JP5569607B2 - Transparent conductive film, transparent conductive film, and flexible transparent electrode - Google Patents
Transparent conductive film, transparent conductive film, and flexible transparent electrode Download PDFInfo
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- JP5569607B2 JP5569607B2 JP2013018942A JP2013018942A JP5569607B2 JP 5569607 B2 JP5569607 B2 JP 5569607B2 JP 2013018942 A JP2013018942 A JP 2013018942A JP 2013018942 A JP2013018942 A JP 2013018942A JP 5569607 B2 JP5569607 B2 JP 5569607B2
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- transparent conductive
- conductive film
- metal
- film
- transparent
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Description
本発明は、液晶表示素子、有機発光素子、無機電界発光素子、太陽電池、電磁波シールド、タッチパネル等の各種分野において好適に用いることができる、高い導電性と良好な透明性を併せ持つ透明導電膜であり、液相成膜により容易に製造できる透明導電膜に関するものであり、さらに、それを用いた透明導電性フィルム及びフレキシブル透明面電極に関するものである。 The present invention is a transparent conductive film having both high conductivity and good transparency, which can be suitably used in various fields such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, solar cells, electromagnetic wave shields, touch panels and the like. The present invention relates to a transparent conductive film that can be easily manufactured by liquid phase film formation, and further relates to a transparent conductive film and a flexible transparent surface electrode using the transparent conductive film.
透明導電性フィルムは、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ、エレクトロクロミックディスプレイ、太陽電池、タッチパネル、電子ペーパー等の透明電極、ならびに電磁波シールド材等に用いられている。 Transparent conductive films are used for liquid crystal displays, electroluminescence displays, plasma displays, electrochromic displays, solar cells, touch panels, transparent electrodes such as electronic paper, and electromagnetic shielding materials.
一般に透明導電材料としては、例えば金属酸化物が用いられており、具体的には、錫や亜鉛をドープした酸化インジウム（ＩＴＯ、ＩＺＯ）、アルミニウムやガリウムをドープした酸化亜鉛（ＡＺＯ、ＧＺＯ）、フッ素やアンチモンをドープした酸化錫（ＦＴＯ、ＡＴＯ）等が挙げられる。一般に、金属酸化物透明導電膜の作製には、真空蒸着法、スパッタリング法、イオンプレーティング法等の気相成膜法が用いられる。しかしながら、これらの成膜方法は真空環境を必要とするため装置が大掛りかつ複雑なものとなり、また成膜に大量のエネルギーを消費するため、製造コストや環境負荷を軽減できる技術の開発が求められていた。また、一方で、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、透明導電材料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た。さらに、大面積の透明電極においては、透明電極の電圧降下の影響が大きくなり、さらなる低抵抗化が求められてきた。 In general, for example, a metal oxide is used as the transparent conductive material. Specifically, indium oxide doped with tin or zinc (ITO, IZO), zinc oxide doped with aluminum or gallium (AZO, GZO), Examples thereof include tin oxide (FTO, ATO) doped with fluorine or antimony. In general, a vapor-phase film forming method such as a vacuum deposition method, a sputtering method, or an ion plating method is used for producing a metal oxide transparent conductive film. However, these film formation methods require a vacuum environment, which makes the apparatus large and complicated, and also consumes a large amount of energy for film formation, so the development of technology that can reduce manufacturing costs and environmental burdens is required. It was done. On the other hand, as represented by a liquid crystal display and a touch display, an increase in the area of the transparent conductive material is aimed at, and accordingly, demands for weight reduction and flexibility of the transparent conductive material have increased. Furthermore, in a large-area transparent electrode, the effect of the voltage drop of the transparent electrode becomes large, and further reduction in resistance has been demanded.
このような要請に対して、導電性微粒子を含有する液状材料を用いて塗布や印刷のような液相成膜法により透明導電膜を形成する方法が提案されている。 In response to such a demand, a method of forming a transparent conductive film by a liquid phase film forming method such as coating or printing using a liquid material containing conductive fine particles has been proposed.
しかしながら、従来の方法では、塗布液を塗布し乾燥して塗膜を形成した後、高導電率の導電性被膜を作製するためには、２００℃以上の加熱処理を施す必要があった。樹脂をはじめとする高分子材料をこのような高温にさらすと、変形や溶融、劣化等の損傷を受けることから、プラスチックフィルムのような樹脂基材上に透明導電膜を形成する場合には適用できない。 However, in the conventional method, after a coating solution is applied and dried to form a coating film, a heat treatment at 200 ° C. or higher is required to produce a conductive film having a high conductivity. When polymer materials such as resins are exposed to such high temperatures, they are damaged by deformation, melting, deterioration, etc., so it is applicable when forming a transparent conductive film on a resin substrate such as a plastic film. Can not.
液相成膜に適した透明導電材料として、π共役系高分子に代表される導電性高分子材料が挙げられる。導電性高分子材料を用いると、適当な溶媒に溶解または分散し、必要に応じてバインダー成分を加えて塗布や印刷することによって透明導電素子を形成することができる。しかし、真空成膜法によるＩＴＯやＺｎＯ等の金属酸化物透明導電素子に対しても導電性は劣りかつ透明性にも劣る。 Examples of transparent conductive materials suitable for liquid phase film formation include conductive polymer materials typified by π-conjugated polymers. When a conductive polymer material is used, a transparent conductive element can be formed by dissolving or dispersing in a suitable solvent and adding or printing a binder component as necessary. However, the conductivity is inferior to the metal oxide transparent conductive elements such as ITO and ZnO formed by the vacuum film forming method, and the transparency is also inferior.
金属酸化物や導電性高分子に比べ、Ａｇ、Ｃｕ、Ａｕ等の金属材料の導電率は２桁以上高く、導電性の観点では好ましいが、透明性を確保できないという問題があった。それに対して、均質な金の超薄膜を形成することにより導電性と透明性を両立できることが報告されている。しかし、均質な金の超薄膜を形成するには、デュアルイオンビームスパッタ法という特殊な真空成膜法が必要であり、製造コストや環境負荷の軽減は実現できない。 Compared to metal oxides and conductive polymers, the conductivity of metal materials such as Ag, Cu, and Au is two orders of magnitude higher, which is preferable from the viewpoint of conductivity, but has a problem that transparency cannot be secured. On the other hand, it has been reported that both conductivity and transparency can be achieved by forming a uniform ultra-thin gold film. However, in order to form a uniform ultra-thin gold film, a special vacuum film forming method called a dual ion beam sputtering method is required, and reduction of manufacturing cost and environmental load cannot be realized.
さらに、酸化銀と還元剤を含有する導電性組成物を塗布した後、加熱処理することにより導電性皮膜を形成する技術が開示されている（例えば、特許文献１参照）。この技術によれば、比較的低温の加熱処理で導電性が発現することから、プラスチックフィルムのような樹脂基材上に透明導電膜を形成する場合に好ましい技術ではある。しかしながら、粒子接合界面でのロスは完全にはなくならないため、金属本来の導電性は発現できていない。さらに、面電極として面全体に導電性皮膜を形成すると透明性は得られない。 Furthermore, a technique for forming a conductive film by applying a conductive composition containing silver oxide and a reducing agent and then performing heat treatment is disclosed (for example, see Patent Document 1). According to this technique, since conductivity is exhibited by a heat treatment at a relatively low temperature, it is a preferable technique when a transparent conductive film is formed on a resin substrate such as a plastic film. However, since the loss at the particle bonding interface is not completely eliminated, the original conductivity of the metal cannot be expressed. Further, if a conductive film is formed on the entire surface as a surface electrode, transparency cannot be obtained.
また、液相成膜が可能な透明導電材料技術として、ＣＮＴ（カーボンナノチューブ）や金属ナノワイヤを導電体として用いる方法（例えば、特許文献２〜７参照）が提案されている。ＣＮＴや金属ナノワイヤのような導電性繊維を導体として用いる透明導電材料においては、導電性繊維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。従って、理想的には全ての導電性繊維が他の導電性繊維と少なくとも２つ以上の接点を有して、空間的に広く分布してネットワークを形成している状態であることが、導電性と透明性を両立するために好ましい。しかし、導電性繊維のネットワーク形成を制御できないため、満足できる導電性を得ることが難しかった。 Further, as a transparent conductive material technology capable of liquid phase film formation, a method using CNT (carbon nanotube) or metal nanowire as a conductor (for example, see Patent Documents 2 to 7) has been proposed. In a transparent conductive material using conductive fibers such as CNTs and metal nanowires as a conductor, conductivity is exhibited by forming an electrical network between the conductive fibers. Therefore, ideally, all the conductive fibers have at least two or more contacts with other conductive fibers, and are in a state where they are widely distributed spatially to form a network. And transparency are preferable. However, it is difficult to obtain satisfactory conductivity because the network formation of the conductive fibers cannot be controlled.
本発明の目的は、高い導電性と良好な透明性を併せ持ち、液相成膜により容易に製造できる透明導電膜を提供することにあり、さらに、この透明導電膜を用いた透明導電性フィルム、さらには大面積においても電極での電圧降下が抑えられたフレキシブル透明面電極を提供することにある。 An object of the present invention is to provide a transparent conductive film that has both high conductivity and good transparency and can be easily produced by liquid phase film formation. Further, a transparent conductive film using the transparent conductive film, Furthermore, it is providing the flexible transparent surface electrode by which the voltage drop in an electrode was suppressed also in a large area.
本発明の上記目的は、以下の構成により達成することができる。 The above object of the present invention can be achieved by the following configuration.
１．金属ナノワイヤ及び金属微粒子を含む透明導電膜において、少なくとも該金属ナノワイヤ、粒状金属化合物及び還元剤を含有する塗布膜を加熱処理することにより、少なくとも一部の金属ナノワイヤが該粒状金属化合物から生成した金属微粒子を介して接合していることを特徴とする透明導電膜。 1. In a transparent conductive film containing metal nanowires and fine metal particles, at least a part of the metal nanowires is produced from the granular metal compound by heat-treating a coating film containing at least the metal nanowires, the granular metal compound and the reducing agent. A transparent conductive film which is bonded through fine particles.
２．前記塗布膜が、少なくとも金属ナノワイヤ、粒状金属化合物及び還元剤を含有する塗布液を基材上に塗布乾燥して得られることを特徴とする前記１記載の透明導電膜。 2. 2. The transparent conductive film according to 1 above, wherein the coating film is obtained by coating and drying a coating solution containing at least metal nanowires, a granular metal compound and a reducing agent on a substrate.
３．少なくとも金属ナノワイヤを含有する塗布液を基材上に塗布乾燥した後、少なくとも粒状金属化合物及び還元剤を含有する塗布液を金属ナノワイヤ塗布膜上に塗布し、さらに、加熱処理することにより、少なくとも一部の金属ナノワイヤが該粒状金属化合物から生成した金属微粒子を介して接合していることを特徴とする前記１記載の透明導電膜。 3. After coating and drying a coating solution containing at least metal nanowires on a substrate, at least one coating solution containing at least a granular metal compound and a reducing agent is coated on the metal nanowire coating film and further subjected to heat treatment. 2. The transparent conductive film according to 1 above, wherein the metal nanowires of the portion are bonded via metal fine particles generated from the granular metal compound.
４．透明樹脂フィルム上に、前記１〜３のいずれか１項記載の透明導電膜を有することを特徴とする透明導電性フィルム。 4). The transparent conductive film which has a transparent conductive film of any one of said 1-3 on a transparent resin film.
５．前記透明導電膜上に、さらに導電性高分子または導電性微粒子含有層が積層されていることを特徴とする前記４記載の透明導電性フィルム。 5. 5. The transparent conductive film according to 4, wherein a conductive polymer or a conductive fine particle-containing layer is further laminated on the transparent conductive film.
６．前記４または５記載の透明導電性フィルムを用いることを特徴とするフレキシブル透明面電極。 6). 6. The transparent transparent electrode according to claim 4, wherein the transparent conductive film is used.
本発明によれば、高い導電性と良好な透明性を併せ持ち、液相成膜により容易に製造できる透明導電膜、さらに、この透明導電膜を用いた透明導電性フィルム、さらには大面積においても電極での電圧降下が抑えられたフレキシブル透明面電極を提供することができる。 According to the present invention, a transparent conductive film that has both high conductivity and good transparency and can be easily manufactured by liquid phase film formation, a transparent conductive film using this transparent conductive film, and even a large area A flexible transparent electrode in which a voltage drop at the electrode is suppressed can be provided.
本発明者は、上記課題に鑑み鋭意検討を行った結果、金属ナノワイヤ及び金属微粒子を含む透明導電膜において、少なくとも該金属ナノワイヤ、粒状金属化合物及び還元剤を含有する塗布膜を加熱処理することにより、少なくとも一部の金属ナノワイヤが該粒状金属化合物から生成した金属微粒子を介して接合している透明導電膜により、高い導電性と良好な透明性を併せ持ち、液相成膜により容易に製造できる透明導電膜が得られることを見出し、本発明に至った次第である。 As a result of intensive studies in view of the above problems, the present inventors have conducted heat treatment on a coating film containing at least the metal nanowire, the granular metal compound, and the reducing agent in the transparent conductive film containing the metal nanowire and the metal fine particles. The transparent conductive film in which at least a part of the metal nanowires are bonded through the metal fine particles generated from the granular metal compound has both high conductivity and good transparency, and can be easily manufactured by liquid phase film formation. It has been found that a conductive film can be obtained and has reached the present invention.
本発明の透明導電膜は、還元剤と粒状金属化合物を加熱処理することにより生成した金属微粒子を介して金属ナノワイヤが接合していることを特徴とする透明導電膜である。本発明によれば、２００℃未満の比較的低温の加熱処理でも、金属ナノワイヤが接合されることから、プラスチックフィルムのような透明脂基材上に透明導電膜を形成することが可能となる。 The transparent conductive film of the present invention is a transparent conductive film in which metal nanowires are bonded via fine metal particles generated by heat-treating a reducing agent and a granular metal compound. According to the present invention, since the metal nanowires are bonded even by heat treatment at a relatively low temperature of less than 200 ° C., a transparent conductive film can be formed on a transparent fat substrate such as a plastic film.
なお、本願において「接合している」とは、金属ナノワイヤや金属微粒子が融着して、電気的に一つの連続体と看做せる状態を意味する。単に接触している場合には、接触抵抗による導電性のロスが発生するが、接合体の場合にはその影響がないため導電性を向上できる。 In the present application, “bonded” means a state in which metal nanowires or metal fine particles are fused and can be regarded as one continuous body electrically. In the case of simple contact, a loss of conductivity due to contact resistance occurs, but in the case of a joined body, there is no influence, so that the conductivity can be improved.
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等について詳細な説明をする。 Hereinafter, the present invention, its components, and the best mode for carrying out the present invention will be described in detail.
〔金属ナノワイヤ〕
本発明の透明導電膜において、金属ナノワイヤは主要な導電体として機能する。本発明では、金属ナノワイヤの金属元素として、バルク状態での導電率が１×１０６Ｓ／ｍ以上の元素を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金属ナノワイヤの金属元素として具体例としては、Ａｇ、Ｃｕ、Ａｕ、Ａｌ、Ｒｈ、Ｉｒ、Ｃｏ、Ｚｎ、Ｎｉ、Ｉｎ、Ｆｅ、Ｐｄ、Ｐｔ、Ｓｎ、Ｔｉ等を挙げることができる。本発明においては２種類以上の金属ナノワイヤを組み合わせて用いることもできるが、導電性の観点から、少なくともＡｇ、Ｃｕ、Ａｕ、Ａｌ、Ｃｏより選択される金属元素を用いることが好ましい。
[Metal nanowires]
In the transparent conductive film of the present invention, the metal nanowire functions as a main conductor. In the present invention, an element having a bulk conductivity of 1 × 10 6 S / m or more can be used as the metal element of the metal nanowire. Specific examples of metal elements of the metal nanowire that can be preferably used in the present invention include Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, Ti, and the like. Can be mentioned. In the present invention, two or more kinds of metal nanowires can be used in combination, but from the viewpoint of conductivity, it is preferable to use at least a metal element selected from Ag, Cu, Au, Al, and Co.
本発明において、金属ナノワイヤの製造手段には特に制限はなく、例えば、液相法や気相法等の公知の手段を用いることができる。また、具体的な製造方法にも特に制限はなく、公知の製造方法を用いることができる。例えば、Ａｇナノワイヤの製造方法としては、Ａｄｖ．Ｍａｔｅｒ．，２００２，１４，８３３〜８３７；Ｃｈｅｍ．Ｍａｔｅｒ．，２００２，１４，４７３６〜４７４５等、Ａｕナノワイヤの製造方法としては特開２００６−２３３２５２号公報等、Ｃｕナノワイヤの製造方法としては特開２００２−２６６００７号公報等、Ｃｏナノワイヤの製造方法としては特開２００４−１４９８７１号公報等を参考にすることができる。特に、上述した、Ａｄｖ．Ｍａｔｅｒ．及びＣｈｅｍ．Ｍａｔｅｒ．で報告されたＡｇナノワイヤの製造方法は、水系で簡便にかつ大量に銀ナノワイヤを製造することができ、また銀の導電率は金属中で最大であることから、本発明に関わる金属ナノワイヤの製造方法として好ましく適用することができる。 In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can produce silver nanowires easily and in large quantities in an aqueous system, and the conductivity of silver is the largest among metals, so that the production of metal nanowires according to the present invention is possible. It can be preferably applied as a method.
本発明において金属ナノワイヤの平均直径は、透明性の観点から２００ｎｍ以下であることが好ましく、導電性の観点から１０ｎｍ以上であることが好ましい。平均直径が２００ｎｍ以下であれば光散乱の影響を軽減でき、平均直径がより小さい方が光透過率低下やヘイズ劣化を抑制することができるため好ましい。一方で、平均直径が１０ｎｍ以上であれば導電体としての機能を有意に発現でき、平均直径がより大きい方が導電性が向上するため好ましい。従って、より好ましくは２０〜１５０ｎｍであり、４０〜１５０ｎｍであることがさらに好ましい。 In the present invention, the average diameter of the metal nanowires is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. If the average diameter is 200 nm or less, the influence of light scattering can be reduced, and a smaller average diameter is preferable because light transmittance reduction and haze deterioration can be suppressed. On the other hand, if the average diameter is 10 nm or more, the function as a conductor can be expressed significantly, and a larger average diameter is preferable because conductivity is improved. Therefore, it is more preferably 20 to 150 nm, and further preferably 40 to 150 nm.
本発明において金属ナノワイヤの平均長さは、導電性の観点から１μｍ以上であることが好ましく、凝集による透明性への影響から１００μｍ以下であることが好ましい。より好ましくは１〜５０μｍであり、３〜５０μｍであることがさらに好ましい。 In the present invention, the average length of the metal nanowires is preferably 1 μm or more from the viewpoint of conductivity, and preferably 100 μm or less from the viewpoint of the effect on the transparency due to aggregation. More preferably, it is 1-50 micrometers, and it is still more preferable that it is 3-50 micrometers.
本発明において上記金属ナノワイヤの平均直径及び平均長さは、ＳＥＭやＴＥＭを用いて十分な数のナノワイヤについて電子顕微鏡写真を撮影し、個々の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。ナノワイヤの長さは、本来直線状に伸ばした状態で求めるべきであるが、現実には屈曲している場合が多いため、電子顕微鏡写真から画像解析装置を用いてナノワイヤの投影径及び投影面積を算出し、円柱体を仮定して算出する（長さ＝投影面積／投影径）ものとする。計測対象のナノワイヤ数は、少なくとも１００個以上が好ましく、３００個以上のナノワイヤを計測するのがさらに好ましい。 In the present invention, the average diameter and average length of the metal nanowires can be obtained from the arithmetic average of the measured values of individual nanowire images by taking electron micrographs of a sufficient number of nanowires using SEM or TEM. The length of the nanowire should be calculated in a straight line, but in reality, it is often bent, so the projection diameter and projected area of the nanowire can be determined from an electron micrograph using an image analyzer. The calculation is performed assuming a cylindrical body (length = projected area / projected diameter). The number of nanowires to be measured is preferably at least 100 or more, and more preferably 300 or more nanowires.
〔粒状金属化合物〕
本発明で用いられる粒状金属化合物の具体的なものとしては、金属酸化物、金属塩、金属錯体等を挙げることができる。金属種としては前述の金属ナノワイヤで挙げた金属種を好ましく用いることができる。本発明においては２種類以上の金属微粒子を組み合わせて用いることもできるが、導電性の観点から、少なくともＡｇ、Ｃｕ、Ａｕ、Ａｌ、Ｃｏより選択される元素を用いることが好ましい。例えば金属種として銀を用いる場合は、粒状金属化合物としては酸化第１銀、酸化第２銀、炭酸銀、酢酸銀、アセチルアセトン銀錯体等が使用できる。これらの粒子状銀化合物を単体、または２種類以上混合して用いることができる。なお、これらの粒子状銀化合物は、製造手段には特に制限はなく、例えば、液相法や気相法等の公知の手段を用いることができる。また、具体的な製造方法にも特に制限はなく、公知の製造方法を用いることができる。
[Granular metal compound]
Specific examples of the particulate metal compound used in the present invention include metal oxides, metal salts, metal complexes and the like. As the metal species, the metal species mentioned in the above-mentioned metal nanowire can be preferably used. In the present invention, two or more kinds of metal fine particles can be used in combination, but from the viewpoint of conductivity, it is preferable to use at least an element selected from Ag, Cu, Au, Al, and Co. For example, when silver is used as the metal species, as the granular metal compound, first silver oxide, second silver oxide, silver carbonate, silver acetate, acetylacetone silver complex and the like can be used. These particulate silver compounds can be used alone or in admixture of two or more. In addition, there is no restriction | limiting in particular in a manufacturing means for these particulate silver compounds, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.
これらの粒子状銀化合物の好ましい平均粒径は０．００１〜１μｍであり、還元反応における加熱温度、用いる還元剤の還元力、透明性への影響、分散性等に応じて適宜選択される。特に、還元反応の速度が速くなることや金属ナノワイヤに対する金属微粒子の個数の関係から、平均粒径が０．５μｍ以下であることがより好ましく、さらに、透明性の観点からは０．１μｍ以下であることがより好ましい。また、分散性や導電性の視点からは０．０１μｍ以上であることがより好ましい。 A preferable average particle diameter of these particulate silver compounds is 0.001 to 1 μm, and is appropriately selected according to the heating temperature in the reduction reaction, the reducing power of the reducing agent used, the influence on transparency, dispersibility, and the like. In particular, the average particle size is more preferably 0.5 μm or less from the viewpoint of the speed of the reduction reaction and the number of metal fine particles with respect to the metal nanowires. Furthermore, from the viewpoint of transparency, the average particle size is 0.1 μm or less. More preferably. Moreover, it is more preferable that it is 0.01 micrometer or more from a viewpoint of dispersibility or electroconductivity.
粒状金属化合物は、透明導電膜中で金属ナノワイヤと金属微粒子の比率は特に制限はないが、例えば質量比で１００：１００〜１００：０．１の範囲で、導電性、熱処理条件、透明性等を考慮して適宜決めることができる。なお、金属微粒子の比率が金属ナノワイヤよりも多くなると透明性が劣ったものとなり、また、１００：０．１よりも小さいと導電性向上効果が小さくなる。 The ratio of the metal nanowires to the metal fine particles in the transparent conductive film is not particularly limited, but for example, the mass ratio is in the range of 100: 100 to 100: 0.1, and the conductivity, heat treatment conditions, transparency, etc. Can be determined as appropriate. In addition, when the ratio of the metal fine particles is larger than that of the metal nanowires, the transparency is inferior, and when the ratio is smaller than 100: 0.1, the conductivity improving effect is reduced.
〔還元剤〕
本発明で用いられる還元剤は、粒状金属化合物を還元するもので、還元反応後の副生成物が気体や揮発性の高い液体となり、生成した導電性膜内に残留しないものが好ましい。このような還元剤の具体的な例としては、エチレングリコール、ホルマリン、ヒドラジン、アスコルビン酸、各種アルコール等が挙げられる。これらの還元剤は、液体であれば溶媒としても用いることができ、このような例としては、エチレングリコール等が挙げられる。
[Reducing agent]
The reducing agent used in the present invention is for reducing the particulate metal compound, and it is preferable that the by-product after the reduction reaction is a gas or a highly volatile liquid and does not remain in the generated conductive film. Specific examples of such a reducing agent include ethylene glycol, formalin, hydrazine, ascorbic acid, various alcohols, and the like. These reducing agents can be used as solvents as long as they are liquid, and examples of such reducing agents include ethylene glycol.
還元剤の使用量は、粒状金属化合物１モルに対して０．０１〜２０モル程度とすることが望ましい。還元反応の効率や、加熱によって揮発することを考慮すると、還元剤を粒状金属化合物と等モルより多めに添加することが望ましいが、最大２０モルを超えて添加しても効果が飽和し、不経済である。一方、還元剤の使用量が、粒状金属化合物１モルに対して０．０１モル未満では、還元反応が十分に進行せず、結果として、金属微粒子の形成が不十分となり、金属ナノワイヤ間の接合が不十分となる。 As for the usage-amount of a reducing agent, it is desirable to set it as about 0.01-20 mol with respect to 1 mol of granular metal compounds. Considering the efficiency of the reduction reaction and volatilization by heating, it is desirable to add the reducing agent in an amount larger than the equimolar amount with the granular metal compound. It is an economy. On the other hand, when the amount of the reducing agent used is less than 0.01 mol with respect to 1 mol of the granular metal compound, the reduction reaction does not proceed sufficiently, and as a result, the formation of metal fine particles becomes insufficient and the metal nanowires are joined. Is insufficient.
上記の還元剤の中には、還元力が高いものがある。その場合は、少なくとも粒状金属化合物及び還元剤を含有する塗布液を塗布する直前に、粒状金属化合物を含む主剤と還元剤を含む副剤を混合すれば、塗布液の保管や塗布の間に、還元反応が起こるのを大幅に抑えることができる。 Some of the above reducing agents have a high reducing power. In that case, immediately before applying the coating liquid containing at least the particulate metal compound and the reducing agent, if the main agent containing the particulate metal compound and the auxiliary agent containing the reducing agent are mixed, during storage and application of the coating liquid, The reduction reaction can be greatly suppressed.
少なくとも金属ナノワイヤを含有する塗布液と、少なく粒状金属化合物及び還元剤を含有する塗布液は一つの液とすることで、塗布乾燥工程が簡略化できて好ましい。一方、別の液として、先に金属ナノワイヤ膜を形成した後に、少なく粒状金属化合物及び還元剤を含有する塗布液を金属ナノワイヤ膜上に塗布することも、各液の分散安定性、造膜性、等を考慮して適宜添加剤や媒質を選択できることから好ましい。 It is preferable that the coating solution containing at least the metal nanowires and the coating solution containing a small amount of the granular metal compound and the reducing agent are made into one solution, whereby the coating and drying process can be simplified. On the other hand, after forming a metal nanowire film as a separate liquid, a coating liquid containing a small amount of a granular metal compound and a reducing agent may be applied onto the metal nanowire film. In view of the above, it is preferable because an additive and a medium can be appropriately selected.
本発明に係る粒状金属化合物は還元剤の存在下で、比較的低温で加熱することにより、容易に金属に還元される。そして、この還元反応時に生じる反応熱によって、還元反応によって形成された金属微粒子が溶融し、隣接する金属ナノワイヤに融着して金属ナノワイヤを結合させる。金属ナノワイヤ自身はバルク金属に近い導電性を示し、また、金属微粒子と金属ナノワイヤの結合部も接触抵抗を低くすることができることから、高い導電性の導電性膜を形成できる。なお、粒状金属化合物は塗布膜乾燥時には表面張力の関係から金属ナノワイヤの交点付近に析出しやすいため、効率的に金属ナノワイヤを結合させることができる。 The granular metal compound according to the present invention is easily reduced to a metal by heating at a relatively low temperature in the presence of a reducing agent. Then, the metal fine particles formed by the reduction reaction are melted by the reaction heat generated during the reduction reaction, and are fused to the adjacent metal nanowires to bond the metal nanowires. Since the metal nanowire itself exhibits conductivity close to that of a bulk metal, and the bonding portion between the metal fine particles and the metal nanowire can also reduce the contact resistance, a highly conductive film can be formed. In addition, since a granular metal compound is easy to precipitate near the intersection of metal nanowire from the relationship of surface tension at the time of coating film drying, a metal nanowire can be combined efficiently.
加熱処理条件としては１２０〜２００℃で、好ましくは１４０〜１６０℃、処理時間は３０秒〜１２０分である。処理方法は、フィルムをロール形態で処理する方法や搬送しながら処理する方法等を用いることができる。特に、搬送しながら処理する方法では、テンタリング法や搬送張力の調整等により、基材の熱変形を抑制することが可能となるので好ましく用いることができる。 The heat treatment conditions are 120 to 200 ° C., preferably 140 to 160 ° C., and the treatment time is 30 seconds to 120 minutes. As a processing method, a method of processing a film in a roll form, a method of processing while transporting, or the like can be used. In particular, the method of processing while transporting can be preferably used because thermal deformation of the substrate can be suppressed by a tentering method, adjustment of transport tension, or the like.
本発明においては、加熱処理の前後で粒状金属化合物の形状が変化する場合があり、金属ナノワイヤや金属微粒子の粒径や材質、接合操作時の様々な条件等によって多様な接合状態を形成することができる。例えば、本発明において「少なくとも一部の金属ナノワイヤが該金属化合物から生成した金属微粒子を介して接合している」状態とは、ａ）少なくとも１つの金属微粒子が、加熱処理前の粒状金属化合物の形状をほとんど保持したままで２つ以上の金属ナノワイヤに接合している状態や、ｂ）少なくとも１つの金属微粒子が、加熱処理前の粒状金属化合物とは大きく形状を変えて２つ以上の金属ナノワイヤに接合している状態、ｃ）複数の金属微粒子が、紐状に連なって２つ以上の金属ナノワイヤに接合している状態、ｄ）複数の金属微粒子が、凝集した状態で２つ以上の金属ナノワイヤに接合している状態等をいう。 In the present invention, the shape of the granular metal compound may change before and after the heat treatment, and various bonding states are formed depending on the particle diameter and material of the metal nanowires and metal fine particles, various conditions during the bonding operation, and the like. Can do. For example, in the present invention, the state that “at least a part of the metal nanowires are bonded via the metal fine particles generated from the metal compound” refers to a) at least one metal fine particle of the granular metal compound before the heat treatment A state in which the shape is almost retained and bonded to two or more metal nanowires; and b) two or more metal nanowires in which at least one metal fine particle is greatly changed in shape from the granular metal compound before the heat treatment. C) a state in which a plurality of metal fine particles are connected to two or more metal nanowires in a string, d) a state in which a plurality of metal fine particles are aggregated and two or more metals This refers to the state of being bonded to the nanowire.
本発明において、透明導電膜における金属ナノワイヤと金属微粒子の換算膜厚は、導電性と透明性の関係から５〜１００ｎｍであることが好ましく、１０〜８０ｎｍであることがより好ましい。ここで換算膜厚とは、透明導電素子単位面積当たりの金属ナノワイヤ及び金属微粒子の平均質量と等しい質量を有する均一な金属膜の厚みを意味する。 In the present invention, the equivalent film thickness of the metal nanowires and the metal fine particles in the transparent conductive film is preferably 5 to 100 nm, more preferably 10 to 80 nm, from the relationship between conductivity and transparency. Here, the equivalent film thickness means the thickness of a uniform metal film having a mass equal to the average mass of the metal nanowires and metal fine particles per unit area of the transparent conductive element.
（透明樹脂）
また、本発明の透明導電膜は、金属ナノワイヤと金属微粒子の他に、透明樹脂を含有してもよい。透明樹脂としては、ポリエステル系樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリウレタン系樹脂、アクリルウレタン系樹脂、ポリカーボネート系樹脂、セルロース系樹脂、ブチラール系樹脂等を単独あるいは複数併用して用いることができる。これらは、少なくとも金属ナノワイヤ、粒状金属化合物及び還元剤を含有する塗布液や、少なくとも金属ナノワイヤを含有する塗布液、少なくとも粒状金属化合物と還元剤を含有する塗布液等に含有させることもできるが、別の塗布液として準備してオーバーコートしてもよい。塗布量としては、金属ナノワイヤが完全には埋もれてしまわない量であることが好ましい。
(Transparent resin)
The transparent conductive film of the present invention may contain a transparent resin in addition to the metal nanowires and the metal fine particles. As the transparent resin, a polyester resin, a polystyrene resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, a polycarbonate resin, a cellulose resin, a butyral resin, or the like can be used alone or in combination. These can be contained in a coating solution containing at least a metal nanowire, a granular metal compound and a reducing agent, a coating solution containing at least a metal nanowire, a coating solution containing at least a granular metal compound and a reducing agent, etc. You may prepare as another coating liquid and may overcoat. The coating amount is preferably such an amount that the metal nanowires are not completely buried.
〔導電性高分子化合物〕
本発明の透明導電膜は、金属ナノワイヤ及び金属微粒子を含む透明導電膜の他に、導電性高分子化合物や導電性微粒子含有層を積層してもよい。これは、金属ナノワイヤ及び金属微粒子を含む透明導電膜のどちらの側に設けてもよいが、金属ナノワイヤ及び金属微粒子を含む透明導電膜の少なくとも一部が、導電性高分子化合物あるいは導電性微粒子含有層と重なっていることがより好ましい。例えば、金属ナノワイヤ及び金属微粒子を含む透明導電膜上に、導電性高分子化合物や導電性微粒子含有塗布液をオーバーコートすることにより形成できる。前述のように、透明樹脂を金属ナノワイヤが完全には埋もれてしまわない量含んだ金属ナノワイヤ及び金属微粒子を含む透明導電膜上に、導電性高分子化合物や導電性微粒子含有塗布液を金属ナノワイヤが完全に埋もれる量オーバーコートすれば、導電性高分子化合物や導電性微粒子含有層による透明性の低下を最低限に収めつつ、かつ、表面を平坦化できるのでより好ましい形態となる。
[Conductive polymer compound]
The transparent conductive film of the present invention may be formed by laminating a conductive polymer compound or a conductive fine particle-containing layer in addition to the transparent conductive film containing metal nanowires and metal fine particles. This may be provided on either side of the transparent conductive film containing metal nanowires and metal fine particles, but at least part of the transparent conductive film containing metal nanowires and metal fine particles contains a conductive polymer compound or conductive fine particles. More preferably, it overlaps the layer. For example, it can be formed by overcoating a conductive polymer compound or a coating solution containing conductive fine particles on a transparent conductive film containing metal nanowires and metal fine particles. As described above, the conductive polymer compound or the conductive fine particle-containing coating solution is applied to the metal nanowire on the metal nanowire and the transparent conductive film containing the metal fine particles containing the transparent resin in an amount that the metal nanowire is not completely buried. Overcoating in an amount that can be completely buried provides a more preferable form because the surface can be flattened while minimizing the decrease in transparency due to the conductive polymer compound or the conductive fine particle-containing layer.
本発明に用いられる導電性高分子としては、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からなる群より選ばれる化合物を挙げることができる。これらの導電性高分子は、１種類を単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。 Examples of the conductive polymer used in the present invention include polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene. And a compound selected from the group consisting of polynaphthalene. One type of these conductive polymers may be used alone, or two or more types may be used in combination.
本発明においては、上記導電性高分子の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、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。中でも、上記長鎖スルホン酸が好ましい。 In the present invention, a doping treatment can be performed in order to further increase the conductivity of the conductive polymer. 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 “long-chain sulfonic acid”) or a polymer thereof (for example, polystyrene sulfonic acid), halogen , 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、本発明の透明導電膜は、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（あるいは増感剤）と称する場合がある。本発明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。中でも、ジメチルスルホキシド、エチレングリコール、ジエチレングリコールから選ばれる少なくとも１種を用いることが特に好ましい。 Moreover, 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 referred to as a dopant (or sensitizer). 2nd. Which can be used in 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. Among these, it is particularly preferable to use at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol.
導電性微粒子としては、透明性から無機半導体微粒子であることが好ましく、例えば、錫や亜鉛をドープした酸化インジウム（ＩＴＯ、ＩＺＯ）、アルミニウムやガリウムをドープした酸化亜鉛（ＡＺＯ、ＧＺＯ）、フッ素やアンチモンをドープした酸化錫（ＦＴＯ、ＡＴＯ）等の微粒子を挙げることができる。 The conductive fine particles are preferably inorganic semiconductor fine particles because of transparency. For example, indium oxide doped with tin or zinc (ITO, IZO), zinc oxide doped with aluminum or gallium (AZO, GZO), fluorine, Examples thereof include fine particles such as tin oxide (FTO, ATO) doped with antimony.
〔添加剤〕
本発明の、金属ナノワイヤ及び金属微粒子を含む透明導電膜においてには、目的に応じて、可塑剤、酸化防止剤等の安定剤、マイグレーション防止剤、界面活性剤、分散剤、染料や顔料等の着色剤等の添加物を含んでいてもよい。
〔Additive〕
In the transparent conductive film containing metal nanowires and metal fine particles of the present invention, depending on the purpose, stabilizers such as plasticizers, antioxidants, migration inhibitors, surfactants, dispersants, dyes and pigments, etc. An additive such as a colorant may be included.
〔疎水化処理〕
本発明においては、水系にて製造した金属ナノワイヤや金属ナノ粒子を、必要に応じて疎水化処理することができる。例えば、金属ナノワイヤを疎水化処理する方法としては、特開２００７−５００６０６号公報等を参考にできる。金属ナノ粒子を疎水化する方法としては、特開２００６−２９９３２９号公報等を参考にできる。
[Hydrophobic treatment]
In the present invention, metal nanowires and metal nanoparticles produced in an aqueous system can be hydrophobized as necessary. For example, as a method for hydrophobizing metal nanowires, JP 2007-500606 A can be referred to. JP, 2006-299329, A, etc. can be referred as a method of hydrophobizing metal nanoparticles.
〔液相成膜法〕
透明な樹脂支持体（以後、単に透明な支持体もしくは支持体ともいう）上に、本発明の透明導電膜を成膜する方法としては、高生産性と生産コスト低減の両立、及び環境負荷軽減の観点から、塗布法や印刷法等の液相成膜法を用いることが好ましい。塗布法としては、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、ドクターコート法等を用いることができる。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、スプレー印刷法、インクジェット印刷法等を用いることができる。
[Liquid phase deposition]
As a method of forming the transparent conductive film of the present invention on a transparent resin support (hereinafter also simply referred to as a transparent support or support), both high productivity and reduction in production cost are achieved, and environmental load is reduced. From this point of view, it is preferable to use a liquid phase film forming method such as a coating method or a printing method. As coating methods, 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, spray coating method, doctor coating method Etc. can be used. As a printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, or the like can be used.
液相成膜法で透明導電膜を形成した後、適宜乾燥処理を施すことができる。乾燥処理の条件として特に制限はないが、透明樹脂支持体や透明導電膜が損傷しない範囲の温度で処理することが好ましい。また、本発明に係る金属ナノワイヤ及び金属微粒子を含む透明導電膜を形成した後、いずれかのタイミングで必要に応じて加圧または加圧加熱処理処理を施すこともできる。これにより、より高い導電性を得たり、表面の平滑化が可能となる。加圧に際しては、プレート上でプレートで加圧する面／面加圧、ロールとロールの間に基材フィルムを通過させながら加圧させるニップロール加圧、プレート上をロールで加圧する組み合わせた加圧を採用することができる。また、加圧に際して加熱すると効果的になるので、４０〜３００℃の範囲で加熱することが好ましい。特に透明樹脂を併用する場合は、透明樹脂のＴｇ以上に加熱することが好ましい。加熱の時間は温度との関係で調節されて、高い温度では短く、低温では長くというようにすることができる。加熱の方法は、ニップロールの場合には、ロールを予め所定の温度に加熱しておく方法やオートクレーブ室のような加熱室内で加熱する方法がある。 After forming a transparent conductive film by a liquid phase film-forming method, a drying process can be suitably performed. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to process at the temperature of the range which does not damage a transparent resin support body and a transparent conductive film. Moreover, after forming the transparent conductive film containing the metal nanowire and the metal fine particles according to the present invention, it is possible to perform pressurization or pressure heat treatment as needed at any timing. Thereby, higher conductivity can be obtained and the surface can be smoothed. In pressurization, surface-to-surface pressurization with the plate on the plate, nip roll pressurization with the base film passing between the rolls, and combined pressurization with the roll on the plate Can be adopted. Moreover, since it becomes effective when it heats at the time of pressurization, it is preferable to heat in the range of 40-300 degreeC. In particular, when a transparent resin is used in combination, it is preferable to heat to a Tg or higher of the transparent resin. The heating time is adjusted in relation to the temperature and can be short at high temperatures and long at low temperatures. In the case of a nip roll, the heating method includes a method of heating the roll to a predetermined temperature in advance and a method of heating in a heating chamber such as an autoclave chamber.
〔透明導電性フィルム〕
本発明の、金属ナノワイヤ及び金属微粒子を含む透明導電膜を、透明樹脂フィルム上に設けることにより透明導電性フィルムとすることができる。金属ナノワイヤ及び金属微粒子を含む透明導電膜の基材として、透明樹脂フィルムを用いて直接透明樹脂フィルム上に設けてもよいし、別の基材上に作製した後に透明樹脂フィルムに転写してもよい。
[Transparent conductive film]
By providing the transparent conductive film containing metal nanowires and metal fine particles of the present invention on a transparent resin film, a transparent conductive film can be obtained. As a substrate of a transparent conductive film containing metal nanowires and metal fine particles, a transparent resin film may be used directly on the transparent resin film, or after being formed on another substrate and transferred to the transparent resin film. Good.
本発明に用いられる透明樹脂フィルムには特に制限はなく、その材料、形状、構造、厚み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、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、変性ポリエステル等のポリエステル系樹脂フィルム、ポリエチレン（ＰＥ）樹脂フィルム、ポリプロピレン（ＰＰ）樹脂フィルム、ポリスチレン樹脂フィルム、環状オレフィン系樹脂等のポリオレフィン類樹脂フィルム、ポリ塩化ビニル、ポリ塩化ビニリデン等のビニル系樹脂フィルム、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂フィルム、ポリサルホン（ＰＳＦ）樹脂フィルム、ポリエーテルサルホン（ＰＥＳ）樹脂フィルム、ポリカーボネート（ＰＣ）樹脂フィルム、ポリアミド樹脂フィルム、ポリイミド樹脂フィルム、アクリル樹脂フィルム、トリアセチルセルロース（ＴＡＣ）樹脂フィルム等を挙げることができるが、可視域の波長（３８０〜７８０ｎｍ）における透過率が８０％以上である樹脂フィルムであれば、本発明に好ましく適用することができる。中でも透明性、耐熱性、取り扱いやすさ、強度及びコストの点から、二軸延伸ポリエチレンテレフタレートフィルム、二軸延伸ポリエチレンナフタレートフィルム、ポリエーテルサルホンフィルム、ポリカーボネートフィルムであることが好ましく、二軸延伸ポリエチレンナフタレートフィルムであることがより好ましい。 There is no restriction | limiting in particular in the transparent resin film used for this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin A film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more in nm), can be preferably applied to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. A polyethylene naphthalate film is more preferable.
透明樹脂フィルムには、塗布液の濡れ性や接着性を確保するために、表面処理を施すことや易接着層を設けることができる。表面処理や易接着層については、従来公知の技術を使用できる。例えば、表面処理とは、コロナ放電処理、火炎処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理等の表面活性化処理を挙げることができる。また、易接着層としてはポリエステル、ポリアミド、ポリウレタン、ビニル系共重合体、ブタジエン系共重合体、アクリル系共重合体、ビニリデン系共重合体、エポキシ系共重合体等を挙げることができる。易接着層は単層でもよいが、接着性を向上させるためには２層以上の構成にしてもよい。 In order to ensure the wettability and adhesiveness of the coating solution, the transparent resin film can be subjected to a surface treatment or an easy adhesion layer. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyesters, polyamides, polyurethanes, vinyl copolymers, butadiene copolymers, acrylic copolymers, vinylidene copolymers, epoxy copolymers, and the like. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
本発明の透明導電性フィルムの全光線透過率は、６０％以上、好ましくは７０％以上、特に好ましくは８０％以上であることが望ましい。全光透過率は、分光光度計やヘイズメーター等を用いた公知の方法に従って測定することができる。 The total light transmittance of the transparent conductive film of the present invention is 60% or 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, a haze meter or the like.
本発明の透明導電性フィルムにおける電気抵抗値としては、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。表面抵抗率は、例えば、ＪＩＳ Ｋ６９１１、ＡＳＴＭ Ｄ２５７等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ができる。 The electrical resistance value in the transparent conductive film of the present invention is preferably 10 4 Ω / □ or less, more preferably 10 3 Ω / □ or less, and more preferably 10 2 Ω / □ or less as the surface resistivity. It is particularly preferred. The surface resistivity can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
本発明の透明導電性フィルムは、後述の各種透明電極や電磁波シールドフィルムとして好ましく用いることができる。 The transparent conductive film of the present invention can be preferably used as various transparent electrodes and electromagnetic wave shielding films described later.
〔フレキシブル透明面電極〕
本発明の金属ナノワイヤ及び金属微粒子を含む透明導電膜を透明樹脂フィルム上に形成した透明導電性フィルムは、フレキシブル透明面電極として好ましく使用でき、例えば、有機ＥＬや無機ＥＬディスプレイや照明、各種電子ペーパー、太陽電池等の透明電極として好ましく使用できる。特に、１０ｃｍやＡ４サイズ程度、あるいはそれ以上といった大きな面積の電極として使用する場合、従来のＩＴＯフィルム等では給電からの距離が遠い部分では電極でのわずかな電圧降下が無視できなくなり悪影響がでる。一方、本発明のフレキシブル透明面電極では、低抵抗の金属ナノワイヤ部により、給電から遠い部分にもほとんど電圧降下なく電流を供給できることから、本発明が特に有効となる。
[Flexible transparent electrode]
A transparent conductive film in which a transparent conductive film containing metal nanowires and metal fine particles of the present invention is formed on a transparent resin film can be preferably used as a flexible transparent surface electrode. For example, organic EL, inorganic EL display, illumination, various electronic papers It can be preferably used as a transparent electrode for solar cells and the like. In particular, when the electrode is used as an electrode having a large area of about 10 cm, A4 size or more, a conventional ITO film or the like has a bad influence because a slight voltage drop at the electrode cannot be ignored at a portion far from the power supply. On the other hand, in the flexible transparent electrode of the present invention, the present invention is particularly effective because a low-resistance metal nanowire portion can supply a current to a portion far from the power supply with almost no voltage drop.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「％」の表示を用いるが、特に断りがない限り「質量％」を表す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
実施例１
〔透明導電性フィルムの作製〕
（下引き済みＰＥＮフィルム）
帝人デュポン社製、膜厚９０μｍの二軸延伸ＰＥＮフィルムの両面に１２Ｗ・ｍｉｎ／ｍ２のコロナ放電処理を施し、それぞれの面に下引き塗布液Ｂ−１を乾燥膜厚０．１μｍになるように塗布し、さらに、それぞれの面のＢ−１乾燥膜上に１２Ｗ・ｍｉｎ／ｍ２のコロナ放電処理を施し、その上に下引き塗布液Ｂ−２を乾燥膜厚０．２μｍになるように塗布した。その後、１２０℃で１．５分の熱処理を実施し、下引き済みＰＥＮフィルムを得た。
Example 1
[Production of transparent conductive film]
(Underdrawn PEN film)
Teijin DuPont's biaxially stretched PEN film with a film thickness of 90 μm is subjected to a corona discharge treatment of 12 W · min / m 2 , and the undercoat coating solution B-1 is dried to a thickness of 0.1 μm on each surface. Further, a corona discharge treatment of 12 W · min / m 2 is applied to the B-1 dry film on each surface, and the undercoating liquid B-2 is formed thereon to a dry film thickness of 0.2 μm. It was applied as follows. Thereafter, a heat treatment was performed at 120 ° C. for 1.5 minutes to obtain an underdrawn PEN film.
〈下引き塗布液Ｂ−１〉
スチレン２０質量部、グリシジルメタクリレート４０質量部、ブチルアクリレート４０質量部の共重合体ラテックス液（固形分３０％） ５０ｇ
ＳｎＯ２ゾル（Ａ） ４４０ｇ
化合物（ＵＬ−１） ０．２ｇ
水で１０００ｍｌに仕上げる
〈下引き塗布液Ｂ−２〉
変性ポリエステルＡ（固形分１８％） ２１５ｇ
化合物（ＵＬ−３） ０．４ｇ
真球状シリカマット剤 シーホスターＫＥ−Ｐ５０（日本触媒社製） ０．３ｇ
水で１０００ｍｌに仕上げる
<Undercoat coating liquid B-1>
Copolymer latex liquid (solid content 30%) of 20 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate and 40 parts by mass of butyl acrylate 50 g
SnO 2 sol (A) 440 g
Compound (UL-1) 0.2g
Finish to 1000 ml with water <Undercoat coating liquid B-2>
Modified polyester A (solid content 18%) 215 g
Compound (UL-3) 0.4g
True spherical silica matting agent Seahoster KE-P50 (Nippon Shokubai Co., Ltd.) 0.3g
Finish to 1000ml with water
〈ＳｎＯ２ゾル（Ａ）の合成〉
ＳｎＣｌ４・５Ｈ２Ｏ ６５ｇを蒸留水２０００ｍｌに溶解して均一溶液とし、次いでこれを煮沸し沈澱物を得た。生成した沈澱物をデカンテーションにより取り出し、蒸留水にて何度も水洗した。沈澱を水洗した蒸留水中に硝酸銀を滴下し、塩素イオンの反応がないことを確認後、洗浄した沈澱物に蒸留水を添加し全量を２０００ｍｌとする。これに３０％アンモニア水４０ｍｌを加え加温することにより、均一なゾルを得た。さらに、アンモニア水を添加しながらＳｎＯ２の固型分濃度が８．３質量％になるまで加熱濃縮し、ＳｎＯ２ゾル（Ａ）を得た。
<Synthesis of SnO 2 sol (A)>
The SnCl 4 · 5H 2 O 65g was dissolved in distilled water 2000ml a homogeneous solution, then was obtained was boiled precipitate. The formed precipitate was taken out by decantation and washed with distilled water many times. Silver nitrate is added dropwise to distilled water in which the precipitate has been washed, and after confirming that there is no reaction of chlorine ions, distilled water is added to the washed precipitate to make a total volume of 2000 ml. To this, 40 ml of 30% aqueous ammonia was added and heated to obtain a uniform sol. Further, while adding ammonia water, the solution was concentrated by heating until the solid content concentration of SnO 2 became 8.3 mass%, to obtain SnO 2 sol (A).
〈変性水性ポリエステルＡの合成〉
重縮合用反応容器に、テレフタル酸ジメチル３５．４質量部、イソフタル酸ジメチル３３．６３質量部、５−スルホ−イソフタル酸ジメチルナトリウム塩１７．９２質量部、エチレングリコール６２質量部、酢酸カルシウム一水塩０．０６５質量部、酢酸マンガン四水塩０．０２２質量部を投入し、窒素気流下において、１７０〜２２０℃でメタノールを留去しながらエステル交換反応を行った後、リン酸トリメチル０．０４質量部、重縮合触媒として三酸化アンチモン０．０４質量部及び１，４−シクロヘキサンジカルボン酸６．８質量部を加え、２２０〜２３５℃の反応温度で、ほぼ理論量の水を留去しエステル化を行った。その後、さらに反応系内を約１時間かけて減圧、昇温し最終的に２８０℃、１３３Ｐａ以下で約１時間重縮合を行い、変性水性ポリエステルＡの前駆体を得た。前駆体の固有粘度は０．３３であった。
<Synthesis of modified aqueous polyester A>
In a reaction vessel for polycondensation, 35.4 parts by mass of dimethyl terephthalate, 33.63 parts by mass of dimethyl isophthalate, 17.92 parts by mass of 5-sulfo-isophthalic acid dimethyl sodium salt, 62 parts by mass of ethylene glycol, calcium acetate monohydrate 0.065 parts by mass of salt and 0.022 parts by mass of manganese acetate tetrahydrate were added, and the ester exchange reaction was performed while distilling off methanol at 170 to 220 ° C. in a nitrogen stream. 04 parts by mass, 0.04 parts by mass of antimony trioxide as a polycondensation catalyst and 6.8 parts by mass of 1,4-cyclohexanedicarboxylic acid were added, and a theoretical amount of water was distilled off at a reaction temperature of 220 to 235 ° C. Esterification was performed. Thereafter, the reaction system was further depressurized and heated for about 1 hour, and finally subjected to polycondensation at 280 ° C. and 133 Pa or less for about 1 hour to obtain a precursor of modified aqueous polyester A. The intrinsic viscosity of the precursor was 0.33.
攪拌翼、環流冷却管、温度計を付した２Ｌの三つ口フラスコに、純水８５０ｍｌを入れ、攪拌翼を回転させながら、１５０ｇの上記前駆体を徐々に添加した。室温でこのまま３０分間攪拌した後、１．５時間かけて内温が９８℃になるように加熱し、この温度で３時間加熱溶解した。加熱終了後、１時間かけて室温まで冷却し、一夜放置して、固形分濃度が１５質量％の溶液を調製した。 850 ml of pure water was put into a 2 L three-necked flask equipped with a stirring blade, a reflux condenser, and a thermometer, and 150 g of the precursor was gradually added while rotating the stirring blade. After stirring for 30 minutes at room temperature, the mixture was heated to an internal temperature of 98 ° C. over 1.5 hours, and heated and dissolved at this temperature for 3 hours. After completion of the heating, the mixture was cooled to room temperature over 1 hour and left overnight to prepare a solution having a solid content concentration of 15% by mass.
攪拌翼、環流冷却管、温度計、滴下ロートを付した３Ｌの四つ口フラスコに、上記前駆体溶液１９００ｍｌを入れ、攪拌翼を回転させながら、内温度を８０℃まで加熱した。この中に、過硫酸アンモニウムの２４％水溶液を６．５２ｍｌ加え、単量体混合液（メタクリル酸グリシジル２８．５ｇ、アクリル酸エチル２１．４ｇ、メタクリル酸メチル２１．４ｇ）を３０分間かけて滴下し、さらに３時間反応を続けた。その後、３０℃以下まで冷却し、濾過して、固形分濃度が１８質量％の変性水性ポリエステルＡの溶液を調製した（ポリエステル成分／アクリル成分＝８０／２０）。 1900 ml of the precursor solution was placed in a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and the internal temperature was heated to 80 ° C. while rotating the stirring blade. To this, 6.52 ml of a 24% aqueous solution of ammonium persulfate was added, and a monomer mixture (28.5 g of glycidyl methacrylate, 21.4 g of ethyl acrylate, 21.4 g of methyl methacrylate) was dropped over 30 minutes. The reaction was continued for another 3 hours. Then, it cooled to 30 degrees C or less, and filtered, and prepared the solution of the modified aqueous polyester A whose solid content concentration is 18 mass% (polyester component / acrylic component = 80/20).
（透明導電性フィルム１０１の作製）
Ｃｈｅｍ．Ｍａｔｅｒ．，２００２，１４，４７３６〜４７４５に記載の方法を参考に、平均直径６０ｎｍ、平均長さ５．５μｍの銀ナノワイヤを作製し、フィルターを用いて銀ナノワイヤを濾別、水洗処理を施した後、エタノール中に再分散して銀ナノワイヤ分散液Ｗ−１０（銀ナノワイヤ含有量０．５％）を調製した。
(Preparation of transparent conductive film 101)
Chem. Mater. , 2002, 14, 4736-4745, silver nanowires having an average diameter of 60 nm and an average length of 5.5 μm were prepared, and the silver nanowires were filtered using a filter, and washed with water. Silver nanowire dispersion liquid W-10 (silver nanowire content: 0.5%) was prepared by redispersion in ethanol.
イオン交換水５０ｍｌに硝酸銀１０．０ｇを溶解し、さらに、これに分散剤としてディスパービック１９０（ビックケミー社製）６．２５ｇを添加した水溶液に、攪拌しながら２Ｍ水酸化ナトリウム水溶液を２９．５ｍｌ滴下し、攪拌を１０〜３０分続けて、酸化銀微粒子の懸濁液を調製した。この懸濁液中の酸化銀微粒子の粒径を、粒径測定器（商品名；ＨＯＲＩＢＡ ＬＡ−９２０、堀場製作所社製）で測定したところ、その平均粒径は０．１μｍであった。次いで、この酸化銀微粒子の懸濁液を、メタノールで２〜５回洗浄し、余分なイオン類を除去した。次いで、これを熱風乾燥炉にて、温度５０℃で、５時間乾燥させて、酸化銀微粒子組成物を得後、エタノール中に再分散して酸化銀分散液（酸化銀微粒子含有量０．５％）を調製した。この分散液の粒径測定器にて測定したところ、その平均粒径は、懸濁液中の酸化銀微粒子の平均粒径と同じであった。次いで、この分散液２００ｇに、還元剤としてエチレングリコールを０．５ｇ添加して還元剤含有酸化銀分散液Ｐ−１０を作製した。 19.5 g of silver nitrate was dissolved in 50 ml of ion-exchanged water, and 29.5 ml of 2M sodium hydroxide aqueous solution was added dropwise with stirring to an aqueous solution in which 6.25 g of Dispersic 190 (manufactured by Big Chemie) was added as a dispersant. Then, stirring was continued for 10 to 30 minutes to prepare a suspension of silver oxide fine particles. When the particle size of the silver oxide fine particles in this suspension was measured with a particle size measuring device (trade name; HORIBA LA-920, manufactured by Horiba, Ltd.), the average particle size was 0.1 μm. Next, the silver oxide fine particle suspension was washed with methanol 2 to 5 times to remove excess ions. Then, this was dried in a hot air drying oven at a temperature of 50 ° C. for 5 hours to obtain a silver oxide fine particle composition, which was then redispersed in ethanol to give a silver oxide dispersion (silver oxide fine particle content 0.5 %) Was prepared. When measured with a particle size measuring device of this dispersion, the average particle size was the same as the average particle size of the silver oxide fine particles in the suspension. Next, 0.5 g of ethylene glycol was added as a reducing agent to 200 g of this dispersion to prepare a reducing agent-containing silver oxide dispersion P-10.
得られたＷ−１０とＰ−１０を、銀ナノワイヤと酸化銀粒子の質量比が１００：１の比率になるよう混合し、銀ナノワイヤと酸化銀粒子と還元剤を含有する塗布液Ｍ−１０を調製した。 The obtained W-10 and P-10 were mixed so that the mass ratio of silver nanowires to silver oxide particles was 100: 1, and coating liquid M-10 containing silver nanowires, silver oxide particles, and a reducing agent. Was prepared.
塗布液Ｍ−１０を、前述の下引き済みＰＥＮフィルム上に換算膜厚が３０ｎｍになるように塗布した後、８０℃にて乾燥処理し、引き続いて１４０℃のオーブンで５分間加熱処理を行った。続いて、ウレタンアクリレートの溶液（メチルイソブチルケトン溶媒）を乾燥後の換算厚さが４０ｎｍ相当になるように塗布し、本発明の透明導電性フィルム１０１を作製した。 The coating solution M-10 is applied on the above-described underdrawn PEN film so that the equivalent film thickness is 30 nm, then dried at 80 ° C., and then heat-treated in an oven at 140 ° C. for 5 minutes. It was. Subsequently, a solution of urethane acrylate (methyl isobutyl ketone solvent) was applied so that the converted thickness after drying was equivalent to 40 nm to produce the transparent conductive film 101 of the present invention.
（透明導電性フィルム１０２の作製）
透明導電性フィルム１０１の作製において、Ｗ−１０とＰ−１０を、銀ナノワイヤと酸化銀粒子の質量比が３０：１の比率になるよう混合した以外は同様にして本発明の透明導電性フィルム１０２を作製した。
(Preparation of transparent conductive film 102)
In producing the transparent conductive film 101, the transparent conductive film of the present invention was similarly prepared except that W-10 and P-10 were mixed so that the mass ratio of silver nanowires and silver oxide particles was 30: 1. 102 was produced.
（透明導電性フィルム１０３の作製）
透明導電性フィルム１０１の作製において、Ｗ−１０とＰ−１０の混合液は作製せずに、銀ナノワイヤと酸化銀粒子の質量比と、乾燥後の換算厚さが同様になるようにＷ−１０を塗布乾燥した後、その上にＰ−１０を塗布した以外は同様にして本発明の透明導電性フィルム１０３を作製した。
(Preparation of transparent conductive film 103)
In the production of the transparent conductive film 101, the mixed liquid of W-10 and P-10 is not produced, but the W—so that the mass ratio between the silver nanowires and the silver oxide particles and the equivalent thickness after drying are the same. 10 was applied and dried, and then the transparent conductive film 103 of the present invention was produced in the same manner except that P-10 was applied thereon.
（透明導電性フィルム２０１の作製）
透明導電性フィルム１０３の作製において、Ｐ−１０の液を塗布しなかった以外は同様にして比較の透明導電性フィルム２０１を作製した。
(Preparation of transparent conductive film 201)
In the production of the transparent conductive film 103, a comparative transparent conductive film 201 was produced in the same manner except that the liquid P-10 was not applied.
（透明導電性フィルム２０２の作製）
透明導電性フィルム１０１の作製において、加熱処理をしなかった以外は同様にして比較の透明導電性フィルム２０２を作製した。
(Preparation of transparent conductive film 202)
In the production of the transparent conductive film 101, a comparative transparent conductive film 202 was produced in the same manner except that no heat treatment was performed.
（比較フィルム２０３の作製）
透明導電性フィルム１０１の作製において、Ｐ−１０の変わりに銀微粒子分散液とした以外は同様にして比較の透明導電性フィルム２０３を作製した。
(Preparation of comparative film 203)
In the production of the transparent conductive film 101, a comparative transparent conductive film 203 was produced in the same manner except that a silver fine particle dispersion was used instead of P-10.
〔透明導電性フィルムの評価〕
作製した各透明導電性フィルムの表面抵抗率及び全光線透過率（以下、単に「透過率」という。）を、各々ＪＩＳ Ｋ ７１９４：１９９４及びＪＩＳ Ｋ ７３６１−１：１９９７に準拠した方法で測定した。得られた結果を表１に示す。
[Evaluation of transparent conductive film]
The surface resistivity and total light transmittance (hereinafter simply referred to as “transmittance”) of each of the produced transparent conductive films were measured by methods according to JIS K 7194: 1994 and JIS K 7361-1: 1997, respectively. . The obtained results are shown in Table 1.
表より、本発明の透明導電性フィルムは比較の透明導電性フィルムに比べ、高い導電性と良好な透明性を有することが分かる。また、各透明導電性フィルムを電子顕微鏡観察したところ、本発明の透明導電性フィルム１０１、１０２、１０３は金属微粒子により金属ナノワイヤが接合している状態を観察できたが、比較の透明導電性フィルム２０２、２０３では金属ナノワイヤに接触している金属微粒子は存在するが接合はしていなかった。 From the table, it can be seen that the transparent conductive film of the present invention has higher conductivity and better transparency than the comparative transparent conductive film. Moreover, when each transparent conductive film was observed with an electron microscope, the transparent conductive films 101, 102, and 103 of the present invention were able to observe the state in which the metal nanowires were joined by metal fine particles. In 202 and 203, metal fine particles in contact with the metal nanowire existed but were not bonded.
実施例２
〔表示素子の作製〕
（透明導電性フィルム１０４の作製）
実施例１で作製した透明導電性フィルム１０１上に、導電性高分子層として、スルホン酸系ドーパントを含有する導電性ポリアニリンの分散液ＯＲＭＥＣＯＮ Ｄ１０３３（ドイツ オルメコン社製）を用いて、乾燥膜厚が１３０ｎｍとなるように塗布乾燥して、本発明の透明導電性フィルム１０４を作製した。
Example 2
[Production of display element]
(Preparation of transparent conductive film 104)
On the transparent conductive film 101 produced in Example 1, a conductive polyaniline dispersion ORMECON D1033 (manufactured by Olmecon, Germany) containing a sulfonic acid dopant as a conductive polymer layer is used. The transparent conductive film 104 of the present invention was produced by applying and drying to 130 nm.
（透明導電性フィルム１０５の作製）
透明導電性フィルム１０４の作製において、導電性高分子の変わりに下記のＩＴＯ微粒子を、ブチラール樹脂ＢＭ−Ｓ（積水化学社製）の溶液（メチルエチルケトン／トルエン＝２／１の質量比の混合溶媒）にＩＴＯ粒子とブチラール樹脂の体積比率が２：１になるように混合して用いた以外は同様にして、本発明の透明導電性フィルム１０５を作製した。
(Preparation of transparent conductive film 105)
In the production of the transparent conductive film 104, the following ITO fine particles were used instead of the conductive polymer, and a solution of butyral resin BM-S (manufactured by Sekisui Chemical Co., Ltd.) (a mixed solvent having a mass ratio of methyl ethyl ketone / toluene = 2/1) A transparent conductive film 105 of the present invention was produced in the same manner except that the volume ratio of ITO particles to butyral resin was 2: 1.
（ＩＴＯ微粒子）
ＩｎＣｌ３を３５質量％含む水溶液と、ＳｎＣｌ４を８０質量％含む水溶液を混合し、２７℃に溶液温度を保ちながら６．３％のアンモニア水を徐々に加えて、水溶液のｐＨが９になるように調整した。この溶液を２７℃で５０分間攪拌しＩｎ、Ｓｎの共沈水酸化物を得た。この共沈物を濾別し、イオン交換水で洗浄した後、５００℃で２．５時間焼成することにより針状ＩＴＯ粒子の凝集体を得た。この粒子を機械的に粉砕することにより、ＩＴＯ微粒子を得た。
(ITO fine particles)
An aqueous solution containing 35% by mass of InCl 3 and an aqueous solution containing 80% by mass of SnCl 4 are mixed, and 6.3% ammonia water is gradually added while maintaining the solution temperature at 27 ° C., so that the pH of the aqueous solution becomes 9. Adjusted as follows. This solution was stirred at 27 ° C. for 50 minutes to obtain a coprecipitated hydroxide of In and Sn. The coprecipitate was separated by filtration, washed with ion exchange water, and then fired at 500 ° C. for 2.5 hours to obtain an aggregate of acicular ITO particles. The particles were mechanically pulverized to obtain ITO fine particles.
（透明導電性フィルム２０４の作製）
帝人デュポン社製、膜厚９０μｍの二軸延伸ＰＥＮフィルムに、公知のスパッタリング法でＩＴＯ膜を作製して比較の透明導電性フィルム２０４を作製した。表面抵抗は１００Ω／□であった。
(Preparation of transparent conductive film 204)
A comparative transparent conductive film 204 was prepared by preparing an ITO film by a known sputtering method on a biaxially stretched PEN film having a thickness of 90 μm manufactured by Teijin DuPont. The surface resistance was 100Ω / □.
（表示素子Ｓ−１０１の作製）
１０ｃｍ×１２ｃｍの透明導電性フィルム１０１を準備して、透明面電極１０１とした。
(Preparation of display element S-101)
A transparent conductive film 101 of 10 cm × 12 cm was prepared and used as a transparent surface electrode 101.
（電解質溶液１の調製）
ジメチルスルホキシド２．５ｇ中に、ヨウ化ナトリウム９０ｍｇ、ヨウ化銀７５ｍｇを加えて完全に溶解した後、酸化チタン０．５ｇを加えて超音波分散機にて酸化チタンを分散した。この溶液にポリビニルアルコール（ケン化度約８７〜８９％、重合度４５００）を１５０ｍｇ加えて１２０℃に加熱しながら１時間攪拌し、電解質溶液１を得た。
(Preparation of electrolyte solution 1)
In 2.5 g of dimethyl sulfoxide, 90 mg of sodium iodide and 75 mg of silver iodide were added and completely dissolved, then 0.5 g of titanium oxide was added, and the titanium oxide was dispersed with an ultrasonic disperser. 150 mg of polyvinyl alcohol (degree of saponification: about 87-89%, degree of polymerization: 4500) was added to this solution and stirred for 1 hour while heating at 120 ° C. to obtain an electrolyte solution 1.
（金属電極の作製）
厚さ１．５ｍｍで１０ｃｍ×１２ｃｍのガラス基板上に、公知のスパッタリング法でＣｕ膜を全面に形成した後、電解メッキによりＣｕ極上に銀を１０μｍ堆積させて、銀電極（電極２）を得た。
(Production of metal electrodes)
A Cu film was formed on the entire surface of a glass substrate having a thickness of 1.5 mm and 10 cm × 12 cm by a known sputtering method, and then 10 μm of silver was deposited on the Cu electrode by electrolytic plating to obtain a silver electrode (electrode 2). It was.
（表示素子の作製）
上記調製した電解質溶液１に、平均粒子径が２０μｍのポリアクリル製の球形ビーズを体積分率として４体積％になるように加えて攪拌した溶液を、上記電極２の上に塗布し、その上から透明面電極１０１を直角方向に組合せて表示素子Ｓ−１０１を作製した。重ね合わされた１０ｃｍ×１０ｃｍの部分が表示部（黒／白ベタ）であり、残りの部分がリード部として用いられる。リード部全体に導電性銀ペーストを十分な膜厚で塗布した。
(Production of display element)
A solution prepared by adding polyacrylic spherical beads having an average particle diameter of 20 μm to the prepared electrolyte solution 1 so that the volume fraction is 4% by volume is applied onto the electrode 2, and Thus, the display element S-101 was manufactured by combining the transparent surface electrodes 101 in the perpendicular direction. The overlapped 10 cm × 10 cm portion is a display portion (black / white solid), and the remaining portion is used as a lead portion. A conductive silver paste was applied to the entire lead portion with a sufficient film thickness.
透明導電性フィルム１０１を、透明導電性フィルム１０４、１０５、２０１、２０２、２０３、２０４に変更し、同様にして表示素子Ｓ−１０４、Ｓ−１０５、Ｓ−２０１、Ｓ−２０２、Ｓ−２０３、Ｓ−２０４を作製した。 The transparent conductive film 101 is changed to the transparent conductive film 104, 105, 201, 202, 203, 204, and the display elements S-104, S-105, S-201, S-202, S-203 are similarly changed. , S-204 was produced.
〔表示素子の評価〕
作製した各表示素子について、単一乾電池を２個直列に接続した電源を用いて、透明電極側に−、電極２側に＋を接続し、全体の表示状態を目視観察で、微小領域の表示状態をルーペ観察した。
[Evaluation of display element]
About each produced display element, using a power source in which two single dry batteries are connected in series,-is connected to the transparent electrode side and + is connected to the electrode 2 side, and the entire display state is visually observed to display a minute region. The state was observed with a loupe.
その結果、本発明の透明面電極を用いたＳ−１０１は目視では全面ほぼ均一な黒表示となった。ルーペで観察すると問題とならないレベルであるが、微妙な濃度ムラが見られた。本発明の透明面電極を用いたＳ−１０４及びＳ−１０５は目視、ルーペ観察とも均一な黒表示となった。これに対し、比較の透明面電極を用いたＳ−２０１、２０２、２０３はリードから遠い部分は濃度がわずかに低下し、目視で分かるレベルであり、ＮＧレベルである。ルーペで観察すると微妙な濃度ムラも見られた。比較の透明面電極を用いたＳ−２０４はリードから遠い部分は濃度が明らかに低下し、ＮＧである。 As a result, S-101 using the transparent electrode of the present invention displayed a substantially uniform black display on the entire surface. Although it was at a level that would not cause a problem when observed with a magnifying glass, subtle density unevenness was observed. S-104 and S-105 using the transparent surface electrode of the present invention showed a uniform black display for both visual observation and loupe observation. On the other hand, S-201, 202, and 203 using the comparative transparent surface electrode have a slightly lower density in the portion far from the lead, which is a level that can be visually observed, and is an NG level. When observed with a magnifying glass, subtle density unevenness was also observed. In S-204 using a comparative transparent electrode, the density of the portion far from the lead is clearly reduced and is NG.
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