JP2012252821A - Transparent electrode and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the occurrence of emission failure, the occurrence of leakage between electrodes, deterioration with time, and damage to a transparent conductive layer.SOLUTION: A transparent electrode 2 according to the present invention comprises a substrate 4, a first conductive layer 6 formed in a pattern on the substrate 4 and made of a metal material, and a second conductive layer 8 containing a conductive polymer. The second conductive layer 8 contains a special compound.

Description

  The present invention is a transparent electrode that can be suitably used in various fields such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, a solar cell, an electromagnetic wave shield, electronic paper, and a touch panel, and further, an organic electro that uses the transparent electrode. The present invention relates to a luminescence element (hereinafter also referred to as an organic EL element).

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays having different display methods, 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.

Conventionally, as transparent electrodes, various metal thin films such as Au, Ag, Pt, Cu, indium oxide doped with tin or zinc (ITO, IZO), zinc oxide doped with aluminum or gallium (AZO, GZO), fluorine, Metal oxide thin films such as tin oxide (FTO, ATO) doped with antimony, conductive nitride thin films such as TiN, ZrN, and HfN, and conductive boride thin films such as LaB ₆ are known and combinations thereof. Bi ₂ O ₃ / Au / Bi ₂ O ₃ , TiO ₂ / Ag / TiO _{2 and the} like are also known. In addition to inorganic materials, transparent electrodes using CNTs (carbon nanotubes) have also been proposed.
However, since the metal thin film, nitride thin film, and boron thin film described above cannot have both light transmission and conductivity characteristics, they are allowed even in special technical fields such as electromagnetic shielding and relatively high resistance values. It was used in the touch panel field. In the field of touch panels, a transparent electrode using a water-soluble resin containing a hydroxyl group and a transparent conductive polymer layer containing polythiophene has also been proposed (Patent Document 1). However, a transparent conductive polymer generally has a high resistance. The problem is that the sheet resistance cannot be kept low enough.

A thin metal wire pattern is formed as the first conductive layer, and a transparent conductive layer is laminated thereon as the second conductive layer so that it can be applied to products that require a large area and a low resistance value such as an organic EL element. A transparent conductive film is known (for example, Patent Document 2).
Although this technology makes it possible to achieve both low resistance and high transparency, the smoothness of the electrode surface deteriorates due to the level difference caused by the metal fine line pattern and the unevenness of the surface of the metal fine line pattern. In an electronic device having a configuration in which a thin layer is laminated on the electrode surface, a problem such as a short circuit occurs between the laminated layers, causing a problem such as a light emitting failure. As a method of smoothing the surface of the electrode by filling the steps of the fine metal wire pattern and the unevenness of the fine metal wire pattern surface, the conductive fine polymer (conductive polymer) and transparent resin are mixed to increase the film thickness, thereby forming the fine metal wire pattern. A method of coating is conceivable, and transparent resins that can be used for such applications have been proposed (Patent Documents 3 and 4).

JP 2010-146945 A JP 2008-277233 A JP 2010-244747 A JP 2010-244746 A

However, a transparent conductive layer that is a mixture of a conductive polymer and a transparent resin emits light due to non-uniform film thickness due to the difference in surface energy between the base material and the fine metal wire when these mixed solutions are applied. There are problems in the occurrence of defects, the occurrence of leaks between electrodes, and the deterioration over time after device formation (sustainability of light emission luminance). Although the uniformity of the film surface is improved by adding a surfactant to the mixture of the conductive polymer and the transparent resin, the transparent conductive layer is damaged when used for a long period of time. There is also a problem that adhesiveness decreases.
Therefore, the main object of the present invention is a transparent electrode in which a transparent conductive polymer layer is laminated on a thin metal wire pattern. Even when it is used for an organic electroluminescence element, the occurrence of light emission defects and leakage between electrodes are prevented. The object is to provide a transparent electrode capable of suppressing generation and deterioration over time, and also capable of suppressing damage to the transparent conductive layer, and further to provide an organic electroluminescence device including the transparent electrode.

According to one aspect of the invention,
A substrate,
A first conductive layer made of a metal material formed in a pattern on the substrate;
In a transparent electrode having a second conductive layer containing a conductive polymer,
A transparent electrode is provided, wherein the second conductive layer contains a compound represented by the general formula (I) or the general formula (II).

  In the formulas (I) and (II), “R1” and “R4” are linear or branched alkyl chains having 3 to 10 carbon atoms, and “R2” and “R3” are hydrogen atoms or carbon atoms. It is an alkyl chain having 1 to 5 atoms, and “m”, “n”, “p” and “q” are numbers in the range of 0-20.

According to another aspect of the invention,
The transparent electrode;
A cathode,
An organic light emitting layer interposed between the transparent electrode and the cathode;
The organic electroluminescent element characterized by including this is provided.

According to the present invention, it is possible to suppress the occurrence of light emission failure, the occurrence of leakage between electrodes, and the deterioration over time in a transparent electrode in which a transparent conductive polymer layer is laminated on a thin metal wire pattern. Can be suppressed.
That is, according to the present invention, the transparent conductive layer obtained by mixing the conductive polymer and the transparent resin has a film thickness resulting from the difference in surface energy between the base material and the metal thin wire when the mixture is applied. There was a problem in the occurrence of light emission failure due to non-uniformity of the material, the occurrence of leakage between electrodes, and the deterioration over time after device formation (sustainability of light emission luminance), but the compound of general formula (I) or general formula (II) Is used as a coating solution for the second conductive layer, it quickly orients to the surface of the solution at the time of coating to lower the surface tension, thereby improving coating properties. This effect is greater than nonionic surfactants such as general polyoxyethylene alkyl ethers and fluorosurfactants, and the effect of improving coating properties is particularly high.
Further, when a device such as an organic EL element is manufactured, when another layer is stacked on the second conductive layer, the other layer is defective on the second conductive layer, unlike the fluorosurfactant. It is possible to laminate without any problem. In particular, when the hole injection layer of the organic EL element is laminated, a remarkable effect is exhibited.
By using the structure of the present invention, a device that enables uniform formation of the second conductive layer and good lamination of adjacent layers, emits light uniformly, and maintains good light emission even when the device is stored. It was found that it can be obtained.

It is sectional drawing which shows schematic structure of the organic electroluminescent element concerning preferable embodiment of this invention.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

<< Organic electroluminescence element (100) >>
First, the configuration of an organic electroluminescence element (organic EL element) will be described.
(1) Transparent electrode 2
As shown in FIG. 1, the organic EL element 100 has a transparent electrode 2.
The transparent electrode 2 is mainly composed of a substrate 4 and a first conductive layer 6 and a second conductive layer 8, and the first conductive layer 6 and the second conductive layer 8 are formed on the substrate 4.
The first conductive layer 6 is made of a metal material and has a pattern with a predetermined shape.
The second conductive layer 8 is a layer containing a conductive polymer, and covers the first conductive layer 6 and the substrate 4 exposed from the gap.

(2) Organic light emitting layer 10
An organic light emitting layer 10 is formed on the transparent electrode 2.
In place of the organic light emitting layer 10, a known organic photoelectric conversion layer, a liquid crystal polymer layer, or the like may be used. However, in the present embodiment, the organic light emitting layer (or organic photoelectric conversion) that is a thin film and current-driven element is used. This is particularly effective in the case of a layer).
In addition to the light emitting layer, the organic light emitting layer 10 is a layer that controls light emission in combination with a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, an electron block layer, or the like. You may have. Since the second conductive layer 8 containing a conductive polymer can also function as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.

Preferred specific examples (i) to (v) of the configuration of the organic light emitting layer 10 are shown below.
(I) (anode) / light emitting layer / electron transport layer / (cathode)
(Ii) (anode) / hole transport layer / light emitting layer / electron transport layer / (cathode)
(Iii) (anode) / hole transport layer / light emitting layer / hole block layer / electron transport layer / (cathode)
(Iv) (anode) / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (cathode)
(V) (anode) / anode buffer layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (cathode)

  The organic EL device 100 according to this embodiment has the configuration of the specific example (iii), and the organic light emitting layer 10 is a stacked layer of a hole transport layer 12, a light emitting layer 14, a hole blocking layer 16, and an electron transport layer 18. Consists of the body.

(2.1) Light emitting layer 14
The light-emitting layer 14 may be a monochromatic light-emitting layer having a light emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm, respectively. A layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element 100 is preferably a white light emitting layer.
Examples of the light emitting material or the doping material that can be used for the organic light emitting layer 10 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, carbazole, azacarbazole, oxadiazole, bis Benzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex Aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyra , Quinacridone, rubrene, distyrylbenzene derivatives, di still arylene derivatives, and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material. The organic light emitting layer 10 is produced by a known method using the above materials, and examples thereof include vapor deposition, coating, and transfer. The thickness of the organic light emitting layer 10 is preferably 0.5 to 500 nm, and particularly preferably 0.5 to 200 nm.

(3) Cathode 20
A cathode 20 is formed on the organic light emitting layer 10.
The cathode 20 may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the cathode 20, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
The cathode 20 can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
The sheet resistance as the cathode 20 is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.
If a metal material is used as the cathode conductive material, the light coming to the cathode side is reflected and returns to the anode side. The anode metal nanowires scatter or reflect a part of the light backward, but by using a metal material as the cathode conductive material, the light can be reused and the extraction efficiency is improved.

(4) Anode 22 etc. The anode 22 is formed on the substrate 4, and the anode 22 and the transparent electrode 2 (second conductive layer 8) are electrically connected (connected).
Note that the transparent electrode 2 itself may be used as the anode without providing the anode 22 separately from the transparent electrode 2.
A flexible sealing member 30 is provided above the substrate 4. The ends of the flexible sealing member 30 are attached to the cathode 20 and the anode 22 with an adhesive 40, and the organic light emitting layer 10 and the like are sealed (covered) with the flexible sealing member 30. The outer sides of the areas where the adhesive 40 is applied at the ends of the cathode 20 and the anode 22 are used as connection terminals.

(5) Photoelectric Conversion Layer A photoelectric conversion layer may be provided instead of the organic light emitting layer 10.
An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the cathode.
The photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.

Examples of the p-type semiconductor material include various condensed polycyclic aromatic compounds and conjugated compounds.
Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, thacumanthracene, bisanthene, zesulene, heptazelene. , Pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and the like, and derivatives and precursors thereof.
Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.
In particular, among polythiophene and oligomers thereof, thiophene hexamer, α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.

Other examples of the polymer p-type semiconductor include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. Japanese Laid-Open Patent Publication No. 2006-36755 and other substituted-unsubstituted alternating copolymer polythiophenes, Japanese Patent Laid-Open No. 2007-51289, Japanese Patent Laid-Open No. 2005-76030, J. Pat. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, etc., polymers having a condensed ring thiophene structure, WO2008 / 000664, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.
Furthermore, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiotetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes of C60, C70, C76, C78, C84, fullerenes such as SWNT, carbon nanotubes such as SWNT, merocyanine dyes, dyes such as hemicyanine dyes, and σ-conjugated polymers such as polysilane and polygermane Organic / inorganic hybrid materials described in Kai 2000-260999 can also be used.

Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.
Examples of pentacenes include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216, and the like. A pentacene derivative described in U.S. Patent Application Publication No. 2003/136964 and the like; Amer. Chem. Soc. , Vol127. Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.
Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable. Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. No. 9, 2706 and the like, acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in U.S. Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.
Among these, the latter precursor type can be preferably used.
This is because the precursor type is insolubilized after conversion, so when forming the hole transport layer, electron transport layer, hole block layer, electron block layer, etc. on the bulk heterojunction layer by a solution process, Since the bulk heterojunction layer will not be dissolved, the material constituting the layer and the material forming the bulk heterojunction layer will not be mixed, thereby further improving the efficiency and life. Because it can.

  The p-type semiconductor material is a compound that has undergone a chemical structural change by a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material. Preferably there is. Of these, compounds that cause a chemical structural change by heat are preferred.

Examples of n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic acid Examples thereof include polymer compounds containing an anhydride, an aromatic carboxylic acid anhydride such as perylenetetracarboxylic acid diimide, or an imidized product thereof as a skeleton.
Among these, fullerene-containing polymer compounds are preferable. Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton. As the fullerene-containing polymer compound, a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.
The fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. Are preferred.
This is not because fullerene is contained in the main chain because the polymer does not have a branched structure, so that it can be packed with high density when solidified, resulting in high mobility. It is estimated that.
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).

As a form which uses the photoelectric conversion element of this invention as photoelectric conversion materials, such as a solar cell, a photoelectric conversion element may be utilized by a single layer and may be laminated | stacked (tandem type) and may be utilized.
Further, since the photoelectric conversion material is not deteriorated by oxygen, moisture, or the like in the environment, the photoelectric conversion material is preferably sealed by a known method.

<< Transparent electrode 2 >>
(1) Substrate 4
The transparent substrate used for the electrode of the present invention is not particularly limited as long as it has high light transmittance. For example, a glass substrate, a resin substrate, a resin film, etc. are mentioned suitably at points, such as being excellent in the hardness as a board | substrate, and the ease of forming the conductive layer on the surface.
There is no particular limitation on the glass substrate that can be used in the present invention. Among them, alkali-free glass is preferably used. In addition, it is preferable to use a thin film glass having a thickness of 10 to 200 μm from the viewpoint of production suitability in roll-to-roll, flexibility of the element when used for a transparent electrode for an organic electroluminescence element, and the like. Further, a thickness of 50 to 120 μm is desirable from the viewpoint of resistance to breakage and ease of roll conveyance. Specifically, a thin film glass described in JP 2010-132532 A as a glass film can be used.
There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent substrate by this invention, The material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.
For example, polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc. Resin films, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like. If the resin film transmittance of 80% or more in 0~780nm), can be preferably applied to a transparent resin film 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.

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 adhesiveness 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. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

(2) First conductive layer 6
(2.1) Configuration The first conductive layer according to the present invention is characterized in that a metal material is formed in a pattern on a substrate. As a result, a film substrate having both a light-impermeable conductive portion made of a metal material and a light-transmissive window portion is obtained, and an electrode substrate excellent in transparency and conductivity can be produced. The metal material is not particularly limited as long as it is excellent in conductivity. For example, the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium. In particular, the shape of the metal material is preferably metal fine particles or metal nanowires from the viewpoint of ease of pattern formation as described later, and the metal material is preferably silver from the viewpoint of conductivity.

The pattern shape is not particularly limited, but for example, the conductive portion may have a stripe shape, a lattice shape, a honeycomb shape, or a random mesh shape, and a stripe shape, a lattice shape, or a honeycomb shape is particularly preferable.
The line width of the pattern is preferably 10 to 200 μm. When the line width of the thin wire is 10 μm or more, desired conductivity is obtained, and when it is 200 μm or less, the transparency is improved. More preferably, it is the range of 10-100 micrometers.
In the stripe-like and lattice-like patterns, the interval between the fine lines is preferably 0.5 to 4 mm. In the honeycomb pattern, the length of one side is preferably 0.5 to 4 mm.
The height of the thin wire is preferably 0.1 to 10 μm. When the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and by making the thickness 10 μm or less, it prevents current leakage and the functional layer thickness distribution from becoming a factor in the formation of organic electronic devices. it can.

The fine line pattern of the first conductive layer according to the present invention can be formed by a printing method such as a gravure printing method, a flexographic printing method, a screen printing method, and an ink jet printing method using a dispersion of metal particles. For each printing method, a method generally used for electrode pattern formation can be applied to the present invention. Specific examples include gravure printing methods described in JP2009-295980, JP2009-259826, JP2009-96189, and JP2009-90662, and flexographic printing methods in JP2004-268319. Examples of the method described in JP-A No. 2003-168560, and examples of the screen printing method include methods described in JP-A 2010-34161, JP-A 2010-10245, and JP-A 2009-302345.
As another method, for example, a metal layer is formed on the entire surface of the substrate, and can be formed by a known photolithography method. Specifically, a conductor layer is formed on the entire surface of the substrate using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, and plating, or a metal foil is bonded with an adhesive. After being laminated on the substrate, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.
Another method is to apply a catalyst ink that can be plated to the desired shape by gravure printing or inkjet method, and then apply plating. Another method is to apply silver salt photographic technology. it can. A method using silver salt photographic technology can be carried out with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and Examples. About the method of carrying out the gravure printing of catalyst ink and plating, it can carry out with reference to Unexamined-Japanese-Patent No. 2007-281290, for example.
As a random network structure, for example, a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 Can be used.

The surface specific resistance of the thin wire portion of the first conductive layer is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
After the metal fine line pattern is provided by printing a paste of metal particles, it is preferably heated and fired in order to increase conductivity. When glass is used for the substrate, the baking temperature is preferably 500 ° C. or lower, and when a PET film is used for the substrate, the baking temperature is preferably 110 ° C. or lower. The metal particles are preferably metal nanoparticles because high conductivity is obtained.

(2.2) Metal nanoparticle The metal nanoparticle refers to a metal in the form of fine particles having a particle diameter of from atomic scale to nm size. As an average particle diameter of a metal nanoparticle, 3-300 nm is preferable and it is more preferable that it is 5-100 nm. The metal used in the metal nanoparticles according to the present invention is preferably silver or copper from the viewpoint of conductivity, and may be silver or copper alone, or a combination of them, either silver and copper alloy, silver or copper. It may be plated with any metal. Among these, silver nanoparticles are particularly preferable. Among these, silver nanoparticles having an average particle size of 30 nm or less are preferable.
Moreover, it is preferable that the 1st conductive layer formed on the board | substrate performs a heat baking process. This is particularly preferable because the fusion of the metal fine particles proceeds and the first conductive layer becomes highly conductive. The temperature for heating and baking is preferably in the range of 100 to 900 ° C, more preferably in the range of 150 to 600 ° C. The preferred range of the heat firing time varies depending on the temperature, but is preferably 1 to 60 minutes.

(3) Second conductive layer 8
(3.1) Configuration, etc. The second conductive layer is a dispersion in which a water-soluble resin and a conductive polymer are mainly mixed and dispersed so as to cover the patterned first conductive layer. A predetermined dispersion containing a nonionic surfactant is applied and dried to form a film.
In addition to the above-described printing methods such as gravure printing, flexographic printing, and screen printing, the second conductive layer is applied by roll coating, bar coating, dip coating, spin coating, casting, and die coating. A coating method such as a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, or an inkjet method can be used.

The second conductive layer contains a water-soluble resin having a hydroxyl group in the repeating unit, and the hydroxyl group concentration in the second conductive layer is 0.5 to 5.0 mmol / g (0.5 mmol / g or more). 5.0 mmol / g or less).
The hydroxyl group concentration in the second conductive layer is preferably 0.7 to 3.0 mmol / g, more preferably 1.4 mmol / g.
The water-soluble resin having a hydroxyl group is more preferably a water-soluble resin having a structural unit represented by the general formula (III). The water-soluble resin having the structural unit represented by the general formula (III) has an effect of enhancing the conductivity of the conductive polymer, and thereby can simultaneously satisfy high conductivity and high transparency.
By forming the conductive layer of the present invention having such a laminated structure, high conductivity that cannot be obtained by a metal thin wire or a conductive polymer layer alone can be obtained uniformly in the electrode plane.
The ratio of the conductive polymer and the water-soluble resin in the second conductive layer is preferably 30 to 900 parts by mass of the water-soluble resin when the conductive polymer is 100 parts by mass. From the viewpoint of the conductivity enhancing effect and transparency of the conductive binder, the water-soluble binder is more preferably 100 parts by mass or more.
The dry thickness of the second conductive layer is preferably 30 nm to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is further preferably 200 nm or more. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.

After apply | coating a 2nd conductive layer, a drying process can be given suitably. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a board | substrate and a conductive layer. Further, by performing heat treatment, the crosslinking reaction of the water-soluble resin can be promoted and completed. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved. In particular, in an organic EL element, effects such as reduction in driving voltage and improvement in life can be obtained. The drying step and the heat treatment step may be the same step or may be performed separately. In the case of separate processes, drying and heat treatment may be continuous, and there may be a time pause between the two processes.
There are no restrictions on the conditions of the drying process and the heat treatment process, but for example, drying can be performed at a temperature of 80 ° C. or higher, for example, as a condition that allows rapid evaporation of moisture, and the upper limit is a temperature at which the conductive layer is not damaged. Up to about 300 ° C is considered a possible region. The time is preferably in the range of about 10 seconds to 10 minutes. Further, the heat treatment is preferably performed at a temperature of 150 ° C. or higher and 300 ° C. or lower. If it is less than 150 ° C., the reaction promoting effect is small, and if it exceeds 300 ° C., the effect is small because thermal damage to the material increases. The heat treatment time is preferably 1 minute or longer. The upper limit of the treatment time is not particularly limited, but is preferably 24 hours or less from the viewpoint of productivity. However, when the heat treatment temperature exceeds 200 ° C., it is preferable to keep it within 30 minutes. The heat treatment may be performed on-line or off-line after applying and drying the conductive layer. In the case of off-line, it is preferable to further perform under reduced pressure because it leads to accelerated drying of moisture.

  In the present invention, the crosslinking reaction of the hydroxyl group-containing nonconductive polymer can be promoted and completed using an acid catalyst. As the acid catalyst, hydrochloric acid, sulfuric acid or ammonium sulfate can be used. Moreover, in the polyanion used as a dopant for a conductive polymer, a dopant and a catalyst can be used together by using a sulfo group-containing polyanion. In addition, the heat treatment described above can be performed in combination with the use of an acid catalyst, which is preferable because it shortens the treatment time.

(3.2) Nonionic surfactant The second conductive layer contains a compound represented by general formula (I) or general formula (II).
This compound is a nonionic surfactant of an acetylenic diol derivative.

In the formulas (I) and (II), “R1” and “R4” are linear or branched alkyl chains having 3 to 10 carbon atoms, and “R2” and “R3” are hydrogen atoms or carbon atoms. It is an alkyl chain having 1 to 5 atoms. “M”, “n”, “p” and “q” are numbers in the range of 0-20. The value of (n + m) is 0 to 30, preferably 1.3 to 15, and more preferably 1.3 to 10. By setting the values of m, n, p, and q within the above ranges, the balance between hydrophilicity and lipophilicity is improved, and a surfactant effect is exhibited. As a result, it becomes possible to obtain a good coating property.
In a preferred embodiment, the acetylenic diol portion of the molecule is 2,4,7,9-tetramethyl-5-decyne-4,7-diol or 2,5,8,11-tetramethyl-6-dodecyne-5. 8-diol.
The amount of the compound represented by general formula (I) or general formula (II) in the second conductive layer is preferably 0.01 to 10% by mass.

(3.3) Water-soluble resin having a hydroxyl group The water-soluble resin having a hydroxyl group according to the present invention is preferably dissolved in about 0.001 g in 100 g of water at 25 ° C. The degree of solubility in water can be measured with a haze meter or a turbidimeter.

(3.3.1) Structural unit represented by general formula (III) The water-soluble resin having a hydroxyl group according to the present invention is a water-soluble resin containing a structural unit represented by general formula (III). Is preferred.

In the structural unit having a hydroxy group represented by formula (III) of the present invention, “R” represents a hydrogen atom or a methyl group. “Q” represents —C (═O) O— or —C (═O) NRa—, and “Ra” represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. These alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl , Aryloxy sulfonyl group, alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxy group and an alkyloxy group are preferable.
The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.
The number of carbon atoms of the cycloalkyl group is preferably 3-20, more preferably 3-12, and still more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group. The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group. The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group. The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group. The number of carbon atoms in the heteroaryl group is preferably 3-20, and more preferably 3-10. Examples of the heteroaryl group include a thienyl group and a pyridyl group. The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group. The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like. The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamido group include a methanesulfonamido group and the like, and the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group. The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group. The acyloxy group preferably has 1 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group. The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group. The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group. The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
The number of carbon atoms of the arylsulfonyloxy group is preferably 6-20, and more preferably 6-12. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.
In the structural unit having a hydroxy group represented by formula (III) of the present invention, “A” represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x —CH ₂ CHRb—. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the above-described substituents. “Rb” represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Further, these alkyl groups may be substituted with the above-described substituents. Furthermore, “x” represents the average number of repeating units, preferably 1 to 100, more preferably 1 to 10. The number of repeating units has a distribution, the notation indicates an average value, and may be expressed by one digit after the decimal point.

(3.3.2) Structural unit represented by general formula (IV) The water-soluble resin having a hydroxyl group according to the present invention is represented by a structural unit represented by general formula (III) and general formula (IV). It may have a structure containing both structural units.

In the structural unit having no hydroxy group represented by the general formula (IV) of the present invention, R, Q, Ra, A, Rb, and x have the same meaning as defined in the general formula (III).
In the structural unit having no hydroxy group represented by the general formula (IV) of the present invention, “y” represents 0 or 1. “Z” represents an alkoxy group, —O—C (═O) —Rc, —O—SO ₂ —Rd or —O—SiRe ₃ , and the alkoxy group preferably has, for example, 1 to 12 carbon atoms; More preferred are a methoxy group and an ethoxy group, and even more preferred is a methoxy group. These alkoxy groups may be substituted with the substituents described above. Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, and an aryl group. The alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. . These alkyl groups may be substituted with the substituent described above. The perfluoroalkyl group preferably has, for example, 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably a trifluoromethyl group. The aryl group is preferably, for example, a phenyl group or a toluyl group, and more preferably a toluyl group. Furthermore, these alkyl groups, perfluoroalkyl groups, and aryl groups may be substituted with the above-described substituents.

The water-soluble resin of the present invention may contain a structural unit in addition to the structural unit represented by the general formula (III) and the structural unit represented by the general formula (IV).
In the water-soluble resin according to the present invention, the molar ratio of the structural unit having a hydroxy group represented by the general formula (III) is preferably 10 to 90%, more preferably 10 to 50%. The water-soluble resin of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.
The number average molecular weight of the water-soluble resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably 5,000 to 100,000.
The water-soluble number average molecular weight and molecular weight distribution of the present invention can be measured by generally known gel permeation chromatography (GPC). The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, more preferably THF and DMF, and still more preferably DMF. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

(3.4) Second water-soluble resin having no hydroxyl group The second conductive layer may contain a water-soluble resin having no hydroxyl group.
By containing a water-soluble resin having no hydroxyl group in the second conductive layer, it is possible to adjust the concentration of the hydroxyl group in the second conductive layer to a desired concentration in combination with the water-soluble resin having a hydroxyl group. Examples of the water-soluble resin having no hydroxyl group used in the present invention include polyvinyl pyrrolidones, polyethylene oxides, and polyacrylic acids, with polyethylene oxides being most preferred. The addition amount of the water-soluble resin having no hydroxyl group is not particularly limited, but is preferably 0.1 to 99.9 wt%. Moreover, although the weight average molecular weight (Mw) of water-soluble resin which does not have a hydroxyl group in particular is not prescribed | regulated, 3000-100000 are preferable. If the molecular weight is in the above range, the film surface strength is sufficient, the viscosity of the coating solution is good, and the coating film of the second conductive layer is also good.

(3.5) Conductive polymer The conductive polymer according to the present invention is a conductive polymer comprising a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemically oxidatively polymerizing a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion described later.

(3.5.1) π-conjugated conductive polymer The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophene, the same shall apply hereinafter), polypyrroles, polypyrrole. Chain conductive polymers of indoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyls Can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(3.5.2) Polyanion Polyanions are substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, and these A copolymer comprising a structural unit having an anionic group and a structural unit having no anionic group.
This polyanion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.
The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Examples include acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

Moreover, the polyanion which has F in a compound may be sufficient.
Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.
Among these, when a compound having a sulfonic acid is formed by applying and drying a conductive polymer-containing layer, when subjected to a heat treatment at a temperature of 100 ° C. or more and 200 ° C. or less for 5 minutes or more, It is more preferable because the cleaning resistance and solvent resistance of the coating film are remarkably improved.
Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive polymer.
The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

Examples of methods for producing polyanions include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And a method of production by polymerization of a functional monomer.
Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.
A commercially available material can be preferably used for such a conductive polymer.
For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.

(3.6) Other additives (3.6.1) Water-soluble organic compound A water-soluble organic compound may be contained as the second dopant.
There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably.
The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

(3.6.2) Surfactant The second conductive layer may contain a surfactant.
Examples of the surfactant according to the present invention include an anionic surfactant and a nonionic surfactant.
For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamido disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalenesulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene. Polyoxypropylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol Fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenation Bran oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. It is done. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Fluorine-based and silicon-based anions and nonionic surfactants can also be used.
Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 1% by mass of the post-treatment liquid.

(3.6.3) Chelating agent The second conductive layer may contain a chelating compound.
For example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetramine hexaacetic acid, its sodium salt; ethylenediamine disuccinic acid, its potassium salt, its sodium salt; Ethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt: nitrilotriacetic acid, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt, Organic sodium phosphonic acid or phosphonoalkanetricarboxylic acid such as its sodium salt; aminotri (methylenephosphonic acid), its potassium salt, its sodium salt and the like.
An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. The addition amount is suitably 0.001 to 1.0% by mass.

(4) Pressurization or pressurization heat treatment of transparent electrode 2 In the present invention, it is also preferable to perform pressurization or pressurization heat treatment for the purpose of improving the conductivity of the mesh part when higher smoothness is required. It is preferable to carry out at least before setting the transparent conductive film (transparent electrode). By this treatment, it is possible to smooth the resin (second conductive layer) surface of the conductive metal pattern (first conductive layer) and the transparent window portion, and the conductive metal pattern and the transparent window portion. It is possible to further reduce the level difference from the resin. Furthermore, since the metal particle density of the conductive metal pattern portion is increased and the particle interface adhesion is improved, the conductivity can also be improved.
In pressurization, the surface is pressed on the plate with the plate / surface pressurization, the nip roll pressurization is performed while passing the base film between the rolls, and the combined pressurization is performed on the plate with the roll. Can be adopted. Although the magnitude | size of a pressurization is arbitrarily possible in the range of 1 kPa to 100 MPa, Preferably it is the range of 10 kPa-10 MPa, More preferably, it is 50 kPa-5 MPa. When the pressure is less than 1 kP, the effect of contact between the particles cannot be obtained, and when the pressure is 100 MPa or more, it is difficult to keep the surface smooth, and the haze increases. Moreover, since it becomes effective when it heats at the time of pressurization, it is preferable to heat in the range of 40 to 300 degreeC. In particular, for the smoothness of the resin surface of the translucent window portion and the reduction in the level difference with the metal pattern, it is preferable to heat to a temperature equal to or higher than the Tg of the resin. The heating time is adjusted in relation to the temperature and can be short at a high temperature and long at a low temperature. In the case of a nip roll, the heating method includes a method in which the roll is heated to a predetermined temperature in advance and a method in which heating is performed in a heating chamber such as an autoclave chamber. A method of laminating a plurality of samples of a predetermined size and heating them at a time is preferable because of high productivity.

(5) Manufacturing method of transparent electrode 2 The electrode for organic electronic devices of the present invention is formed by sequentially laminating a conductive metal fine wire (first conductive layer) and a transparent conductive polymer layer (second conductive layer) on a transparent substrate. This is the simplest and preferred method.
The conductive metal fine wire or the transparent conductive polymer layer may be formed by laminating a plurality of layers having the same configuration or different configurations. The lamination of the conductive metal fine wire and the transparent conductive polymer layer can be performed by a general coating method or printing method.
For example, an inkjet method, an extrusion coating method, a gravure printing method, a flexographic printing method, and the like can be given. After laminating the conductive metal wires, drying and heating are performed, and then contacted with an aqueous solution containing a surfactant and / or a chelating agent. The supply of the aqueous solution to the substrate can be suitably carried out by any method of immersion or shower.
After contacting with an aqueous solution containing a surfactant and / or chelating agent, it is preferable to further wash with normal water.
In these washing steps, means such as applying ultrasonic waves of washing water and heating can be used to promote the washing effect. After laminating the transparent conductive polymer layer, it is fixed to the substrate through a drying process, a heating process, and the like to obtain an electrode for an organic electronic device.

(6) Application Examples The above transparent electrode 2 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, It can be suitably used in fields such as electromagnetic wave shields and touch panels. Among these, it can use especially preferably as a transparent electrode of the organic electroluminescent element (organic EL element 100) and organic thin-film solar cell element by which the smoothness of the transparent electrode surface is calculated | required severely.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the configuration of the present invention is not limited to these embodiments.

<< Preparation of Example Sample 1 (Transparent Electrode) >>
(1) Formation of First Conductive Layer Using a silver nanoparticle ink 1 (TEC-PR-020; manufactured by InkTec) on a glass substrate having a thickness of 100 μm, the first conductive layer is formed in a grid pattern having a width of 50 μm and an interval of 1 mm. One conductive layer was printed. The area for printing the pattern was 18 mm square. As a printing machine, a gravure printing tester K303MULTICOATER manufactured by RK Print Coat Instruments Ltd was used.
The glass substrate after printing was baked at 250 ° C. for 2 minutes using an electric furnace to form a first conductive layer on the glass substrate.
When the pattern of the first conductive layer was measured with a high brightness non-contact three-dimensional surface shape roughness meter WYKO NT9100, the pattern height was 0.7 μm, and the average roughness Ra measured along the center line on the pattern fine line was It was 0.01 μm.

(2) Formation of Second Conductive Layer A second conductive layer coating solution having the following composition was pattern-coated on the glass substrate having the first conductive layer patterned obtained above with a wet film thickness of 10 μm using an applicator. The area of the pattern was 20 mm square at the position covering the first conductive layer.
The glass substrate after application of the pattern was dried at 90 ° C. for 1 minute using a circulating thermostat and then baked at 230 ° C. for 2 minutes using an electric furnace to form a second conductive layer.
As a result, Sample 1 (transparent electrode) was obtained.

(Second conductive layer coating solution composition)
Conductive polymer dispersion (Clevios PH510; manufactured by HCStarck, solid content 1.7% by mass) 17.6 g
Compound of general formula (I) (2,4,7,9-tetramethyl-5-decyne-4,7-diol (m + n = 6, p + q = 0)) 0.02 g
Polyethylene oxide (adjusted to a solid content of 20% by mass) 3.5 g
Dimethyl sulfoxide 1.0g

  The chemical structural formula of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (m + n = 6, p + q = 0) of the general formula (I) compound is shown below.

<< Preparation of Example Sample 1 (Organic EL Element) >>
(1) Formation of anode In each of the produced transparent electrodes, a square tile-shaped transparent pattern having a pattern side length of 20 mm was cut into a 30 mm square so as to be arranged in the center, and this was used as the first electrode (anode). An organic EL element was produced by the following procedure.

(2) Formation of organic light-emitting layer The cut out transparent pattern electrode is set in a commercially available vacuum deposition apparatus, and each of the vapor deposition crucibles in the vacuum deposition apparatus is filled with the optimum amount of each layer constituent material for device fabrication. did. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
Subsequently, each light emitting layer was provided in the following procedures.
First, after depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, the energization crucible containing the following α-NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer. Was provided.
Ir-1 and Ir-14 and the following compound 1-7 were co-deposited at a deposition rate of 0.1 nm / sec so that the following Ir-1 would be 13% by mass and the following Ir-14 would be 3.7% by mass. Then, a green-red phosphorescent light emitting layer having an emission maximum wavelength of 622 nm and a thickness of 10 nm was formed.
Subsequently, E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and a blue phosphorescent light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm. Formed.
Thereafter, the following M-1 was deposited to a thickness of 5 nm to form a hole blocking layer, and CsF was co-deposited with M-1 so that the film thickness ratio was 10%. Formed.
The compounds used for forming each layer are shown below.

(3) Formation of cathode On the formed electron carrying layer, Al was vapor-deposited under the vacuum of 5x10 <^-4> Pa, and the 100-nm-thick cathode was formed.

(4) on the sealing film electron transport layer formed form of a polyethylene terephthalate as a substrate, using a flexible sealing member which is deposited to a thickness 300nm of Al ₂ O _3. After the adhesive was applied and bonded to the flexible sealing member, the adhesive was cured by heat treatment and sealed. Sample 1 (organic EL element) was prepared using ITO that had come out of the sealing member as an external extraction terminal for the anode and cathode.

<< Production of other samples (transparent electrode, organic EL element) >>
(1) Example 2
In the second conductive layer coating solution of Example 1, 3.5 g of polyvinyl alcohol (adjusted to a solid content of 20% by mass) was added instead of polyethylene oxide.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

(2) Examples 3 to 9
In the second conductive layer coating solution of Example 1, 3.5 g of a polyhydroxyethyl acrylate aqueous solution (adjusted to a solid content of 20% by mass) was added as a compound of the general formula (III), and polyethylene oxide was not added.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

(3) Example 10
In the second conductive layer coating solution of Example 1, the compound of the general formula (II) ((2,5,8,11-tetramethyl-6-dodecyne-5,8-diol ( m + n = 4, p + q = 0)) 0.02 g, 3.5 g of polyhydroxyethyl acrylate aqueous solution (adjusted to a solid content of 20% by mass) as a compound of general formula (III) is added, and polyethylene oxide is not added. did.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

(4) Example 11
In the second conductive layer coating solution of Example 1, the compound of general formula (I) (2,4,7,9-tetramethyl-5-decyne-4,7-diol (m + n = 6, p + q = 0) / same as on the left. (M + n = 5, p + q = 2)) were added in an amount of 0.01 g each, and 3.5 g of a polyhydroxyethyl acrylate aqueous solution (adjusted to a solid content of 20% by mass) was added as a general formula (III) compound, Oxide was not added.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

(5) Comparative Example 1
In the second conductive layer coating solution of Example 1, the compound of general formula (I) was not added, and 3.5 g of an aqueous solution of polyhydroxyethyl acrylate (adjusted to a solid content of 20% by mass) was added as the compound of general formula (III). No polyethylene oxide was added.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

(6) Comparative Examples 2 and 3
In the second conductive layer coating solution of Example 1, the compound of general formula (I) is not added, and 3.5 g of a polyhydroxyethyl acrylate aqueous solution (adjusted to a solid content of 20% by mass) is added as the compound of general formula (III). In Comparative Example 2, 0.02 g of a fluorosurfactant (Zonyl FSO manufactured by Dupont) was used instead of polyethylene oxide, and in Comparative Example 3, polyoxyethylene alkyl ether (Emulgen 147 manufactured by Kao) was used instead of polyethylene oxide. 02 g was added respectively.
Otherwise, a transparent electrode and an organic EL device were produced in the same manner as in Example 1.

  Tables 1 and 2 briefly show the composition of the second conductive layer coating solution of each sample.

<Measurement and evaluation of sample>
The performance of each sample produced as described above was evaluated by the following method.
(1) Light emission unevenness Using a KEITHLEY source measure unit 2400 type, a direct current voltage was applied to each organic EL element to emit light so that the luminance became 1000 cd / m ² , and the light emission state was visually evaluated according to the following criteria. The evaluation results are shown in Table 3.
“◎”: Completely uniform light emission, no problem “◯”: Almost uniform light emission, no problem “Δ”: Light emission unevenness is partially observed, but practically acceptable “×” : Uneven light emission is observed over the entire surface, which is unacceptable

(2) Rectification ratio The current value when a voltage of +3 V / -3 V was applied to each organic EL element was measured, the rectification ratio was determined by the following calculation formula, and evaluated according to the following criteria. The evaluation results are shown in Table 3.
If there is leakage between electrodes, the rectification ratio becomes a low value.
If the rectification ratio of 10 ² or more, a practical range.
“Rectification ratio” = Current value when +3 V is applied / Current value when −3 V is applied “◎”: Rectification ratio 10 ³ or more “◯”: Rectification ratio 10 ² or more and less than 10 ³ “Δ”: Rectification ratio 10 ¹ or more 10 Less than ² “×”: Rectification ratio less than 10 ¹

(3) Preservability Each organic EL element was preserve | saved with the 80 degreeC thermostat. It was taken out from the thermostat every 12 hours, the voltage at the time of initial 1000 cd / m ² emission was applied, the luminance at that time was measured, and the time when the luminance was reduced by half was defined as the storage time. An organic EL device using ITO vapor-deposited glass instead of the transparent electrode of the present invention as an anode electrode was prepared by the same method as described above, and the ratio to this (= storage time when using transparent electrode / when using ITO vapor-deposited glass) The storage time was determined and evaluated according to the following index (standard). The evaluation results are shown in Table 3.
The ratio is preferably 100% or more, and more preferably 120% or more.
“◎”: 120% or more “◯”: less than 100 to 120% “△”: less than 80 to 100% “×”: less than 80%

(4) Damage test by rocking test After patterning the second conductive layer, 30 wet reciprocating Kimwipes were applied on the second conductive layer while applying a load of 100 gf / cm ² , and then the surface of each transparent electrode Damage was visually evaluated according to the following criteria. The evaluation results are shown in Table 3.
“◎”: No damage was observed even when viewed with a loupe.
“O”: The surface is slightly damaged by looking through the loupe.
“Δ”: The surface is slightly damaged visually.
"X": Damage is confirmed visually.

(5) Summary As shown in Table 3, when the samples of Examples 1 to 11 and Comparative Examples 1 to 3 are compared, the compound of the general formula (I) or the general formula (II) is added to the coating solution of the second conductive layer. In the added samples of Examples 1 to 11, the results were good. In particular, in the sample to which the compound of the general formula (I) was added, the results of the samples of Examples 4 to 7, 9, and 11 in which the value of (n + m) in the compound was 1.3 to 10 appeared remarkably. It was. Moreover, comparing the samples of Examples 1 and 2 and Example 6, the sample of Example 6 containing a water-soluble resin having a structural unit represented by the general formula (III) in the coating solution of the second conductive layer. The result was good.
From the above, in order to suppress the occurrence of light emission defects, the occurrence of leakage between electrodes, deterioration with time, and damage to the transparent conductive layer (second conductive layer), the second conductive layer may be represented by the general formula (I) or the general formula ( It can be seen that it is useful that the compound of II) is contained, and that it is useful that a water-soluble resin having a structural unit represented by the general formula (III) is contained.

DESCRIPTION OF SYMBOLS 2 Transparent electrode 4 Board | substrate 6 1st conductive layer 8 2nd conductive layer 10 Organic light emitting layer 12 Hole transport layer 14 Light emitting layer 16 Hole block layer 18 Electron transport layer 20 Cathode 22 Anode 30 Flexible sealing member 40 Adhesive 100 Organic electroluminescence device

Claims (3)

A substrate,
A first conductive layer made of a metal material formed in a pattern on the substrate;
In a transparent electrode having a second conductive layer containing a conductive polymer,
The transparent electrode, wherein the second conductive layer contains a compound represented by general formula (I) or general formula (II).

(In the formulas (I) and (II), “R1” and “R4” are linear or branched alkyl chains having 3 to 10 carbon atoms, and “R2” and “R3” are hydrogen atoms or (It is an alkyl chain having 1 to 5 carbon atoms, and "m", "n", "p" and "q" are numbers in the range of 0 to 20.) The transparent electrode according to claim 1,
The second conductive layer contains a water-soluble resin,
The said water-soluble resin has a structural unit represented by general formula (III), The transparent electrode characterized by the above-mentioned.

(In Formula (III), “R” represents a hydrogen atom or a methyl group. “Q” represents —C (═O) O— or —C (═O) NRa—. “Ra” represents a hydrogen atom or Represents an alkyl group, “A” represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x —CH ₂ CHRb—, “Rb” represents a hydrogen atom or an alkyl group, and “x” represents an average repeating unit. Represents a number.) The transparent electrode according to claim 1 or 2,
A cathode,
An organic light emitting layer interposed between the transparent electrode and the cathode;
An organic electroluminescence device comprising:

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