphoric acid, sulfonic acid, carboxylic acid, nonionic, cationic, etc. It is preferable to use at least one dispersant having one or more functional groups capable of coordinating to a metal such as an amide group, a carboxylic acid group, a phosphine group, or a sulfonic acid group. The molecular weight of the dispersant is preferably 50,000 or less, more preferably 100 to 20,000, and most preferably 500 to 10,000. If the molecular weight is too large, the dispersant is not preferable because it forms bridging aggregates between metal nanowires or inhibits conductivity between metal nanowires. If the molecular weight is too small, the molecular chain is short and sufficient steric hindrance effect cannot be obtained.
本発明に係る金属ナノワイヤを、非水系溶媒に分散する場合には、アミノ基、チオール基、ジスルフィド基、アミド基、カルボン酸基、ホスフィン基、スルホン酸基などの金属に配位することのできる官能基を１つ以上有し、かつ非水系溶媒に親和性のある化合物を分散剤を用いることが好ましい。 When the metal nanowire according to the present invention is dispersed in a non-aqueous solvent, it can be coordinated to a metal such as an amino group, a thiol group, a disulfide group, an amide group, a carboxylic acid group, a phosphine group, or a sulfonic acid group. It is preferable to use a dispersant having a compound having one or more functional groups and having an affinity for a non-aqueous solvent.
本発明の製造方法における分散操作は、超音波分散機や高速攪拌型分散機のいずれか、またはそれらを組み合わせて、本発明に係る金属ナノワイヤ分散液を上記分散剤の存在下に分散処理することにより実施できる。メディア分散機は、金属ナノワイヤを傷つけたり変形させたりする可能性があるため、本発明においては使用に適さない。
分散工程に要する時間は、粒子（金属ナノワイヤ）の分散進行性や使用する分散機のパワーによって異なるため、分散進行状態を確認して決定することが好ましい。
The dispersion operation in the production method of the present invention is to disperse the metal nanowire dispersion liquid according to the present invention in the presence of the above-mentioned dispersant by using either an ultrasonic disperser or a high-speed stirring disperser or a combination thereof. Can be implemented. The media disperser is not suitable for use in the present invention because it may damage or deform the metal nanowires.
Since the time required for the dispersion process varies depending on the dispersion progress of the particles (metal nanowires) and the power of the disperser to be used, it is preferable to determine by confirming the dispersion progress state.
超音波分散機は超音波によって発生したキャビテーション（真空泡）が潰れるときに発生するエネルギーを用いて分散を行うもので、本発明において好ましく用いることができる。本発明で用いることができる具体的な装置例として、ＳＭＴ社ＵＨ１５０や日本精機製作所ＵＳ−３００Ｔなどが挙げられる。 The ultrasonic disperser performs dispersion using energy generated when cavitation (vacuum bubbles) generated by ultrasonic waves is crushed, and can be preferably used in the present invention. Specific examples of apparatuses that can be used in the present invention include SMT UH150 and Nippon Seiki Seisakusho US-300T.
高速攪拌型分散機は高速攪拌している攪拌羽根近傍のせん断力により粒子を分散させるもので、本発明で用いることができる具体的な装置例として、プライミクス社ＴＫホモミクサーＭＡＲＫIIやＭテクニッククレアミックスＣＬＭ−３．７などが挙げられる。 The high-speed agitation type disperser disperses particles by the shearing force in the vicinity of the agitation blades that are agitated at high speed. -3.7 and the like.
〔塗布工程〕
本発明においては、少なくとも金属ナノワイヤを含む分散液を透明支持体上に塗布して、本発明に係る導電層を形成することができる。塗布法によって導電層を形成することにより、生産性と生産コストの改善、平滑性や均一性などの透明導電膜品質の向上、環境負荷の軽減など多くのメリットが得られる。
[Coating process]
In the present invention, a conductive layer according to the present invention can be formed by applying a dispersion containing at least metal nanowires on a transparent support. By forming the conductive layer by the coating method, many merits such as improvement of productivity and production cost, improvement of the quality of the transparent conductive film such as smoothness and uniformity, and reduction of environmental load can be obtained.
なお、本発明における「塗布」とは、塗布法や印刷法、インクジェット法などの一般的な液相成膜法全てを含むものである。従って、本発明における塗布工程では、塗布法として、ロールコート法、バーコート法、ディップコーティング法、スピンコーティング法、キャスティング法、ダイコート法、ブレードコート法、バーコート法、グラビアコート法、カーテンコート法、スプレーコート法、ドクターコート法などを用いることができる。また、印刷法としては、凸版（活版）印刷法、孔版（スクリーン）印刷法、平版（オフセット）印刷法、凹版（グラビア）印刷法などを用いることができる。 The “application” in the present invention includes all general liquid phase film forming methods such as a coating method, a printing method, and an ink jet method. Therefore, in the coating step in the present invention, the roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method are used as the coating method. Spray coating method, doctor coating method and the like can be used. Moreover, as a printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a planographic (offset) printing method, an intaglio (gravure) printing method, etc. can be used.
さらに、印刷法やインクジェット法を用いて、金属ナノワイヤを含む分散液を透明支持体上にパターン様に印画して本発明に係る導電層を形成し、透明配線や透明回路を形成することもできる。 Furthermore, the conductive liquid according to the present invention can be formed by printing a dispersion containing metal nanowires in a pattern on a transparent support using a printing method or an ink jet method, thereby forming a transparent wiring or a transparent circuit. .
なお、必要に応じて、密着性・塗工性を向上させるための予備処理として、塗布工程に先立ち、透明支持体表面にコロナ放電処理、プラズマ放電処理などの物理的表面処理を施すこともできる。 If necessary, as a pretreatment for improving adhesion and coating properties, the surface of the transparent support can be subjected to physical surface treatment such as corona discharge treatment or plasma discharge treatment prior to the coating step. .
以下に実施例を挙げて本発明の効果を具体的に説明する。以下の実施態様における各種条件は、本発明の特徴や趣旨を逸脱しない限り適宜変更することができ、本発明の範囲は以下の実施例により限定的に解釈されるべきものではない。なお、実施例において「部」あるいは「％」の表示を用いるが、特に断りがない限り「質量部」あるいは「質量％」を表す。 The effects of the present invention will be specifically described with reference to examples. Various conditions in the following embodiments can be appropriately changed without departing from the features and spirit of the present invention, and the scope of the present invention should not be construed as being limited by the following examples. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.
実施例１
〔透明導電膜ＴＣＦ−０１の作製：本発明〕
（粒子形成工程）
前記非特許文献１（Ａｄｖ．Ｍａｔｅｒ．２００２，１４，８３３〜８３７）に記載の方法を参考に、還元剤としてエチレングリコール（ＥＧ、関東化学：純度＞９９．５％）を、形態制御剤（兼保護コロイド剤）としてポリビニルピロリドン（ＰＶＰ、東京化成：平均分子量４０，０００の）を使用し、かつ核形成工程と粒子成長工程とを分離して粒子形成を行い、銀ナノワイヤ分散液を調製した。
Example 1
[Preparation of Transparent Conductive Film TCF-01: Present Invention]
(Particle formation process)
With reference to the method described in Non-Patent Document 1 (Adv. Mater. 2002, 14, 833 to 837), ethylene glycol (EG, Kanto Chemical: purity> 99.5%) as a reducing agent was used as a form control agent ( Polyvinylpyrrolidone (PVP, Tokyo Kasei: average molecular weight 40,000) was used as a colloidal protective agent), and the nucleation step and the particle growth step were separated to form particles to prepare a silver nanowire dispersion. .
《核形成工程》
反応容器内で１６０℃に保持したＥＧ液１００ｍｌを攪拌しながら、硝酸銀（関東化学：純度＞９９．８％）のＥＧ溶液（硝酸銀濃度：１．５×１０-4モル／ｌ）１０ｍｌを、一定の流量で１０秒間かけて添加した。その後、１６０℃で１０分間保持しながら銀イオンを還元して銀の核粒子を形成した。反応液は、ナノサイズの銀微粒子の表面プラズモン吸収に由来する黄色を呈しており、銀イオンが還元されて銀の微粒子（核粒子）が形成されたことを確認した。
《Nucleation process》
While stirring 100 ml of EG solution maintained at 160 ° C. in a reaction vessel, 10 ml of EG solution (silver nitrate concentration: 1.5 × 10 −4 mol / l) of silver nitrate (Kanto Chemical: purity> 99.8%) It was added over 10 seconds at a constant flow rate. Thereafter, the silver ions were reduced while being held at 160 ° C. for 10 minutes to form silver core particles. The reaction solution exhibited a yellow color derived from surface plasmon absorption of nano-sized silver fine particles, and it was confirmed that silver ions were reduced to form silver fine particles (nuclear particles).
《粒子成長工程》
上記核形成工程１を終了した後の核粒子を含む反応液を、攪拌しながら１６０℃に保持し、硝酸銀のＥＧ溶液（硝酸銀濃度：１．０×１０-1モル／ｌ）１００ｍｌと、ＰＶＰのＥＧ溶液（ビニルピロリドン濃度換算：６．０×１０-1モル／ｌ）１００ｍｌを、ダブルジェット法を用いて一定の流量で１２０分間かけて添加した。粒子成長工程において、２０分毎に反応液を採取して電子顕微鏡で確認したところ、核形成工程で形成された核粒子が時間経過に伴ってワイヤ状の形態に成長しており、粒子成長工程における新たな微粒子の生成は認められなかった。最終的に得られた銀ナノワイヤについて、電子顕微鏡写真を撮影し、３００個の銀ナノワイヤ粒子像の長軸方向および短軸方向の粒径を測定して算術平均を求めた。短軸方向の平均粒径は９４ｎｍ、長軸方向の平均粒径は８．１μｍであった。
<Grain growth process>
The reaction liquid containing the core particles after the completion of the nucleation step 1 is maintained at 160 ° C. with stirring, 100 ml of an EG solution of silver nitrate (silver nitrate concentration: 1.0 × 10 −1 mol / l), and PVP 100 ml of EG solution (vinyl pyrrolidone concentration conversion: 6.0 × 10 −1 mol / l) was added over 120 minutes at a constant flow rate using the double jet method. In the particle growth step, the reaction solution was sampled every 20 minutes and confirmed with an electron microscope. As a result, the core particles formed in the nucleation step grew into a wire-like form over time. The formation of new fine particles was not observed. About the silver nanowire finally obtained, the electron micrograph was image | photographed, the particle size of the major axis direction and the minor axis direction of 300 silver nanowire particle images was measured, and the arithmetic average was calculated | required. The average particle size in the minor axis direction was 94 nm, and the average particle size in the major axis direction was 8.1 μm.
（形態制御剤除去工程）
上記粒子形成工程を終了した反応液を室温まで冷却した後、反応容器から反応液を分画分子量０．２μｍの限外濾過膜（ＶＩＶＡＦＬＯＷ ５０ Ｚａｒｔｏｒｉｕｓ社）と送液ポンプに外部循環させて、ＰＶＰや残存原料、副生成物を含むフラックスを限外濾過膜から排出することにより、形態制御剤の除去工程を実施した。「液量を初期量の１５％まで濃縮した後、ＥｔＯＨを添加して初期量に戻す。」という形態制御剤除去サイクルを３回繰り返し、最後に液量を１００ｍｌまで濃縮して銀ナノワイヤのＥｔＯＨ分散液を調製した。
(Form control agent removal step)
After cooling the reaction liquid after the particle formation step to room temperature, the reaction liquid is externally circulated from the reaction vessel to an ultrafiltration membrane (VIVAFLOW 50 Zartorius) having a molecular weight cut off of 0.2 μm and a liquid feed pump to obtain PVP. The form control agent removal step was carried out by discharging flux containing residual materials and by-products from the ultrafiltration membrane. The form control agent removal cycle of “concentrate the liquid volume to 15% of the initial volume and then add EtOH to return to the initial volume” was repeated three times. Finally, the liquid volume was concentrated to 100 ml and EtOH of the silver nanowires. A dispersion was prepared.
形態制御剤除去工程終了後の銀ナノワイヤ分散液からサンプルを採取し、２００℃で乾燥させて残留するＥＧを除去した後、ＴＧ（熱天秤）を用いてＰＶＰと銀ナノワイヤの質量を求めた。その結果、形態制御剤除去工程終了後のＰＶＰの含有率（＝ＰＶＰ質量／銀ナノワイヤ質量）は、２．５％であることが判った。 A sample was taken from the silver nanowire dispersion liquid after completion of the form control agent removal step, dried at 200 ° C. to remove residual EG, and then the masses of PVP and silver nanowires were determined using TG (thermobalance). As a result, it was found that the content of PVP (= PVP mass / silver nanowire mass) after completion of the form control agent removal step was 2.5%.
（塗布工程）
反射防止加工を施した全光透過率９３％のポリエチレンテレフタレート（ＰＥＴ）支持体にコロナ放電処理を施した後、目付け量が０．３ｇ／ｍ2となるように銀ナノワイヤのＥｔＯＨ分散液をスピンコーターを用いて塗布し乾燥して銀ナノワイヤの導電層を形成した。続いて、銀ナノワイヤ導電層にカレンダー処理を施した後、ウレタンアクリレートのメチルイソブチルケトン溶液をスピンコーターを用いて塗布し乾燥して、透明導電体ＴＣＦ−０１を作製した。なお、ウレタンアクリレート層の膜厚は、銀ナノワイヤ導電層を完全に埋没させず、その一部がウレタンアクリレート層から露出する厚さで、かつ銀ナノワイヤ層を支持体に固定化できる厚さに設定した。
(Coating process)
A polyethylene terephthalate (PET) support with 93% total light transmittance that has undergone antireflection treatment is subjected to corona discharge treatment, and then a silver nanowire EtOH dispersion is spun so that the basis weight is 0.3 g / m 2. It was applied using a coater and dried to form a conductive layer of silver nanowires. Subsequently, the silver nanowire conductive layer was calendered, and then a methyl isobutyl ketone solution of urethane acrylate was applied using a spin coater and dried to prepare a transparent conductor TCF-01. The thickness of the urethane acrylate layer is set to a thickness that does not completely embed the silver nanowire conductive layer, a part of which is exposed from the urethane acrylate layer, and the silver nanowire layer can be fixed to the support. did.
〔透明導電膜ＴＣＦ−０２の作製：本発明〕
上記透明導電膜ＴＣＦ−０１の製造方法において、形態制御剤除去工程における形態制御剤除去サイクルを４回に変更した以外はＴＣＦ−０１と同様にして、透明導電体ＴＣＦ−０２を作製した。
[Preparation of Transparent Conductive Film TCF-02: Present Invention]
In the method for producing the transparent conductive film TCF-01, a transparent conductor TCF-02 was produced in the same manner as TCF-01 except that the form control agent removal cycle in the form control agent removal step was changed to four times.
〔透明導電膜ＴＣＦ−０３の作製：本発明〕
上記透明導電膜ＴＣＦ−０１の製造方法において、形態制御剤除去工程における形態制御剤除去サイクルを５回に変更した以外はＴＣＦ−０１と同様にして、透明導電体ＴＣＦ−０３を作製した。
[Preparation of Transparent Conductive Film TCF-03: Present Invention]
In the method for producing the transparent conductive film TCF-01, a transparent conductor TCF-03 was produced in the same manner as TCF-01 except that the form control agent removal cycle in the form control agent removal step was changed to 5.
〔透明導電膜ＴＣＦ−０４の作製：本発明〕
上記透明導電膜ＴＣＦ−０３の製造方法において、形態制御剤除去工程終了後に、以下のような分散工程を実施した以外はＴＣＦ−０１と同様にして、透明導電体ＴＣＦ−０４を作製した。
[Preparation of Transparent Conductive Film TCF-04: Present Invention]
In the method for producing the transparent conductive film TCF-03, a transparent conductor TCF-04 was produced in the same manner as TCF-01 except that the following dispersion process was performed after the form control agent removal process.
（分散工程）
形態制御剤除去工程終了後の銀ナノワイヤのＥｔＯＨ分散液に、分散剤としてオレイルアミンを５．０×１０-5モル相当量加えた後、ＳＭＴ社製超音波分散機ＵＨ−３００を用いて３０分間分散処理を施した。
(Dispersion process)
After adding the amount equivalent to 5.0 × 10 −5 mol of oleylamine as a dispersing agent to the EtOH dispersion of silver nanowires after completion of the shape control agent removing step, 30 minutes using an ultrasonic dispersing machine UH-300 manufactured by SMT Dispersion treatment was performed.
〔透明導電膜ＴＣＦ−０５の作製：比較例〕
上記透明導電膜ＴＣＦ−０１の製造方法において、形態制御剤除去工程を以下のように実施した以外はＴＣＦ−０１と同様にして、透明導電体ＴＣＦ−０５を作製した。
[Preparation of Transparent Conductive Film TCF-05: Comparative Example]
In the method for producing the transparent conductive film TCF-01, a transparent conductor TCF-05 was produced in the same manner as TCF-01 except that the form control agent removing step was performed as follows.
（形態制御剤除去工程）
粒子形成工程を終了した反応液を室温まで冷却した後、反応液全量を複数の遠沈管に分割して、遠心分離機を用いたデカンテーション法により、形態制御剤の除去工程を実施した。「２０００ｒｐｍで２０分間遠心分離を施した後上澄みを捨て、ＥｔＯＨを初期量まで添加して超音波分散を施し再分散する。」という形態制御剤除去サイクルを４回繰り返した。最後に再度遠心分離を施し、沈降した銀ナノワイヤを集めて１００ｍｌの銀ナノワイヤのＥｔＯＨ分散液を調液した。
(Form control agent removal step)
After cooling the reaction solution after completing the particle formation step to room temperature, the total amount of the reaction solution was divided into a plurality of centrifuge tubes, and a form control agent removal step was performed by a decantation method using a centrifuge. The form control agent removal cycle was repeated four times, saying that after centrifugation at 2000 rpm for 20 minutes, the supernatant was discarded, and EtOH was added to the initial amount, followed by ultrasonic dispersion and redispersion. Finally, centrifugation was performed again, and the precipitated silver nanowires were collected to prepare 100 ml of EtOH dispersion of silver nanowires.
〔透明導電膜ＴＣＦ−０６の作製：比較例〕
上記透明導電膜ＴＣＦ−０５の製造方法において、形態制御剤除去工程における形態制御剤除去サイクルを９回に変更した以外はＴＣＦ−０５と同様にして、透明導電体ＴＣＦ−０６を作製した。
[Preparation of Transparent Conductive Film TCF-06: Comparative Example]
In the method for producing the transparent conductive film TCF-05, a transparent conductor TCF-06 was produced in the same manner as TCF-05 except that the form control agent removal cycle in the form control agent removal step was changed to 9 times.
〔透明導電膜ＴＣＦ−０７の作製：比較例〕
上記透明導電膜ＴＣＦ−０１の製造方法において、形態制御剤除去工程を以下のように実施した以外はＴＣＦ−０１と同様にして、透明導電体ＴＣＦ−０７を作製した。
[Preparation of Transparent Conductive Film TCF-07: Comparative Example]
In the method for producing the transparent conductive film TCF-01, a transparent conductor TCF-07 was produced in the same manner as TCF-01 except that the form control agent removing step was performed as follows.
（形態制御剤除去工程）
粒子形成工程を終了した反応液を室温まで冷却した後、平均孔径０．２μｍのフィルターを用いたフィルタリング法により、形態制御剤の除去工程を実施した。「反応液を０．２μｍのフィルターで吸引濾過し、銀ナノワイヤを濾別する。濾別した銀ナノワイヤを集めＥｔＯＨを加えて初期量とする。」という形態制御剤除去サイクルを４回繰り返した。
(Form control agent removal step)
After cooling the reaction liquid which completed the particle | grain formation process to room temperature, the removal process of the shape control agent was implemented with the filtering method using the filter with an average hole diameter of 0.2 micrometer. The form control agent removal cycle of “reaction filtration of the reaction solution through a 0.2 μm filter and filtering out silver nanowires. Collecting the filtered silver nanowires and adding EtOH to an initial amount” was repeated four times.
最後に再度フィルターで濾過し、濾別した銀ナノワイヤを集めて１００ｍｌの銀ナノワイヤのＥｔＯＨ分散液を調液した。なお、この方法では、濾液を濾過しきる度に、銀ナノワイヤはフィルター上で乾燥状態にさらされた。 Finally, the solution was filtered again, and the silver nanowires separated by filtration were collected to prepare 100 ml of an EtOH dispersion of silver nanowires. In this method, every time the filtrate was completely filtered, the silver nanowires were exposed to a dry state on the filter.
〔透明導電膜ＴＣＦ−０８の作製：比較例〕
上記透明導電膜ＴＣＦ−０７の製造方法において、形態制御剤除去工程における形態制御剤除去サイクルを９回に変更した以外はＴＣＦ−０７と同様にして、透明導電体ＴＣＦ−０８を作製した。
[Preparation of Transparent Conductive Film TCF-08: Comparative Example]
A transparent conductor TCF-08 was produced in the same manner as TCF-07 except that in the method for producing the transparent conductive film TCF-07, the shape control agent removal cycle in the form control agent removal step was changed to nine.
実施例２
実施例１で作製した各透明導電膜について、全光透過率と表面抵抗率の測定を行った。全光透過率は、ＪＩＳ Ｋ７１０５に準拠して測定した。また、表面抵抗率は、ＪＩＳ Ｋ７１９４に準拠して測定した。得られた結果を表１に示す。
Example 2
About each transparent conductive film produced in Example 1, the total light transmittance and the surface resistivity were measured. The total light transmittance was measured according to JIS K7105. The surface resistivity was measured according to JIS K7194. The obtained results are shown in Table 1.
表１に記載の結果より明らかな様に、形態制御剤除去工程をデカンテーション法やフィルタリング法で実施した比較例のＴＣＦ−０５〜０７に対して、限外濾過膜を用いた膜分離法によって形態制御剤除去工程を実施した本発明の透明導電体ＴＣＦ−０１〜０４は、優れた導電性と透明性を有している。 As is clear from the results shown in Table 1, compared to TCF-05-07 of the comparative example in which the morphological agent removal step was performed by the decantation method or the filtering method, the membrane separation method using an ultrafiltration membrane was used. The transparent conductors TCF-01 to 04 of the present invention that have undergone the form control agent removal step have excellent conductivity and transparency.
本発明の透明導電体における優れた導電性は、形態制御剤の残存率に現れているように、膜分離法によって形態制御剤除去工程を実施することにより、銀ナノワイヤ表面に吸着した形態制御剤も除去され、銀ナノワイヤネットワークの導電性が向上したことによりもたらされたと考えられる。 As shown in the residual rate of the shape control agent, the excellent conductivity in the transparent conductor of the present invention is a shape control agent adsorbed on the surface of the silver nanowire by carrying out the shape control agent removal step by a membrane separation method. It is thought that this was also caused by the removal of the silver nanowire network and the improved conductivity of the silver nanowire network.
また、本発明の透明導電体における優れた透明性は、本発明の形態制御剤除去方法では、光散乱を劣化させる銀ナノワイヤの凝集沈降や乾燥凝集が生じないためと思われる。 Further, the excellent transparency of the transparent conductor of the present invention is considered to be because the aggregation control agent removal method of the present invention does not cause aggregation and sedimentation of silver nanowires that deteriorate light scattering or dry aggregation.
また、透明導電体ＴＣＦ−０３と０４の比較から、本発明の製造方法において分散工程を実施することにより、導電性と透明性をさらに改良できることが判る。 Moreover, it turns out that electroconductivity and transparency can further be improved by implementing a dispersion | distribution process in the manufacturing method of this invention from the comparison of transparent conductor TCF-03 and 04.
比較例のＴＣＦ−０５と０６、およびＴＣＦ−０７と０８の関係をみると、デカンテーション法やフィルタリング法では、形態制御剤除去工程を２倍実施しても形態制御剤の残存率にあまり変化が認められない。これは、デカンテーション法やフィルタリング法では銀ナノワイヤ表面に吸着した形態制御剤を除去できないことを示唆するものである。また、デカンテーション法やフィルタリング法では、そのサイクルを増やすことによって、沈降凝集や乾燥凝集が発生し、むしろ導電性と透明性は劣化してしまう。 Looking at the relationship between TCF-05 and 06 of the comparative example and TCF-07 and 08, the decantation method and the filtering method change much in the residual rate of the form control agent even if the form control agent removal step is performed twice. Is not allowed. This suggests that the shape control agent adsorbed on the silver nanowire surface cannot be removed by the decantation method or the filtering method. In addition, in the decantation method and the filtering method, by increasing the number of cycles, sedimentation aggregation and dry aggregation occur, and rather conductivity and transparency are deteriorated.
以上のように、本発明の透明導電膜の製造方法によれば、優れた導電性と透明性を有する透明導電膜を製造することができる。 As mentioned above, according to the manufacturing method of the transparent conductive film of this invention, the transparent conductive film which has the outstanding electroconductivity and transparency can be manufactured.
Claims (6)
前記粒子形成工程は、
還元剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、金属の微粒子からなる核粒子を形成する核形成工程と、
還元剤、前記核粒子、および前記形態制御剤を含む溶液中に、少なくとも１種の金属塩溶液を添加して金属イオンを還元して、前記核形成工程において形成した前記核粒子をワイヤ状の形態を有する金属粒子に成長させる粒子成長工程と、
を含むことを特徴とする透明導電膜の製造方法。 In a method for producing a transparent conductive film having a conductive layer containing metal nanowires on a transparent support, the production method forms the metal nanowires in a solution containing a form control agent which is a hydrophilic polymer or an amphiphilic molecule. to include a step (particle forming step), and have a step (form control agent removing step) of removing the morphology control agent by diafiltration using an ultrafiltration membrane after the particle formation process,
The particle forming step includes
A nucleation step in which at least one metal salt solution is added to a solution containing a reducing agent to reduce metal ions to form core particles composed of metal fine particles;
At least one metal salt solution is added to a solution containing a reducing agent, the core particles, and the shape control agent to reduce metal ions, and the core particles formed in the nucleation step are formed into wire-like shapes. A particle growth step for growing metal particles having a shape;
The manufacturing method of the transparent conductive film characterized by including .
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| US10224126B2 (en) | 2014-10-07 | 2019-03-05 | Sharp Kabushiki Kaisha | Transparent conductor, method for producing transparent conductor, and touch panel |
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