JP2014175272A - Method of producing transparent electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a transparent electrode which removes reliably a high-boiling-point water-soluble organic solvent and moisture in a conductive polymer layer and provides a transparent electrode excellent in transparency and conductivity.SOLUTION: A method of producing a transparent electrode is for producing a transparent electrode by an application method by using a conductive polymer and includes a conductive polymer containing layer formation step of forming a conductive polymer containing layer on a transparent substrate by applying a fluid dispersion containing a conductive polymer and a high-boiling-point water-soluble organic solvent onto a transparent substrate, a low-boiling-point water-soluble organic solvent supply step of supplying a low-boiling-point water-soluble organic solvent which has a boiling point lower than that of the high-boiling-point water-soluble organic solvent and is azeotropic with the high-boiling-point water-soluble organic solvent onto the conductive polymer containing layer, after the conductive polymer containing layer formation step, and a heating drying step of vaporizing the high-boiling-point water-soluble organic solvent and the low-boiling-point water-soluble organic solvent, after the low-boiling-point water-soluble organic solvent supply step.

Description

  The present invention relates to a method for producing a transparent electrode, and particularly relates to a method for producing a transparent electrode having excellent transparency and conductivity.

In recent years, organic electronic elements such as organic electroluminescent elements (hereinafter also referred to as organic EL elements) and organic solar cells have attracted attention. In such organic electronic elements, transparent electrodes are an essential component.
Conventionally, an ITO transparent electrode in which a composite oxide (ITO) film of indium-tin is formed on a transparent substrate such as glass or a plastic film by a vacuum deposition method or a sputtering method has been mainly used. . However, indium, which is a raw material used for ITO, is a rare metal, and therefore has many unstable factors such as high prices and difficulty in obtaining it. Recently, indium removal is strongly desired.

In manufacturing a transparent electrode in place of the ITO transparent electrode, a manufacturing method using a wet coating method has been studied in place of a dry coating method with low productivity such as a vacuum deposition method and a sputtering method which have been conventionally used.
For example, as described in Patent Document 1, a conductive polymer dispersion containing a conductive material such as a conductive polymer represented by poly-3,4-ethylenedioxythiophene / polystyrene sulfonic acid (PEDOT-PSS) A method for producing a transparent electrode by a wet coating method has been developed, in which a liquid is directly coated on a transparent substrate and dried to form a conductive polymer-containing layer.
In such a transparent electrode using a conductive polymer, the conductive polymer dispersion is made conductive by supplying a high-boiling water-soluble organic solvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or ethylene glycol. Is known to improve.
In particular, when a transparent electrode using a conductive polymer is applied to an organic electronic device such as an organic EL device or an organic solar cell, the transparent electrode is required to have high conductivity. It is essential to supply a basic organic solvent.

When a transparent electrode using a conductive polymer is applied to an organic electronic element such as an organic EL element or an organic solar battery, moisture remaining in the conductive polymer-containing layer may cause, for example, generation of dark spots during light emission of the organic EL element. It has been known so far that it is one of the factors that degrade the performance of organic electronic elements, such as element lifetime degradation.
However, recently, it has been clarified that the high-boiling water-soluble organic solvent causes deterioration of the performance of the organic electronic device more than moisture due to its residual. Therefore, the removal of the high boiling water-soluble organic solvent in the conductive polymer-containing layer has not been discussed so far.

  On the other hand, with the increase in area and productivity of organic electronic devices, production of transparent electrodes using a roll-to-roll method using a flexible substrate (flexible transparent substrate) such as a resin substrate Technology is desired. In particular, when a conductive polymer transparent electrode using a resin substrate as a transparent substrate is applied to an organic electronic element, the method for drying the conductive polymer coating film, due to the heat resistance in the resin substrate itself and the above-described problems of device performance deterioration. Was a big issue.

  Patent Document 2 describes that a transparent electrode having a conductive polymer-containing layer composed of a conductive polymer and a binder is subjected to a wet multi-step cleaning process, but mainly improves current leakage of organic electronic elements by removing foreign substances and impurities. Therefore, no mention is made of the removal of the high-boiling water-soluble organic solvent in the conductive polymer-containing layer.

  From the above, in a transparent electrode having a conductive polymer-containing layer using a resin substrate as a transparent substrate, the high-boiling water-soluble organic solvent and moisture in the conductive polymer-containing layer are removed without damaging the resin substrate. There has been a strong demand for a technique that can be removed to produce a transparent electrode having excellent transparency and conductivity.

JP 2011-132527 A JP 2011-096437 A

  The present invention has been made in view of the above-described problems and situations, and the solution to the problem is to reliably remove the high-boiling water-soluble organic solvent and moisture in the conductive polymer layer, and to have excellent transparency and conductivity. It is providing the manufacturing method of a transparent electrode.

In order to solve the above-mentioned problems, the present inventor applied a dispersion containing a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate in the course of studying the cause of the above-mentioned problem. After forming the containing layer, a low boiling water-soluble organic solvent having a lower boiling point than the high boiling water-soluble organic solvent and azeotropic with the high boiling water-soluble organic solvent is supplied onto the conductive polymer-containing layer, It was found that, by drying, the high-boiling water-soluble organic solvent and moisture in the conductive polymer-containing layer can be reliably removed, and a transparent electrode excellent in transparency and conductivity can be produced. .
That is, the said subject which concerns on this invention is solved by the following means.
1. A method for producing a transparent electrode by producing a transparent electrode by a coating method using a conductive polymer,
A conductive polymer-containing layer forming step of forming a conductive polymer-containing layer by applying a dispersion containing a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate;
After the conductive polymer-containing layer forming step, the low-boiling water-soluble organic having a lower boiling point than the high-boiling water-soluble organic solvent and azeotropic with the high-boiling water-soluble organic solvent is formed on the conductive polymer-containing layer. A low-boiling water-soluble organic solvent supplying step of supplying a solvent;
A heating / drying step of volatilizing the high-boiling water-soluble organic solvent and the low-boiling water-soluble organic solvent after the low-boiling water-soluble organic solvent supplying step.
2. The method for producing a transparent electrode according to item 1, wherein the transparent substrate is a transparent resin substrate.
3. The method for producing a transparent electrode according to item 1 or 2, wherein the heating / drying step is a step of performing infrared irradiation within a range of a maximum energy wavelength of 0.8 to 3 µm.
4). The method for producing a transparent electrode according to any one of Items 1 to 3, wherein the high-boiling water-soluble organic solvent is a polyhydric alcohol.
5. The method for producing a transparent electrode according to any one of Items 1 to 4, wherein the low-boiling water-soluble organic solvent is ethanol or isopropanol.

By the above means of the present invention, the high-boiling water-soluble organic solvent and water in the conductive polymer-containing layer can be reliably removed, and a transparent electrode excellent in transparency and conductivity can be provided.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
After forming a conductive polymer-containing layer by applying a dispersion containing a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate, the high-boiling water-soluble organic solvent is formed on the conductive polymer-containing layer. The low-boiling water-soluble organic solvent having a low boiling point and azeotropically with the high-boiling water-soluble organic solvent is supplied and dried, so that the high-boiling water-soluble organic solvent and the low-boiling water-soluble organic solvent azeotrope. The high boiling point water-soluble organic solvent and moisture in the conductive polymer-containing layer are volatilized and removed. As a result, it can be set as the transparent electrode excellent in transparency and electroconductivity.

The method for producing a transparent electrode of the present invention is a method for producing a transparent electrode by producing a transparent electrode by a coating method using a conductive polymer, comprising a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate. A conductive polymer-containing layer forming step of forming a conductive polymer-containing layer by applying a dispersion liquid, and after the conductive polymer-containing layer forming step, on the conductive polymer-containing layer, the high-boiling water-soluble organic solvent A low boiling water soluble organic solvent supplying step for supplying a low boiling water soluble organic solvent azeotropic with the high boiling water soluble organic solvent, and after the low boiling water soluble organic solvent supplying step, A heating / drying step for volatilizing the high-boiling water-soluble organic solvent and the low-boiling water-soluble organic solvent.
This feature is a technical feature common to the inventions according to claims 1 to 5.
As an embodiment of the present invention, it is preferable that the transparent substrate is a transparent resin substrate from the viewpoint of manifesting the effects of the present invention. As a result, the high-boiling water-soluble organic solvent and moisture in the conductive polymer-containing layer can be removed without damaging the transparent resin substrate, which is effective.
Moreover, it is preferable that the said heating and drying process is a process of performing infrared irradiation within the range whose maximum energy wavelength is 0.8-3 micrometers. That is, the low-boiling water-soluble organic solvent has a strong absorption wavelength due to OH (hydroxy group) stretching vibration in the vicinity of about 3 μm. Therefore, after supplying the low-boiling water-soluble organic solvent onto the conductive polymer-containing layer, the maximum energy is reduced. By irradiating infrared rays having a wavelength in the range of 0.8 to 3 μm, the low-boiling water-soluble organic solvent is more efficiently volatilized, and the high-boiling water-soluble organic solvent is volatilized together with the low-boiling water-soluble organic solvent. Promoted by boiling.
Moreover, it is preferable that the high boiling water-soluble organic solvent is a polyhydric alcohol in that the volatilization of the high boiling water-soluble organic solvent itself can be further promoted.
Furthermore, it is preferable that the low-boiling water-soluble organic solvent is ethanol or isopropanol because the volatilization of the low-boiling water-soluble organic solvent itself can be further promoted.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Method for producing transparent electrode]
The method for producing a transparent electrode of the present invention is a method for producing a transparent electrode by producing a transparent electrode by a coating method using a conductive polymer, comprising a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate. A conductive polymer-containing layer forming step of applying a dispersion to form a conductive polymer-containing layer, and after the conductive polymer-containing layer forming step, the conductive polymer-containing layer is lower than the high-boiling water-soluble organic solvent on the conductive polymer-containing layer. A low-boiling water-soluble organic solvent supplying step for supplying a low-boiling water-soluble organic solvent having a boiling point and azeotropically with the high-boiling water-soluble organic solvent, and a high-boiling water-soluble organic solvent after the low-boiling water-soluble organic solvent supplying step And a heating / drying step for volatilizing the low-boiling water-soluble organic solvent.

(1) Conductive polymer-containing layer forming step In the conductive polymer-containing layer forming step, a conductive polymer-containing layer is formed by applying a dispersion containing a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate. It is a process to do.
In addition to printing methods such as gravure printing, flexographic printing, screen printing, and inkjet printing, the application method for dispersions containing conductive polymers and high-boiling water-soluble organic solvents includes roll coating and dip coating. Coating methods such as a method, a spin coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used.

(2) Low-boiling water-soluble organic solvent supplying step The low-boiling water-soluble organic solvent supplying step has a lower boiling point than the high-boiling water-soluble organic solvent on the conductive polymer-containing layer after the conductive polymer-containing layer forming step. And a step of forming a low-boiling water-soluble organic solvent that azeotropes with the high-boiling water-soluble organic solvent.
The method for supplying the low-boiling water-soluble organic solvent on the conductive polymer-containing layer is not particularly limited, but a method for applying or spraying the low-boiling water-soluble organic solvent on the conductive polymer-containing layer, Examples include a method of immersing the transparent substrate on which the polymer-containing layer is formed in a low-boiling water-soluble organic solvent.

  As a method for applying the low-boiling water-soluble organic solvent, a known method can be used, for example, a roll coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, Methods such as spray coating and doctor coating can be used, and printing methods such as gravure printing, flexographic printing, screen printing, and inkjet printing can also be used.

  The amount of the low-boiling water-soluble organic solvent to be applied is sufficient to act on the conductive polymer-containing layer to promote the volatilization of the high-boiling water-soluble organic solvent. It is preferable to be the same as or more than.

The method of immersing in the low-boiling water-soluble organic solvent is not particularly limited, and a method of directly immersing the transparent substrate on which the conductive polymer-containing layer is formed in the low-boiling water-soluble organic solvent tank for a predetermined time, or a roll -A method of immersing for a predetermined time while transporting through a low boiling water-soluble organic solvent tank by a to-roll method can be used.
The temperature for dipping in the low-boiling water-soluble organic solvent is preferably carried out at room temperature, and the dipping time is preferably within a range of 10 seconds to 10 minutes. Thereby, it can be made to fully act with respect to the conductive polymer content layer in the present invention, and film peeling etc. do not arise.

(3) Heating / drying step In the heating / drying step, the supplied high-boiling water-soluble organic solvent and low-boiling water-soluble organic solvent are volatilized after the low-boiling water-soluble organic solvent supplying step, and the conductive polymer-containing layer is heated. -It is a process of drying.
As the heating / drying method, for example, the conductive polymer-containing layer is irradiated with infrared rays having a maximum energy wavelength in the range of 0.8 to 3 μm, or at a temperature at which the transparent substrate is not deformed, Although the method of drying by heating within the range of 80-250 degreeC with an oven etc. is mentioned, In this invention, it is preferable to irradiate with infrared rays.

In general, infrared refers to light radiation longer than the wavelength of visible radiation. In the present invention, irradiation is performed with infrared light having a maximum energy wavelength in the range of 0.8 to 3 μm.
Since the low-boiling water-soluble organic solvent of the present invention has a strong absorption wavelength due to OH (hydroxy group) stretching vibration in the vicinity of about 3 μm, it is efficiently volatilized by infrared irradiation with a maximum energy wavelength of 3 μm or less, resulting in high-boiling water-solubility. Volatilization of the organic solvent is also promoted by azeotropy with the low-boiling water-soluble organic solvent. Furthermore, volatilization of the high-boiling water-soluble organic solvent is further promoted by using a polyhydric alcohol as the high-boiling water-soluble organic solvent.
Moreover, since the polyester resin film preferably used for the transparent substrate of the present invention does not have a strong absorption wavelength in the infrared wavelength region where the maximum energy wavelength is 3 μm or less, the base material deformation due to heating does not occur in the infrared irradiation process of 3 μm or less. Therefore, in a conductive polymer transparent electrode using a resin substrate, the high-boiling water-soluble organic solvent and moisture in the conductive polymer-containing layer can be volatilized and removed without damaging the substrate.

Although there is no limitation in particular about the method of infrared irradiation in the range whose maximum energy wavelength in this invention is 0.8-3 micrometers, It is preferable to carry out with an infrared heater. In the case of using an infrared heater, it is known that when the temperature of the filament of the infrared heater increases, the maximum energy wavelength of the emission spectrum shifts to the short wavelength side, and the Wien's displacement law λ max = 0.002898 / T
λ: wavelength [m]
T: Absolute temperature (Celsius [° C.] + 273)
Thus, the maximum energy wavelength of the infrared radiation spectrum can be obtained from the temperature of the filament. When the filament temperature of the infrared heater is set to 700 ° C. or higher, the maximum energy wavelength of the radiation spectrum is preferably 3 μm or less from the above formula.

As the infrared heater used for infrared irradiation within the range of the maximum energy wavelength of 0.8 to 3 μm in the present invention, for example, the outer periphery of the filament of the infrared heater as described in Japanese Patent No. 4790092 is made of quartz glass. And a glass having a structure in which a cooling fluid flow path is formed between the plurality of glass tubes to suppress an increase in the surface temperature of the infrared heater. It is preferable. This is because when emitting infrared rays, quartz glass, borosilicate crown glass, etc. function as a low-pass filter that transmits infrared rays with a wavelength of 3.5 μm or less and absorbs infrared rays with a wavelength of 3.5 μm or more. This is because the deformation of the substrate due to heat due to the secondary radiation from the glass tube can be suppressed.
In the present invention, the irradiation time of infrared rays having a maximum energy wavelength in the range of 0.8 to 3 μm can be arbitrarily set depending on the volatility of the high-boiling water-soluble organic solvent, but in the range of 1 second to 30 minutes. It is preferable to carry out within.

Moreover, as long as the deformation of the transparent substrate does not occur, a preliminary heat treatment step may be separately provided before the heating / drying step (before the infrared irradiation step).
The preheating treatment method is not particularly limited, and examples thereof include an electric furnace such as a hot plate, a box furnace, and a conveyor furnace, a near infrared heater, a mid infrared heater, a far infrared heater, hot air, hot air, and microwave. These may be used alone or in combination.

Hereinafter, the transparent electrode manufactured by the manufacturing method of the transparent electrode of this invention is demonstrated.
[Transparent electrode]
The transparent electrode according to the present invention includes a transparent substrate and a conductive polymer-containing layer.
The total light transmittance of the transparent electrode is 70% or more, preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.
Further, as the electric resistance value of the conductive part of the transparent electrode, the surface specific resistance is preferably 1000Ω / □ or less, more preferably 100Ω / □ or less, and further 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.

In the transparent electrode according to the present invention, the conductive polymer-containing layer is preferably formed so as to cover the metal fine line pattern provided on the transparent substrate from the viewpoint of obtaining higher conductivity.
Although there is no restriction | limiting in particular in a metal fine wire pattern, It is preferable to form from a metal nanoparticle containing composition. A metal nanoparticle means the metal or metal oxide of a fine particle shape whose particle diameter is atomic size to nm size. In general, the metal nanoparticles are preferably spherical, but may have an indefinite shape close to a sphere.
The metal material of the metal nanoparticles is not particularly limited as long as it has excellent conductivity. For example, an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium may be used. Silver is preferred from the viewpoint.
Here, the average particle diameter of the metal nanoparticles is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm, and even more preferably in the range of 1 to 30 nm.
The pattern shape of the fine metal wire pattern is not particularly limited. For example, the pattern shape may be a stripe shape, a honeycomb shape, or a mesh shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency.

An aperture ratio is the ratio which the electroconductive part which has translucency accounts to the whole. For example, when the light-impermeable metal fine line pattern has a stripe 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 within the range of 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, sufficient transparency as a transparent electrode is obtained.
The height of the thin wire is preferably within the range of 0.1 to 5 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and if it is 5 μm or less, the unevenness difference does not affect the film thickness distribution of the functional layer in the formation of the organic electronic element. It is a range.

  As a method of forming the metal fine line pattern, a method of printing the metal nanoparticle-containing composition in a desired shape is preferable. There is no restriction | limiting in particular as a printing method, It can print and form in a desired shape by well-known printing methods, such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing.

<Transparent substrate>
As the transparent substrate according to the present invention, a transparent resin substrate or a transparent glass substrate can be used. In particular, it is preferable to use a transparent resin substrate in that the effects of the present invention can be more effectively exhibited.
The transparent resin substrate is not particularly limited as long as it has high transparency, and the total light transmittance is preferably 70% or more, and preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. The transparent resin substrate is preferably a film-like transparent resin film.

There is no restriction | limiting in particular as a 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. If the resin film total light transmittance of 80% or more in the range of 80~780nm), can be preferably applied to a transparent resin film according to the present invention.
Among them, biaxially stretched biaxially oriented polyethylene terephthalate resin film, biaxially oriented polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. in terms of transparency, heat resistance, ease of handling, strength and cost. A stretched polyester resin film is preferable, and a biaxially stretched polyethylene terephthalate resin film and a biaxially stretched polyethylene naphthalate resin film are more preferable.

In the transparent substrate according to the present invention, a protective layer may be formed on one side or both sides.
The protective layer may be a combination of an organic protective layer and an inorganic protective layer. From the viewpoint of imparting sufficient durability, impact resistance and smoothness to the transparent resin film, the organic protective layer is preferably a hard coat layer. In order to be suitably used for organic electronic devices, the inorganic protective layer is a gas barrier. A layer is preferred.
As the formation order of the protective layer, it is preferable to form the transparent resin substrate, the organic protective layer, and the inorganic protective layer in this order.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. .
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.

The thickness of the hard coat layer is usually in the range of 0.5 to 50 μm, preferably in the range of 1 to 20 μm, more preferably in the range of 2 to 10 μm, most preferably 3 to 7 μm. Within range.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

There is no restriction | limiting in particular as a gas barrier layer and its formation method, The film | membrane by inorganic compounds, such as a silica, can be formed by vacuum evaporation or CVD method. Further, after coating and drying a coating liquid containing a polysilazane compound, it may be oxidized by irradiation with ultraviolet light in a nitrogen atmosphere containing oxygen and water vapor to form a gas barrier layer, or an inorganic or organic coating or a hybrid coating of both. May be formed. The gas barrier layer may be a single layer or may be a laminate of two layers or three layers. Further, a stress relaxation layer may be sandwiched between the gas barrier layers.
Whether it is a single layer or a laminated layer, the thickness of one gas barrier layer is preferably in the range of 30 to 1000 nm, more preferably in the range of 30 to 500 nm, and particularly in the range of 90 to 500 nm. When it is 30 nm or more, the film thickness uniformity is good and the gas barrier performance is excellent. When the thickness is 1000 nm or less, cracks due to bending are rarely abruptly entered, and an increase in internal stress during film formation can be suppressed, and generation of defects can be prevented.

As the gas barrier property of the gas barrier layer, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10 ⁻³ g. / (M ² · 24h) or less is preferable.
Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1.01325 × 10 ⁵ Pa). The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

<Conductive polymer-containing layer>
The conductive polymer-containing layer according to the present invention is formed from a composition containing at least a conductive polymer and a high-boiling water-soluble organic solvent having a hydroxy group.
The dry layer thickness (also referred to as “dry film thickness”) of the conductive polymer-containing layer is preferably in the range of 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 50 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is further preferably 300 nm or more. Further, from the viewpoint of transparency, the thickness is more preferably 1000 nm or less, and further preferably 800 nm or less.
In addition to the aforementioned gravure printing method, flexographic printing method, screen printing method, ink jet printing method, etc., the coating of the conductive polymer-containing layer is a roll coating method, dip coating method, spin coating method, casting method, die coating method. Coating methods such as a method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used.

≪Conductive polymer≫
The conductive polymer only needs to have conductivity, and preferably includes 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 polyanion described later. .

≪π-conjugated conductive polymer≫
The π-conjugated conductive polymer that can be used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, and polyacetylenes. A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds can be used. Of these, polythiophenes and polyanilines are preferred from the viewpoints of conductivity, transparency, stability, and the like, and ease of adsorption to metal nanoparticles. Most preferred is polyethylene dioxythiophene.

≪π-conjugated conductive polymer precursor monomer≫
The precursor monomer used to form a π-conjugated conductive polymer has a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, a π-conjugated system is formed in the main chain. Is. 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-carboxypyrrole, 3-methyl-4-carboxypyrrole, 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-hexylthiop , 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-diethoxythiophene 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 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-isobutylaniline, 2-aniline sulfonic acid, 3-aniline sulphone Examples include phonic acid.

≪Polyanion≫
The polyanion used in the present invention is an acidic polymer in a free acid state, and is a polymer of a monomer having an anionic group, or a copolymer of a monomer having an anionic group and a monomer having no anionic group.
The free acid may be in the form of a partially neutralized salt. 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 copolymer thereof, at least having an anionic group Is included.
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 any functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among these, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A substituted 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 mono-substituted 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.
Further, it may be a polyanion 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 may be formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment within a range of 100 to 120 ° C. for 5 minutes or more. This is 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 hydroxy 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 polyanion production method include a method of directly introducing an anion group into a polymer having no anion group using an acid, a method of sulfonating a polymer having no anion group with a sulfonating agent, and an anion group-containing polymerizability. Examples thereof include a method of producing by polymerization of monomers.
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, this is maintained 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 changing 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 the π-conjugated conductive polymer and the polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion” is preferably in the range of 1: 1 to 20 in terms of mass ratio. A range of 1: 2 to 10 is more preferable from the viewpoint of conductivity and dispersibility.

The oxidant used when the precursor monomer for 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, inexpensive 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 as needed. The use of persulfates, organic acids and iron (III) salts of inorganic acids containing organic residues has great application advantages because it is not corrosive.

  Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, For example, methane or dodecanesulfonic acid; aliphatic carboxylic acid having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as sulphur Examples include acids and aromatic, optionally substituted C1-C20 alkyl-substituted sulfonic acids, such as Fe (III) salts of benzenecene sulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid. Furthermore, oxidative polymerization can be performed using a known oxidation catalyst.

  As such a conductive polymer, a commercially available material can also be preferably used. For example, a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (abbreviated as PEDOT-PSS) is a Clevios series from Heraeus, 483095 and 560596 of PEDOT-PSS from Aldrich, It is commercially available as a Denatron series from Nagase Chemtex. Polyaniline is commercially available from Nissan Chemical Industries as the ORMECON series. In the present invention, such an agent can also be preferably used.

<High boiling water-soluble organic solvent>
The high-boiling water-soluble organic solvent according to the present invention refers to a water-soluble organic solvent having a boiling point of 10 ° C. or higher under the same atmospheric pressure as compared with a low-boiling water-soluble organic solvent described later. The high boiling water-soluble organic solvent is used for the purpose of improving the conductivity of the conductive polymer.
There is no restriction | limiting in particular as a high boiling water-soluble organic solvent, 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 carbonyl group-containing compound, an ether group-containing compound, a sulfoxide group-containing compound, an amide group-containing compound, and a hydroxy group-containing compound.

Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone (NMP) and the like.
Examples of the ether group-containing compound include diethylene glycol monoethyl ether.
Examples of the sulfoxide group-containing compound include dimethyl sulfoxide.
Examples of the amide group-containing compound include dimethylformamide.
Examples of the hydroxy group-containing compound include polyhydric alcohols, which are more efficiently volatilized by the improvement in the conductivity of the conductive polymer and the infrared irradiation within the range of the maximum energy wavelength in the present invention of 0.8 to 3 μm. It is preferable that it is a polyhydric alcohol.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-butanediol, triethylene glycol, tetraethylene glycol, tripropylene glycol, 1,4-propanediol, 1,3-butanediol, 2-methyl-1,3-butanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3 , 3,5-trimethyl-1,6-hexanediol, 2,3,5-trimethylpentanediol, 1,6-hexanediol, glycerin, pentaerythritol and the like. These may be used alone or in combination of two or more, but it is preferable to use at least one selected from ethylene glycol, diethylene glycol, and propylene glycol.

<Other additives>
The conductive polymer-containing layer according to the present invention may contain a transparent resin component or additive in order to ensure film formability and film strength.
The transparent resin component is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer, and may be a thermosetting resin or a thermoplastic resin. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like. In particular, it is preferable to form a binder resin or a water-soluble binder resin that can be uniformly dispersed in an aqueous solvent from the viewpoint of obtaining high surface smoothness while maintaining high transparency and conductivity.

<Low boiling water-soluble organic solvent>
The low-boiling water-soluble organic solvent according to the present invention is a compound having a boiling point of 10 ° C. or more lower than that of the high-boiling water-soluble organic solvent under the same atmospheric pressure and azeotropic with the high-boiling water-soluble organic solvent. is there. As the low-boiling water-soluble organic solvent according to the present invention, a low-boiling alcohol is preferable.
Low boiling alcohols include methanol, ethanol, n-propanol, isopropanol, butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, Monovalent lower alcohols such as 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, and the like include ethylene glycol monomethyl ether (methicero), ethylene glycol monoethyl ether (ethicero) ), Polyhydric alcohol derivatives such as ethylene glycol monobutyl ether (buticero), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and the like.
These may be used singly or in combination of two or more, but ethanol and isopropanol are preferably used from the viewpoint of the boiling point of the solvent and ease of handling.

[Organic electronic devices]
The organic electronic device has a transparent electrode and an organic functional layer produced by the method of the present invention.
For example, the transparent electrode manufactured by the method of the present invention is used as a first electrode portion, an organic functional layer is formed on the first electrode portion, and a second electrode portion is formed on the organic functional layer as a counter electrode. By forming it, an organic electronic device can be obtained.
Examples of the organic functional layer include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like without any particular limitation. However, the present invention is an organic light emitting layer in which the organic functional layer is a thin film and is of a current driving system. In the case of an organic photoelectric conversion layer, it is particularly effective.

Hereinafter, the component in case the organic electronic element which concerns on this invention is an organic EL element and an organic photoelectric conversion element is demonstrated.
<Organic EL device>
In the present invention, an organic EL device having an organic light emitting layer as an organic functional layer includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, an electron block layer, etc. in addition to the organic light emitting layer. A layer for controlling the light emission may be used in combination with the organic light emitting layer.
Since the conductive polymer layer on the transparent electrode of the present invention can also serve as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.

Although the preferable specific example of a structure is shown below, this invention is not limited to these.
(I) (first electrode part) / light emitting layer / electron transport layer / (second electrode part)
(Ii) (first electrode part) / hole transport layer / light emitting layer / electron transport layer / (second electrode part)
(Iii) (first electrode part) / hole transport layer / light emitting layer / hole block layer / electron transport layer / (second electrode part)
(Iv) (first electrode part) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / (second electrode part)
(V) (first electrode part) / anode buffer layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (second electrode part)

  Here, the light-emitting layer 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, and these at least three light emitting layers are laminated. A white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL device of the present invention is preferably a white light emitting layer.

In addition, as the light emitting material or doping material that can be used in the organic light emitting layer in the present invention, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, 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, pyran, quinacridone, Bren, distyrylbenzene derivatives, di still arylene derivatives, and various fluorescent dyes and rare earth metal complex, there is a phosphorescent material such as, but not limited thereto.
It is also preferable to include a light emitting material selected from these compounds in a range of 90 to 99.5 parts by mass and a doping material in a range of 0.5 to 10 parts by mass.
The organic light emitting layer is produced by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.

≪First electrode part, second electrode part≫
The transparent electrode according to the present invention is used in the first electrode portion or the second electrode portion. In a preferred embodiment, the first electrode portion is an anode and the second electrode portion is a cathode.
The second electrode portion may be a single conductive material layer, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the second electrode portion, 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 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 is preferably several hundred Ω / □ or less, and the film thickness is usually selected within the range of 10 nm to 5 μm, preferably within the range of 50 to 200 nm.

  If a metal material is used as the conductive material of the second electrode part, the light coming to the second electrode part side is reflected and returns to the first electrode part side. By using a metal material as the conductive material of the second electrode portion, this light can be reused, and the extraction efficiency is further improved.

<Organic photoelectric conversion element>
The organic photoelectric conversion element has a structure in which a first electrode portion, a photoelectric conversion layer (hereinafter also referred to as a bulk heterojunction layer) having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer), and a second electrode portion are stacked. It is preferable to have. The transparent electrode according to the present invention is used at least on the incident light side.
An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the second electrode portion.

≪Photoelectric conversion layer≫
The photoelectric conversion layer is a layer that converts light energy into electric energy, and preferably 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.
As the condensed polycyclic aromatic compound, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, 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 Oligomers 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. Substituted-unsubstituted alternating copolymer polythiophenes such as JP-A-2006-36755, JP-A-2007-51289, JP-A-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 _complex, C _{60, C} 70 fullerenes, such _{as, C 76, C 78, C} 84, carbon nanotube, merocyanine dyes such as SWNT, dyes such as hemicyanine dyes, further, polysilanes, such polygermane σ conjugated polymers and organic / inorganic hybrid materials described in JP-A-2000-260999 can also be used.

Among these 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 pentacene having substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6690029, Japanese Patent Application Laid-Open No. 2004-107216, and the like. Derivatives, pentacene precursors described in U.S. Patent Application Publication No. 2003/0136964 and the like; Amer. Chem. Soc. , Vol. 127, no. And substituted acenes described in 14.4986 and the like and derivatives thereof.

Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process can be performed, can form a crystalline thin film after drying, and can achieve high mobility is 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, and acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in US Patent Application Publication No. 2003/0136964, 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 hetero junction layer by solution process, bulk hetero junction This is because the layer does not dissolve and the material constituting the layer and the material forming the bulk heterojunction layer are not mixed, and further improvement in efficiency and life can be achieved. .
The p-type semiconductor material is a compound that has been converted into a p-type semiconductor material by causing a chemical structural change by exposing the p-type semiconductor material precursor to a vapor of a compound that causes heat, light, radiation, or a chemical reaction. Preferably there is. Among them, compounds that cause a scientific 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. As a fullerene-containing polymer compound, fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₄ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed fullerene, fullerene nanotube, multi-wall nanotube, single-wall nanotube, Examples thereof include a polymer compound having a nanohorn (conical type) or the like as a skeleton. The fullerene-containing polymer compound, a polymer compound having a fullerene C ₆₀ skeleton (derivatives) are preferred.

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 organic electronic element which concerns on this invention as photoelectric conversion devices, such as a solar cell, an organic electronic element may be utilized by a single layer and may be laminated | stacked and utilized (tandem type).
In addition, since the photoelectric conversion device is not deteriorated by oxygen, moisture, or the like in the environment, the photoelectric conversion device is preferably sealed by a known method.

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.
(1) Example 1
[Preparation of transparent electrode]
<Preparation of transparent electrode TCG-1>
Using a non-alkali glass (EAGLE-XG; manufactured by Corning) having a thickness of 0.7 mm and a size of 30 mm × 30 mm, the conductive polymer liquid-1 prepared as follows was used as a conductive polymer-containing layer. After applying so as to have a dry average layer thickness of 75 nm using a spin coater, heat treatment was performed on a hot plate at 180 ° C. for 30 minutes to produce a transparent electrode TCG-1.
≪Conductive polymer liquid-1≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Dimethyl sulfoxide (high boiling water-soluble organic solvent) 0.10g

<Preparation of transparent electrode TCG-2>
In preparation of TCG-1, after applying the conductive polymer liquid-1, it was pre-dried on a hot plate at 80 ° C. for 2 minutes, then immersed in ethanol for 1 minute, and then hot plate at 180 ° C. for 30 minutes. A transparent electrode TCG-2 was produced in the same manner as TCG-1 except that heat treatment was performed.

<Preparation of transparent electrode TCF-1>
Spinning a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 100 μm and a size of 30 mm × 30 mm with a hard coat layer and a gas barrier layer on both sides, and conducting polymer solution-1 as a conductive polymer-containing layer After coating so that the dry average film thickness became 75 nm using a coater, heat treatment was performed on a hot plate at 110 ° C. for 30 minutes to produce a transparent electrode TCF-1.

<Preparation of transparent electrode TCF-2>
In preparation of TCF-1, after applying the conductive polymer liquid-1, it was pre-dried on a hot plate at 80 ° C. for 2 minutes, and then immersed in ethanol, which is a low-boiling water-soluble organic solvent, for 1 minute. A transparent electrode TCF-2 was produced in the same manner as TCF-1, except that heat treatment was performed on a hot plate at 110 ° C. for 30 minutes.

<Preparation of transparent electrode TCF-3>
In preparation of TCF-2, instead of performing heat treatment at 110 ° C. for 30 minutes with a hot plate, referring to Japanese Patent No. 4790092, an infrared heater having an air cooling mechanism in a quartz double tube is used, and the filament temperature is 600 A transparent electrode TCF-3 was produced in the same manner as TCF-2 except that the output was adjusted to be 0 ° C. and infrared irradiation was performed from the conductive polymer-containing layer forming surface side with an irradiation time of 1 minute. The filament temperature was measured with a radiation thermometer (IR-AHU; manufactured by Chino Corporation). The infrared maximum energy wavelength at a filament temperature of 600 ° C. is 3.3 μm.

<Preparation of transparent electrode TCF-4>
In the production of TCF-3, a transparent electrode TCF-4 was produced in the same manner as TCF-3 except that the filament temperature of the infrared heater was set to 700 ° C. The infrared maximum energy wavelength at a filament temperature of 700 ° C. is 3.0 μm.

<Preparation of transparent electrode TCF-5>
In the production of TCF-4, a transparent electrode TCF-5 was produced in the same manner as TCF-4 except that the low-boiling water-soluble organic solvent to be immersed was changed from ethanol to isopropanol.

<Preparation of transparent electrode TCF-6>
In the production of TCF-4, the transparent electrode TCF-6 was prepared in the same manner as TCF-4 except that the conductive polymer liquid was changed from the conductive polymer liquid-1 to the conductive polymer liquid-2 prepared as follows. Was made.
≪Conductive polymer liquid-2≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Dimethylformamide (high boiling water-soluble organic solvent) 0.10 g

<Preparation of transparent electrode TCF-7>
Transparent electrode TCF-7 was prepared in the same manner as TCF-4 except that the conductive polymer liquid was changed from conductive polymer liquid-1 to conductive polymer liquid-3 prepared as follows in the production of TCF-4. Was made.
≪Conductive polymer liquid-3≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
N-methyl-2-pyrrolidone (high boiling water-soluble organic solvent) 0.10 g

<Preparation of transparent electrode TCF-8>
In the production of TCF-4, the transparent electrode TCF-8 was prepared in the same manner as TCF-4 except that the conductive polymer liquid was changed from the conductive polymer liquid-1 to the conductive polymer liquid-4 prepared as follows. Was made.
≪Conductive polymer liquid-4≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Ethylene glycol (high boiling water-soluble organic solvent) 0.10g

<Preparation of transparent electrode TCF-9>
In the production of TCF-4, the transparent electrode TCF-9 was prepared in the same manner as TCF-4 except that the conductive polymer liquid was changed from the conductive polymer liquid-1 to the conductive polymer liquid-5 prepared as follows. Was made.
≪Conductive polymer liquid-5≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Diethylene glycol (high boiling water-soluble organic solvent) 0.10 g

<Preparation of transparent electrode TCF-10>
In the production of TCF-4, the transparent electrode TCF-10 was prepared in the same manner as TCF-4 except that the conductive polymer liquid was changed from the conductive polymer liquid-1 to the conductive polymer liquid-6 prepared as follows. Was made.
≪Conductive polymer liquid-6≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Propylene glycol (high boiling water-soluble organic solvent) 0.10g

<Preparation of transparent electrode TCF-11>
In preparation of TCF-10, instead of immersing in ethanol for 1 minute, a spin coater was applied from above the conductive polymer-containing layer so that the wet average film thickness was the same as the dry average film thickness of the conductive polymer-containing layer. A transparent electrode TCF-11 was produced in the same manner as TCF-10 except that ethanol was applied.

<Preparation of transparent electrode TCF-12>
In the production of TCF-10, a transparent electrode TCF-12 was produced in the same manner as TCF-10 except that the filament temperature of the infrared heater was 1200 ° C. The infrared maximum energy wavelength at a filament temperature of 1200 ° C. is 2.0 μm.

<Preparation of transparent electrode TCF-13>
In the production of TCF-10, a transparent electrode TCF-13 was produced in the same manner as TCF-10 except that the filament temperature of the infrared heater was 2500 ° C. The infrared maximum energy wavelength at a filament temperature of 2500 ° C. is 1.0 μm.

<Preparation of transparent electrode TCF-14>
In the production of TCF-12, the conductive polymer liquid was changed from the conductive polymer liquid-6 to the conductive polymer liquid-7 prepared as described below, and the dry average film thickness of the conductive polymer-containing layer was 500 nm. A transparent electrode TCF-14 was produced in the same manner as TCF-12 except that the conductive polymer liquid-7 was applied.
≪Conductive polymer liquid-7≫
CLEVIOS PH510 (manufactured by Heraeus, solids concentration 1.89%) 1.60 g
Plus Coat Z-561 (manufactured by Reciprocal Chemical Co., Ltd., solid content concentration 25%) 0.32 g
Dimethyl sulfoxide (high boiling water-soluble organic solvent) 0.10 g

<Preparation of transparent electrode TCF-15>
A silver nanoparticle ink 1 (TEC-PA-010; manufactured by InkTec Co., Ltd.) is formed on a biaxially stretched polyethylene naphthalate (PEN) film having a thickness of 100 μm and a size of 200 mm × 200 mm, having a hard coat layer and a gas barrier layer formed on both sides. ) Using a small thick film semi-automatic printing machine STF-150IP (manufactured by Tokai Shoji Co., Ltd.) with a screen pattern of 50 μm width, 1 mm pitch, and square lattice shape, the height of fine wires after heat treatment becomes 1 μm. The metal fine line pattern was printed by the screen printing method. The area of the pattern printing area was 150 mm × 150 mm. After printing, heat treatment was performed on a hot plate at 140 ° C. for 5 minutes.
Next, on the fine metal wire pattern, the conductive polymer liquid-7 is adjusted to the printed region of the fine metal wire pattern, and using an applicator with a coating width of 150 mm, the dry polymer thickness is 500 nm as the conductive polymer-containing layer. Then, unnecessary peripheral portions were wiped off so as to be the same as the printed region of the metal fine line pattern. Then, it preliminarily dried on a hot plate at 80 ° C. for 2 minutes, and then immersed in ethanol, which is a low-boiling water-soluble organic solvent, for 1 minute. Furthermore, using an infrared heater having an air cooling mechanism in the quartz double tube, the output is adjusted so that the filament temperature is 1200 ° C., and infrared irradiation is performed from the conductive polymer-containing layer forming surface side with an irradiation time of 1 minute, A transparent electrode TCF-15 was produced.

Table 1 below shows the conditions for producing the transparent electrode produced above.

[Evaluation of transparent electrode]
By the following method, it measured about the total light transmittance and surface specific resistance of the electroconductive part of each transparent electrode, and evaluated transparency and electroconductivity.
<Total light transmittance>
The total light transmittance was determined by measuring the total light transmittance (%) of the transparent electrode using an AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

<Surface specific resistance>
The surface specific resistance was determined by measuring the surface specific resistance (Ω / □) of the transparent electrode by a four-terminal method using a resistivity meter Loresta GP manufactured by Mitsubishi Chemical Analytech.
The measurement results are shown in Table 2 below.

(2) Example 2
[Production of organic EL element]
Using the transparent electrodes TCG-1 and TCG-1 and TCF-1 to 15 produced in Example 1 as the first electrode part (anode), organic EL elements were produced in the following procedure. In addition, about transparent electrode TCG-1, 2 and TCF-1-14, what wiped off the unnecessary peripheral part was used so that a light emission part area might become a 5 square mm.
On the first electrode part, PEDOT-PSS CLEVIOS P AI4083 (solid content 1.5%) (manufactured by Heraeus) is applied on the conductive polymer-containing layer so that the dry film thickness becomes 30 nm using a spin coater. After the unnecessary peripheral portion was wiped off so as to be the same as the conductive polymer-containing layer forming region, it was dried.
Next, the transparent electrode was set in a commercially available vacuum deposition apparatus, and each of the deposition materials in the vacuum deposition apparatus was filled with the constituent material of each layer in an optimum amount for device fabrication. 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 established.
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.
Next, E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 would be 10% by mass, and blue phosphorescence was emitted with a maximum emission wavelength of 471 nm and a thickness of 15 nm. A layer was formed.
Thereafter, the following M-1 was vapor-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%, and an electron transport layer having a thickness of 45 nm. Formed.

On the formed electron transport layer, Al was mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as a material for forming a first electrode portion external extraction terminal and a 150 mm × 150 mm second electrode portion (cathode), A second electrode portion having a thickness of 100 nm was formed.
Further, an adhesive is applied around the second electrode part except for the end part so that the external extraction terminals of the first electrode part and the second electrode part can be formed, and a polyethylene terephthalate resin film is used as a substrate to thicken Al ₂ O ₃ . After bonding the flexible sealing member deposited at a thickness of 300 nm, the adhesive was cured by heat treatment to form a sealing film, and an organic EL element was produced.
The adhesive used was a two-component epoxy compounded resin (manufactured by Three Bond) 2016B and 2103 blended at a ratio of 100: 3.

In addition, the compound used for each layer formation is shown below.

[Evaluation of organic EL elements]
The light emission state, drive voltage, and light emission lifetime of each organic EL element produced as described above were evaluated by the following methods.
<Light emission state>
The light emission state was obtained by visually observing the light emission state when the luminance of each organic EL element was 1000 cd / m ² . In the organic EL element using the transparent electrode TCF-1 as the first electrode part, a large number of minute black non-light emitting points called dark spots were seen on the entire light emitting surface. All other organic EL elements emitted light uniformly.

<Drive voltage>
The driving voltage was a voltage value at which the luminance of each organic EL element was 1000 cd / m ² . A drive voltage of 4 V or less is good in terms of luminous efficiency.

<Luminescent life>
Each organic EL element was allowed to emit light continuously at a constant voltage so that the initial luminance was 5000 cd / m ² , and the time until the luminance was reduced by half was determined. The half-life time of the organic EL element using the transparent electrode TCG-1 as the first electrode part was set to 100, and the relative value was evaluated.

The measurement results are shown in Table 2 below.

  From the results shown in Table 2, the transparent electrode of the present invention is excellent in transparency and conductivity, and the organic EL device using the transparent electrode of the present invention emits light uniformly and has a low driving voltage. It can be seen that the emission lifetime is also good.

Claims (5)

A method for producing a transparent electrode by producing a transparent electrode by a coating method using a conductive polymer,
A conductive polymer-containing layer forming step of forming a conductive polymer-containing layer by applying a dispersion containing a conductive polymer and a high-boiling water-soluble organic solvent on a transparent substrate;
After the conductive polymer-containing layer forming step, the low-boiling water-soluble organic having a lower boiling point than the high-boiling water-soluble organic solvent and azeotropic with the high-boiling water-soluble organic solvent is formed on the conductive polymer-containing layer. A low-boiling water-soluble organic solvent supplying step of supplying a solvent;
A heating / drying step of volatilizing the high-boiling water-soluble organic solvent and the low-boiling water-soluble organic solvent after the low-boiling water-soluble organic solvent supplying step.   The method for producing a transparent electrode according to claim 1, wherein the transparent substrate is a transparent resin substrate.   The method for producing a transparent electrode according to claim 1, wherein the heating / drying step is a step of performing infrared irradiation within a range of a maximum energy wavelength of 0.8 to 3 μm.   The method for producing a transparent electrode according to any one of claims 1 to 3, wherein the high-boiling water-soluble organic solvent is a polyhydric alcohol.   The method for producing a transparent electrode according to any one of claims 1 to 4, wherein the low-boiling water-soluble organic solvent is ethanol or isopropanol.