JP2011238471A - Manufacturing method of transparent electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a transparent electrode, capable of manufacturing the transparent electrode usable for organic electronic devices and having excellence in conductivity, transparency, flexibility and plane uniformity of current, without damaging the electrode and a film substrate.SOLUTION: In the manufacturing method of the transparent electrode, having a first conductive layer, composed of a pattern-shaped metal material formed on the film substrate, and a second conductive layer having a conductive polymer, the second conductive layer includes a hydroxyl group-containing non-conductive polymer. Further, in a state that the first conductive layer or the second conductive layer contacts a conductive member or a semiconductor conductive member on the surface of a support table, microwave irradiation is performed from the film substrate side.

Description

  The present invention relates to a method for producing a transparent electrode excellent in conductivity, transparency, flexibility, and current surface uniformity used in an organic electronic device.

  In recent years, organic electronic devices such as organic EL and organic solar cells have attracted attention. In such devices, transparent electrodes have become an essential constituent technology. Conventionally, a transparent electrode is an ITO transparent electrode obtained by forming a composite oxide (ITO) film of indium-tin on a transparent substrate by a vacuum deposition method or a sputtering method. From the viewpoint of performance such as conductivity and transparency, It has been mainly used. However, a transparent electrode using a vacuum deposition method or a sputtering method has a problem in that the productivity is low and thus the manufacturing cost is high, and since it is inferior in flexibility, it cannot be applied to a device application requiring flexibility. Furthermore, in recent years, transparent electrodes used in organic electronic devices have been required to have a large area and a low resistance value, and the resistance value of ITO transparent electrodes has become insufficient.

  Therefore, a transparent conductive film such as a conductive polymer is laminated on a thin metal wire formed in a pattern so that it can be applied to products that require such a large area and a low resistance value, and the surface uniformity of current is high. A transparent conductive film having both conductivity has been developed (see, for example, Patent Documents 1 and 2). However, in such a configuration, it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent conductive film such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer. . Since the conductive polymer is colored, the transparency of the transparent electrode is significantly reduced when the film is thickened. In addition, when using a transparent conductive film such as a conductive polymer, it is known that if moisture remains in the transparent conductive film, the performance of the organic electronic device is deteriorated, and the transparent conductive film must be dried. It becomes. However, in recent years, transparent films have been increasingly used from the viewpoint of flexibility and cost for transparent substrates, and when a transparent conductive film such as a conductive polymer is heated at a low temperature below the glass transition temperature Tg at which the film does not deform, Moisture remained in the transparent conductive film, and drying of the transparent conductive film was a problem.

  On the other hand, as a method of forming an electrode on a film substrate and drying at a low temperature, drying heating by microwaves has been proposed (see Patent Document 3). However, when this method is used for an electrode having a fine metal wire, a part of the fine metal wire is discharged and the electrode is damaged. Further, a method for manufacturing an electrode is proposed in which a semiconductor fine particle thin film such as titanium oxide is formed on a film substrate, the thin film is brought into contact with a conductor, microwaves are applied from the film substrate side, and heat drying is performed (Patent Document 4). reference). However, an electrode manufactured by this method uses semiconductor fine particles as a conductive layer, and thus has a high resistance value, inferior flexibility, and weak film strength, which is unsuitable for continuous production such as roll-to-roll. .

JP 2005-302508 A JP 2009-87843 A JP 2005-94132 A JP 2006-60064 A

  The present invention has been made in view of the above problems, and its purpose is to provide a transparent electrode excellent in conductivity, transparency, flexibility, and surface uniformity of current that can be used in an organic electronic device. It is providing the manufacturing method of the transparent electrode manufactured without damaging a film substrate.

  The above object of the present invention is achieved by the following configurations.

  1. A method for producing a transparent electrode having a first conductive layer made of a metal material formed in a pattern on a film substrate and a second conductive layer containing a conductive polymer, wherein the second conductive layer contains a hydroxyl group Irradiating microwaves from the film substrate side, containing a non-conductive polymer, and the first conductive layer or the second conductive layer is in contact with the conductor or semiconductor conductor on the surface of the support base A method for producing a transparent electrode.

  2. 2. The method for producing a transparent electrode according to 1 above, wherein the hydroxyl group-containing non-conductive polymer is a polymer represented by the following general formula (A).

(Wherein, X ^{1 to} X ³ represent a hydrogen atom or a methyl group, and R ^{1 to} R ³ each represent an alkylene group having 5 or less carbon atoms. L, m, and n represent a composition ratio (mol%), 50 ≦ l + m + n ≦ 100.)
3. 3. The method for producing a transparent electrode according to 1 or 2, wherein the metal material is metal fine particles or metal nanowires.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the transparent electrode excellent in electroconductivity, transparency, flexibility, and the surface uniformity of an electric current which can be used for an organic electronic device, without damaging an electrode and a film board | substrate is provided. be able to. Moreover, the conductive layer of the transparent electrode obtained by this manufacturing method has high strength, and this manufacturing method is suitable for continuous production of roll-to-roll.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.

  In the present invention, any one of a first conductive layer made of a metal material formed in a pattern on a film substrate and a second conductive layer containing a conductive polymer and a hydroxyl group-containing non-conductive polymer is provided on the surface of the support base. The microwave irradiation is performed from the film substrate side in a state of being in contact with a conductor or a semiconductor. By irradiating the microwave from the film side while either the first conductive layer or the second conductive layer is in contact with the conductor or semiconductor on the surface of the support base, the conductive layer is not damaged. Can be dried by heating at a low temperature. The transparent electrode produced by this method can be suitably used for organic electronic devices, and a transparent electrode (film) having excellent electrical conductivity, transparency, flexibility, current surface uniformity, and strong conductive layer strength can be obtained. It is done. In the present invention, by using a polymer represented by the general formula (A) described later as the hydroxyl group-containing nonconductive polymer, a transparent electrode having more transparency and conductivity can be obtained.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.

<Film substrate>
The film substrate used for the transparent electrode of the present invention has high light transparency, excellent flexibility, sufficiently low dielectric loss coefficient, and microwave absorption smaller than that of the conductive layer to be heated. If it is a material, there will be no restriction | limiting in particular. For example, although a resin substrate, a resin film, etc. are mentioned suitably, it is preferable to use a transparent resin film from a viewpoint of productivity, a viewpoint of performance, such as lightness and a softness | flexibility.

  If it is a transparent resin film, it is resistant to deformation and impact due to external force, and is difficult to break. There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably 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. A resin film having a transmittance of 80% or more at a visible wavelength (380 to 780 nm) is preferably used as a film substrate used in the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, and a polycarbonate film are preferable, and a biaxially stretched polyethylene terephthalate film. A biaxially stretched polyethylene naphthalate film is more preferred.

  The film 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.

In addition, an inorganic film, an organic film, or a hybrid film of both may be formed on the front surface or the back surface of the film substrate, and the water vapor transmission rate (25 ± 0.00%) measured by a method based on JIS K 7129-1992. 5 ° C., relative humidity (90 ± 2)% RH) is preferably a barrier film of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and further conforms to JIS K 7126-1987. The oxygen permeability measured by the method is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 × 10 A high barrier film of ⁻³ g / (m ² · 24 h) or less is preferable.

  As a material for forming a barrier film formed on the front or back surface of the film substrate in order to obtain a high barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

<< First conductive layer >>
The first conductive layer according to the present invention is characterized in that a metal material is formed in a pattern on a film 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. For example, the conductive portion may be a stripe shape, a mesh shape, or a random network shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. The aperture ratio is the ratio of the light-impermeable conductive portion to the whole. For example, when the conductive portion has a stripe shape or a mesh shape, the aperture ratio of the stripe pattern having a line width of 100 μm and a line interval of 1 mm is about 90%. The line width of the pattern is preferably 10 to 200 μm.

  Desired conductivity can be obtained by setting the line width of the fine line to 10 μm or more, and transparency is improved by setting the line width to 200 μm or less. The height of the fine wire is preferably 0.1 to 10 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity can be obtained, and if it is 10 μm or less, it causes current leakage and poor function layer thickness distribution in the formation of organic electronic devices. Can be prevented.

  There is no particular limitation on the method for forming the stripe-shaped or mesh-shaped electrode of the conductive portion, and a conventionally known method can be used. For example, a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method. Specifically, a conductor layer is formed on the entire surface using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, etc., or a metal foil is used as an adhesive. After being laminated on the base material, the film can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used. 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.

  As another method, for example, a method of forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.

  The metal nanowire refers to a fibrous structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.

As the metal nanowire, 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, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. The average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. Basis weight of the metal nanowires is preferably ^{0.005~0.5g / m 2, 0.01~0.2g / m} 2 is more preferable.

  As the metal used for the metal nanowire, copper, iron, cobalt, gold, silver or the like can be used, and silver is preferable from the viewpoint of conductivity. In addition, although a single metal may be used, in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745, a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871. In particular, the above-described method for producing silver nanowires can be preferably applied because silver nanowires can be easily produced in an aqueous solution, and the conductivity of silver is maximum in metals.

  Further, the surface specific resistance of the thin wire portion of the first conductive layer is preferably 100 Ω / □ or less, and more preferably 20 Ω / □ or less for increasing the area. 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.

  Moreover, it is preferable to heat-process a 1st conductive layer in the range which does not damage a film substrate. Thereby, fusion of metal fine particles and metal nanowires progresses and the first conductive layer becomes highly conductive, which is particularly preferable.

<< Second conductive layer >>
<Conductive polymer>
In the present invention, the second conductive layer contains a conductive polymer.

  The conductive polymer according to the present invention is a conductive polymer having a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemical oxidative polymerization of 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 poly anion described later. .

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers 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.

(Π-conjugated conductive polymer precursor monomer)
Precursor monomers used in the formation of π-conjugated conductive polymers have a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidant, a π-conjugated system is formed in the main chain. It is what is done. 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.

(Poly anion)
The polyanion used in the present invention includes a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a co-polymer thereof. A polymer comprising a structural unit having an anionic group and a structural unit having no anionic group.

  This poly anion 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 any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, 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, poly Isoprene sulfonic 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, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Further, it may be a poly anion further having F (fluorine atom) in the compound. Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.

  Among these, the compound having a sulfonic acid is formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more before irradiating the microwave. May be. This promotes the crosslinking reaction, which is preferable since the washing 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 poly anions have high compatibility with the hydroxyl group-containing non-conductive polymer, 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 the method for producing a polyanion 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 an anionic group containing The method of manufacturing by superposition | polymerization of a polymerizable monomer is mentioned.

  Examples of the method for producing an anionic group-containing polymerizable monomer by polymerization include a method for producing an anionic 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.

  The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion”, is preferably 1: 1 to 20 in mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 10 is more preferable.

The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.

  Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate half esters of alkanols such as lauryl sulfate; alkyl sulfonic acids of 1 to 20 carbons such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic (optionally) alkyl-substituted sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

  As such a conductive polymer, a commercially available material can also be preferably used. 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-PSS 483095, 560596, 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.

  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 hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. 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.

  The second conductive layer may completely cover the patterned first conductive layer, or may partially cover or contact it. The second conductive layer is formed into a film by applying and drying a dispersion composed of a conductive polymer and a hydroxyl group-containing nonconductive polymer. 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.

  As a means for producing a transparent electrode in which a part of the first conductive layer is covered or in contact with the second conductive layer, the first conductive layer is formed on the transfer film by the above-described method, and the second conductive layer is further formed. There is a method of transferring a laminate of the above to the above film substrate. Moreover, the method etc. which form a 2nd conductive layer by the well-known method by the inkjet method etc. in the nonelectroconductive part of a 1st conductive layer are mentioned.

  The second conductive layer is further characterized by containing a hydroxyl group-containing nonconductive polymer. Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength can be obtained.

  By forming the conductive layer of the present invention having such a structure, high conductivity that cannot be obtained with a metal or metal oxide fine wire or a conductive polymer layer alone can be obtained uniformly in the electrode plane. .

  The ratio of the conductive polymer of the second conductive layer to the hydroxyl group-containing nonconductive polymer is preferably 30 to 900 parts by mass of the hydroxyl group-containing nonconductive polymer when the conductive polymer is 100 parts by mass. From the viewpoint of leakage prevention, the conductivity enhancing effect of the hydroxyl group-containing nonconductive polymer, and transparency, the hydroxyl group-containing nonconductive polymer is more preferably 100 parts by mass or more.

  The dry film thickness of the second conductive layer is preferably 30 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 base material or a conductive layer. For example, the drying process can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes. In the present invention, after the drying is completed, the crosslinking reaction of the hydroxyl group-containing nonconductive polymer can be promoted and completed by further performing microwave heating. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is improved. In particular, in an organic EL element, effects such as reduction in driving voltage and improvement in life can be obtained.

  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 use of an acid catalyst is preferable because it leads to shortening of the microwave processing time.

  The dispersion containing the conductive polymer and the hydroxyl group-containing non-conductive polymer according to the present invention may further contain other transparent non-conductive polymers, additives, and the like in a range that simultaneously satisfies the conductivity, transparency, and smoothness of the conductive layer. You may contain a crosslinking agent.

  As the transparent non-conductive polymer, a natural polymer resin or a synthetic polymer resin can be widely selected and used, and a water-soluble polymer or an aqueous polymer emulsion is particularly preferable. Examples of water-soluble polymers include natural polymers such as starch, gelatin, and agar, semi-synthetic polymers such as hydroxypropylmethylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, cellulose derivatives, synthetic polymers such as polyvinyl alcohol, and polyacrylic acid polymers. , Polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc., and aqueous polymer emulsions include acrylic resins (acrylic silicone modified resins, fluorine modified acrylic resins, urethane modified acrylic resins, epoxy modified acrylic resins, etc.), polyester resins, urethanes Resin, vinyl acetate resin and the like can be used.

  In addition, as the synthetic polymer resin, a transparent thermoplastic resin (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride) A transparent curable resin (for example, a melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, or a silicone resin such as an acrylic-modified silicate) that can be cured by heat, light, electron beam, or radiation can be used.

  Examples of the additive include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments. Furthermore, from the viewpoint of improving workability such as coating properties, solvents (for example, organic solvents such as water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.

  Examples of the crosslinking agent for the hydroxyl group-containing non-conductive polymer include oxazoline crosslinking agent, carbodiimide crosslinking agent, blocked isocyanate crosslinking agent, epoxy crosslinking agent, melamine crosslinking agent, hole mualdehyde crosslinking agent, etc. It can be used in combination.

  A microwave absorber can also be added to the second conductive layer. The microwave absorbent is arbitrary as long as it is a substance that absorbs microwaves in the frequency band to be irradiated. However, when the second conductive layer is formed by coating and drying, it has a boiling point that does not evaporate and disappear. preferable.

  Specifically, sulfolane, dimethyl sulfone, dimethyl sulfoxide, 3-sulfolene, 3,4-dibromosulfolane, divinyl sulfone, dipropyl sulfone, dibutyl sulfone, dibutyl sulfoxide, 4,4-dioxo-1,4-oxathiane, 3 , 4-dichlorothiophene 1,1-dioxide, ethyl methyl sulfone, 2-hydroxyethyl methyl sulfone, isopropyl methyl sulfone, 3-methyl sulfolane, methylsulfonylacetonitrile, methyl (methylsulfinyl) methyl sulfide, methyl methanesulfonyl acetate, 3- Examples include sulfone compounds such as methyl sulfolene-3-carboxylate, and sulfoxide compounds. Particularly preferred are sulfolane, dimethyl sulfone, and dimethyl sulfoxide.

<Hydroxyl-containing non-conductive polymer>
In the present invention, by using a conductive polymer and a hydroxyl group-containing non-conductive polymer in combination in the conductive layer, it becomes possible to increase the film thickness without deteriorating the transparency. By embedding the unevenness of the layer, it is possible to suppress a short circuit between the electrodes, which is a preferred embodiment.

  The hydroxyl group-containing non-conductive polymer used in the present invention is not particularly limited as long as it is a polymer that can be dissolved or dispersed in an aqueous solvent. For example, a polyester resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, A polycarbonate resin, a cellulose resin, a polyvinyl acetal resin, a polyvinyl alcohol resin, etc. can be mentioned. Specific examples of the compound include Vylonal MD1200, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.) as polyester resins.

  The hydroxyl group of the hydroxyl group-containing non-conductive polymer according to the present invention reacts with a crosslinking agent to form a stronger film. Specific compounds of the hydroxyl group-containing nonconductive polymer according to the present invention include polyvinyl alcohol PVA-203, PVA-224, PVA-420 (manufactured by Kureha), hydroxypropyl methylcellulose 60SH-06, 60SH-50, 60SH-4000, 90SH-100 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), methylcellulose SM-100 (made by Shin-Etsu Chemical Co., Ltd.), cellulose acetate L-20, L-40, L-70 (above, manufactured by Daicel Chemical Industries, Ltd.) ), Carboxymethyl cellulose CMC-1160 (manufactured by Daicel Chemical Industries, Ltd.), hydroxyethyl cellulose SP-200, SP-600 (manufactured by Daicel Chemical Industries, Ltd.), alkyl acrylate copolymer Jurimer AT-210, AT-510 (above, , Manufactured by Toagosei Co., Ltd.), polyhydroxyethyla Relate, mention may be made of polyhydroxyethyl methacrylate.

  In particular, when the hydroxyl group-containing non-conductive polymer contains a certain amount of the polymer represented by the general formula (A) (hereinafter also referred to as polymer (A)), this compound can be used without using the second dopant. By using the conductive polymer-containing layer, the conductivity of the conductive polymer-containing layer can be improved, and the compatibility with the conductive polymer is good and high transparency and smoothness can be achieved. Furthermore, when the poly anion has a sulfo group, if the polymer (A) is used, the sulfo group effectively acts as a dehydration catalyst, and a dense cross-linked layer can be obtained without using an additional agent such as a cross-linking agent. This is a more preferable embodiment.

  In the polymer (A) according to the present invention, the main copolymerization component is the monomers 1 to 3 represented by the following general formulas 1 to 3, and the component of 50 mol% or more of the copolymerization component is any of the following monomers 1 to 3. Or it is a copolymer with the sum total of the component of the following monomers 1-3 being 50 mol% or more. It is more preferable that the total of the components of the following monomers 1 to 3 is 80 mol% or more, and it may be a homopolymer formed from any one of the following monomers 1 to 3, and in a preferred embodiment. is there.

(In the formula, X ^{1 to} X ³ each independently represents a hydrogen atom or a methyl group. R ^{1 to} R ³ each independently represents an alkylene group having 5 or less carbon atoms.)
In the polymer (A), other monomer components may be copolymerized, but a monomer component having high hydrophilicity is more preferable.

  The polymer (A) preferably has a molecular weight of 1000 or less in the number average molecular weight of 0 to 5% by mass or less. When the amount of the low molecular component is small, it is possible to further reduce the storage stability of the device and the behavior of having a barrier in the direction perpendicular to the layer when exchanging charges in the direction perpendicular to the conductive layer.

  In the number average molecular weight of the polymer (A), the content of a molecular weight of 1000 or less is 0 to 5% by mass or less. For example, a redispersion method or a preparative GPC is synthesized with a monodisperse polymer by living polymerization. A method of removing the low molecular weight component or suppressing the generation of the low molecular weight component can be used. In the reprecipitation method, the polymer is dissolved in a solvent in which the polymer can be dissolved and dropped into a solvent having a lower solubility than the solvent in which the polymer is dissolved, thereby precipitating the polymer and removing low molecular weight components such as monomers, catalysts, and oligomers. It is a method to do. Further, preparative GPC is, for example, recycled preparative GPCLC-9100 (manufactured by Japan Analytical Industrial Co., Ltd.), polystyrene gel column, and can be divided by molecular weight by passing a polymer-dissolved solution through the column. It is a method that can be removed. In the living polymerization, the generation of the starting species does not change with time, and there are few side reactions such as termination reaction, and a polymer having a uniform molecular weight can be obtained. Since the molecular weight can be adjusted by the addition amount of the monomer, for example, if a polymer having a molecular weight of 20,000 is synthesized, the formation of a low molecular weight body can be suppressed. From the viewpoint of production suitability, reprecipitation and living polymerization are preferred.

The number average molecular weight and molecular weight distribution of the polymer (A) according to 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 polymer (A) is dissolved, and THF, DMF, and CH ₂ Cl ₂ are preferable, THF and DMF are more preferable, and DMF is more preferable. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

  The number average molecular weight of the polymer (A) according to the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, and still more preferably 5,000 to 100,000.

  The molecular weight distribution of the polymer (A) according to the present invention is preferably from 1.01 to 1.30, more preferably from 1.01 to 1.25. The molecular weight distribution is represented by a ratio of (weight average molecular weight / number average molecular weight).

  For the content with a molecular weight of 1000 or less, the ratio was converted by integrating the area with a molecular weight of 1000 or less and dividing by the area of the entire distribution in the distribution obtained by GPC.

  The living radical polymerization solvent is inactive under the reaction conditions and is not particularly limited as long as it can dissolve the monomer and the polymer to be formed, but a mixed solvent of an alcohol solvent and water is preferable. The living radical 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 ratio of the conductive polymer to the polymer (A) is preferably 30 to 900 parts by weight of the polymer (A) when the conductive polymer is 100 parts by weight. From the viewpoint of sex, the polymer (A) is more preferably 100 parts by mass or more.

<< conductor or semiconductor >>
The present invention is characterized in that the first conductive layer or the second conductive layer is heated by microwaves in contact with the conductor or semiconductor on the surface of the support base. Thereby, concentration of electric charges on the conductive layer on the substrate can be prevented, discharge on the conductive layer due to microwaves can be prevented, the substrate film is not damaged, and heating by microwaves is possible.

  The conductor or the semiconductor is not particularly limited as long as it has conductivity. For example, a metal body such as nickel, aluminum, iron, and stainless steel or a semiconductor such as silicon may be used. The conductor or semiconductor may have any shape such as a tray or a sheet. Moreover, since the surface shape can adjust the heating temperature of a conductive layer, it may be smooth or porous, and is not particularly limited.

  Since the conductor or the semiconductor is used for preventing the concentration of electric charges in the conductive layer, the contact may be made by contacting one of the first conductive layer and the second conductive layer. The contact part should just be a part of the whole conductive layer contacting, and 5-100% should just contact. Further, the size of the conductor or semiconductor is sufficient if it covers 30 to 500% of the conductive layer composed of the first conductive layer and the second conductive layer, and microwave heating can be performed with a high output and processing can be performed in a short time. Therefore, it is preferably 50% or more.

《Microwave》
The present invention is characterized by irradiating a conductive layer (a first conductive layer or a second conductive layer) with a microwave. By irradiating the conductive layer with microwaves, the molecules forming the conductive layer can be vibrated, and by this vibration, adjacent molecules rub against each other to generate frictional heat, heating the conductive layer, It can be removed and the conductive layer can be dried. Thereby, the conductive layer can be heated at a low temperature, and the conductive layer can be heated without damaging the film substrate. In particular, when an aqueous solvent is used for the first conductive layer or the second conductive layer, it can be suitably used because it absorbs microwaves well.

  Further, the present invention is characterized in that microwaves are irradiated from the film substrate side. The film substrate side refers to the side where the conductive layer is not laminated. Thereby, since the microwave is irradiated from the film substrate side, the conductive layer can be heated by the microwave before all the microwave is absorbed by the conductor. Furthermore, it is preferable to apply a voltage with a frequency of about several hundred MHz to several hundred GHz mainly for microwave irradiation. For example, a voltage with a frequency of 2.45 GHz or 28 GHz can be suitably used. The microwave output and the microwave irradiation time can be arbitrarily set according to the type of film substrate, the amount of moisture in the substrate, the size of the substrate, etc., but the output is 10 ˜2000 W is preferable, and the irradiation time is preferably 10 seconds to 20 minutes. This is because when the output is small and the irradiation time is short, the conductive layer is insufficiently dried, and when the output is large and the irradiation time is long, the film substrate is damaged. Further, the invention of the present application is not particularly limited with respect to an apparatus for performing the microwave heat treatment, and a conventionally known apparatus may be used.

《Organic electronic device》
The transparent electrode of the present invention can be used for various organic electronic devices. An organic electronic device has an anode electrode and a cathode electrode on a support, and has at least one organic functional layer between the electrodes. Examples of the organic functional layer include, but are not particularly limited to, an organic light emitting layer, an organic photoelectric conversion layer, and a liquid crystal polymer layer. INDUSTRIAL APPLICABILITY The present invention is particularly effective when the functional layer is a thin film and is an organic light emitting layer or an organic photoelectric conversion layer, which is a current drive device, and can be applied to organic electronic devices such as organic EL elements and solar cells.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example <Production of Film Substrate>
An average after applying a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 made by JSR Co., Ltd. on the surface of 100 μm-thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) that is not undercoated. After coating with a wire bar so that the film thickness becomes 4 μm, after drying at 80 ° C. for 3 minutes, curing is performed under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere, and a smooth layer is formed. Formed.

  Next, a gas barrier layer was formed on the sample provided with the smooth layer under the following conditions.

(Gas barrier layer coating solution)
A 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS, AZ Electronic Materials Co., Ltd. Aquamica NN320) was applied with a wireless bar so that the (average) film thickness after drying was 0.30 μm. A coated sample was obtained.

(First step; drying treatment)
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.

(Second step; dehumidification treatment)
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

(Modification A)
The sample subjected to the dehumidification treatment was modified under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com
The sample fixed on the operation stage was modified under the following conditions.

(Reforming treatment conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds A film substrate for a transparent electrode having gas barrier properties was produced as described above.

<Formation of first conductive layer>
A first conductive layer was formed on the non-barrier surface of the transparent electrode film substrate having gas barrier properties obtained above by the following method.

(Thin wire grid)
The fine wire lattice (metal material) was prepared by gravure printing or photolithography as shown below.

(1) Gravure printing Silver nanoparticle paste 1 (M-Dot SLP manufactured by Mitsuboshi Belting) using RK Print Coat Instruments Ltd. gravure printing tester K303MULTICOATER is a thin wire having a line width of 50 μm, a height of 1.5 μm, and an interval of 1.0 mm. After printing the lattice, a drying treatment was performed at 110 ° C. for 5 minutes.

(2) Photolithographic method Silver nanoparticle paste 1 (M-Dot SLP, manufactured by Mitsuboshi Belting) was uniformly applied to a film thickness of 1.5 μm using a screen printer, then dried at 110 ° C. for 5 minutes, and further subjected to photo A thin wire grid having a line width of 50 μm and an interval of 1.0 mm was prepared by lithography.

(Random network structure)
A random network structure was prepared using silver nanowires as shown below.

The silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m ² , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced.

  Silver nanowire dispersions are described in Adv. Mater. , 2002, 14, 833 to 837, by using PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were produced. Silver nanowires are filtered and washed using a filtration membrane, and then redispersed in an aqueous solution in which 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to silver to prepare a silver nanowire dispersion. did.

<< Preparation of transparent electrode >>
<Preparation of transparent electrode 1>
The following coating liquid A is extruded on the transparent electrode in which the first conductive layer is formed by gravure printing on the film substrate for the transparent electrode having gas barrier properties, using an extrusion method so as to have a dry film thickness of 300 nm. The slit gap was adjusted and applied, and heated and dried at 110 ° C. for 5 minutes to form a second conductive layer composed of a conductive polymer and a hydroxyl group-containing nonconductive polymer, thereby producing an electrode.

<Formation of second conductive layer>
(Coating liquid A)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) 1.59 g
Poly (2-hydroxyethyl acrylate) (P-1, 20% solid content aqueous solution)
0.35g
Dimethyl sulfoxide (DMSO) 0.08g
(P-1: Synthesis of poly (2-hydroxyethyl acrylate))
<Living Radical Polymerization Using ATRP (Atom Transfer Radical Polymerization) Method>
Initiator 1: Synthesis of Methoxycapped Oligoethylene Glycol-2-Bromoisobutyrate 2-Bromoisobutyryl bromide (7.3 g, 35 mmol), triethylamine (2.48 g, 35 mmol) and THF (into a 50 ml three neck flask) 20 ml) was added, and the internal temperature was kept at 0 ° C. with an ice bath. In this solution, 30 ml of 33% THF solution of methoxy-capped oligoethylene glycol (10 g, 23 mmol, ethylene glycol units 7 to 8, manufactured by Laporte Specialties) was added dropwise. After stirring for 30 minutes, the solution was brought to room temperature and further stirred for 4 hours. After THF was removed under reduced pressure by a rotary evaporator, the residue was dissolved in diethyl ether and transferred to a separatory funnel. Water was added and the ether layer was washed three times, and then the ether layer was dried with MgSO ₄ . The ether was distilled off under reduced pressure using a rotary evaporator to obtain 8.2 g (yield 73%) of initiator 1.

P-1: Synthesis of poly (2-hydroxyethyl acrylate)
Initiator 1 (500 mg, 1.02 mmol), 2-hydroxyethyl acrylate (4.64 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 50 ml of 50:50 v / v% methanol / water mixed solvent was put into a Schlenk tube, and the pressure was reduced. The Schlenk tube was immersed in liquid nitrogen for 10 minutes. The Schlenk tube was taken out of liquid nitrogen and replaced with nitrogen after 5 minutes. After performing this operation three times, bipyridine (400 mg, 2.56 mmol) and CuBr (147 mg, 1.02 mmol) were added under nitrogen, and the mixture was stirred at 20 ° C. After 30 minutes, the reaction solution was dropped onto a 4 cm Kiriyama funnel with filter paper and silica, and the reaction solution was recovered under reduced pressure. The solvent was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 2.60 g (yield 84%) of water-soluble binder P-1 having a number average molecular weight of 13100, a molecular weight distribution of 1.17, and a number average molecular weight of <1000 was obtained.

The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.

<GPC measurement conditions>
Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Next, the obtained electrode was cut out into 8 × 8 cm, and was placed so that the conductive layer surface was in contact with a 10 cm × 10 cm foamed nickel sheet (Mitsubishi Materials Corporation, pore diameter 600 μm). Irradiated from the substrate side, the transparent electrode 1 was produced.

(Preparation of transparent electrode 2)
In the production of the transparent electrode 1, the transparent electrode 2 was produced in the same manner except that the electrode cut into 8 × 8 cm was heated in an oven at 110 ° C. for 30 minutes.

(Preparation of transparent electrode 3)
In the production of the transparent electrode 2, a transparent electrode 3 was produced in the same manner except that the electrode cut into 8 × 8 cm was heated using an oven at 130 ° C. for 30 minutes.

(Preparation of transparent electrode 4)
In the production of the transparent electrode 1, the electrode cut out to 8 × 8 cm was installed using an IR heater (Nihon Heater Co., Ltd.) so that the surface temperature of the film substrate was 130 ° C. and heated for 30 minutes. A transparent electrode 4 was produced in the same manner except for the above.

(Preparation of transparent electrode 5)
In the production of the transparent electrode 1, an electrode cut out to 8 × 8 cm was placed so that the conductive layer surface was in contact with a 10 cm × 10 cm foamed nickel sheet (Mitsubishi Materials Corporation, pore diameter 600 μm), and 200 W microwave for 5 minutes A transparent electrode 5 was produced in the same manner except that was irradiated from the conductive layer side.

(Preparation of transparent electrode 6)
In the production of the transparent electrode 1, the transparent electrode 6 was produced in the same manner except that the electrode cut into 8 × 8 cm was irradiated with microwaves from the film substrate side at 200 W for 5 minutes.

(Preparation of transparent electrode 7)
In the production of the transparent electrode 1, an electrode cut out to 8 × 8 cm was placed so that the conductive layer surface was in contact with 10 cm × 10 cm glass, and the microwave was irradiated from the film substrate side at 200 W for 5 minutes in the same manner. Thus, a transparent electrode 7 was produced.

(Preparation of transparent electrode 8)
In the production of the transparent electrode 1, an electrode cut into 8 × 8 cm was placed so that the surface of the conductive layer was in contact with a 10 cm × 10 cm silicon wafer, and the microwave was irradiated from the film substrate side at 200 W for 5 minutes. Thus, a transparent electrode 8 was produced.

(Preparation of transparent electrode 9)
In the production of the transparent electrode 1, an electrode cut out to 8 × 8 cm was placed so that the conductive layer surface was in contact with a 10 cm × 10 cm foamed nickel sheet (Mitsubishi Materials Corporation, pore diameter 150 μm), 400 W for 3 minutes microwave A transparent electrode 9 was produced in the same manner except that was irradiated from the film substrate side.

(Preparation of transparent electrode 10)
In the production of the transparent electrode 1, an electrode cut out to 8 × 8 cm was placed so that the surface of the conductive layer was in contact with an aluminum sheet of 10 cm × 10 cm, and the same except that the microwave was irradiated from the film substrate side at 400 W for 3 minutes. Thus, the transparent electrode 10 was produced.

(Preparation of transparent electrode 11)
In the production of the transparent electrode 1, the conductive layer surface is in contact with a 10 cm × 10 cm foamed nickel sheet (Mitsubishi Materials Corporation, hole diameter 600 μm) of the electrode cut out to 8 × 8 cm, replacing the coating solution A with the following coating solution B. The transparent electrode 11 was produced in the same manner except that the microwave was irradiated from the film substrate side at 200 W for 5 minutes.

(Coating solution B)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck)
(Preparation of transparent electrode 12)
In the production of the transparent electrode 1, the transparent electrode 12 was produced in the same manner except that a thin metal wire was formed by photolithography as the first electrode.

(Preparation of transparent electrode 13)
In the production of the transparent electrode 1, the second conductive layer was formed using the coating liquid A on the transparent electrode in which a random network structure was formed with silver nanowires, and the electrode cut out to 8 × 8 cm was 10 cm × 10 cm. The transparent electrode 13 was produced in the same manner except that the conductive sheet surface was placed in contact with the aluminum sheet, and the microwave was irradiated from the film substrate side at 400 W for 3 minutes.

(Preparation of transparent electrode 14)
A thin metal wire is formed on the non-undercoated surface of a 100 μm-thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) using the above photolithography method, and the coating liquid A is dried thereon. The film was applied by adjusting the slit gap of the extrusion head so as to have a film thickness of 300 nm, and dried and heated at 110 ° C. for 10 minutes. Further, UV curable transparent resin NN803 (manufactured by JSR Corporation) is applied under the condition that the film thickness after drying is 1.5 μm, the solvent component is vaporized to form an adhesive layer, and then a transparent electrode having gas barrier properties The film substrate was bonded to a non-barrier surface. Subsequently, ultraviolet rays were irradiated to sufficiently cure the adhesive layer, and the film was peeled off to produce an electrode having a first conductive layer and a second conductive layer on the surface of the film substrate. The obtained electrode was cut into 8 × 8 cm similarly to the transparent electrode 1 and placed so that the conductive layer surface was in contact with a 10 cm × 10 cm nickel foam sheet (Mitsubishi Materials Corporation, pore diameter 600 μm), 200 W, 5 minutes The transparent electrode 14 was produced by irradiating microwaves from the film substrate side.

(Preparation of transparent electrode 15)
On the surface of the transparent electrode film substrate having a gas barrier property, a substrate having ITO (indium tin oxide) deposited to a thickness of 150 nm by sputtering is immersed in isopropyl alcohol, and an ultrasonic cleaner BRANSONIC 3510J-MT. An ultrasonic cleaning treatment was performed for 10 minutes (manufactured by Nippon Emerson) to produce an ITO substrate. Next, a titanium dioxide dispersion was prepared by the following method. This dispersion was applied onto the ITO film using a bar coater and dried at 110 ° C. for 5 minutes to form a titanium dioxide-containing coating film having a thickness of 10 μm, whereby a transparent electrode 15 was produced.

(Preparation of titanium dioxide dispersion)
Titanium tetraisopropoxide 142.1 g and triethanolamine 149.2 g were mixed at room temperature in a dry box and allowed to stand for 2 hours. The mixed solution was taken out from the dry box, diluted with distilled water to a total volume of 1000 ml, and used as a mother liquor. 100 ml of the mother liquor and 100 ml obtained by adding 2.85 ml of acetic acid to distilled water were mixed. After heating in a sealed container at 100 ° C. for 24 hours to obtain a white gel, the temperature was raised to 140 ° C. and further heated for 72 hours. After cooling to room temperature, the supernatant was removed to obtain a pale reddish brown precipitate. The mass of the precipitate containing water was 33 g. To the resulting precipitate, 1.0 g of polyethylene glycol having a molecular weight of 500,000 was added and kneaded for 20 minutes with a kneader to obtain a titanium dioxide dispersion having a mass concentration of 12%. The average particle diameter of the titanium dioxide particles contained in the dispersion A was about 16 nm.

  The obtained electrode was cut out into 8 × 8 cm and placed so that the conductive layer surface was in contact with a 10 cm × 10 cm foamed nickel sheet (Mitsubishi Materials Corporation, hole diameter 600 μm), and 500 W for 4 minutes from the film substrate side. Irradiation was performed to produce a transparent electrode 15.

(Preparation of transparent electrode 16)
In the production of the transparent electrode 11, the transparent electrode 16 was produced in the same manner except that the slit gap of the extrusion head was adjusted to a dry film thickness of 100 nm.

(Preparation of transparent electrode 17)
A transparent electrode 17 was produced in the same manner as in the production of the transparent electrode 1, except that the coating liquid A was replaced with the following coating liquid C.

(Coating liquid C)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) 1.59 g
Polyhydroxyethyl vinyl ether (P-2, number average molecular weight 20,000, solid content 20% aqueous solution) 0.35 g
(P-2: Synthesis of polyhydroxyethyl vinyl ether)
In the synthesis of the poly (2-hydroxyethyl acrylate), polyhydroxyethyl vinyl ether (number average molecular weight of about 20,000, number average molecular weight <1000 content 0%) is similarly obtained except that hydroxyethyl vinyl ether is used as a monomer. Obtained.

(Preparation of transparent electrode 18)
A transparent electrode 18 was produced in the same manner as in the production of the transparent electrode 1 except that the coating liquid A was replaced with the following coating liquid D.

(Coating liquid D)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) 1.59 g
Polyhydroxyethylacrylamide (P-3, number average molecular weight 20,000, solid content 20% aqueous solution) 0.35 g
(P-3: Synthesis of polyhydroxyethylacrylamide)
In the synthesis of the poly (2-hydroxyethyl acrylate), polyhydroxyethylacrylamide (number average molecular weight of about 20,000, number average molecular weight <1000 content 0%) was similarly obtained except that hydroxyethylacrylamide was used as a monomer. Obtained.

(Preparation of transparent electrode 19)
A transparent electrode 19 was produced in the same manner as in the production of the transparent electrode 1, except that the coating liquid A was replaced with the following coating liquid E.

(Coating liquid E)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) 1.59 g
Poly (2-hydroxyethyl acrylate) / polyhydroxyethyl vinyl ether copolymer (P-4, number average molecular weight 20,000, solid content 20% aqueous solution) 0.35 g
(P-4: Synthesis of poly (2-hydroxyethyl acrylate) / polyhydroxyethyl vinyl ether copolymer)
In the synthesis of poly (2-hydroxyethyl acrylate), poly (2-hydroxyethyl acrylate) / polyhydroxyethyl vinyl ether copolymer was used except that equimolar amounts of 2-hydroxyethyl acrylate and hydroxyethyl vinyl ether were used as monomers. A coalescence (number average molecular weight of about 20,000, number average molecular weight <1000 content 0%) was obtained.

(Preparation of transparent electrode 20)
In the production of the transparent electrode 1, the transparent electrode 20 was produced in the same manner except that the coating liquid A was replaced with the following coating liquid F.

(Coating fluid F)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) 1.59 g
Polyvinyl alcohol (PVA-235, manufactured by Kureha, 2% solid content aqueous solution)
3.50g
Dimethyl sulfoxide 0.10g
Epoxy crosslinking agent (Denacol EX-521, Nagase ChemteX Corporation)
0.5g
<< Evaluation of transparent electrode >>
The film shape, transparency, conductivity and film strength of the obtained transparent electrode were evaluated as follows.

(Film shape)
The deformation of the film shape before and after heating was visually observed and evaluated according to the following criteria. For use in organic electronic devices, the film is preferably not deformed.

○: No deformation Δ: Deflection or wrinkle occurs, part of the shape of the film is deformed ×: Wrinkle or sagging is deformed throughout the film, and the original shape is not maintained.

(transparency)
Total light transmittance was measured using a HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. Since it is used for an organic electronic device, it is preferably 75% or more.

A: 80% or more B: 75% to less than 80% B: 70% to less than 75% X: 0% to less than 70% −: The film substrate is deformed and cannot be evaluated.

(Conductivity)
The surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.). The surface resistance is preferably 100Ω / □ or less, and preferably 20Ω / □ or less in order to increase the area of the organic electronic device.

(Membrane strength)
The strength of the conductive layer film was evaluated by a tape peeling method.

  Crimping / peeling was repeated 10 times on the conductive layer using a Scotch tape manufactured by Sumitomo 3M Co., and the dropping of the conductive layer was visually observed and evaluated according to the following criteria.

◎: No change after 5 times of pressure bonding / peeling ○: No change after 3 times of pressure peeling / bonding △: Peeling is observed after 1 time of pressure peeling, but more than 80% pattern remains ×: 1 time of pressure peeling Peeling is observed, and the remaining pattern is less than 80%. −: The film substrate is deformed and cannot be evaluated.

  The evaluation results are shown in Table 1.

<< Production of organic EL devices >>
The prepared transparent electrode (excluding transparent electrodes 11 and 16) substrate was washed with ultrapure water, then cut into a 30 mm square so that one square tile-shaped transparent pattern with a pattern side length of 20 mm was placed in the center, and used as an anode electrode Then, an organic EL device was produced by the following procedure. The hole transport layer and subsequent layers were formed by vapor deposition. The transparent electrodes 11 and 16 were not cleaned because a part of the conductive layer was peeled off by cleaning. Organic EL devices 1 to 20 were produced from the transparent electrodes 1 to 20, respectively.

  Each crucible for vapor deposition in a commercially available vacuum vapor deposition apparatus was filled with a constituent material of each layer in a necessary amount for device production. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

  First, an organic EL layer including a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.

<Formation of hole transport layer>
After depressurizing to a vacuum of 1 × 10 ⁻⁴ Pa, the deposition crucible containing compound 1 was heated by energization, and deposited at a deposition rate of 0.1 nm / second to provide a 30 nm thick hole transport layer. It was.

<Formation of organic light emitting layer>
Next, each light emitting layer was provided in the following procedures.

  Compound 2, Compound 3 and Compound 5 are deposited on the formed hole transport layer so that Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass. Co-evaporation was performed in the same region as the hole transport layer at a speed of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.

  Next, compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass. Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.

<Formation of hole blocking layer>
Further, a hole blocking layer was formed by depositing compound 6 in a thickness of 5 nm on the same region as the formed organic light emitting layer.

<Formation of electron transport layer>
Subsequently, in the same region as the formed hole blocking layer, CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm.

<Formation of cathode electrode>
On the formed electron transport layer, a transparent electrode is used as an anode and an anode external takeout terminal and Al as a 15 mm × 15 mm cathode forming material are mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa, and a 100 nm thick anode Formed.

Further, a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al ₂ O ₃ is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed. After pasting the members, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

<< Evaluation of organic EL devices >>
The obtained organic EL device was evaluated for light emission unevenness and lifetime as follows.

(Light emission unevenness)
The light emission unevenness was evaluated by visually evaluating the light emission state according to the following criteria using a source measure unit 2400 type manufactured by KEITHLEY, applying a direct current voltage to each organic EL element to emit light with a luminance of 1000 cd / m ² .

◎: Completely uniform light emission, satisfactory ○: Almost uniform light emission, no problem △: Some light emission unevenness is partially observed, but acceptable ×: Light emission unevenness is observed over the entire surface, Unacceptable xx: No light emission-: The film is deformed and an organic EL device cannot be produced.

(lifespan)
The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL device in which the anode electrode was ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. 100% or more is preferable, and 150% or more is more preferable.

A: 150% or more B: 100 to less than 150% B: 80 to less than 100% X: less than 80% XX: No light emission-: The film is deformed and an organic EL device cannot be produced.

  The evaluation results are shown in Table 2.

  From the transparent electrodes 2, 3, and 4 (Comparative Examples) in Tables 1 and 2, it can be seen that the film is damaged when the electrode is heated at a high temperature, and the strength of the conductive layer and the performance of the organic EL device are poor when the electrode is heated at a low temperature. . In addition, from the transparent electrodes 11 and 16 (comparative example), if the second conductive layer does not contain a hydroxyl group-containing non-conductive polymer, the transparency is insufficient and the strength of the conductive layer is weak, so there is no suitability for continuous production. Furthermore, since the substrate cannot be cleaned, the performance of the organic EL device is also poor. From the transparent electrodes 6 and 7 (comparative example), a micro of a transparent electrode having a first conductive layer made of a metal material formed in a pattern and a second conductive layer containing a conductive polymer and a hydroxyl group-containing non-conductive polymer. It can be seen that the wave heating requires a conductor or semiconductor in order not to damage the film substrate. In the configuration of the transparent electrode 15 (comparative example), the strength of the conductive layer is weak, so that it is not suitable for continuous production, and the performance of the organic EL device is also poor. Moreover, it turns out that it is necessary to perform irradiation from the film substrate side in order to produce the effect of microwave heating from the comparison between the transparent electrodes 1 (present invention) and 5 (comparative example).

  On the other hand, it can be seen from the transparent electrodes 1, 8, 9, 10 (invention) that the conductor or semiconductor may be any of various metals and semiconductors. Further, it can be seen from the transparent electrodes 1, 12, 13 (invention) that the first conductive layer may be formed by a conventionally known method. From the transparent electrodes 1, 17, 18, 19, 20 (invention) As long as the two conductive layers contain a conductive polymer and a hydroxyl group-containing non-conductive polymer, various hydroxyl group-containing non-conductive polymers can be used. Further, it can be seen from the transparent electrodes 1 and 14 (the present invention) that microwave heating can be effectively performed if the first conductive layer or the second conductive layer is in contact with the conductor or the semiconductor.

Claims (3)

  A method for producing a transparent electrode having a first conductive layer made of a metal material formed in a pattern on a film substrate and a second conductive layer containing a conductive polymer, wherein the second conductive layer contains a hydroxyl group Irradiating microwaves from the film substrate side, containing a non-conductive polymer, and the first conductive layer or the second conductive layer is in contact with the conductor or semiconductor conductor on the surface of the support base A method for producing a transparent electrode. The method for producing a transparent electrode according to claim 1, wherein the hydroxyl group-containing non-conductive polymer is a polymer represented by the following general formula (A).

(Wherein, X ^{1 to} X ³ represent a hydrogen atom or a methyl group, and R ^{1 to} R ³ each represent an alkylene group having 5 or less carbon atoms. L, m, and n represent a composition ratio (mol%), 50 ≦ l + m + n ≦ 100.)   The method for producing a transparent electrode according to claim 1, wherein the metal material is metal fine particles or metal nanowires.