JP5625256B2 - Transparent electrode, method for producing transparent electrode, and organic electroluminescence element - Google Patents
Transparent electrode, method for producing transparent electrode, and organic electroluminescence element Download PDFInfo
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- JP5625256B2 JP5625256B2 JP2009089857A JP2009089857A JP5625256B2 JP 5625256 B2 JP5625256 B2 JP 5625256B2 JP 2009089857 A JP2009089857 A JP 2009089857A JP 2009089857 A JP2009089857 A JP 2009089857A JP 5625256 B2 JP5625256 B2 JP 5625256B2
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Images
Description
本発明は、透明電極、透明電極の製造方法及び該透明電極を有する有機エレクトロルミネッセンス素子に関し、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、電子ペーパー、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、透明電極、透明電極の製造方法及び該透明電極を有する有機エレクトロルミネッセンス素子（以後有機ＥＬ素子ともいう）に関する。 The present invention relates to a transparent electrode, a method for producing the transparent electrode, and an organic electroluminescent element having the transparent electrode, and various kinds of liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, solar cells, electromagnetic wave shields, electronic paper, touch panels, and the like. The present invention relates to a transparent electrode, a method for producing the transparent electrode, and an organic electroluminescence element (hereinafter also referred to as an organic EL element) having the transparent electrode, which can be suitably used in the field.
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、電子ペーパー、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、透明電極は欠くことのできない技術要素となっている。 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 with different display methods, the transparent electrode is an essential constituent technology. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.
従来透明電極は、ガラスや透明なプラスチックフィルム等の透明基材上に、インジウム−スズの複合酸化物（ＩＴＯ）膜を真空蒸着法やスパッタリング法で製膜したＩＴＯ透明電極が主に使用されてきた。しかし、ＩＴＯに用いられているインジウムはレアメタルであり、且つ価格の高騰により、脱インジウムが望まれている。また、ディスプレイの大画面化、生産性向上に伴い、フレキシブル基板を用いたロール ｔｏ ロールが所望されている。 Conventionally, an ITO transparent electrode in which a composite oxide (ITO) film of indium-tin is formed on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method has been mainly used. It was. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. In addition, roll-to-roll using a flexible substrate has been desired along with an increase in display screen and productivity.
導電性繊維を用いる技術が開示されており、導電性繊維の一部を透明樹脂膜でフレキシブル基板に固定し、かつ導電性繊維の一部を透明樹脂膜表面に突起させて電極を形成することが提案されている（例えば、特許文献１参照）。しかし、このような構成の電極は、表面に導電性繊維が突起した部分にしか導電性がないため、表面に導電性繊維が突起しており、電極表面の平滑性が求められる技術用途には適用できないという課題を有していた。 A technique using a conductive fiber is disclosed, and a part of the conductive fiber is fixed to a flexible substrate with a transparent resin film, and a part of the conductive fiber is projected on the surface of the transparent resin film to form an electrode. Has been proposed (see, for example, Patent Document 1). However, since the electrode having such a structure has conductivity only at the portion where the conductive fiber protrudes on the surface, the conductive fiber protrudes on the surface, and for the technical application in which the smoothness of the electrode surface is required. It had the problem that it was not applicable.
また、透明基板上に塗布された銀ナノワイヤ上にポリウレタンをオーバーコートし、電極表面が平滑な透明電極が提案されている（例えば、特許文献２参照）。しかし、この透明電極上に塗布型有機ＥＬ素子を積層すると、面発光性及び発光寿命が悪く、面均一性の向上という課題を有していた。 Also, a transparent electrode has been proposed in which polyurethane is overcoated on silver nanowires coated on a transparent substrate and the electrode surface is smooth (see, for example, Patent Document 2). However, when a coating type organic EL element is laminated on the transparent electrode, the surface light emission and the light emission life are poor, and there is a problem of improving the surface uniformity.
ＩＴＯ透明電極において、その表面の平均粗さ（Ｒａ）が、２ｎｍ以下であることが開示されている（例えば、特許文献３参照）。また、有機エレクトロルミネッセンス素子に用いられるＩＴＯ透明導電膜表面の平均表面粗さ（Ｒａ）が、１．２ｎｍ以下であることが提案されている（例えば、特許文献４参照）。上記特許文献１〜３のように透明電極表面に突起が存在する電極を用いて有機エレクトロルミネッセンス素子を作製すると、陽極と陰極の短絡等のように、突起を起点にショートするという問題がある。また、突起間は透明樹脂が存在し、面電極としての機能が得られないという課題を有していた。 It is disclosed that the average roughness (Ra) of the surface of the ITO transparent electrode is 2 nm or less (see, for example, Patent Document 3). Moreover, it is proposed that the average surface roughness (Ra) of the ITO transparent conductive film surface used for an organic electroluminescent element is 1.2 nm or less (for example, refer patent document 4). When an organic electroluminescence element is manufactured using an electrode having protrusions on the surface of the transparent electrode as in Patent Documents 1 to 3, there is a problem that the protrusions are short-circuited from the starting point, such as a short circuit between the anode and the cathode. Further, there is a problem that a transparent resin exists between the protrusions and a function as a surface electrode cannot be obtained.
また、生産性に優れた透明電極として、π共役系高分子に代表される導電性高分子材料を適当な溶媒に溶解または分散した塗液を用いて、塗布や印刷によって透明電極を形成する方法も提案されている（例えば、特許文献５参照）。しかし、真空成膜法によるＩＴＯ等の金属酸化物透明電極に較べると、導電性が低くかつ透明性にも劣り、高導電性と高透過率・透明性とを両立させるという課題を有していた。 In addition, as a transparent electrode excellent in productivity, a method of forming a transparent electrode by coating or printing using a coating solution obtained by dissolving or dispersing a conductive polymer material typified by a π-conjugated polymer in an appropriate solvent Has also been proposed (see, for example, Patent Document 5). However, compared with metal oxide transparent electrodes such as ITO by vacuum film-forming method, it has low conductivity and inferior in transparency, and has the problem of achieving both high conductivity and high transmittance / transparency. It was.
本発明は、上記課題に鑑みなされたものであり、本発明の目的は、高温、高湿度環境下における環境試験後でも高い導電性と透明性を有しかつ良好な平滑性を併せ持ち、安定性（全光線透過率、表面抵抗、表面粗さ（Ｒａ、Ｒｙ））の優れた透明電極、該透明電極の製造方法、及び該透明電極を用いた発光均一性に優れた有機エレクトロルミネッセンス素子を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to have high conductivity and transparency even after an environmental test under a high temperature and high humidity environment, and to have good smoothness and stability. Provided are a transparent electrode having excellent total light transmittance, surface resistance, and surface roughness (Ra, Ry), a method for producing the transparent electrode, and an organic electroluminescence device having excellent light emission uniformity using the transparent electrode. There is to do.
本発明の上記目的は、下記の構成により達成される。 The above object of the present invention can be achieved by the following constitution.
１．透明基材上に、導電性繊維、導電性高分子、及びバインダー樹脂を有する透明導電層を有してなる透明電極において、
該バインダー樹脂が水系溶剤に均一に分散可能なバインダー樹脂であることを特徴とする透明電極。
1. In a transparent electrode having a transparent conductive layer having a conductive fiber, a conductive polymer, and a binder resin on a transparent substrate,
A transparent electrode, wherein the binder resin is a binder resin that can be uniformly dispersed in an aqueous solvent.
２．前記導電性繊維、導電性高分子、及び水系溶剤に均一に分散可能なバインダー樹脂を透明基材上の透明導電層に含有することを特徴とする前記１に記載の透明電極。 2. 2. The transparent electrode according to 1, wherein the conductive fiber, the conductive polymer, and a binder resin that can be uniformly dispersed in an aqueous solvent are contained in a transparent conductive layer on a transparent substrate.
３．前記導電性繊維を透明基材上の第一の透明導電層に含有し、前記導電性高分子及び水系溶剤に均一分散可能なバインダー樹脂を該第一の透明導電層上の第二の透明導電層に含有することを特徴とする前記１に記載の透明電極。 3. A second transparent conductive material on the first transparent conductive layer containing the conductive fiber in a first transparent conductive layer on a transparent substrate and a binder resin that can be uniformly dispersed in the conductive polymer and an aqueous solvent. 2. The transparent electrode as described in 1 above, which is contained in a layer.
４．前記導電性繊維が銀ナノワイヤであることを特徴とする前記１〜３のいずれか１項に記載の透明電極。 4). 4. The transparent electrode according to any one of 1 to 3, wherein the conductive fiber is a silver nanowire.
５．前記水系溶剤に均一に分散可能なバインダー樹脂がアクリル系樹脂およびウレタン系樹脂から選択される少なくとも１種であることを特徴とする前記１〜４のいずれか１項に記載の透明電極。 5. 5. The transparent electrode according to any one of 1 to 4, wherein the binder resin that can be uniformly dispersed in the aqueous solvent is at least one selected from an acrylic resin and a urethane resin.
６．透明基材上に、導電性繊維、導電性高分子、及びバインダー樹脂を有する透明導電層を有してなる透明電極の製造方法において、
該バインダー樹脂が水系溶剤に均一に分散可能なバインダー樹脂であることを特徴とする透明電極の製造方法。
6). In the method for producing a transparent electrode having a transparent conductive layer having a conductive fiber, a conductive polymer, and a binder resin on a transparent substrate,
A method for producing a transparent electrode, wherein the binder resin is a binder resin that can be uniformly dispersed in an aqueous solvent.
７．前記導電性繊維、導電性高分子、及び水系溶剤に均一に分散可能なバインダー樹脂を含有する水系分散物を、透明基材上に塗布することにより透明導電層を形成することを特徴とする前記６に記載の透明電極の製造方法。 7). A transparent conductive layer is formed by applying an aqueous dispersion containing a conductive resin, a conductive polymer, and a binder resin that can be uniformly dispersed in an aqueous solvent on a transparent substrate. 6. The method for producing a transparent electrode according to 6.
８．前記導電性繊維を含む第一の透明導電層を透明基材上に塗布する工程と、
該第一の透明導電層上に前記導電性高分子と水系溶剤に均一分散可能なバインダー樹脂を 含む水系分散液を塗布することにより第二の透明導電層を形成する工程と、
を有することを特徴とする前記６に記載の透明電極の製造方法。
8). Applying a first transparent conductive layer containing the conductive fibers on a transparent substrate;
Forming a second transparent conductive layer by applying an aqueous dispersion containing a binder resin that can be uniformly dispersed in the conductive polymer and an aqueous solvent on the first transparent conductive layer;
The method for producing a transparent electrode as described in 6 above, wherein:
９．前記導電性繊維が銀ナノワイヤであることを特徴とする前記６〜８のいずれか１項に記載の透明電極の製造方法。 9. The method for producing a transparent electrode according to any one of 6 to 8, wherein the conductive fiber is a silver nanowire.
１０．前記水系溶剤に均一に分散可能なバインダー樹脂がアクリル系樹脂およびウレタン系樹脂から選択される少なくとも１種であることを特徴とする前記６〜９のいずれか１項に記載の透明電極の製造方法。 10. 10. The method for producing a transparent electrode according to any one of 6 to 9, wherein the binder resin that can be uniformly dispersed in the aqueous solvent is at least one selected from an acrylic resin and a urethane resin. .
１１．前記１〜５のいずれか１項に記載の透明電極を有することを特徴とする有機エレクトロルミネッセンス素子。 11. 6. An organic electroluminescence device comprising the transparent electrode according to any one of 1 to 5 above.
本発明によれば、高温、高湿度環境下における環境試験後でも高い導電性と透明性を有しかつ良好な平滑性を併せ持ち、安定性（全光線透過率、表面抵抗、表面粗さ（Ｒａ、Ｒｙ））の優れた透明電極、該透明電極の製造方法、及び該透明電極を用いた発光均一性に優れた有機エレクトロルミネッセンス素子を提供することができる。 According to the present invention, it has high conductivity and transparency even after an environmental test under a high temperature and high humidity environment, and has good smoothness, stability (total light transmittance, surface resistance, surface roughness (Ra , Ry)), a transparent electrode, a method for producing the transparent electrode, and an organic electroluminescence device having excellent light emission uniformity using the transparent electrode.
以下、本発明を実施するための形態について説明するが、本発明はこれらに限定されない。 Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.
本発明は、透明基材上に、導電性繊維、導電性高分子、及びバインダー樹脂を有する透明導電層を有する透明電極において、該バインダー樹脂が水系溶剤に均一に分散可能なバインダー樹脂であることを特徴とする。 The present invention provides a transparent electrode having a transparent conductive layer having conductive fibers, a conductive polymer, and a binder resin on a transparent substrate, and the binder resin is a binder resin that can be uniformly dispersed in an aqueous solvent. It is characterized by.
本発明においては、特に、水系溶剤に均一に分散可能なバインダー樹脂を透明電極に含有させることで、高温、高湿度環境下における環境試験後でも高い導電性と透明性を有しかつ良好な平滑性を併せ持ち、安定性（全光線透過率、表面抵抗、表面粗さ（Ｒａ、Ｒｙ））の優れた透明電極、及び該透明電極を用いた発光均一性に優れた有機エレクトロルミネッセンス素子が得られる。 In the present invention, in particular, by including a binder resin that can be uniformly dispersed in an aqueous solvent in a transparent electrode, it has high conductivity and transparency even after an environmental test under a high temperature and high humidity environment, and has a good smoothness. And an organic electroluminescence device having excellent stability (total light transmittance, surface resistance, surface roughness (Ra, Ry)) and excellent light emission uniformity using the transparent electrode. .
本発明を更に詳しく説明する。 The present invention will be described in more detail.
〔透明基材〕
本発明において、「透明」とは、ＪＩＳ Ｋ ７３６１−１（ＩＳＯ １３４６８−１に対応）の「プラスチック−透明材料の全光線透過率の試験方法」に準拠した方法で測定した可視光波長領域における全光線透過率が６０％以上であることをいう。
(Transparent substrate)
In the present invention, “transparent” means in the visible light wavelength region measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1 (corresponding to ISO 13468-1). It means that the total light transmittance is 60% or more.
本発明の透明電極に用いられる透明基材としては、高い光透過性を有していればそれ以外に特に制限はない。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、樹脂フィルムなどの基材が好適に挙げられるが、軽量性と柔軟性の観点から透明樹脂フィルムを用いることが好ましい。 The transparent substrate used for the transparent electrode of the present invention is not particularly limited as long as it has high light transmittance. For example, a substrate such as a glass substrate, a resin substrate, or a resin film is preferably used in terms of excellent hardness as a substrate and easy formation of a conductive layer on the surface. It is preferable to use a transparent resin film from the viewpoint of flexibility.
本発明で透明基材として好ましく用いることができ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、本発明に係る透明基材の透明樹脂フィルム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であることがより好ましい。 There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent base material by 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 a transparent resin film of a transparent substrate according 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. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.
本発明に用いられる透明基材には、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、表面処理としては、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。透明樹脂フィルムが二軸延伸ポリエチレンテレフタレートフィルムである場合は、フィルムに隣接する易接着層の屈折率を１．５７〜１．６３とすることで、フィルム基材と易接着層との界面反射を低減して透過率を向上させることができるのでより好ましい。屈折率を調整する方法としては、酸化スズゾルや酸化セリウムゾル等の比較的屈折率の高い酸化物ゾルとバインダー樹脂との比率を適宜調整して塗設することで実施できる。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。また、透明基材にはバリアコート層が予め形成されていてもよいし、透明導電層を転写する反対側にはハードコート層が予め形成されていてもよい。 The transparent substrate used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to ensure the wettability and adhesion of the coating solution. 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 polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. When the transparent resin film is a biaxially stretched polyethylene terephthalate film, by making the refractive index of the easy adhesion layer adjacent to the film 1.57-1.63, the interface reflection between the film substrate and the easy adhesion layer can be achieved. Since it can reduce and can improve the transmittance | permeability, it is more preferable. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion. Moreover, the barrier coat layer may be formed in advance on the transparent substrate, or the hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred.
〔透明電極〕
本発明の透明電極の構造模式図を図１に示す。図１は、本発明の代表的な透明電極の構造模式図であって、透明基材５１上に透明導電層３１を有し、該透明導電層は導電性繊維１１と導電性材料２１を含み構成される。本発明において、その他の構成には特に制限はない。
[Transparent electrode]
A structural schematic diagram of the transparent electrode of the present invention is shown in FIG. FIG. 1 is a structural schematic diagram of a typical transparent electrode of the present invention, which has a transparent
尚、透明基材には前述のように表面処理を施したり、目的に応じて各種の機能性層を設けることができる。 The transparent substrate can be subjected to surface treatment as described above, and various functional layers can be provided depending on the purpose.
本発明の透明電極においては、全光線透過率が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、本発明の透明電極における透明導電層の電気抵抗値としては、表面抵抗率として１０００Ω／□以下であることが好ましく、１００Ω／□以下であることがより好ましい。さらには、電流駆動型オプトエレクトロニクスデバイスに適用するためには、５０Ω／□以下であることが好ましく、１０Ω／□以下であることが特に好ましい。１０３Ω／□以下であると各種オプトエレクトロニクスデバイスにおいて、透明電極として機能することができて好ましい。前記表面抵抗率は、例えば、ＪＩＳ Ｋ ７１９４：１９９４（導電性プラスチックの４探針法による抵抗率試験方法）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ができる。 In the transparent electrode of the present invention, the total light transmittance 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. Moreover, as an electrical resistance value of the transparent conductive layer in the transparent electrode of this invention, it is preferable that it is 1000 ohms / square or less as surface resistivity, and it is more preferable that it is 100 ohms / square or less. Furthermore, in order to apply to a current drive type optoelectronic device, it is preferably 50Ω / □ or less, particularly preferably 10Ω / □ or less. It is preferable that it is 10 3 Ω / □ or less because it can function as a transparent electrode in various optoelectronic devices. The surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method using a conductive plastic four-probe method), and can be easily performed using a commercially available surface resistivity meter. Can be measured.
本発明の透明電極の厚み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、厚みが薄くなるほど透明性や柔軟性が向上するためより好ましい。 There is no restriction | limiting in particular in the thickness of the transparent electrode of this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and a softness | flexibility improve, so that thickness becomes thin. More preferred.
〔透明導電層〕
本発明の態様としては、導電性繊維が金属ナノワイヤおよびカーボンナノチューブの群から選ばれる少なくとも１種であること、導電性材料が導電性高分子及び導電性金属酸化物微粒子の群から選ばれる少なくとも１種であることが好ましい。
[Transparent conductive layer]
As an aspect of the present invention, the conductive fiber is at least one selected from the group of metal nanowires and carbon nanotubes, and the conductive material is at least one selected from the group of conductive polymer and conductive metal oxide fine particles. Preferably it is a seed.
本発明に係る透明導電層は、導電性繊維と導電性材料の他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、塗布液を形成できる透明な樹脂であれば特に制限はなく、例えば、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。 The transparent conductive layer according to the present invention may contain a transparent binder material or additive in addition to the conductive fiber and the conductive material. The transparent binder material is not particularly limited as long as it is a transparent resin capable of forming a coating solution. For example, a polyester resin, a polystyrene resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, a polycarbonate resin, Cellulose resins, butyral resins, etc. can be used alone or in combination.
本発明に係る透明導電層の厚さは、使用する導電性繊維や導電性材料の形状や含有量によって異なるが、大凡の目安として、導電性繊維の平均直径以上５００ｎｍ以下が好ましい。後述の加圧方法などにより、本発明に係る透明導電層の厚さを薄くすると、厚さ方向の導電性繊維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 transparent conductive layer according to the present invention varies depending on the shape and content of the conductive fiber or conductive material to be used, but as a rough guide, the average diameter of the conductive fiber is preferably 500 nm or less. It is preferable to reduce the thickness of the transparent conductive layer according to the present invention by a pressurizing method described later, because the network formation of conductive fibers in the thickness direction can be made dense.
〔表面の平滑性〕
本発明において、透明導電層の表面の平滑性を表すＲｙとＲａは、Ｒｙ＝最大高さ（表面の山頂部と谷底部との高低差）とＲａ＝算術平均粗さを意味し、ＪＩＳ Ｂ６０１（１９９４）に規定される表面粗さに準ずる値である。本発明の透明電極は、透明導電層の表面の平滑性がＲｙ≦５０ｎｍ、また、併せて透明導電層の表面の平滑性はＲａ≦５ｎｍであることが好ましい。本発明においてＲｙやＲａの測定には、市販の原子間力顕微鏡（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｙ：ＡＦＭ）を用いることができ、例えば、以下の方法で測定できる。
[Surface smoothness]
In the present invention, Ry and Ra representing the smoothness of the surface of the transparent conductive layer mean Ry = maximum height (the difference in height between the top and bottom of the surface) and Ra = arithmetic mean roughness, JIS B601. It is a value according to the surface roughness specified in (1994). In the transparent electrode of the present invention, the smoothness of the surface of the transparent conductive layer is preferably Ry ≦ 50 nm, and the smoothness of the surface of the transparent conductive layer is preferably Ra ≦ 5 nm. In the present invention, for the measurement of Ry and Ra, a commercially available atomic force microscope (AFM) can be used. For example, it can be measured by the following method.
ＡＦＭとして、セイコーインスツルメンツ社製ＳＰＩ３８００Ｎプローブステーション及びＳＰＡ４００多機能型ユニットを使用し、約１ｃｍ角の大きさに切り取った試料を、ピエゾスキャナー上の水平な試料台上にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、ＸＹ方向にスキャンし、その際の試料の凹凸をＺ方向のピエゾの変位で捉える。ピエゾスキャナーは、ＸＹ２０μｍ、Ｚ２μｍが走査可能なものを使用する。カンチレバーは、セイコーインスツルメンツ社製シリコンカンチレバーＳＩ−ＤＦ２０で、共振周波数１２０〜１５０ｋＨｚ、バネ定数１２〜２０Ｎ／ｍのものを用い、ＤＦＭモード（Ｄｙｎａｍｉｃ Ｆｏｒｃｅ Ｍｏｄｅ）で測定する。測定領域８０×８０μｍを、走査周波数１Ｈｚで測定する。 Using an SPI 3800N probe station manufactured by Seiko Instruments Inc. and a SPA400 multifunctional unit as the AFM, set a sample cut to a size of about 1 cm square on a horizontal sample table on a piezo scanner, and place the cantilever on the sample surface. When approaching and reaching the region where the atomic force works, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 1 Hz.
本発明において、Ｒｙの値は４０ｎｍ以下であることがより好ましく、３０ｎｍ以下であることがさらに好ましい。同様に、Ｒａの値は３ｎｍ以下であることがより好ましく、１ｎｍ以下であることがさらに好ましい。 In the present invention, the value of Ry is more preferably 40 nm or less, and further preferably 30 nm or less. Similarly, the value of Ra is more preferably 3 nm or less, and further preferably 1 nm or less.
〔導電性繊維〕
本発明に係る導電性繊維とは、導電性を有し、かつその長さが直径（太さ）に比べて十分に長い形状を持つものである。本発明に係る導電性繊維は、透明導電層内において導電性繊維が互いに接触し合うことにより３次元的な導電ネットワークを形成し補助電極として機能すると考えられる。従って、導電性繊維が長い方が導電ネットワーク形成に有利であるため好ましい。一方で、導電性繊維が長くなると導電性繊維が絡み合って凝集体を生じ、光学特性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、導電性繊維の剛性や直径等も影響するため、使用する導電性繊維に応じて最適な平均アスペクト比（アスペクト＝長さ／直径）のものを使用することが好ましい。大凡の目安として、平均アスペクト比は、１０〜１０，０００であるものが好ましい。
[Conductive fiber]
The conductive fiber according to the present invention is conductive and has a shape whose length is sufficiently longer than its diameter (thickness). The conductive fiber according to the present invention is considered to function as an auxiliary electrode by forming a three-dimensional conductive network when the conductive fibers contact each other in the transparent conductive layer. Accordingly, a longer conductive fiber is preferable because it is advantageous for forming a conductive network. On the other hand, when the conductive fibers are long, the conductive fibers are entangled to form aggregates, which may deteriorate the optical characteristics. Since the conductive fiber formation and aggregate formation are also affected by the stiffness and diameter of the conductive fibers, use the one with the optimum average aspect ratio (aspect = length / diameter) according to the conductive fibers used. Is preferred. As a rough guide, the average aspect ratio is preferably 10 to 10,000.
形状としては中空チューブ状、ワイヤ状、ファイバー状のもの等があり、例えば、金属でコーティングした有機繊維や無機繊維、導電性金属酸化物繊維、金属ナノワイヤ、炭素繊維、カーボンナノチューブ等がある。本発明においては、透明性の観点から太さが３００ｎｍ以下の導電性繊維であることが好ましく、併せて導電性も満足するために、導電性繊維は金属ナノワイヤ及びカーボンナノチューブの群から選ばれる少なくとも１種であることが好ましい。さらには、コスト（原材料費、製造費）と性能（導電性、透明性、可撓性）の観点から、銀ナノワイヤを最も好ましく用いることができる。 Examples of the shape include a hollow tube shape, a wire shape, and a fiber shape, such as organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, and carbon nanotubes. In the present invention, from the viewpoint of transparency, it is preferable that the conductive fiber has a thickness of 300 nm or less, and in order to satisfy the conductivity, the conductive fiber is at least selected from the group of metal nanowires and carbon nanotubes. One type is preferable. Furthermore, silver nanowires can be most preferably used from the viewpoint of cost (raw material costs, manufacturing costs) and performance (conductivity, transparency, flexibility).
本発明において上記導電性繊維の長さや直径、アスペクト比の平均値は、十分な数の導電性繊維について電子顕微鏡写真を撮影し、個々の導電性繊維像の計測値の算術平均から求めることができる。導電性繊維の長さは、本来直線状に伸ばした状態で測定すべきであるが、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）こともできる。また、長さや直径の相対標準偏差は、測定値の標準偏差を平均値で除した値に１００を乗じた値で表す。計測対象の導電性繊維のサンプル数は、少なくとも１００個以上が好ましく、３００個以上がより好ましい。 In the present invention, the average value of the length, diameter, and aspect ratio of the conductive fiber can be obtained from an arithmetic average of measured values of individual conductive fiber images by taking an electron micrograph of a sufficient number of conductive fibers. it can. The length of the conductive fiber should be measured in a linearly stretched state, but in reality, it is often bent. It is also possible to calculate the projected area and assume a cylindrical body (length = projected area / projected diameter). The relative standard deviation of length and diameter is expressed by a value obtained by multiplying 100 by the value obtained by dividing the standard deviation of the measured value by the average value. The number of conductive fiber samples to be measured is preferably at least 100 or more, more preferably 300 or more.
相対標準偏差［％］＝測定値の標準偏差／平均値×１００
〔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。
Relative standard deviation [%] = standard deviation of measured value / average value × 100
[Metal nanowires]
In general, the 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.
本発明に係る導電性繊維に適用される金属ナノワイヤとしては、１つの金属ナノワイヤで長い導電パスを形成するために、平均長さが３μｍ以上であることが好ましく、さらには３〜５００μｍが好ましく、特に、３〜３００μｍであることが好ましい。併せて、長さの相対標準偏差は４０％以下であることが好ましい。また、平均直径は、透明性の観点からは小さいことが好ましく、一方で、導電性の観点からは大きい方が好ましい。本発明においては、金属ナノワイヤの平均直径として１０〜３００ｎｍが好ましく、３０〜２００ｎｍであることがより好ましい。併せて、直径の相対標準偏差は２０％以下であることが好ましい。 As the metal nanowire applied to the conductive fiber according to the present invention, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, In particular, the thickness is preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.
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なく、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することができるが、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。また、導電性と安定性（金属ナノワイヤの硫化や酸化耐性、及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も好ましい。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。 There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, 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. Further, in order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires, and resistance to magnesium), it is also preferable to include silver and at least one metal belonging to a noble metal other than 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.
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Ａｇ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、本発明に係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 be easily produced in an aqueous system, and since the conductivity of silver is the highest among metals, it is preferable as the method for producing metal nanowires according to the present invention. Can be applied.
〔カーボンナノチューブ〕
カーボンナノチューブは、厚さ数原子層のグラファイト状炭素原子面（グラフェンシート）が筒形に巻かれた形状からなる炭素系繊維材料であり、その周壁の構成数から単層ナノチューブ（ＳＷＮＴ）と多層ナノチューブ（ＭＷＮＴ）とに大別され、また、グラフェンシートの構造の違いからカイラル（らせん）型、ジグザグ型、アームチェア型に分けられ、各種のものが知られている。
〔carbon nanotube〕
A carbon nanotube is a carbon-based fiber material having a shape in which a graphite-like carbon atomic plane (graphene sheet) having a thickness of several atomic layers is wound into a cylindrical shape, and single-walled nanotubes (SWNT) and multilayers are formed from the number of peripheral walls. It is roughly divided into nanotubes (MWNT), and it is divided into a chiral type, a zigzag type, and an armchair type depending on the structure of the graphene sheet, and various types are known.
本発明に係る導電性繊維に適用されるカーボンナノチューブとしては、いずれのタイプのカーボンナノチューブも用いることができ、また、これらの種々のカーボンナノチューブを複数混合して用いてもよいが、導電性に優れた単層カーボンナノチューブであることが好ましく、さらには金属性のアームチェア型単層カーボンナノチューブであることがより好ましい。 As the carbon nanotube applied to the conductive fiber according to the present invention, any type of carbon nanotube can be used, and a mixture of these various carbon nanotubes may be used. An excellent single-walled carbon nanotube is preferable, and a metallic armchair-type single-walled carbon nanotube is more preferable.
本発明に係るカーボンナノチューブの形状としては、１つのカーボンナノチューブで長い導電パスを形成するために、アスペクト比（＝長さ／直径）が大きい、すなわち細くて長い単層カーボンナノチューブであることが好ましい。例えば、アスペクト比が１０２以上、好ましくは１０３以上のカーボンナノチューブが挙げられる。カーボンナノチューブの平均長さは、３μｍ以上であることが好ましく、さらには３〜５００μｍが好ましく、特に、３〜３００μｍであることが好ましい。併せて、長さの相対標準偏差は４０％以下であることが好ましい。また、平均直径は１００ｎｍより小さいことが好ましく、１〜５０ｎｍが好ましく、１〜３０ｎｍであることがより好ましい。併せて、直径の相対標準偏差は２０％以下であることが好ましい。 The shape of the carbon nanotube according to the present invention is preferably a single-walled carbon nanotube having a large aspect ratio (= length / diameter), that is, a thin and long carbon nanotube, in order to form a long conductive path with one carbon nanotube. . For example, carbon nanotubes having an aspect ratio of 102 or more, preferably 103 or more can be mentioned. The average length of the carbon nanotubes is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is smaller than 100 nm, 1-50 nm is preferable and it is more preferable that it is 1-30 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.
本発明で使用されるカーボンナノチューブの製造方法は特に限定されるものではなく、二酸化炭素の接触水素還元、アーク放電法、レーザー蒸発法、ＣＶＤ法、気相成長法、一酸化炭素を高温高圧化で鉄触媒と共に反応させて気相で成長させるＨｉＰｃｏ法等の公知の手段を用いることができる。また、副生成物や触媒金属等の残留物を除去するために、洗浄法、遠心分離法、ろ過法、酸化法、クロマトグラフ法等の種々の精製法によって、より高純度化されたカーボンナノチューブの方が、各種機能を十分に発現できることから好ましい。 The production method of the carbon nanotube used in the present invention is not particularly limited, and catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, high temperature and high pressure of carbon monoxide. Well-known means such as HiPco method in which the reaction is carried out together with an iron catalyst and grown in the gas phase can be used. Moreover, in order to remove residues such as by-products and catalytic metals, carbon nanotubes that have been further purified by various purification methods such as washing methods, centrifugal separation methods, filtration methods, oxidation methods, chromatographic methods, etc. Is more preferable because various functions can be sufficiently expressed.
〔導電性材料〕
本発明において導電性材料とは、製膜した状態において透明性を有し、かつ均一な導電性を有する膜を形成できる材料である。このような導電性材料として、例えば、導電性高分子や導電性金属酸化物微粒子、金属微粒子、金属でコーティングした有機微粒子や無機微粒子等がある。本発明においては、透明性と導電性の観点から、導電性材料は導電性高分子や導電性金属酸化物ナノ粒子の群から選ばれる少なくとも１種であることが好ましい。導電性高分子が特に好ましい。
[Conductive material]
In the present invention, the conductive material is a material that can form a film having transparency and uniform conductivity in the formed state. Examples of such conductive materials include conductive polymers, conductive metal oxide fine particles, metal fine particles, organic fine particles coated with metal, inorganic fine particles, and the like. In the present invention, from the viewpoints of transparency and conductivity, the conductive material is preferably at least one selected from the group of conductive polymers and conductive metal oxide nanoparticles. Conductive polymers are particularly preferred.
〔導電性高分子〕
本発明に係る導電性材料に適用さ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の各誘導体からなる群より選ばれる化合物等を挙げることができる。
[Conductive polymer]
Examples of the conductive polymer applied to the conductive material according to the present invention include, for example, polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, Examples thereof include compounds selected from the group consisting of polyphenylacetylene, polydiacetylene and polynaphthalene derivatives.
本発明に係る導電性材料は、１種類の導電性高分子を単独に含有してもよいし、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 conductive material according to the present invention may contain one type of conductive polymer alone, or may contain two or more types of conductive polymers in combination, From the viewpoint, 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 It is more preferable that at least one compound selected from the group consisting of polythiophene derivatives having a repeating unit represented by
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.
本発明に係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 according to 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、本発明の導電性材料は、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 conductive material 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.
本発明に係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 according to the present invention, a conductive polymer modified with a metal disclosed in JP-T-2001-511581, JP-A-2004-99640, JP-A-2007-165199, or the like is used. You can also.
本発明に係る導電性高分子を含む導電性材料には、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。本発明の導電性材料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、ジメチルスルホキシド（ＤＭＳＯ）やジエチレングリコール、その他酸素含有化合物が好適に挙げられる。 The conductive material containing the conductive polymer according to 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. Which can be used in the conductive material of the present invention. There is no restriction | limiting in particular in a dopant, It can select suitably from well-known things, For example, a dimethyl sulfoxide (DMSO), diethylene glycol, and another oxygen containing compound are mentioned suitably.
本発明に係る導電性高分子を含む導電性材料においては、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 material containing the conductive polymer according to 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.
本発明に係る導電性高分子を含む導電性材料は、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 material containing the conductive polymer according to 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
導電性材料には、導電性を改善するためにポリアニオンを用いても良い。本発明で用いられるポリアニオンは、高分子カルボン酸、高分子スルホン酸及びこれらの塩の各誘導体からなる群より選ばれる化合物等を挙げることができ、好ましくは高分子スルホン酸及びその塩である。ポリアニオンは単独に含有してもよいし、２種類以上を組み合わせて含有してもよい。また、ポリアニオンは、カルボン酸、スルホン酸を有する構造単位と酸残基を有していないモノマー、例えばアクリレート、メタクリレート及びスチレン等と共重合体を形成してもよい。 A polyanion may be used for the conductive material in order to improve conductivity. Examples of the polyanion used in the present invention include compounds selected from the group consisting of polymeric carboxylic acids, polymeric sulfonic acids and derivatives of these salts, and preferred are polymeric sulfonic acids and salts thereof. The polyanions may be contained alone or in combination of two or more. The polyanion may form a copolymer with a structural unit having carboxylic acid or sulfonic acid and a monomer having no acid residue, such as acrylate, methacrylate, styrene, or the like.
高分子カルボン酸、高分子スルホン酸及びこれらの塩の具体例としては、例えばポリアクリル酸、ポリメタクリル酸またはポリマレイン酸、高分子スルホン酸、ポリスチレンスルホン酸及びポリビニルスルホン酸及びこれらの塩であり、好ましくは、ポリスチレンスルホン酸及びその塩である。 Specific examples of the polymer carboxylic acid, polymer sulfonic acid and salts thereof include, for example, polyacrylic acid, polymethacrylic acid or polymaleic acid, polymer sulfonic acid, polystyrene sulfonic acid and polyvinyl sulfonic acid and salts thereof. Polystyrene sulfonic acid and its salt are preferable.
〔水系溶剤に均一分散可能なバインダー樹脂〕
本発明は、透明基材上に、導電性繊維、導電性高分子、及びバインダー樹脂を有する透明導電層を有する透明電極において、該バインダー樹脂が水系溶剤に均一に分散可能なバインダー樹脂であることを特徴とする。
[Binder resin that can be uniformly dispersed in aqueous solvents]
The present invention provides a transparent electrode having a transparent conductive layer having conductive fibers, a conductive polymer, and a binder resin on a transparent substrate, and the binder resin is a binder resin that can be uniformly dispersed in an aqueous solvent. It is characterized by.
本発明に係る水系溶剤に均一分散可能なバインダー樹脂とは、水系溶剤に均一分散可能なものであり、本発明において、「水系溶剤に均一分散可能」とは、水系溶剤中に凝集せずにバインダー樹脂からなるコロイド粒子が分散している状況であることを意味する。コロイド粒子の大きさは一般的に０．００１〜１μｍ（１〜１０００μｍ）程度である。 The binder resin that can be uniformly dispersed in the aqueous solvent according to the present invention is one that can be uniformly dispersed in the aqueous solvent. In the present invention, the phrase “uniformly dispersible in the aqueous solvent” means that the binder resin does not aggregate in the aqueous solvent. This means that colloidal particles made of a binder resin are dispersed. The size of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 μm).
上記のコロイド粒子については、光散乱光度計により測定することができる。 The colloidal particles can be measured with a light scattering photometer.
また、上記水系溶剤とは、純水（蒸留水、脱イオン水を含む）のみならず酸、アルカリ、塩などを含む水溶液、含水の有機溶媒、さらには親水性の有機溶媒など溶媒であることを意味し、純水（蒸留水、脱イオン水を含む）、メタノール、エタノール等のアルコール系溶媒、水とアルコールの混合溶媒等が挙げられる。 The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, and a hydrophilic organic solvent. And pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, mixed solvents of water and alcohol, and the like.
本発明に係る水系溶剤に均一分散可能なバインダー樹脂としては透明であることが好ましい。 The binder resin that can be uniformly dispersed in the aqueous solvent according to the present invention is preferably transparent.
本発明の水系溶剤に均一分散可能なバインダーとしては、フィルムを形成する媒体であれば、特に限定はない。水系溶剤に均一分散可能なバインダーとしては、例えば：アクリル系樹脂エマルジョン、水性ウレタン樹脂等が挙げられる。アクリル系樹脂エマルジョンは、酢酸ビニル、アクリル酸、アクリル酸−スチレンの重合体、或いはその他のモノマーとの共重合体からなる。また、酸部分がリチウム、ナトリウム、カリウム、アンモニウム塩とつい塩を形成したアニオン性、窒素原子を有するモノマーとの共重合体からなり、窒素原子が塩酸塩等を形成したカチオン性があるが、好ましくはアニオン性である。 The binder that can be uniformly dispersed in the aqueous solvent of the present invention is not particularly limited as long as it is a medium for forming a film. Examples of the binder that can be uniformly dispersed in the aqueous solvent include: acrylic resin emulsion, aqueous urethane resin, and the like. The acrylic resin emulsion is made of vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers. In addition, the acid part is composed of a copolymer of an anionic lithium salt, sodium salt, potassium salt, ammonium salt, and a monomer having a nitrogen atom, and a cationic nitrogen atom forming a hydrochloride salt, Preferably it is anionic.
水性ウレタン樹脂としては、水分散型ウレタン樹脂、アイオノマー型水性ウレタン樹脂（アニオン性）等がある。水分散型ウレタン樹脂には、ポリエーテル系ウレタン樹脂、ポリエステル系ウレタン樹脂があり、好ましくはポリエステル系ウレタン樹脂である。 Examples of aqueous urethane resins include water-dispersed urethane resins and ionomer-type aqueous urethane resins (anionic). The water-dispersed urethane resin includes a polyether-based urethane resin and a polyester-based urethane resin, preferably a polyester-based urethane resin.
アイオノマー型水性ウレタン樹脂には、ポリエステル系ウレタン樹脂、ポリエーテル系ウレタ樹脂、ポリカーボネート系ウレタン樹脂等があり、好ましくはポリエステル系ウレタン樹脂、ポリエーテル系ウレタ樹脂である。 Examples of the ionomer-type water-based urethane resin include a polyester-based urethane resin, a polyether-based urethane resin, a polycarbonate-based urethane resin, and the like, preferably a polyester-based urethane resin and a polyether-based urethane resin.
市販品として、ボンコートＡＮ−１５５−Ｅ、ボンコートＡＣ−５０１、ボンコートＡＮ−２００、ボンコートＲ−３３８０−Ｅ（アクリル系樹脂エマルジョン（アニオン性））、ボンディック１９４０ＮＥ（水分散型ポリウレタン樹脂、ポリエーテル系ウレタン樹脂）、ボンディック２２１０、ボンディック２２２０（水分散型ポリウレタン樹脂、ポリエステル系ウレタン樹脂）、ハイドラン１４０ＳＦ、ハイドランＡＰ−４０（Ｆ）、ハイドランＡＰ−４０Ｎ（アイオノマー型水性ウレタン樹脂、ポリエステル系ウレタン樹脂）、ハイドランＨＷ−３１２Ｂ、ハイドランＷＬＳ−２０１（アイオノマー型水性ウレタン樹脂、ポリエーテル系ウレタン樹脂）（すべてＤＩＣ社製）を用いることができる。上記水系溶剤に均一分散可能なバインダーは１種でも複数種でも使用することができる。 As commercial products, Boncoat AN-155-E, Boncoat AC-501, Boncoat AN-200, Boncoat R-3380-E (acrylic resin emulsion (anionic)), Bondick 1940NE (water-dispersed polyurethane resin, polyether) -Based urethane resin), Bondick 2210, Bondick 2220 (water-dispersed polyurethane resin, polyester-based urethane resin), Hydran 140SF, Hydran AP-40 (F), Hydran AP-40N (Ionomeric aqueous urethane resin, polyester-based urethane) Resin), Hydran HW-312B, Hydran WLS-201 (ionomer type water-based urethane resin, polyether urethane resin) (all manufactured by DIC) can be used. One or more binders that can be uniformly dispersed in the aqueous solvent can be used.
本発明の水系溶剤に均一分散可能なバインダーの使用量としては、導電性高分子に対して１〜２００質量％が好ましく、より好ましくは５〜１００質量である。 As the usage-amount of the binder which can be uniformly disperse | distributed to the aqueous solvent of this invention, 1-200 mass% is preferable with respect to a conductive polymer, More preferably, it is 5-100 mass.
〔製造方法〕
本発明の透明電極の製造方法において、透明基材上に導電性繊維からなる補助電極と導電性材料を含む透明導電層を形成する方法に特に制限はないが、生産性の改善、平滑性や均一性などの電極品質の向上、環境負荷軽減の観点から、透明導電層の形成には塗布法や印刷法など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、ドクターコート法など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などを用いることができる。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、離型性基材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ができる。
〔Production method〕
In the method for producing a transparent electrode of the present invention, there is no particular limitation on the method for forming an auxiliary electrode made of conductive fibers and a transparent conductive layer containing a conductive material on a transparent substrate, but improvement in productivity, smoothness, From the viewpoint of improving the electrode quality such as uniformity and reducing the environmental load, it is preferable to use a liquid phase film forming method such as a coating method or a printing method for forming the transparent conductive layer. 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 the 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, and the like can be used. In addition, as necessary, physical surface treatment such as corona discharge treatment or plasma discharge treatment can be applied to the surface of the releasable substrate as a preliminary treatment for improving the adhesion and coating properties.
本発明の透明電極の製造方法において、平滑な離型性基材の離型面上に、導電性繊維と導電性材料を含む透明導電層を形成した後、該透明導電層を透明基材上に転写することにより透明電極を形成する方法を用いることが好ましい。この方法を用いることにより、透明電極の透明導電層表面を簡便にかつ安定に高平滑化することができる。 In the method for producing a transparent electrode of the present invention, after forming a transparent conductive layer containing conductive fibers and a conductive material on a release surface of a smooth release substrate, the transparent conductive layer is placed on the transparent substrate. It is preferable to use a method in which a transparent electrode is formed by transferring the film onto the surface. By using this method, the surface of the transparent conductive layer of the transparent electrode can be easily and stably highly smoothed.
本発明の透明電極の製造方法で用いられる離型性基板としては、樹脂基板や樹脂フィルムなどが好適に挙げられる。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、塩化ビニル系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリイミド樹脂、ポリエチレン樹脂、ポリプロピレン樹脂などの合成樹脂の単層あるいは複数層からなる基板やフィルムが好適に用いられる。更にガラス基板や金属基板を用いることもできる。また、離型性基板の表面（離型面）には、必要に応じてシリコーン樹脂やフッ素樹脂、ワックスなどの離型剤を塗布して表面処理を施してもよい。 Preferred examples of the releasable substrate used in the method for producing a transparent electrode of the present invention include a resin substrate and a resin film. There is no restriction | limiting in particular in this resin, It can select suitably from well-known things, For example, synthesis | combination, such as a polyethylene terephthalate resin, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyimide resin, a polyethylene resin, a polypropylene resin A substrate or film composed of a single layer or multiple layers of resin is preferably used. Furthermore, a glass substrate or a metal substrate can also be used. Further, the surface (release surface) of the releasable substrate may be subjected to a surface treatment by applying a release agent such as silicone resin, fluororesin, or wax as necessary.
離型性基板表面は、透明導電層を転写した後の表面の平滑性に影響を与えるため、高平滑であることが望ましく、具体的にはＲｙ≦５０ｎｍであることが好ましく、Ｒｙ≦４０ｎｍであることがより好ましく、Ｒｙ≦３０ｎｍであることが更に好ましい。また、Ｒａ≦５ｎｍであることが好ましく、Ｒａ≦３ｎｍであることがより好ましく、Ｒａ≦１ｎｍであることが更に好ましい。 Since the surface of the releasable substrate affects the smoothness of the surface after the transparent conductive layer is transferred, it is desirable that the surface of the releasable substrate be highly smooth. Specifically, Ry ≦ 50 nm is preferable, and Ry ≦ 40 nm. More preferably, Ry ≦ 30 nm is still more preferable. Further, Ra ≦ 5 nm is preferable, Ra ≦ 3 nm is more preferable, and Ra ≦ 1 nm is still more preferable.
透明基材上に、導電性繊維と導電性材料を含む平滑性に優れた透明導電層を形成する具体的な方法として、例えば次のようなプロセスを挙げることができる。 As a specific method for forming a transparent conductive layer excellent in smoothness including conductive fibers and a conductive material on a transparent substrate, for example, the following process can be exemplified.
離型性基板の離型面上に、導電性繊維の分散液を塗布（または印刷）・乾燥して導電性繊維からなる導電ネットワーク構造を形成する。次いで、該導電性繊維のネットワーク構造上に導電性材料の分散液を塗布（または印刷）し、基板表面上の導電性繊維のネットワーク構造の隙間に導電性材料を含浸させ、導電性繊維と導電性材料を含む透明導電層を形成する。次いで、該透明導電層または別の透明基材上に接着層を塗設して両者を貼合する。接着層を硬化させた後、離型性基板を剥離することによって透明導電層を透明基材に転写する。 On the release surface of the release substrate, a conductive fiber dispersion is applied (or printed) and dried to form a conductive network structure made of conductive fibers. Next, a dispersion liquid of a conductive material is applied (or printed) on the network structure of the conductive fibers, and a conductive material is impregnated in a gap between the network structures of the conductive fibers on the substrate surface. A transparent conductive layer containing a conductive material is formed. Next, an adhesive layer is applied on the transparent conductive layer or another transparent substrate, and both are bonded together. After the adhesive layer is cured, the transparent conductive layer is transferred to the transparent substrate by peeling the release substrate.
このプロセスによれば、導電性材料層内に導電性繊維のネットワーク構造が３次元的に配置されるため、導電性繊維と導電性材料の接触面積が増えて導電性繊維の補助電極機能を十分に活用することができ、導電性に優れた透明導電層を形成することができる。 According to this process, since the conductive fiber network structure is three-dimensionally arranged in the conductive material layer, the contact area between the conductive fiber and the conductive material increases, and the auxiliary electrode function of the conductive fiber is sufficient. Therefore, a transparent conductive layer excellent in conductivity can be formed.
上記のプロセスにおいて、導電性繊維を塗布・乾燥した後、カレンダー処理や熱処理を施し導電性繊維間の密着性を高めることや、プラズマ処理を施し導電性繊維間の接触抵抗を低減することは、導電性繊維のネットワーク構造の導電性を向上させる方法として有効である。また、上記プロセスにおいて、離型性基板の離型面は、予めコロナ放電（プラズマ）などにより親水化処理していてもよい。 In the above process, after applying and drying conductive fibers, calender treatment or heat treatment to increase the adhesion between the conductive fibers, or plasma treatment to reduce the contact resistance between the conductive fibers, This is effective as a method for improving the conductivity of the network structure of conductive fibers. In the above process, the release surface of the release substrate may be previously hydrophilized by corona discharge (plasma) or the like.
上記プロセスにおいて、接着層は離型性基板側に設けても良いし、透明基材側に設けても良い。接着層に用いられる接着剤としては、可視領域で透明で転写能を有する材料であれば特に限定されない。透明であれば、硬化型樹脂でも良いし、熱可塑性樹脂でも良い。 In the above process, the adhesive layer may be provided on the releasable substrate side or on the transparent base material side. The adhesive used for the adhesive layer is not particularly limited as long as it is a material that is transparent in the visible region and has transfer ability. As long as it is transparent, a curable resin or a thermoplastic resin may be used.
硬化型樹脂として、熱硬化型樹脂、紫外線硬化型樹脂、電子線硬化型樹脂などが挙げられるが、これらの硬化型樹脂のうちでは、樹脂硬化のための設備が簡易で作業性に優れることから、紫外線硬化型樹脂を用いることが好ましい。紫外線硬化型樹脂とは紫外線照射により架橋反応等を経て硬化する樹脂で、エチレン性不飽和二重結合を有するモノマーを含む成分が好ましく用いられる。例えば、アクリルウレタン系樹脂、ポリエステルアクリレート系樹脂、エポキシアクリレート系樹脂、ポリオールアクリレート系樹脂等が挙げられる。本発明では、バインダーとしてアクリル系、アクリルウレタン系の紫外線硬化型樹脂を主成分とすることが好ましい。 Examples of curable resins include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these curable resins, the equipment for resin curing is simple and excellent in workability. It is preferable to use an ultraviolet curable resin. The ultraviolet curable resin is a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation, and a component containing a monomer having an ethylenically unsaturated double bond is preferably used. For example, acrylic urethane type resin, polyester acrylate type resin, epoxy acrylate type resin, polyol acrylate type resin and the like can be mentioned. In the present invention, it is preferable that an acrylic or acrylic urethane-based ultraviolet curable resin is a main component as a binder.
アクリルウレタン系樹脂は、一般にポリエステルポリオールにイソシアネートモノマー、またはプレポリマーを反応させて得られた生成物にさらに２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート（以下アクリレートにはメタクリレートを包含するものとしてアクリレートのみを表示する）、２−ヒドロキシプロピルアクリレート等の水酸基を有するアクリレート系のモノマーを反応させることによって容易に得ることができる。例えば、特開昭５９−１５１１１０号に記載のものを用いることができる。例えば、ユニディック１７−８０６（大日本インキ（株）製）１００部とコロネートＬ（日本ポリウレタン（株）製）１部との混合物等が好ましく用いられる。 Acrylic urethane-based resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.
紫外線硬化型ポリエステルアクリレート系樹脂としては、一般にポリエステルポリオールに２−ヒドロキシエチルアクリレート、２−ヒドロキシアクリレート系のモノマーを反応させると容易に形成されるものを挙げることができ、特開昭５９−１５１１１２号に記載のものを用いることができる。 Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.
紫外線硬化型エポキシアクリレート系樹脂の具体例としては、エポキシアクリレートをオリゴマーとし、これに反応性希釈剤、光反応開始剤を添加し、反応させて生成するものを挙げることができ、特開平１−１０５７３８号に記載のものを用いることができる。 Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.
紫外線硬化型ポリオールアクリレート系樹脂の具体例としては、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、アルキル変性ジペンタエリスリトールペンタアクリレート等を挙げることができる。 Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.
樹脂モノマーとしては、例えば、不飽和二重結合が一つのモノマーとして、メチルアクリレート、エチルアクリレート、ブチルアクリレート、ベンジルアクリレート、シクロヘキシルアクリレート、酢酸ビニル、スチレン等の一般的なモノマーを挙げることができる。また不飽和二重結合を二つ以上持つモノマーとして、エチレングリコールジアクリレート、プロピレングリコールジアクリレート、ジビニルベンゼン、１，４−シクロヘキサンジアクリレート、１，４−シクロヘキシルジメチルアジアクリレート、前出のトリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリルエステル等を挙げることができる。 Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
これらの中で、バインダーの主成分として、１，４−シクロヘキサンジアクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパン（メタ）アクリレート、トリメチロールエタン（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，２，３−シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレートから選択されるアクリル系の活性線硬化樹脂が好ましい。 Among these, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate as the main component of the binder , An acrylic selected from dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate A system active ray curable resin is preferred.
これら紫外線硬化型樹脂の光反応開始剤としては、具体的には、ベンゾイン及びその誘導体、アセトフェノン、ベンゾフェノン、ヒドロキシベンゾフェノン、ミヒラーズケトン、α−アミロキシムエステル、チオキサントン等及びこれらの誘導体を挙げることができる。光増感剤と共に使用してもよい。上記光反応開始剤も光増感剤として使用できる。また、エポキシアクリレート系の光反応開始剤の使用の際、ｎ−ブチルアミン、トリエチルアミン、トリ−ｎ−ブチルホスフィン等の増感剤を用いることができる。紫外線硬化型樹脂組成物に用いられる光反応開始剤また光増感剤は該組成物１００質量部に対して０．１〜１５質量部であり、好ましくは１〜１０質量部である。 Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.
透明導電層を形成した離型性基板と透明基材とを接着（貼合）し、紫外線等を照射して接着剤を硬化した後に離型性基板を剥離することにより、透明導電層を透明基材側に転写することができる。ここで、接着方法は特に限定されることなく、シートプレス、ロールプレス等により行うことができるが、ロールプレス機を用いて行うことが好ましい。ロールプレスは、ロールとロールの間に接着すべきフィルムを挟んで圧着し、ロールを回転させる方法である。ロールプレスは均一に圧力がかけられ、シートプレスよりも生産性が良く好適に用いることができる。 The transparent conductive layer is made transparent by bonding (bonding) the release substrate formed with the transparent conductive layer and the transparent base material, curing the adhesive by irradiating ultraviolet rays and the like, and then peeling the release substrate. It can be transferred to the substrate side. Here, the bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine. The roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated. The roll press is uniformly applied with pressure, and has a higher productivity than the sheet press and can be used preferably.
〔パターニング方法〕
本発明に係る透明導電層はパターニングすることができる。パターニングの方法やプロセスには特に制限はなく、公知の手法を適宜適用することができる。例えば、離型面上にパターニングされた透明導電層を形成した後、透明基材上に転写することによってパターニングされた透明電極を形成する方法を用いることができ、具体的には、以下のような方法を好ましく用いることができる。
ｉ）離型性基板上に印刷法を用いて本発明に係る透明導電層をパターン様に直接形成する方法
ii）離型性基板上に本発明に係る透明導電層を一様に形成した後、一般的なフォトリソプロセスを用いてパターニングする方法
iii）例えば紫外線硬化型樹脂を含む導電性材料を使用して本発明に係る透明導電層を一様に形成した後、フォトリソプロセス様にパターニングする方法
iv）離型性基板上に予めフォトレジストで形成したネガパターン上に本発明に係る透明導電層を一様に形成し、リフトオフ法を用いてパターニングする方法
上記のいずれの方法においても、離型性基板上でパターニングした透明導電層を透明基材上に転写することにより、パターニングされた本発明の透明電極を形成することができる。
[Patterning method]
The transparent conductive layer according to the present invention can be patterned. There is no particular limitation on the patterning method or process, and a known method can be applied as appropriate. For example, a method of forming a patterned transparent electrode by forming a patterned transparent conductive layer on a release surface and then transferring it onto a transparent substrate can be used. Such a method can be preferably used.
i) A method of directly forming a transparent conductive layer according to the present invention in a pattern-like manner on a releasable substrate using a printing method.
ii) A method in which a transparent conductive layer according to the present invention is uniformly formed on a releasable substrate and then patterned using a general photolithography process.
iii) A method of patterning like a photolithography process after uniformly forming the transparent conductive layer according to the present invention using a conductive material containing, for example, an ultraviolet curable resin
iv) A method of uniformly forming a transparent conductive layer according to the present invention on a negative pattern previously formed of a photoresist on a releasable substrate and patterning it using a lift-off method. By transferring the transparent conductive layer patterned on the conductive substrate onto the transparent substrate, the patterned transparent electrode of the present invention can be formed.
〔好ましい用途〕
本発明の透明電極は高い導電性と透明性を併せ持ち、液晶表示素子、有機発光素子、無機電界発光素子、電子ペーパー、有機太陽電池、無機太陽電池等の各種オプトエレクトロニクスデバイスや、電磁波シールド、タッチパネル等の分野において好適に用いることができる。その中でも、透明電極表面の平滑性が厳しく求められる有機エレクトロルミネッセンス素子の透明電極として特に好ましく用いることができる。
[Preferred use]
The transparent electrode of the present invention has both high conductivity and transparency, and various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, electromagnetic wave shields, touch panels. It can be suitably used in such fields. Among these, it can use especially preferably as a transparent electrode of the organic electroluminescent element by which the smoothness of the surface of a transparent electrode is calculated | required severely.
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「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。 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 "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.
［銀ナノワイヤの作製］
非特許文献２に記載の方法を参考に、下記の方法で銀ナノワイヤを作製した。
[Production of silver nanowires]
With reference to the method described in Non-Patent Document 2, silver nanowires were produced by the following method.
（核形成工程）
反応容器内で１７０℃に保持したエチレングリコール（ＥＧ）液１０００ｍｌを攪拌しながら、硝酸銀のＥＧ溶液（硝酸銀濃度：１．５×１０−４モル／Ｌ）１００ｍｌを一定の流量で１０秒間で添加した。その後、１７０℃で１０分間熟成を施し、銀の核粒子を形成した。熟成終了後の反応液は、銀ナノ粒子の表面プラズモン吸収に由来した黄色を呈しており、銀イオンが還元されて、銀ナノ粒子が形成されたことが確認された。
(Nucleation process)
While stirring 1000 ml of ethylene glycol (EG) liquid maintained at 170 ° C. in a reaction vessel, 100 ml of silver nitrate EG solution (silver nitrate concentration: 1.5 × 10 −4 mol / L) was added at a constant flow rate for 10 seconds. did. Thereafter, aging was carried out at 170 ° C. for 10 minutes to form silver core particles. The reaction solution after completion of ripening exhibited a yellow color derived from surface plasmon absorption of silver nanoparticles, and it was confirmed that silver ions were reduced and silver nanoparticles were formed.
（粒子成長工程）
上記の熟成を終了した核粒子を含む反応液を攪拌しながら１７０℃に保持し、硝酸銀のＥＧ溶液（硝酸銀濃度：１．０×１０−１モル／Ｌ）１０００ｍｌと、ＰＶＰ Ｋ３０（分子量５万；ＩＳＰ社製）のＥＧ溶液（ＰＶＰ濃度換算：５．０×１０−１モル／Ｌ）１０００ｍｌを、ダブルジェット法を用いて一定の流量で１００分間で添加した。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銀ナノ粒子が時間経過に伴って、主にナノワイヤの長軸方向に成長しており、粒子成長工程における新たな核粒子の生成は認められなかった。
(Particle growth process)
The reaction solution containing the core particles after completion of the ripening is kept at 170 ° C. with stirring, and 1000 ml of an EG solution of silver nitrate (silver nitrate concentration: 1.0 × 10 −1 mol / L) and PVP K30 (molecular weight 50,000). 1000 ml of EG solution (PVP concentration conversion: 5.0 × 10 −1 mol / L) of ISP Co., Ltd. was added at a constant flow rate for 100 minutes using the double jet method. When the reaction solution was sampled every 20 minutes in the particle growth process and confirmed with an electron microscope, the silver nanoparticles formed in the nucleation process grew mainly in the long axis direction of the nanowires over time. No new core particles were observed in the grain growth process.
（水洗工程）
粒子成長工程終了後、反応液を室温まで冷却した後、フィルターを用いて濾過し、濾別された銀ナノワイヤをエタノール中に再分散した。フィルターによる銀ナノワイヤの濾過とエタノール中への再分散を５回繰り返し、最終的に銀ナノワイヤの水分散液を調製して、銀ナノワイヤを作製した。
(Washing process)
After completion of the particle growth step, the reaction solution was cooled to room temperature, filtered using a filter, and the silver nanowires separated by filtration were redispersed in ethanol. Filtration of silver nanowires with a filter and redispersion in ethanol were repeated 5 times, and finally an aqueous dispersion of silver nanowires was prepared to produce silver nanowires.
得られた分散液を微量採取し、電子顕微鏡で確認したところ、平均直径８５ｎｍ、平均長さ７．４μｍの銀ナノワイヤが形成されたことが確認できた。 When a small amount of the obtained dispersion was collected and confirmed with an electron microscope, it was confirmed that silver nanowires having an average diameter of 85 nm and an average length of 7.4 μm were formed.
実施例１
〔透明電極ＴＣ−１０１の作製；本発明〕
作製した銀ナノワイヤの水分散液を易接着加工を施した厚さ１００μｍのポリエチレンテレフタレートフィルム支持体上に、銀ナノワイヤの目付け量が０．０５ｇ／ｍ２となるように、銀ナノワイヤの分散液をスピンコーターを用いて塗布し乾燥した。続いて、銀ナノワイヤの塗布層にカレンダー処理を施した後、公知のフォトリソグラフィー法により電極パターン幅１０ｍｍのストライプ状透明パターン電極ＴＣＦ−１を作製した。
Example 1
[Preparation of Transparent Electrode TC-101; Present Invention]
The dispersion of silver nanowires was applied to a polyethylene terephthalate film support having a thickness of 100 μm that had been subjected to easy adhesion processing of the aqueous dispersion of silver nanowires so that the basis weight of the silver nanowires was 0.05 g / m 2. It was applied and dried using a spin coater. Subsequently, the silver nanowire coating layer was calendered, and then a striped transparent pattern electrode TCF-1 having an electrode pattern width of 10 mm was produced by a known photolithography method.
次いで、導電性高分子としての、ＰＥＤＯＴ：ＰＳＳ（ポリスチレンスルホン酸）＝１：２．５の分散液であるＢａｙｔｒｏｎ ＰＨ５１０（Ｈ．Ｃ．Ｓｔａｒｃｋ社製、固形分濃度１．３％）（Ｐ−１という。）に、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を導電性高分子の固形分に対して１０質量％となるように添加したものを、乾燥膜厚が３００ｎｍとなるようにスピンコーターにて塗布、乾燥し、透明電極ＴＣ−１０１を作製した。 Next, Baytron PH510 (manufactured by HC Starck, solid content concentration 1.3%) which is a dispersion of PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5 as a conductive polymer (P- 1)), Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is 10% by mass with respect to the solid content of the conductive polymer. The thus added was applied and dried by a spin coater so that the dry film thickness was 300 nm, and a transparent electrode TC-101 was produced.
〔透明電極ＴＣ−１０２の作製；本発明〕
透明電極ＴＣ−１０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を、水系溶剤に均一分散可能なバインダー樹脂であるボンディック１９４０ＮＥ（大日本インキ社製、固形分濃度５０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−１０２を作製した。
[Preparation of Transparent Electrode TC-102; Present Invention]
In the production of the transparent electrode TC-101, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is a binder resin that can be uniformly dispersed in an aqueous solvent. A transparent electrode TC-102 was produced by performing the same operation except that Bondic 1940NE (Dainippon Ink Co., Ltd., solid content concentration: 50%) was used.
〔透明電極ＴＣ−１０３の作製；本発明〕
透明電極ＴＣ−１０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を、水系溶剤に均一分散可能なバインダー樹脂であるボンディック２２１０（大日本インキ社製、固形分濃度４０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−１０３を作製した。
[Preparation of Transparent Electrode TC-103; Present Invention]
In the production of the transparent electrode TC-101, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is a binder resin that can be uniformly dispersed in an aqueous solvent. A transparent electrode TC-103 was produced by performing the same operation except that Bondic 2210 (Dainippon Ink Co., Ltd., solid content concentration: 40%) was used.
〔透明電極ＴＣ−１０４の作製；本発明〕
透明電極ＴＣ−１０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を、水系溶剤に均一分散可能なバインダー樹脂であるハイドランＡＰ−４０（Ｆ）（大日本インキ社製、固形分濃度２２％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−１０４を作製した。
[Preparation of Transparent Electrode TC-104; Present Invention]
In the production of the transparent electrode TC-101, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is a binder resin that can be uniformly dispersed in an aqueous solvent. A transparent electrode TC-104 was produced in the same manner as described above except that it was replaced with Hydran AP-40 (F) (Dainippon Ink Co., Ltd., solid content concentration 22%).
〔透明電極ＴＣ−１０５の作製；本発明〕
透明電極ＴＣ−１０１の作製において、銀ナノワイヤー分散液にカルボキシメチルセルロース（信越化学工業社製）を銀質量あたり２５％添加し、さらにアルデヒド系架橋剤グリオキザールをカルボキシメチルセルロースの質量あたり１０％添加した後、硫酸及びアンモニアを添加しｐＨを７．３に調整した銀ナノワイヤー分散液を用いた以外は同様の操作を行い、透明電極ＴＣ−１０５を作製した。
[Preparation of Transparent Electrode TC-105; Present Invention]
In the production of the transparent electrode TC-101, after adding carboxymethyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) 25% to the silver nanowire dispersion and further adding 10% of the aldehyde-based crosslinking agent glyoxal to the carboxymethyl cellulose. A transparent electrode TC-105 was prepared in the same manner as above except that a silver nanowire dispersion liquid adjusted to pH 7.3 by adding sulfuric acid and ammonia was used.
〔透明電極ＴＣ−１０６の作製；本発明〕
透明電極ＴＣ−１０１の作製において、銀ナノワイヤー分散液にカルボキシメチルセルロース（信越化学工業社製）を銀質量あたり５％添加し、さらに熱硬化性樹脂含有ＰＥＤＯＴ Ｄｅｎａｔｒｏｎ Ｇ−２００１Ａ（ナガセケムテックス社製）を固形分として２０％添加した銀ナノワイヤー分散液を用いた以外は同様の操作を行い、透明電極ＴＣ−１０６を作製した。
[Preparation of Transparent Electrode TC-106; Present Invention]
In the production of the transparent electrode TC-101, 5% of carboxymethyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silver nanowire dispersion per silver mass, and thermosetting resin-containing PEDOT Denatron G-2001A (manufactured by Nagase ChemteX Corporation) is added. ) Was used to produce a transparent electrode TC-106, except that a silver nanowire dispersion liquid containing 20% as a solid content was used.
〔透明電極ＴＣ−１０７〜１１２の作製；本発明〕
透明電極ＴＣ−１０１〜１０６の作製において、導電性高分子ＰＥＤＯＴ：ＰＳＳ（ポリスチレンスルホン酸）＝１：２．５の分散液であるＢａｙｔｒｏｎ ＰＨ５１０（Ｈ．Ｃ．Ｓｔａｒｃｋ社製、固形分濃度１．３％）を、ポリアニリンＭ（ティーエーケミカル社製、固形分濃度６．０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−１０７〜１１２を作製した。
[Preparation of Transparent Electrodes TC-107-112; Present Invention]
In the production of the transparent electrodes TC-101 to 106, Baytron PH510 (manufactured by HC Starck, solid content concentration: 1.2.5), which is a dispersion of the conductive polymer PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5. 3%) was replaced with polyaniline M (manufactured by TA Chemical Co., Ltd., solid content concentration 6.0%), and the same operation was performed to produce transparent electrodes TC-107 to 112.
〔透明電極ＴＣ−１１３、ＴＣ−１１４の作製；比較例〕
透明電極ＴＣ−１０１、ＴＣ−１０７の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を添加しない以外は同様の操作を行い、透明電極ＴＣ−１１３、ＴＣ−１１４を作製した。
[Preparation of Transparent Electrodes TC-113 and TC-114; Comparative Example]
In the production of the transparent electrodes TC-101 and TC-107, the same operation was performed except that Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, was not added. Then, transparent electrodes TC-113 and TC-114 were produced.
〔透明電極ＴＣ−１１５の作製；比較例〕
透明電極ＴＣ−１０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を３０％ポリウレタン樹脂ＭＥＫ溶液であるバイロンＵＲ−３２２０（東洋紡社製）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−１１５を作製した。
[Preparation of Transparent Electrode TC-115; Comparative Example]
In the production of the transparent electrode TC-101, BONCOAT AN-155E (manufactured by Dainippon Ink Co., Ltd., solid concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is used as a Byron UR-3220, which is a 30% polyurethane resin MEK solution. A transparent electrode TC-115 was produced in the same manner as described above except that it was replaced with (Toyobo Co., Ltd.).
《評価》
以上のように作製した透明電極ＴＣ−１０１〜ＴＣ−１１５に対して、以下の方法にて全光線透過率、表面抵抗率、表面平滑性（Ｒａ、Ｒｙ）を求めた。また、透明電極の経時安定性を評価するため、８０℃９０％ＲＨの環境下で３日間置く強制劣化試験後の透明電極試料の全光線透過率、表面抵抗率、表面粗さ（Ｒａ、Ｒｙ）評価を行った。
<Evaluation>
With respect to the transparent electrodes TC-101 to TC-115 produced as described above, total light transmittance, surface resistivity, and surface smoothness (Ra, Ry) were determined by the following methods. Further, in order to evaluate the temporal stability of the transparent electrode, the total light transmittance, surface resistivity, and surface roughness (Ra, Ry) of the transparent electrode sample after a forced deterioration test placed in an environment of 80 ° C. and 90% RH for 3 days. ) Evaluated.
［全光線透過率］
ＪＩＳ Ｋ ７３６１−１：１９９７に準拠して、スガ試験機（株）製のヘイズメーターＨＧＭ−２Ｂを用いて測定した。
[Total light transmittance]
Based on JIS K 7361-1: 1997, it measured using the haze meter HGM-2B by Suga Test Instruments Co., Ltd.
［表面抵抗］
ＪＩＳ Ｋ ７１９４：１９９４に準拠して、三菱化学社製ロレスターＧＰ（ＭＣＰ−Ｔ６１０型）を用いて、測定した。
[Surface resistance]
Based on JIS K7194: 1994, it measured using the Lorester GP (MCP-T610 type | mold) by Mitsubishi Chemical Corporation.
［表面粗さ（Ｒａ、Ｒｙ）］
表面粗さは、ＡＦＭ（セイコーインスツルメンツ社製ＳＰＩ３８００Ｎプローブステーション及びＳＰＡ４００多機能型ユニット）を使用し、約１ｃｍ角の大きさに切り取った試料を用いて前記の方法で（ＪＩＳ Ｂ６０１（１９９４）に規定される表面粗さに準ずる。）測定した。
[Surface roughness (Ra, Ry)]
The surface roughness is specified in (JIS B601 (1994)) using a sample cut into a size of about 1 cm square using AFM (SPI3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc.). According to the surface roughness to be measured.)
結果を表１に示す。 The results are shown in Table 1.
表１中、
（導電性高分子）：
Ｐ−１：Ｂａｙｔｒｏｎ ＰＨ５１０（ポリ（３，４−エチレンジオキシチオフェン）（ドーパントとしてポリスチレンスルホン酸を含有）、Ｈ．Ｃ．Ｓｔａｒｃｋ社製、固形分濃度１．３％）
Ｐ−２：ポリアニリンＭ（ポリアニリン、ティーエーケミカル社製、固形分濃度６．０％）
（水系溶剤に均一分散可能なバインダー樹脂）：
ボンコートＡＮ−１５５Ｅ：アクリル系樹脂エマルジョン（アニオン性）（大日本インキ社製、固形分濃度５５％）
ボンディック１９４０ＮＥ：水分散型ポリウレタン樹脂、ポリエーテル系ウレタン樹脂（大日本インキ社製、固形分濃度５０％）
ボンディック２２１０：水分散型ポリウレタン樹脂、ポリエステル系ウレタン樹脂（大日本インキ社製、固形分濃度４０％）
ハイドランＡＰ−４０（Ｆ）：アイオノマー型水性ウレタン樹脂、ポリエステル系ウレタン樹脂（大日本インキ社製、固形分濃度２２％）
（水系溶剤に均一分散不可能なバインダー樹脂）：
バイロンＵＲ−３２２０（３０％ポリウレタン樹脂ＭＥＫ溶液、東洋紡績社製）（水系溶剤に均一分散不可能なバインダー樹脂）
表１に示した結果から、本発明の場合には、透明電極の経時安定性（全光線透過率、表面抵抗率、表面平滑性（Ｒａ、Ｒｙ））に優れることがわかる。
In Table 1,
(Conductive polymer):
P-1: Baytron PH510 (poly (3,4-ethylenedioxythiophene) (containing polystyrene sulfonic acid as a dopant), manufactured by HC Starck, solid content concentration 1.3%)
P-2: Polyaniline M (polyaniline, manufactured by TA Chemical Co., Ltd., solid content concentration 6.0%)
(Binder resin that can be uniformly dispersed in an aqueous solvent):
Boncoat AN-155E: Acrylic resin emulsion (anionic) (Dainippon Ink Co., Ltd., solid content concentration 55%)
Bondic 1940NE: Water-dispersed polyurethane resin, polyether urethane resin (Dainippon Ink Co., Ltd., solid content concentration 50%)
Bondic 2210: Water-dispersed polyurethane resin, polyester urethane resin (Dainippon Ink Co., Ltd., solid content concentration 40%)
Hydran AP-40 (F): ionomer-type water-based urethane resin, polyester-based urethane resin (Dainippon Ink Co., Ltd., solid content concentration 22%)
(Binder resin that cannot be uniformly dispersed in an aqueous solvent):
Byron UR-3220 (30% polyurethane resin MEK solution, manufactured by Toyobo Co., Ltd.) (binder resin that cannot be uniformly dispersed in an aqueous solvent)
From the results shown in Table 1, it can be seen that in the case of the present invention, the transparent electrode is excellent in temporal stability (total light transmittance, surface resistivity, surface smoothness (Ra, Ry)).
銀ナノワイヤー上に導電性ポリマーのみ、或いは水系溶剤に均一分散可能なバインダー樹脂のみ、を塗布した透明電極ＴＣ−１１３〜ＴＣ−１１５は８０℃９０％ＲＨの環境下３日間置いた後の表面抵抗及び表面平滑性が悪く、本発明の透明電極ＴＣ−１０１〜１１２の表面抵抗及び表面平滑性の方が安定していることが明らかとなった。 Transparent electrodes TC-113 to TC-115 coated with only a conductive polymer or only a binder resin that can be uniformly dispersed in an aqueous solvent on silver nanowires are surfaces after being placed in an environment of 80 ° C. and 90% RH for 3 days. It was revealed that the resistance and surface smoothness were poor and the surface resistance and surface smoothness of the transparent electrodes TC-101 to 112 of the present invention were more stable.
実施例２
〔透明電極ＴＣ−２０１の作製；本発明〕
作製した銀ナノワイヤ分散液に導電性高分子として、固形分濃度が１３％になるまでロータリーエバポレーターで濃縮したＰＥＤＯＴ：ＰＳＳ（ポリスチレンスルホン酸）＝１：２．５の分散液であるＢａｙｔｒｏｎ ＰＨ５１０（Ｈ．Ｃ．Ｓｔａｒｃｋ社製、固形分濃度１３％）を銀重量の１０倍加え、更に水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を導電性高分子の固形分に対して１０質量％となるように添加した。この分散液を易接着加工を施した厚さ１００μｍのポリエチレンテレフタレートフィルム支持体上に、乾燥膜厚が３００ｎｍとなるようにスピンコーターにて塗布し、乾燥した。
〈金属ナノワイヤ除去剤ＢＦ−１の作製〉
エチレンジアミン４酢酸第２鉄アンモニウム ６０ｇ
エチレンジアミン４酢酸 ２ｇ
メタ重亜硫酸ナトリウム １５ｇ
チオ硫酸アンモニウム ７０ｇ
マレイン酸 ５ｇ
純水で１Ｌに仕上げ、硫酸またはアンモニア水でｐＨを５．５に調整し金属ナノワイヤ除去剤ＢＦ−１を作製した。
Example 2
[Preparation of Transparent Electrode TC-201; Present Invention]
Baytron PH510 (H), which is a dispersion of PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5, which is concentrated as a conductive polymer in the produced silver nanowire dispersion liquid by a rotary evaporator until the solid content concentration becomes 13%. Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent. Was added so that it might become 10 mass% with respect to solid content of a conductive polymer. This dispersion was applied on a polyethylene terephthalate film support having a thickness of 100 μm that had been subjected to easy adhesion processing, and dried by a spin coater so that the dry film thickness was 300 nm.
<Preparation of metal nanowire remover BF-1>
Ethylenediaminetetraacetic acid ferric ammonium 60g
Ethylenediaminetetraacetic acid 2g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5g
The metal nanowire remover BF-1 was prepared by finishing to 1 L with pure water and adjusting the pH to 5.5 with sulfuric acid or ammonia water.
続いて、銀ナノワイヤの塗布層にカレンダー処理を施した後、グラビア塗布機Ｋプリンティングプルーファー（松尾産業株式会社製）に、１０ｍｍのストライプ状パターンと逆の印刷パターンを形成した版を取り付け、作製した金属ナノワイヤ除去剤ＢＦ−１の粘度をＣＭＣ（カルボキシメチルセルロース、シグマアルドリッチ社製）で適宜調整し、銀ナノワイヤ塗布層の上に塗布膜厚３０μｍとなるよう印刷回数を調整してグラビア印刷を行った。印刷後１分間放置し、次いで流水による水洗処理を行い、透明電極ＴＣ−２０１を作製した。 Subsequently, a calender treatment was applied to the silver nanowire coating layer, and then a gravure coating machine K printing proofer (manufactured by Matsuo Sangyo Co., Ltd.) was attached with a plate having a printing pattern opposite to the 10 mm stripe pattern. The viscosity of the metal nanowire remover BF-1 was adjusted as appropriate with CMC (carboxymethylcellulose, Sigma-Aldrich), and gravure printing was performed by adjusting the number of printings so that the coating film thickness was 30 μm on the silver nanowire coating layer. It was. After printing, it was left for 1 minute, and then washed with running water to produce a transparent electrode TC-201.
〔透明電極ＴＣ−２０２の作製；本発明〕
透明電極ＴＣ−２０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）をボンディック１９４０ＮＥ（大日本インキ社製、固形分濃度５０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−２０２を作製した。
[Preparation of Transparent Electrode TC-202; Present Invention]
In the production of the transparent electrode TC-201, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is bonded to Bondic 1940NE (manufactured by Dainippon Ink Co., Ltd., solid content). A transparent electrode TC-202 was produced in the same manner except that the concentration was changed to 50%.
〔透明電極ＴＣ−２０３の作製；本発明〕
透明電極ＴＣ−２０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）をボンディック２２１０（大日本インキ社製、固形分濃度４０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−２０３を作製した。
[Preparation of Transparent Electrode TC-203; Present Invention]
In the production of the transparent electrode TC-201, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is bonded to Bondic 2210 (manufactured by Dainippon Ink Co., Ltd., solid content). A transparent electrode TC-203 was produced in the same manner except that the concentration was changed to 40%.
〔透明電極ＴＣ−２０４の作製；本発明〕
透明電極ＴＣ−２０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）をハイドランＡＰ−４０（Ｆ）（大日本インキ社製、固形分濃度２２％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−２０４を作製した。
[Preparation of Transparent Electrode TC-204; Present Invention]
In the production of the transparent electrode TC-201, Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, was applied to Hydran AP-40 (F) (Dainippon Ink Co., Ltd.). A transparent electrode TC-204 was produced in the same manner except that the product was replaced with a solid content concentration of 22%.
〔透明電極ＴＣ−２０５の作製；本発明〕
透明電極ＴＣ−２０１の作製において、銀ナノワイヤー分散液にカルボキシメチルセルロース（信越化学工業社製）を銀質量あたり２５％添加し、さらにアルデヒド系架橋剤グリオキザールをカルボキシメチルセルロースの質量あたり１０％添加した後、硫酸及びアンモニアを添加しｐＨを７．３に調整した銀ナノワイヤー分散液を用いた以外は同様の操作を行い、透明電極ＴＣ−２０５を作製した。
[Preparation of Transparent Electrode TC-205; Present Invention]
In the production of the transparent electrode TC-201, 25% carboxymethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silver nanowire dispersion, and 10% of the aldehyde-based crosslinking agent glyoxal is added to the carboxymethylcellulose. A transparent electrode TC-205 was produced in the same manner as above except that a silver nanowire dispersion liquid adjusted to pH 7.3 by adding sulfuric acid and ammonia was used.
〔透明電極ＴＣ−２０６の作製；本発明〕
透明電極ＴＣ−２０１の作製において、銀ナノワイヤー分散液にカルボキシメチルセルロース（信越化学工業社製）を銀質量あたり５％添加し、さらに熱硬化性樹脂含有ＰＥＤＯＴ Ｄｅｎａｔｒｏｎ Ｇ−２００１Ａ（ナガセケムテックス社製）を固形分として２０％添加した銀ナノワイヤー分散液を用いた以外は同様の操作を行い、透明電極ＴＣ−２０６を作製した。
[Preparation of Transparent Electrode TC-206; Present Invention]
In the production of the transparent electrode TC-201, 5% of carboxymethyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silver nanowire dispersion per silver mass, and further, a thermosetting resin-containing PEDOT Denatron G-2001A (manufactured by Nagase ChemteX Corporation). ) Was used in the same manner except that a silver nanowire dispersion liquid added with 20% as a solid content was used to produce a transparent electrode TC-206.
〔透明電極ＴＣ−２０７〜２１２の作製；本発明〕
透明電極ＴＣ−２０１〜２０６の作製において、ＰＥＤＯＴ：ＰＳＳ（ポリスチレンスルホン酸）＝１：２．５の分散液であるＢａｙｔｒｏｎ ＰＨ５１０（Ｈ．Ｃ．Ｓｔａｒｃｋ社製、固形分濃度１．３％）をポリアニリンＭ（ティーエーケミカル社製、固形分濃度６．０％）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−２０７〜２１２を作製した。
[Production of Transparent Electrodes TC-207 to 212; Present Invention]
In the production of the transparent electrodes TC-201 to 206, Baytron PH510 (manufactured by HC Starck, solid content concentration 1.3%) which is a dispersion of PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5 is used. Transparent electrodes TC-207 to 212 were prepared in the same manner except that the polyaniline M (manufactured by TA Chemical Co., Ltd., solid content concentration 6.0%) was used.
〔透明電極ＴＣ−２１３、ＴＣ−２１４の作製；比較例〕
透明電極ＴＣ−２０１、ＴＣ−２０７の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を添加しない以外は同様の操作を行い、透明電極ＴＣ−２１３、ＴＣ−２１４を作製した。
[Preparation of Transparent Electrodes TC-213 and TC-214; Comparative Example]
In the production of the transparent electrodes TC-201 and TC-207, the same operation was performed except that Boncoat AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, was not added. Then, transparent electrodes TC-213 and TC-214 were produced.
〔透明電極ＴＣ−２１５の作製；比較例〕
透明電極ＴＣ−２０１の作製において、水系溶剤に均一分散可能なバインダー樹脂であるボンコートＡＮ−１５５Ｅ（大日本インキ社製、固形分濃度５５％）を３０％ポリウレタン樹脂ＭＥＫ溶液であるバイロンＵＲ−３２２０（東洋紡社製）に置き換えた以外は同様の操作を行い、透明電極ＴＣ−２１５を作製した。
[Preparation of Transparent Electrode TC-215; Comparative Example]
In the production of the transparent electrode TC-201, BONCOAT AN-155E (manufactured by Dainippon Ink and Co., Ltd., solid content concentration 55%), which is a binder resin that can be uniformly dispersed in an aqueous solvent, is used by Byron UR-3220, which is a 30% polyurethane resin MEK solution. A transparent electrode TC-215 was produced in the same manner as described above except that it was replaced with (Toyobo Co., Ltd.).
《評価》
以上のように作製した透明電極ＴＣ−２０１〜ＴＣ−２１５に対して、実施例１記載の方法にて、全光線透過率、表面抵抗率、表面平滑性（Ｒａ、Ｒｙ）を求めた。また、透明電極の安定性を評価するため、８０℃９０％ＲＨの環境下で３日間置く強制劣化試験後の透明電極試料の全光線透過率、表面抵抗率、表面平滑性（Ｒａ、Ｒｙ）、についても求めた。
<Evaluation>
With respect to the transparent electrodes TC-201 to TC-215 produced as described above, the total light transmittance, the surface resistivity, and the surface smoothness (Ra, Ry) were determined by the method described in Example 1. In addition, in order to evaluate the stability of the transparent electrode, the total light transmittance, surface resistivity, and surface smoothness (Ra, Ry) of the transparent electrode sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 3 days. , Also asked for.
結果を表２に示す。 The results are shown in Table 2.
表２から、本発明の場合には、透明電極の経時安定性（全光線透過率、表面抵抗率、表面平滑性（Ｒａ、Ｒｙ））に優れることがわかる。 From Table 2, in the case of this invention, it turns out that it is excellent in the temporal stability (total light transmittance, surface resistivity, surface smoothness (Ra, Ry)) of a transparent electrode.
銀ナノワイヤー上に導電性ポリマーのみ、或いは水系溶剤に均一分散可能なバインダー樹脂のみ、を塗布した透明電極ＴＣ−２１３〜ＴＣ−２１５は８０℃９０％ＲＨの環境下３日間置いた後の表面抵抗及び表面平滑性が悪く、本発明の透明電極ＴＣ−２０１〜ＴＣ−２１２の表面抵抗及び表面平滑性の方が安定していることが明らかとなった。 Transparent electrodes TC-213 to TC-215 in which only a conductive polymer or only a binder resin that can be uniformly dispersed in an aqueous solvent are coated on silver nanowires are surfaces after being placed in an environment of 80 ° C. and 90% RH for 3 days. It was revealed that the resistance and surface smoothness were poor and the surface resistance and surface smoothness of the transparent electrodes TC-201 to TC-212 of the present invention were more stable.
実施例３
［有機エレクトロルミネッセンス素子（有機ＥＬ素子）の作製］
作製した透明電極ＴＣ−１０１〜１１５を第一電極（アノード電極）に用いて、以下の手順でそれぞれ有機ＥＬ素子ＯＥＬ−３０１〜３１５を作製した。
〈正孔輸送層の形成〉
第１電極上に、１，２−ジクロロエタン中に１質量％となるように正孔輸送材料の４，４′−ビス〔Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ〕ビフェニル（ＮＰＤ）を溶解させた正孔輸送層形成用塗布液をスピンコート装置で塗布した後、８０℃、６０分間乾燥して、厚さ４０ｎｍの正孔輸送層を形成した。
〈発光層の形成〉
正孔輸送層が形成された各フィルム上に、ホスト材のポリビニルカルバゾール（ＰＶＫ）に対して、赤ドーパント材Ｂｔｐ２Ｉｒ（ａｃａｃ）が１質量％、緑ドーパント材Ｉｒ（ｐｐｙ）３が２質量％、青ドーパント材ＦＩｒ（ｐｉｃ）が３質量％にそれぞれなるように混合し、ＰＶＫと３種ドーパントの全固形分濃度が１質量％となるように１，２−ジクロロエタン中に溶解させた発光層形成用塗布液をスピンコート装置で塗布した後、１００℃、１０分間乾燥して、厚さ６０ｎｍの発光層を形成した。
Example 3
[Production of organic electroluminescence element (organic EL element)]
Using the produced transparent electrodes TC-101 to 115 as the first electrode (anode electrode), organic EL elements OEL-301 to 315 were produced in the following procedure.
<Formation of hole transport layer>
On the first electrode, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), which is a hole transport material, was added to 1% by mass in 1,2-dichloroethane. The dissolved coating solution for forming a hole transport layer was applied by a spin coater and then dried at 80 ° C. for 60 minutes to form a hole transport layer having a thickness of 40 nm.
<Formation of light emitting layer>
On each film in which the hole transport layer is formed, the red dopant material Btp 2 Ir (acac) is 1% by mass and the green dopant material Ir (ppy) 3 is 2% with respect to polyvinylcarbazole (PVK) as the host material. %, Blue dopant material FIr (pic) is mixed so as to be 3% by mass, and the light emission is dissolved in 1,2-dichloroethane so that the total solid concentration of PVK and the three dopants is 1% by mass. The coating liquid for layer formation was applied with a spin coater and then dried at 100 ° C. for 10 minutes to form a light emitting layer having a thickness of 60 nm.
〈電子輸送層の形成〉
形成した発光層上に、電子輸送層形成用材料としてＬｉＦを５×１０−４Ｐａの真空下にて蒸着し、厚さ０．５ｎｍの電子輸送層を形成した。
〈第２電極の形成〉
形成した電子輸送層の上に、第２電極形成用材料としてＡｌを５×１０−４Ｐａの真空下にて蒸着し、厚さ１００ｎｍの第２電極を形成した。
〈封止膜の形成〉
形成した電子輸送層の上に、ポリエチレンテレフタレートを基材とし、Ａｌ２Ｏ３を厚さ３００ｎｍで蒸着した可撓性封止部材を使用した。第１電極及び第２電極の外部取り出し端子が形成出来る様に端部を除き第２電極の周囲に接着剤を塗り、可撓性封止部材を貼合した後、熱処理で接着剤を硬化させた。
<Formation of electron transport layer>
On the formed light emitting layer, LiF was evaporated as a material for forming an electron transport layer under a vacuum of 5 × 10 −4 Pa to form an electron transport layer having a thickness of 0.5 nm.
<Formation of second electrode>
On the formed electron carrying layer, Al was vapor-deposited as a 2nd electrode formation material under the vacuum of 5 * 10 <-4> Pa, and the 2nd electrode with a thickness of 100 nm was formed.
<Formation of sealing film>
On the formed electron transport layer, a polyethylene terephthalate as a substrate, using a flexible sealing member which is deposited to a thickness 300nm of Al 2 O 3. Apply the adhesive around the second electrode except for the end so that the external lead terminals of the first electrode and the second electrode can be formed, paste the flexible sealing member, and then cure the adhesive by heat treatment It was.
［発光均一性（発光輝度ムラ）］
ＫＥＩＴＨＬＥＹ製ソースメジャーユニット２４００型を用いて、直流電圧を有機ＥＬ素子に印加し、２３±３℃、５５±３％ＲＨの環境下で、発光させた。２００ｃｄ／ｍ２で発光させた有機ＥＬ素子ＯＥＬ−３０１〜ＯＥＬ−３１５について、５０倍の顕微鏡で各々の発光均一性を観察した。また、有機ＥＬ素子ＯＥＬ−３０１〜ＯＥＬ−３１５をオーブンにて８０℃６０％ＲＨ３０分加熱したのち、再び前記２３±３℃、５５±３％ＲＨの環境下で１時間以上調湿した後、同様に発光均一性を観察した。
[Light emission uniformity (light emission unevenness)]
Using a source measure unit 2400 made by KEITHLEY, a direct current voltage was applied to the organic EL element to emit light in an environment of 23 ± 3 ° C. and 55 ± 3% RH. Regarding the organic EL elements OEL-301 to OEL-315 that emitted light at 200 cd / m 2 , the respective light emission uniformity was observed with a 50 × microscope. In addition, after heating the organic EL elements OEL-301 to OEL-315 in an oven at 80 ° C. and 60% RH for 30 minutes, the humidity was adjusted again in the environment of 23 ± 3 ° C. and 55 ± 3% RH for 1 hour or more. Similarly, the emission uniformity was observed.
発光均一性の評価基準
◎：ＥＬ素子全体が均一に発光している
○：ＥＬ素子全体がほぼ均一に発光している
△：ＥＬ素子の発光にややムラが認められる
×：ＥＬ素子の発光に明らかなムラが認められる
上記評価結果を表３に示す。
Evaluation Criteria for Emission Uniformity ◎: The entire EL element emits light uniformly ○: The entire EL element emits light almost uniformly Δ: Some unevenness is observed in the light emission of the EL element x: Light emission of the EL element Obvious unevenness is observed Table 3 shows the evaluation results.
表３から、有機ＥＬ素子ＯＥＬ−３１３〜ＯＥＬ−３１５は８０℃６０％ＲＨ３０分の加熱（強制劣化）後、発光均一性が著しく劣化するのに対し、本発明有機ＥＬ素子ＯＥＬ−３０１〜ＯＥＬ−３１２の発光均一性は加熱後でも安定していることが明らかとなった。 From Table 3, the organic EL elements OEL-313 to OEL-315 are significantly deteriorated in light emission uniformity after heating (forced deterioration) at 80 ° C. and 60% RH for 30 minutes, whereas the organic EL elements OEL-301 to OEL of the present invention It was revealed that the emission uniformity of −312 was stable even after heating.
実施例４
［有機エレクトロルミネッセンス素子（有機ＥＬ素子）の作製］
作製した透明電極ＴＣ−２０１〜２１５を第一電極に用いて、実施例３の手順と同様な方法で有機ＥＬ素子ＯＥＬ−４０１〜４１５を作製した。
Example 4
[Production of organic electroluminescence element (organic EL element)]
Using the produced transparent electrodes TC-201 to 215 as first electrodes, organic EL elements OEL-401 to 415 were produced in the same manner as in the procedure of Example 3.
評価結果を表４に示す。 The evaluation results are shown in Table 4.
表４から、有機ＥＬ素子ＯＥＬ−４１３〜ＯＥＬ−４１５は８０℃６０％ＲＨ３０分の加熱後、発光均一性が著しく劣化するのに対し、本発明有機ＥＬ素子ＯＥＬ−４０１〜ＯＥＬ−４１２の発光均一性は加熱後でも安定していることが明らかとなった。 From Table 4, the organic EL elements OEL-413 to OEL-415 are significantly degraded in light emission uniformity after heating at 80 ° C. and 60% RH for 30 minutes, whereas the organic EL elements OEL-401 to OEL-412 of the present invention emit light. It became clear that the uniformity was stable even after heating.
１１ 導電性繊維
２１ 導電性材料
３１ 透明導電層３
４１ 透明樹脂
５１ 透明基材
11 Conductive fiber 21
41
Claims (7)
前記透明導電層は、カーボンナノチューブを含まず、
該バインダー樹脂が純水に均一に分散可能なバインダー樹脂であることを特徴とする透明電極。 In a transparent electrode having a transparent conductive layer having a silver nanowire, a conductive polymer, and a binder resin (excluding the conductive polymer) on a transparent substrate,
The transparent conductive layer does not contain carbon nanotubes,
A transparent electrode, wherein the binder resin is a binder resin that can be uniformly dispersed in pure water.
前記銀ナノワイヤ、導電性高分子、及び前記バインダー樹脂を含有する水系分散物を、透明基材上に塗布することにより透明導電層を形成することを特徴とする透明電極の製造方法。 It is a manufacturing method of the transparent electrode according to claim 2,
A method for producing a transparent electrode, comprising forming a transparent conductive layer by applying an aqueous dispersion containing the silver nanowire, a conductive polymer, and the binder resin on a transparent substrate.
前記銀ナノワイヤを含む第一の透明導電層を透明基材上に塗布する工程と、
該第一の透明導電層上に前記導電性高分子と前記バインダー樹脂を含む水系分散液を塗布することにより第二の透明導電層を形成する工程と、
を有することを特徴とする透明電極の製造方法。 It is a manufacturing method of the transparent electrode according to claim 3,
Applying a first transparent conductive layer containing the silver nanowire on a transparent substrate;
Forming a second transparent conductive layer by applying an aqueous dispersion containing the conductive polymer and the binder resin on the first transparent conductive layer;
The manufacturing method of the transparent electrode characterized by having.
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| JP4807817B2 (en) * | 2004-08-05 | 2011-11-02 | 三菱レイヨン株式会社 | Method for producing conductive molded body and conductive molded body |
| US7645497B2 (en) * | 2005-06-02 | 2010-01-12 | Eastman Kodak Company | Multi-layer conductor with carbon nanotubes |
| US8018563B2 (en) * | 2007-04-20 | 2011-09-13 | Cambrios Technologies Corporation | Composite transparent conductors and methods of forming the same |
| JPWO2009035059A1 (en) * | 2007-09-12 | 2010-12-24 | 株式会社クラレ | Conductive film, conductive member, and method of manufacturing conductive film |
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