WO2014034920A1

WO2014034920A1 - Transparent electrode, method for producing same and organic electronic device

Info

Publication number: WO2014034920A1
Application number: PCT/JP2013/073468
Authority: WO
Inventors: 孝敏末松; 松村　智之
Original assignee: コニカミノルタ株式会社
Priority date: 2012-09-03
Filing date: 2013-09-02
Publication date: 2014-03-06
Also published as: JPWO2014034920A1

Abstract

Disclosed is a transparent electrode in which adhesion between a transparent resin substrate and a metal thin wire pattern is improved and the occurrence of separation of the metal thin wire pattern or cracking of a porous layer is suppressed. A transparent electrode (1) comprises a transparent resin substrate (10), a porous layer (20), a metal thin wire pattern (30) and a transparent conductive protection layer (40). The porous layer (20) and the metal thin wire pattern (30) are formed on the transparent resin substrate (10), and the transparent conductive protection layer (40) is formed on the porous layer (20) and the metal thin wire pattern (30). In this transparent electrode (1), the ratio of the thickness (22) of the porous layer (20) to the thickness (32) of the metal thin wire pattern (30) is within the range of 5-40%, and the thickness (32) of the metal thin wire pattern (30) is within the range of 0.3-3.0 μm.

Description

Transparent electrode, method for producing the same, and organic electronic device

The present invention relates to a transparent electrode, a manufacturing method thereof, and an organic electronic device using the transparent electrode.

In recent years, organic electronic devices such as organic electroluminescence devices (hereinafter referred to as organic EL devices) and organic solar cells have been required to be larger, lighter, and flexible. Therefore, a transparent electrode used for an organic electronic device is required to have a low resistance, a light weight substrate, and a flexible substrate. Furthermore, from the viewpoint of cost, use of an inexpensive resin substrate such as a PET substrate and adaptation to a mass production method by a roll-to-roll process are required.

Conventionally, as a transparent electrode, an ITO transparent electrode in which an indium-tin composite oxide (hereinafter abbreviated as ITO) film is formed on a transparent substrate by a vacuum deposition method or a sputtering method has its conductivity and transparency. It has been widely used because of its characteristic advantages. However, ITO transparent electrodes have high resistance and cannot be used for large organic electronic devices. Moreover, when it uses for a flexible board | substrate, when bending, an ITO layer cannot follow the bending of a board | substrate, and a crack will arise.
On the other hand, a transparent electrode in which a conductive polymer such as PEDOT: PSS is formed on a substrate is known. The conductive polymer is excellent in flexibility and can be used in a roll-to-roll process. However, since the volume resistance of the conductive polymer itself is high and there is absorption in the visible light region, it is difficult to produce a low-resistance electrode while maintaining high transparency.

Furthermore, while aiming to reduce the resistance and flexibility of the transparent electrode, a transparent metal layer is formed on the substrate, and a transparent conductive layer is laminated on the transparent electrode. An electrode has been developed (Patent Document 1).
As a method for forming a metal fine line pattern, a method is known in which a metal nanoparticle dispersion containing nanoparticles such as silver, gold, and copper is printed and then the metal nanoparticles are fired. However, since heat treatment at 200 ° C. or higher is required to sinter the metal nanoparticles to ensure electrical conduction between the metal nanoparticles, it was difficult to apply the heat treatment to an inexpensive resin substrate with low heat resistance. .

Then, examination of the metal nanoparticle dispersion liquid which can be baked at low temperature is performed (patent document 2). Such a metal nanoparticle dispersion that can be fired at a low temperature is produced by a method in which an organic compound having a low molecular weight and a low boiling point is used as a protective molecule for the metal nanoparticles, and a binder is not used or is minimized. Is done. The reason why the binder is kept to a minimum is that the binder hinders firing of the metal nanoparticles, making firing at low temperatures difficult and increasing the resistance of the fine metal wire pattern after firing.
The dispersion prepared as described above has a low viscosity and can be suitably used for ink jet printing and the like because it has a small amount of binder as an adhesion component to the substrate, but has a problem of low adhesion to the substrate. For example, in a roll-to-roll process, when a resin substrate with a fine metal wire pattern that has been patterned and baked is wound with a roll, the fine metal wire pattern peels off due to friction with the back surface of the substrate that comes into contact. Problems arise.
Further, as a method for firing a metal fine wire pattern formed from a metal nanoparticle dispersion at a low temperature, firing by flash light irradiation is known. Since the firing of the thin metal wire pattern by flash light irradiation is a process at a low temperature and in a short time, it can be suitably used for a roll-to-roll process using an inexpensive resin film with low heat resistance. However, if the fine metal wire pattern made of the metal nanoparticle dispersion with a small amount of binder is fired by flash light irradiation, there is a problem that a part of the fine metal wire pattern is peeled off due to low adhesion to the substrate. It was.

On the other hand, it is generally known to install a porous ink-receiving layer on a substrate in order to improve ink absorbability when printing by an inkjet method, and several methods have been proposed.
For example, a method of providing a porous layer containing particles having a porous structure such as diatomaceous earth or pearlite powder on a support (Patent Document 3), after applying a plastic having low miscibility to each other in a solvent A method of providing a porous layer by coagulating plastic in a coagulation bath (Patent Document 4), a method of providing a porous layer comprising a colloidal silica particle-containing hydrophilic inorganic organic composite layer on a substrate (Patent Document 5), and metal oxide particles A method of providing an ink receiving film containing a hydrolysis-condensate of an alkoxide compound (Patent Document 6), a method of providing a porous layer selected from silica, anhydrous aluminum oxide and aluminum oxide on a substrate (Patent Document 7), metal There is a method of providing an ink receiving film containing oxide particles and a polyimide precursor (Patent Document 8).
In Patent Documents 3 to 6, there is no suggestion of a problem relating to the adhesion of the coated material to the substrate or suggestion of a solution thereof.
Patent Documents 7 and 8 refer to the improvement of adhesion by forming a porous layer. However, since there is no detailed description of the thickness of the porous layer and the metal film, the porous layer is used as a transparent electrode. If used, there may be a problem that the transparency of the transparent electrode is lowered or current leakage occurs when used in an organic electronic device. The porous layer described in Patent Documents 7 and 8 is flexible like a transparent resin substrate. If formed on a simple substrate, there is a problem that cracks may occur in the porous layer during bending.

US Patent Application Publication No. 2010/255323 JP 2010-265543 A Japanese Patent Laid-Open No. 61-8385 JP 62-197183 A Japanese Patent Laid-Open No. 2-147233 JP 2007-169604 A JP 2009-76455 A JP 2010-161118 A

As described above, there is a problem in adhesion to the substrate in forming a metal fine wire pattern using metal nanoparticles, and a resin substrate with a metal fine wire pattern is particularly required for production in a roll-to-roll process. There has been a problem that the fine metal wire pattern is peeled off in the step of winding with a roll or the firing step by flash light irradiation.
Further, when used for a flexible substrate such as a transparent resin substrate, there has been a problem that a crack occurs in the porous layer during bending.

In view of the above problems, the main object of the present invention is a transparent electrode having a fine metal wire pattern with good adhesion to the substrate, and peeling of the fine metal wire pattern such as when winding or flash light irradiation is performed. Another object of the present invention is to provide a transparent electrode capable of suppressing the occurrence of cracks in the porous layer when the transparent electrode is bent.

In order to solve the above-mentioned problems, the present inventor has studied as follows and has reached the present invention.
That is, a porous layer including an ink receiving layer is used as an anchor layer, and a metal nanoparticle dispersion containing nanoparticles such as silver, gold, and copper, or an ink such as a metal complex ink, for example, By forming a fine metal line pattern by printing with a known patterning method such as inkjet, screen printing, gravure printing, offset gravure printing, flexographic printing, etc., the ink penetrates into the voids in the porous layer, resulting in metal A part of the fine line pattern has a shape embedded in the porous layer. Therefore, a metal fine wire pattern expresses strong adhesion to the substrate together with the porous layer.
In particular, if the thickness of the fine metal wire pattern is a thin film of 0.3 to 3.0 μm and a porous layer having a thickness of 5% or more with respect to the thickness of the fine metal wire pattern is formed, the substrate and the fine metal wire pattern It has been found that sufficient adhesion can be obtained during this period, and peeling of the fine metal wire pattern and generation of cracks in the porous layer can be suppressed.

Moreover, in the transparent electrode, a transparent polymer containing a conductive polymer and a resin binder is formed on a porous layer without a metal fine wire pattern and a metal fine wire pattern in order to make a surface of current necessary for an organic electronic device such as an organic EL device uniform. It is necessary to form a conductive protective layer. Further, the transparent conductive protective layer serves as a reinforcing film for the fine metal wire pattern and the porous layer, and can surely prevent peeling of the fine metal wire pattern and occurrence of cracks in the porous layer.
In order to eliminate current leakage when used in an organic electronic device, such a transparent conductive protective layer needs to fill the voids of the porous layer and further bury the irregularities on the surface of the porous layer. At this time, if the porous layer is thick, it is necessary to increase the thickness of the transparent conductive protective layer containing the conductive polymer. Since the conductive polymer has colorability, the transparency of the transparent electrode is lowered. To do. Therefore, by setting the thickness of the porous layer to 40% or less with respect to the thickness of the fine metal wire pattern, it is possible to provide a transparent electrode free from current leakage when used in an organic electronic device without impairing transparency. I found.

From the above, according to the present invention,
It has a transparent resin substrate, a porous layer, a metal fine wire pattern and a transparent conductive protective layer, and the porous layer and the metal fine wire pattern are formed on the transparent resin substrate, and the porous layer and the metal fine wire pattern In the transparent electrode on which the transparent conductive protective layer is formed,
The transparent layer characterized in that the thickness of the porous layer with respect to the fine metal wire pattern is in the range of 5 to 40%, and the thickness of the fine metal wire pattern is in the range of 0.3 to 3.0 μm. An electrode is provided.

According to the present invention, since the thickness of the metal fine line pattern itself and the thickness of the porous layer with respect to the metal fine line pattern are within a certain range, the adhesion between the transparent resin substrate and the metal fine line pattern is good, Generation of cracks in the porous layer such as peeling of the fine metal wire pattern when winding or flash light irradiation or bending of the transparent electrode can be suppressed.

It is sectional drawing which shows schematic structure of a transparent electrode.

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

[Transparent electrode (1)]
As shown in FIG. 1, the transparent electrode 1 is mainly composed of a transparent resin substrate 10, a porous layer 20, a fine metal wire pattern 30, and a transparent conductive protective layer 40.
A porous layer 20 is formed on the transparent resin substrate 10, and a fine metal wire pattern 30 is formed on the porous layer 20.
The thickness of the porous layer 20 with respect to the fine metal wire pattern 30 is in the range of 5 to 40%. Specifically, the ratio of the thickness 22 of the porous layer 20 to the thickness 32 of the fine metal wire pattern 30 is in the range of 5 to 40%. The metal fine line pattern 30 penetrates into the porous layer 20 because the metal nanoparticle dispersion and the metal complex ink are applied using a known printing method. Here, the “thickness 32 of the fine metal wire pattern 30” means the height from the upper surface of the transparent resin substrate 10 to the top of the fine metal wire pattern 30 itself.
The thickness 32 of the fine metal line pattern 30 is in the range of 0.3 to 3.0 μm.
A transparent conductive protective layer 40 is formed on the porous layer 20 and the fine metal wire pattern 30. The transparent conductive protective layer 40 is formed by applying a certain coating liquid on the porous layer 20 and the fine metal wire pattern 30, and permeates into the porous layer 20 by such a configuration.
Hereafter, the structure of each member, the manufacturing method of a transparent electrode, the organic electronic device using this transparent electrode, etc. are demonstrated in detail.

[Transparent resin substrate (10)]
“Transparent” in a transparent resin substrate means a total light transmittance of 70% in the visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (Plastic—Testing method of total light transmittance of transparent material). That's it.
The material for the transparent resin substrate is not particularly limited as long as it is a transparent resin material, and known materials can be used.
In particular, it is preferable to use a transparent resin film or the like from the viewpoint of performance such as lightness and flexibility and the viewpoint of roll-to-roll process suitability.
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. 80 ~ 780 nm) transmittance at 80% or more.
Among them, biaxial stretching of biaxially stretched polyethylene terephthalate resin film, biaxially stretched polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. in terms of transparency, heat resistance, ease of handling, strength and cost A polyester resin film is preferable, and a biaxially stretched polyethylene terephthalate resin film and a biaxially stretched polyethylene naphthalate resin film are more preferable.

Moreover, the transparent resin substrate may have a barrier coat layer formed in advance as necessary, or a hard coat layer formed in advance.
As the barrier coat layer, an inorganic film, an organic film, or a hybrid film of both may be formed on the front surface or the back surface, and the water vapor transmission rate (25 ± 0 0.5 ° C. and relative humidity (90 ± 2)% RH) is preferably a transparent resin substrate having a barrier property of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and JIS K 7126 -Oxygen permeability measured by a method according to 1987 is 1 × 10 ^-3 ml / (m ² · 24h · atm) or less, water vapor permeability (25 ± 0.5 ° C, relative humidity (90 ± 2) % RH) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.
The material for forming the barrier layer may be any material as long as it has a function of suppressing intrusion of devices that cause deterioration of devices such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
In order to further improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. 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.

[Porous layer (20)]
The porous layer is used to hold and adhere the fine metal wire pattern and the transparent conductive protective layer on the transparent resin substrate.
The porous layer has a thickness of 5% to 40% with respect to the thickness of the fine metal wire pattern. When the thickness of the porous layer is 5% or more with respect to the thickness of the fine metal wire pattern, sufficient adhesion can be obtained between the transparent resin substrate and the fine metal wire pattern. On the other hand, if the thickness is 40% or less with respect to the thickness of the fine metal wire pattern, the transparent conductivity necessary for embedding the voids and irregularities on the surface of the porous layer is eliminated in order to eliminate current leakage when used in organic electronic devices. An increase in the thickness of the protective layer can be suppressed, and the transparency of the transparent electrode can be prevented from decreasing. Further, in a flexible substrate such as a transparent resin substrate, it is possible to suppress cracks in the porous layer during bending.

The porous layer has a porosity of at least 90% or less, preferably in the range of 30 to 77%, and more preferably in the range of 55 to 75%. When the porosity is within the above-mentioned range, the gas emitted when the organic matter such as the protective agent, binder and solvent in the metal nanoparticle dispersion is instantly vaporized by flash light irradiation is diffused around the fine metal wire pattern. In addition, since a large adhesion area with the fine metal wire pattern can be ensured, the fine metal wire pattern can effectively function to prevent peeling.
The porosity of the porous layer can be determined by a known method such as the Bristow method, the electric (electrostatic) capacitance method, the swelling pressure measurement method, the measurement method from a change in light reflectance, or the electric conductivity method. Here, the “porosity of the porous layer” is a value measured with respect to light having a wavelength of 550 nm using a lens reflectometer (model number: USPM-RU, manufactured by Olympus Corporation).

The transparency of the porous layer can be arbitrarily selected depending on the use, but the higher the transparency, the more applicable to a transparent electrode or the like, which is preferable from the viewpoint of expanding the use.
The total light transmittance of the porous layer is 70% or more, preferably 80% or more.

The composition of the porous layer is preferably mainly composed of an inorganic compound and an organic compound.
The inorganic compound here is a compound other than an organic compound as generally understood, and specifically, a compound composed of a simple part of a carbon compound and an element other than carbon. As representative examples of inorganic compounds constituting the porous layer, various metal oxides containing at least one metal such as magnesium, aluminum, silicon, titanium, zinc, yttrium, zirconium, molybdenum, tin, barium, tantalum, Although carbide, nitride, boride, etc. can be mentioned, it is preferable that the porous layer concerning this embodiment is comprised including at least 1 sort (s) of transparent metal oxide.
The inorganic compound in the porous layer is preferably a hydrolysis-condensate of metal oxide particles and an alkoxide compound or mesoporous silica.

As a method for forming a porous layer of a hydrolysis-condensation product of a metal oxide particle and an alkoxide compound as a porous layer, the composition (silicon-based oxide aggregate particles) described in JP 2007-169604 A is preferably used. Can be used.
The silicon-based oxide aggregate particles are metal oxide particles having a primary particle diameter of 2 to 200 nm and containing 25 mass% or more of aggregate particles in which two or more particles are bonded.
The silicon-based oxide aggregate particles may be silica particles alone, or may contain titania, zirconia and alumina. By using such a particulate matter, pores can be formed in the porous layer, and as a result, absorbability is imparted.
The silicon-based oxide aggregate particles need to contain 25% by mass or more of aggregate particles formed by combining two or more primary particles. By including such aggregate particles in the porous layer, coating layer processability is improved, cracks after layer formation can be prevented, and absorbability is further improved. The content of the aggregate particles is preferably 40% by mass or more, more preferably 60% by mass or more.
The particle diameter of the primary particles is from 2 to 200 nm, preferably from 5 to 50 nm, more preferably from 10 to 30 nm, from the viewpoint of pore formation and maintaining high transparency. The number of connected primary particles is preferably as small as possible, but is usually 3 to 100, preferably 5 to 50, more preferably 7 to 30.
Examples of the form of the aggregate particles include those having a long chain structure in which primary particles are connected in a bead shape, those in which connected aggregate particles are branched and / or bent.
Such aggregate particles can be produced by a conventionally known method. For example, primary particles of a spherical metal oxide can be obtained by linking with metal ions having a valence of 2 or more, for example, Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ , Ti ^{4+ and the} like. About the bead-like silica sol, the manufacturing method is described in WO00 / 15552, for example.
There is no particular limitation on the method for adjusting the content of the aggregate particles formed by combining two or more particles in the particles, but for example, the particles that are substantially 100% agglomerated and the particles that are not substantially agglomerated A method of mixing the particles is simple and preferable.
On the other hand, mesoporous silica may be directly formed on a substrate as disclosed in JP2010-132485A, or particles may be formed by a method as described in JP2010-13804A and JP2010-173894A. After the production, it may be coated with an organic compound and dried to form a porous film.

The composition of the porous layer is such that the ratio of the inorganic compound is 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more among all the materials constituting the porous layer. When the proportion of the inorganic compound is 70% by mass or more, sufficient adhesion can be obtained between the fine metal wire pattern and the porous layer.
As a ratio of the organic compound which comprises a porous layer, 30 mass% or less is preferable, 20 mass% or less is more preferable, 10 mass% or less is more preferable, It is good that it is 5 mass% or more. When the ratio of the organic compound is 5% by mass or more, sufficient adhesion can be obtained between the porous layer and the transparent resin substrate. Moreover, when the organic compound ratio is 30% by mass or less, the organic compound is filled in the holes of the porous layer of the inorganic compound, and sufficient adhesion between the fine metal wire pattern and the porous layer cannot be obtained. The phenomenon can be avoided.

[Metallic fine wire pattern (30)]
The metal fine line pattern has a thickness of 0.3 μm or more and 3.0 μm or less.
When the thickness of the metal fine line pattern is 0.3 μm or more, a desired resistance can be obtained, and when it is 3.0 μm or less, the metal fine line pattern can be completely covered with the transparent conductive protective layer, and the transparent Current leakage can be prevented when the electrode is used in an organic electronic device. In addition, depending on the metal nanoparticle dispersion selected, cracking of the fine metal wire pattern may occur when the transparent resin substrate is bent, resulting in an increase in resistance of the fine metal wire pattern, and current leakage when used in organic electronic devices. However, if the thickness of the fine metal wire pattern falls within the above range, this phenomenon can be suppressed.
The thickness of the fine metal wire pattern indicates not the height from the surface (upper surface) of the porous layer but the height from the surface (upper surface) of the transparent resin substrate as described above.

The metal fine line pattern is formed in a pattern so that the metal nanoparticle dispersion or metal complex ink (metal complex solution) has openings on the transparent resin substrate on which the porous layer is formed, using a known printing method. It is obtained by doing.
An opening part is a part which does not have a metal fine wire pattern among transparent resin substrates, and is a translucent part of a metal fine wire pattern.
There is no particular limitation on the shape of the pattern.
The shape of the pattern may be, for example, a stripe shape (parallel line shape), a lattice shape, a honeycomb shape, or a random network shape, and is preferably a stripe shape from the viewpoint of transparency.
In the transparent electrode, the ratio of the opening to the entire surface electrode, that is, the opening ratio, is preferably 80% or more from the viewpoint of transparency.
For example, when the conductive portion 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 approximately 90%.
The line width of the metal fine line pattern is preferably 10 to 200 μm, more preferably 10 to 100 μm. When the line width of the metal fine line pattern is 10 μm or more, desired conductivity is obtained, and when the line width is 200 μm or less, the transparency is improved.
In the stripe-like and lattice-like patterns, the interval between the fine lines is preferably 0.5 to 4 mm.

The surface specific resistance of the fine wire portion of the metal fine wire pattern is preferably 10 Ω / □ or less, more preferably 5 Ω / □ or less, and more preferably 2 Ω / □ or less from the viewpoint of increasing the area. preferable.
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.

There are no particular restrictions on the method of forming the stripe-like, lattice-like, or honeycomb-like metal fine line pattern, and a conventionally known printing method such as gravure printing, flexographic printing, screen printing, ink jet printing, or the like may be used. it can. In particular, metal nanoparticle dispersions and metal complex inks with a small amount of binder are often low-viscosity inks because of a small amount of binder components, and the ink jet printing method can be suitably used.
For each printing method, a method generally used for forming an electrode pattern can be applied to this embodiment.

Metal nanoparticles having an average particle diameter of 5 to 100 nm are preferably used.
The metal used for the fine metal wire pattern is not particularly limited as long as it has excellent conductivity, and examples thereof include alloys in addition to metals such as gold, silver, copper, iron, nickel, and chromium. From the viewpoint of conductivity, silver or copper is preferable, and silver or copper may be used alone or in combination. Silver and copper alloys, silver or copper may be plated with one metal.
Among these, in particular, when a resin substrate or a resin film is used as the transparent resin substrate, it is preferable to use silver nanoparticles (a dispersion of the silver nanoparticles) that can be fired at a low temperature with an average particle diameter of 3 nm to 100 nm.
The metal nanoparticle dispersion contains metal nanoparticles in a solvent such as water or alcohol, but may contain a binder, a dispersant for dispersing the metal, and the like as necessary. However, it is preferable to minimize the binder and dispersant in order to enable firing at a low temperature. For example, NPS-JL (Harima Kasei Co., Ltd.), CCI300 (Cabot), etc. are mentioned as a commercially available ink which can be baked at low temperature using silver nanoparticles.

A metal complex ink refers to a compound in which a ligand is coordinated to a metal ion, as in general understanding.
As a metal complex for forming a metal fine line pattern, a known material can be used. It can be preferably used.

[Transparent conductive protective layer (40)]
The transparent conductive protective layer is a transparent and conductive layer containing at least a conductive polymer and a water-soluble binder or an aqueous dispersion binder.
By including a water-soluble binder or a water-dispersed binder, the transparent conductive protective layer enhances the conductivity of the conductive polymer and provides high conductivity and high transparency that cannot be obtained with the conductive polymer alone.
The transparent conductive protective layer serves as a reinforcing film for the fine metal wire pattern and the porous layer, and prevents peeling of the fine metal wire pattern and porous cracks.

The transparent conductive protective layer is formed by applying a coating liquid containing a conductive polymer and a water-soluble binder or a water-dispersed binder onto the metal fine line pattern and the porous layer and drying. By forming a conductive layer having such a laminated structure, high conductivity that cannot be obtained by a metal fine line pattern or a conductive polymer layer alone can be obtained uniformly in the electrode plane.
The ratio of the conductive polymer and the binder component of the transparent conductive protective layer is preferably 30 to 900 parts by mass of the binder component when the conductive polymer is 100 parts by mass. From the viewpoint of enhancing conductivity and transparency, the binder component is more preferably 100 parts by mass or more.

The dry layer thickness of the transparent conductive protective layer is preferably 100 to 700 nm.
The dry layer thickness is more preferably 100 nm or more from the viewpoint of conductivity. When the transparent electrode according to this embodiment is used for an organic electronic device, the unevenness of the metal fine line pattern is smoothed, and the functional layer From the viewpoint of reducing the influence on the layer thickness distribution, the thickness is more preferably 150 nm or more. The dry layer thickness is more preferably 500 nm or less, and further preferably 400 nm or less, from the viewpoint of transparency.

(1) Conductive polymer As the conductive polymer, a conductive polymer comprising a π-conjugated conductive polymer and a polyanion can be preferably used.
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. .

(1.1) π-conjugated conductive polymer As π-conjugated conductive polymer, polythiophene (including basic polythiophene, the same shall apply hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes. A chain conductive polymer such as polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, and polythiazyl compounds 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.

(1.2) Precursor monomer of π-conjugated conductive polymer The precursor monomer has a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, A conjugated system is formed.
Examples of the precursor monomer 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.

(1.3) Poly anion The poly anion is an oligomer or polymer having a plurality of anionic groups.
The polyanion is preferably 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. A compound composed of a structural unit having an anionic group and a structural unit having no anionic group is preferably used.
The 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 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.

In addition, it is preferable that the compound contains a polyanion having fluorine in the compound because the rectification ratio is improved when the transparent electrode according to this embodiment is used in an organic electronic device.
Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.
Among these, a compound having a sulfonic acid is more preferable because the washing resistance and solvent resistance of the transparent conductive protective layer are remarkably improved by performing the heat treatment.
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 water-soluble binder described later, 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, an anionic group A method of producing by polymerization of the containing polymerizable monomer may be mentioned.
Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst.
Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.
When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

Ratio of π-conjugated conductive polymer and polyanion contained in conductive polymer (solid content ratio), “π-conjugated conductive polymer”: “Poly anion” is mass from the viewpoint of conductivity and dispersibility The ratio is preferably in the range of 1: 1 to 1:10, more preferably in the range of 1: 2 to 1: 8.

Examples of the oxidizing agent used for obtaining a conductive polymer by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer in the presence of a polyanion are described in J. Pat. 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 hemiesters having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexyl carboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And especially the aromatic, optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

(1.4) Commercially Available Materials Commercially available materials can be preferably used for these conductive polymers.
For example, a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (abbreviated as PEDOT-PSS) is available from Heraeus as CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, Nagase Chemtex. It is commercially available from the company as the Denatron series.
Polyaniline is also commercially available from Nissan Chemical as the ORMECON series.
In the present embodiment, such an agent can also be preferably used.

(2) Second dopant 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. Examples of the oxygen-containing compound include dimethyl sulfoxide (DMSO) and ethylene glycol.
The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound.
Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone, and the like.
These may be used individually by 1 type and may use 2 or more types together.

(3) Resin component The transparent conductive protective layer is a transparent resin other than a conductive polymer containing at least a π-conjugated conductive polymer and a polyanion in order to ensure film formability and film strength. Ingredients and additives may be included.
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.
Among these, it is preferable to use a water-dispersed binder or a water-soluble binder from the viewpoint of obtaining high surface smoothness while maintaining high transparency and conductivity.

(3.1) Water-dispersed binder A water-dispersed binder is one that can be uniformly dispersed in an aqueous solvent, and is a state in which colloidal particles made of the binder are dispersed without being aggregated in the aqueous solvent. means.
The size of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 nm). The colloidal particles can be measured with a light scattering photometer.
The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, and a hydrophilic organic solvent. And pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, mixed solvents of water and alcohol, and the like.
The water-dispersed binder is preferably transparent.
The water-dispersed binder is not particularly limited as long as it is a medium for forming a film. Examples of the water-dispersed binder include: acrylic resin emulsion, aqueous urethane resin, aqueous polyester resin, and the like.
The acrylic resin emulsion is made of vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers. In addition, the acid part is composed of a copolymer of an anionic lithium salt, sodium salt, potassium salt, ammonium salt, and a monomer having a nitrogen atom, and a cationic nitrogen atom forming a hydrochloride salt, Preferably it is anionic.
Examples of aqueous urethane resins include water-dispersed urethane resins and ionomer-type aqueous urethane resins (anionic). The water-dispersed urethane resin includes a polyether-based urethane resin and a polyester-based urethane resin, preferably a polyester-based urethane resin. Examples of the ionomer type water-based urethane resin include polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins, and polyester-based urethane resins and polyether-based urethane resins are preferable.
The aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
The polybasic acid component is, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, etc., and these may be used alone. Two or more types may be used in combination, and as the polybasic acid component that can be used particularly preferably, terephthalic acid and isophthalic acid are industrially produced in large quantities and inexpensive. Particularly preferred.
Typical examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, bisphenol, and the like. These may be used singly or may be used in combination of two or more. The polyol component that can be particularly suitably used is inexpensive because it is industrially mass-produced, Ethylene glycol, propylene glycol, or neopentyl glycol is particularly preferable because various properties such as improvement in solvent resistance and weather resistance of the resin coating are balanced.
The water-dispersed binder can be used alone or in combination.
The amount of the polymer dispersible in the aqueous solvent is preferably 50 to 1000% by mass with respect to the conductive polymer from the viewpoint of transparency and conductivity, and more preferably 100 to 900% with respect to the conductive polymer. % By mass, and more preferably 200 to 800% by mass with respect to the conductive polymer.

(3.2) Water-soluble binder The water-soluble binder is preferably a water-soluble binder containing a structural unit represented by the following general formula (1).

General formula (1);

In the general formula (1), R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, and A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) xCH ₂ CHRb—. Rb represents a hydrogen atom or an alkyl group, x represents the average number of repeating units, and is in the range of 0 to 100, but preferably in the range of 0 to 10.
Since such a resin can be easily mixed with a conductive polymer and also has the effect of the second dopant described above, by using the water-soluble binder in combination, the conductivity and transparency are not reduced. The film thickness of the polymer-containing layer can be increased.
A water-soluble binder is a water-soluble binder, and means a binder in which 0.001 g or more is dissolved in 100 g of water at 25 ° C. The dissolution can be measured with a haze meter or a turbidimeter.
The water-soluble binder is preferably transparent.
The water-soluble binder preferably has a structure including the structural unit represented by the general formula (1). The homopolymer represented by the general formula (1) may be used, or other components may be copolymerized. When copolymerizing other components, the structural unit represented by the general formula (1) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.
The water-soluble binder is preferably contained in the conductive polymer-containing layer in an amount of 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.
The number average molecular weight of the water-soluble binder is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably in the range of 5000 to 100,000.
The number average molecular weight and molecular weight distribution of the water-soluble binder can be measured by a generally known gel permeation chromatography (GPC). The solvent to be used is not particularly limited as long as the binder dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), 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.

Further, by performing the heat treatment, the solvent in the coating solution can be evaporated, and the condensation reaction between the water-soluble binder of the transparent conductive protective layer or between the conductive polymer and the water-soluble binder can be promoted and completed. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved.
In particular, in an organic EL device, effects such as reduction in driving voltage and improvement in life can be obtained.
The drying step and the heat treatment step may be the same step or may be performed separately. In the case of separate processes, drying and heat treatment may be continuous, and there may be a time pause between the two processes.

[Method for producing transparent electrode]
The manufacturing method of the transparent electrode is basically
(1) forming a porous layer on a transparent resin substrate;
(2) forming a fine metal wire pattern on the porous layer;
(3) forming a transparent conductive protective layer on the porous layer and the fine metal wire pattern;
It is composed of
Hereinafter, the processing content of each process is demonstrated.

(1) Porous layer forming step In the step of forming the porous layer, the composition constituting the porous layer is formed on the transparent resin substrate using the following coating method, followed by hot air drying or infrared drying. It can be formed by drying by a known heat drying method such as natural drying or the like. In the step of forming the porous layer, after the drying process or instead of the drying process, a curing process such as heat firing, ultraviolet irradiation, plasma discharge, or the like may be performed.
In such a case, the thickness of the porous layer with respect to the fine metal wire pattern is within the range of 5 to 40% by appropriately selecting the type of the composition or adjusting the film formation, drying conditions, and curing conditions. Execute (set) the process.
As the method for forming the porous layer, any appropriate method can be selected. For example, as a coating method, various printing methods such as a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, and an ink jet printing can be used. In addition, various coating methods such as a roll coating method, a bar 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, a spray coating method, and a doctor coating method can be used. .
When it is preferable to form the porous layer in a pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, or an ink jet printing method.
Although the temperature in the case of heating in the porous layer forming step can be appropriately selected according to the type of the transparent resin substrate to be used, it is generally preferably carried out at a temperature of 150 ° C. or lower.

(2) Formation process of a metal fine wire pattern In the process of forming a metal fine wire pattern, the following printing and firing processes are executed.
In such a case, the thickness of the fine metal wire pattern after firing is within a range of 0.3 to 3.0 μm by appropriately selecting the type of metal nanoparticles, metal complex, etc., or adjusting printing and firing conditions. The process is executed (set) as follows.

(2.1) Printing of metal fine wire pattern First, a metal nanoparticle dispersion or a metal complex ink is printed in a predetermined pattern on a transparent resin substrate on which a porous layer is formed.
There is no restriction | limiting in particular as a printing method of a metal fine wire pattern, The gravure printing method, flexographic printing method, screen printing method, inkjet printing method etc. which are conventionally well-known printing methods can be used.
In particular, metal nanoparticle dispersions and metal complex inks with a small amount of binder often have a low viscosity due to a small amount of binder components, and an ink jet printing method can be suitably used.

(2.2) Firing of fine metal wire pattern A metal nanoparticle dispersion or a metal complex ink is baked after forming a pattern on the transparent resin substrate by the printing method described above.
By such firing treatment, fusion of metal particles proceeds, and the metal fine wire pattern can be made highly conductive.
For the firing of fine metal wire patterns, there are generally used methods such as a method using a contact heat transfer heat source such as a hot plate, a method using hot air, and a method using radiant heat from a high temperature heat source such as an infrared heater. In addition, there is a method using photothermal conversion of a metal fine line pattern by high energy light irradiation.
When a contact heat transfer heat source is used, it is preferable to heat the transparent resin substrate at a temperature that does not damage the transparent resin substrate in a temperature range of 100 ° C. or higher and 300 ° C. or lower. When using a resin film for a transparent resin substrate, it is more preferable to heat in a temperature range of 100 ° C. or more and 150 ° C. or less.
Although the heating time depends on the temperature and the size of the metal particles to be used, it is preferably 10 seconds or longer and 30 minutes or shorter. From the viewpoint of productivity, it is preferably 10 seconds or longer and 15 minutes or shorter, and 10 seconds or longer. More preferably, it is 5 minutes or less.

As described above, preferred transparent resin substrates used in the present embodiment include transparent resin films, but general transparent resin films that can be obtained relatively inexpensively, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN). In the case of using, baking using photothermal conversion by high energy light irradiation, which enables baking without raising the temperature of these transparent resin substrates, is preferable.

(*) Flash light irradiation One example of firing using photothermal conversion is flash light irradiation mainly having a wavelength in the visible light region.
As a discharge tube of a flash lamp used for flash light irradiation, a discharge tube of xenon, helium, neon, argon or the like can be used, but a xenon lamp is preferably used.
A preferable spectral band of the flash lamp is preferably 240 nm to 2000 nm because the transparent resin substrate is not damaged by thermal irradiation or the like by flash light irradiation.
The light irradiation conditions of the flash lamp are arbitrary, but the total light irradiation energy is preferably 0.1 to 50 J / cm ² , more preferably 0.5 to 10 J / cm ² . The light irradiation time is preferably 10 μsec to 100 msec, more preferably 100 μsec to 10 msec. The number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1 to 50 times. By performing flash light irradiation in these preferable condition ranges, the fine metal wire pattern can be heated and fired without damaging the transparent resin substrate, and high conductivity can be obtained.
The irradiation of the flash lamp to the transparent resin substrate is preferably performed from the front side on which the fine metal line pattern is printed. However, since the transparent resin substrate is a transparent body, it may be irradiated from the back side or from both sides. May be.
The flash light irradiation may be performed in the air, but may be performed in an inert gas atmosphere such as nitrogen, argon, or helium as necessary.
The temperature of the transparent resin substrate at the time of flash light irradiation is the heat resistance temperature of the transparent resin substrate, the boiling point (vapor pressure) of the ink dispersion medium containing metal nanoparticles and metal complexes, the type and pressure of the atmospheric gas, and ink dispersion. The temperature may be determined in consideration of the thermal behavior such as the property and the oxidizing property, and is preferably performed at room temperature or higher and 200 ° C. or lower.
Note that the substrate on which the fine metal wire pattern has been formed may be heat-treated in advance before performing the flash light irradiation.
The light irradiation device of the flash lamp may be any device that satisfies the above irradiation energy and irradiation time.

(3) Step of forming transparent conductive protective layer In the step of forming the transparent conductive protective layer, a coating solution containing a conductive polymer and a water-soluble binder or a water-dispersed binder is applied to the metal fine wire pattern and the porous layer. Apply to dry.
As the method for forming the conductive polymer-containing layer, any appropriate method can be selected. For example, as a coating method, various printing methods such as a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, and an inkjet printing method. In addition to these methods, use various coating methods such as roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, curtain coating, spray coating, and doctor coating. Can do.
In the case of forming a pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, or an ink jet printing method.

After applying the coating liquid for the transparent conductive protective layer, a drying treatment can be appropriately performed.
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 transparent resin substrate and a metal fine wire pattern.
Specific examples include heating using a heater or IR heater, reduced pressure drying, induction heating, microwave heating, laser heating, plasma heating, etc. From the viewpoint of simplicity of temperature and humidity control, a heater was used. Heating is preferred.
Although the temperature in the case of heat-drying can be suitably selected according to the kind of transparent resin substrate to be used, it is preferable to implement at the temperature of 150 degrees C or less.
When using infrared drying, in order to selectively heat the conductive polymer-containing layer, it is preferable to select an infrared wavelength region in which the transparent resin substrate absorbs little. For example, when the transparent resin substrate is a PET or PEN film, it is preferable to use near infrared rays of up to 1500 nm. Alternatively, it is also preferable to select an infrared wavelength region in the vicinity of 3 μm where water absorption maximum exists in order to heat and dry quickly.

[Organic electronic devices]
The organic electronic device has the transparent electrode and the organic functional layer.
For example, by using the transparent electrode as a first electrode portion, an organic functional layer is formed on the first electrode portion, and a second electrode portion disposed oppositely on the organic functional layer is formed, thereby forming an organic layer. An 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. In the case of an organic photoelectric conversion layer, it is particularly effective.
Hereinafter, the component in case an organic electronic device is an organic EL device and an organic photoelectric conversion device is demonstrated.

(1) Organic EL device (1.1) Organic functional layer configuration (organic light emitting layer)
Organic EL devices that have an organic light-emitting layer as an organic functional layer control light emission from the hole injection layer, hole transport layer, electron transport layer, electron injection layer, hole block layer, electron block layer, etc. The layer to be used may be used in combination with the organic light emitting layer.
Since the conductive polymer layer on the transparent electrode can also function as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.
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, or by laminating at least three of these light emitting layers. A white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers.
In the organic EL device according to this embodiment, the light emitting layer is preferably a white light emitting layer.
Examples of the light emitting material or doping material that can be used for the organic light emitting layer include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, 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, rubrene, distil Benzene derivatives, di still arylene derivatives and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material.
The organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.

(1.2) Electrode The transparent electrode is used in the first electrode part or the second electrode part described above, and the first electrode part is preferably a transparent electrode and an anode according to the present embodiment. .
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 as an electrode material 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, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this from the viewpoint of electron injecting property and durability against oxidation, 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 in the range of 10 nm to 5 μm, preferably 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 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.

(2) Organic photoelectric conversion device The organic photoelectric conversion device includes a first electrode part, a photoelectric conversion layer having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer) (hereinafter also referred to as a bulk heterojunction layer), and a second electrode. It is preferable to have a structure in which the portions are laminated.
The transparent electrode according to this embodiment 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.

(2.1) Photoelectric conversion layer The photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. It is preferable.
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-sexithiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.
Other examples of the polymer p-type semiconductor include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. JP-A 2006-36755 and other substituted-unsubstituted alternating copolymer polythiophenes, JP-A 2007-51289, JP-A 2005-76030, J. Org. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, and other polymers having a condensed thiophene structure, WO2008 / 000664, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.
Further, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiotetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes of C60, C70, C76, C78, C84, fullerenes such as SWNT, carbon nanotubes such as SWNT, merocyanine dyes, dyes such as hemicyanine dyes, and σ-conjugated polymers such as polysilane and polygermane Organic / inorganic hybrid materials described in Kai 2000-260999 can also be used.

Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.
Examples of pentacenes include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216, and the like. A pentacene derivative described in U.S. Patent Application Publication No. 2003/136964 and the like; Amer. Chem. Soc. , Vol127. Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.
Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable.
Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, 2706 and the like, and acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in US Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.
Among these, the latter precursor type can be preferably used. This is because the precursor type is insolubilized after conversion, so when forming a hole transport layer, electron transport layer, hole block layer, electron block layer, etc. on the bulk hetero junction layer by a 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 undergone a chemical structural change by a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material. Preferably there is. Among them, compounds that cause a scientific structural change by heat are preferable.

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

Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
As a form which uses the photoelectric conversion device concerning this embodiment as photoelectric conversion devices, such as a solar cell, a photoelectric conversion device may be utilized by a single | mono layer and may be laminated | stacked and utilized (tandem type). Moreover, it is preferable to seal a photoelectric conversion device by a well-known method so that it may not degrade with oxygen, moisture, etc. in the environment.

Hereinafter, the present invention will be specifically described by way of 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.

<< Production of fine metal wire pattern 1 >>
(1) Printing of fine metal wire pattern A silver nanoparticle dispersion on one surface of a polyethylene naphthalate (PEN) film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides. (NPS-JL; manufactured by Harima Kasei Co., Ltd.) in a strip form (50 μm width, 1 mm pitch, and the thickness of the fine wire after firing becomes 1.0 μm) using an ink jet printing method over a plurality of times. Printing was performed while laminating the silver nanoparticle dispersion.
Here, patterning of the metal thin wire was performed while heating the substrate as appropriate so as to obtain a desired line width.
As the ink jet printing method, an ink jet head having an ink droplet ejection amount of 4 pl was used, and the coating speed and ejection frequency were adjusted to print a pattern.
As the ink jet printing apparatus, a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an ink jet head (manufactured by Konica Minolta IJ Co., Ltd.) was used and controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta IJ Co., Ltd.).
(2) Firing of fine metal wire pattern After printing the fine metal wire pattern, heat treatment was performed on a hot plate at 120 ° C. for 30 minutes to produce fine metal wire 1.

<< Production of fine metal wire patterns 2-5 >>
(1) Formation of porous layer As described in JP-A-2007-169604, one surface of a PEN film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides is described. With reference to Examples 2 and 10 (paragraphs 0065 and 0078), etc., a porous layer composed of 90% by mass of an inorganic compound was prepared so that the average thickness after drying was as shown in Table 1. Formed.

Specifically, a “dispersion” containing silicon-based oxide aggregate particles was prepared. The method for preparing the dispersion is as follows.
Separately, 306.84 g of glycidoxypropyltrimethoxysilane and 266.87 g of titanium tetraisopropoxide were dissolved in 257.26 g of ethyl cellosolve, and 100.68 g of concentrated nitric acid, 31.61 g of water and ethyl cellosolve 36 were dissolved therein. After dropping .75 g of the mixed solution, a “binder solution” with a solid content concentration of 30 mass% was prepared by reacting at 30 ° C. for 4 hours.
Thereafter, 620 g of cyclohexanone and then 20 g of the binder liquid were dropped into 360 g of the dispersion while stirring, and the mixture was stirred at room temperature for 1 hour to prepare a “coating liquid” having a solid content concentration of 6 mass%.
Then, on one side of a polyethylene terephthalate (PET) film having a thickness of 110 μm and a size of 180 mm × 180 mm provided with a hard coat layer on both sides, the average film thickness after drying is 0.8 μm by the bar coat method. The above coating solution was applied, heated at 120 ° C. for 1 minute, and then aged at 60 ° C. for 3 days to form a porous porous layer composed of 90% by mass of an inorganic compound.

(Preparation of dispersion)
Pure water was added to commercially available JIS No. 3 water glass (SiO ₂ / Na ₂ O molar ratio 3.22, SiO ₂ concentration 28.5 wt%) to obtain a sodium silicate aqueous solution having an SiO ₂ concentration of 3.6 wt%. . By passing the sodium silicate aqueous solution through a column of cation exchange resin packed under the trade name Amberlite 120B, which is separately prepared, active silicic acid having a SiO ₂ concentration of 3.60 wt%, a pH of 2.90, and an electric conductivity of 580 μS / cm is obtained. A colloidal aqueous solution was obtained.
888 g of colloidal aqueous solution of active silicic acid (SiO ₂ content 32.0 g) is put into a glass container, 600 g of pure water is added with stirring, and colloidal aqueous solution of active silicic acid having a SiO ₂ concentration of 2.15 wt% and pH 3.07 It was. Next, 59 g (CaO content 2.02 g) of a 10 wt% calcium nitrate aqueous solution (pH 4.32) was added thereto at room temperature with stirring, and stirring was continued for 30 minutes. The added calcium nitrate was 6.30% by weight with respect to SiO ₂ as CaO.
On the other hand, acidic spherical silica sol snowtex O-40 (manufactured by Nissan Chemical Industries, Ltd.) having an average particle size (nitrogen adsorption method / D2) of 20.5 nm (specific gravity 1.289, viscosity 4.10 mPa · s, pH 2.67, Conductivity 942 μS / cm, SiO ₂ concentration 40.1 wt%) 2000 g (SiO ₂ content 802 g) was put into another glass container, and 5 wt% sodium hydroxide aqueous solution 6.0 g was added with stirring. Stirring was continued for 30 minutes to obtain an acidic silica sol having a pH of 4.73 and a SiO ₂ concentration of 40.0% by weight.
The particle diameter (D1) measured by the dynamic light scattering method of this silica sol was 35.0 nm, and the D1 / D2 value was 1.71. According to electron microscope observation, the colloidal silica particles in the silica sol were spherical and showed a dispersion close to monodispersion, and no bonding or aggregation between the colloidal particles was observed.
The acidic spherical silica sol of 20.5 nm was added to the colloidal aqueous solution of active silicic acid to which the calcium nitrate was added [mixture (a)] with stirring, and stirring was continued for 30 minutes. The obtained mixed liquid (b) is a ratio A / B (weight ratio) of the silica content (A) derived from the acidic spherical silica sol and the silica content (B) derived from the colloidal aqueous solution of active silicic acid [mixed liquid (a)]. ) Was 25.1, pH was 3.60, conductivity was 2580 μS / cm, and the total silica content (A + B) in the mixed solution (b) was 23.5 wt% as the SiO ₂ concentration. The calcium ion in the liquid was 0.242% by weight with respect to SiO ₂ as CaO.
Next, 330 g of a 1.97 wt% aqueous sodium hydroxide solution was added to the obtained mixed solution (b) over 10 minutes with stirring, and stirring was further continued for 1 hour. The mixture (c) obtained by adding this sodium hydroxide aqueous solution had a pH of 9.22, an electric conductivity of 3266 μS / cm, an SiO ₂ concentration of 21.5 wt%, and an SiO ₂ / Na ₂ O molar ratio of 163.5. there were. A small amount of silica gel was observed in the mixture (c).
Next, 1800 g of the alkaline mixed liquid (c) was charged into a stainless steel autoclave, heated at 145 ° C. with stirring for 3 hours, and then cooled to take out 1800 g of contents. The resulting liquid was a transparent colloidal colored silica sol [beaded silica sol A], which was used as a dispersion containing silicon-based oxide aggregate particles.
The beaded silica sol A contains SiO ₂ concentration of 21.5% by weight, SiO ₂ / Na ₂ O molar ratio 200, pH 9.62, specific gravity 1.141, viscosity 91.7 mPa · s, conductivity 3290 μS / cm, transmission The rate was 59.0%, and the particle diameter (D1) measured by the dynamic light scattering method was 177 nm.
Therefore, the D1 / D2 ratio is 8.63. According to the electron microscope observation, the colloidal silica particles in the obtained silica sol are composed of spherical colloidal silica particles and silica joining them, and the spherical colloidal silica particles are connected in a rosary shape with 5-30 beads in a single plane. Colloidal silica particles and no three-dimensional gel structure particles were observed. The accumulated pore volume of the dried product of the sol measured by a mercury porosimeter was 1.23 cc / g, and the average pore diameter was 49 nm.

(2) Printing of fine metal wire pattern Next, on the porous layer forming surface side of the PEN film with a porous layer, the fine metal wire pattern 1 In the same manner, a metal fine line pattern was printed.
(3) Firing of fine metal wire pattern The fine metal wire pattern after printing was subjected to heat treatment at 120 ° C. for 30 minutes on a hot plate to produce fine metal wire patterns 2-5.

<< Production of fine metal wire patterns 6-18 >>
(1) Formation of porous layer On one side of a polyethylene naphthalate (PEN) film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides, JP 2010-132485 A With reference to Examples 1 and 6 (paragraphs 0050 and 0055) described in the publication, etc., a porous layer made of mesoporous silica is prepared so that the average thickness after drying becomes the thickness shown in Table 1. Formed.

For more information, to pH2 hydrochloric acid (0.01 N) 40 g, n-hexadecyl trimethyl ammonium chloride (manufactured by Kanto Chemical Co., Inc.) 1.21g (0.088mol / L), and block copolymers _{_{HO (C 2 H 4 O)}} 106 - ( C ₃ H ₆ O) _70- (C ₂ H ₄ O) ₁₀₆ H (trade name “Pluronic F127”, Sigma-Aldrich) 2.41 g (0.0043 mol / L) was added, and the mixture was stirred at 25 ° C. for 1 hour. Add 4.00 g (0.45 mol / L) of tetraethoxysilane (manufactured by Kanto Chemical Co., Inc.) and stir at 25 ° C. for 1 hour, then add 3.94 g (1.51 mol / L) of 28% by mass ammonia water to adjust the pH. 10.6 and stirred at 25 ° C. for 0.5 hour.
Thereafter, a solution of the obtained surfactant-mesoporous silica nanoparticle composite was formed into a polyethylene naphthalate (PEN) film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides. One surface was coated by spin coating so that the average thickness after drying was as shown in Table 1, dried at 80 ° C for 0.5 hours, and then fired at 150 ° C for 48 hours in an air atmosphere. Then, a porous layer made of mesoporous silica was formed.

(2) Printing of fine metal wire pattern Next, on the porous layer forming surface side of the PEN film with a porous layer, the fine metal wire pattern 1 In the same manner, a metal fine line pattern was printed.
(3) Firing of fine metal wire patterns The fine metal wire patterns after printing were heat-treated on a hot plate at 120 ° C. for 30 minutes to produce fine metal wire patterns 6 to 18.

≪Metallic fine wire pattern 19≫
As a substrate, a substrate (Canon Inc.) having a porous layer (ink receiving layer) mainly composed of alumina fine particles used in Example 1 (paragraph 0147) described in JP-A-2009-76455 is used. ) Photographic paper / Glossy Professional PR-201) was used to print and fire the metal fine line pattern in the same manner as the metal fine line pattern 1 to obtain a metal fine line pattern 19.

≪Preparation of transparent electrodes 1-19 (sample) ≫
(1) Water-soluble binder 1: Synthesis of polyhydroxyethyl acrylate (abbreviated as PHEA) (Exemplary Compound I-1)
200 ml of tetrahydrofuran (hereinafter abbreviated as THF) was added to a 500 ml three-necked flask, and the mixture was heated to reflux for 10 minutes and then cooled to room temperature under nitrogen.
Then, 2-hydroxyethyl acrylate (10.0 g, 86 mmol, molecular weight: 116.05) and azobisisobutyronitrile (hereinafter abbreviated as AIBN, 1.41 g, 8.5 mmol, molecular weight: 164.11). The mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 5000 ml of methyl ethyl ketone (hereinafter abbreviated as MEK) and stirred for 1 hour. After decanting MEK, the polymer was washed three times with 200 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF 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, 9.0 g (yield 90%) of water-soluble binder 1 (polyhydroxyethyl acrylate, PHEA) having a number average molecular weight of 35,700 and a molecular weight distribution of 2.3 was obtained.
The molecular weight was measured using GPC (Waters 2695, manufactured by Waters) under the following measurement conditions.
<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

(2) Preparation of coating solution for forming transparent conductive protective layer The following transparent conductive protective layer forming materials were sequentially mixed and then dissolved by heating to prepare a coating solution 1 for forming a transparent conductive protective layer.
1) Conductive polymer 1 (PEDOT-PSS CLEVIOS PH510, manufactured by Heraeus, solid content concentration: 1.89%, PEDOT: PSS (solid content ratio) = 1: 2.5) 15.9 g
2) 3.5 g of water-soluble binder 1 (PHEA)
3) Polar solvent (dimethylsulfoxide, abbreviation: DMSO, log P value: -0.68) 4.2 g
4) Glycol ether (ethylene glycol monobutyl ether, abbreviation: EGBu) 4.2 g

(3) Formation of a transparent conductive protective layer The transparent conductive protective layer forming coating solution 1 is applied to the substrate on which the metal fine wire patterns 1 to 19 are formed by an ink jet printing method to form a transparent conductive protective layer. did.
As an ink jet printing method, an ink jet head with an ink droplet ejection amount of 42 pl is used, and the coating speed and ejection frequency are adjusted so that the adhesion amount after drying becomes the value shown in Table 1. A pattern was printed. After printing, heat treatment was performed at 150 ° C. for 60 minutes using a heater to obtain transparent electrodes 1 to 19.
As the ink jet printing apparatus, a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an ink jet head (manufactured by Konica Minolta IJ Co., Ltd.) was used and controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta IJ Co., Ltd.).

≪Evaluation of transparent electrodes 1-19 (sample) ≫
For each transparent electrode produced as described above, the porosity of the porous layer, the layer thickness of the porous layer, the average line width of the metal fine wire pattern, the thickness of the metal fine wire pattern were measured, and the sheet resistance, after the bending treatment Sheet resistance and the presence or absence of peeling of the fine metal wire pattern were evaluated as follows. The obtained results are shown in Tables 1 and 2.

(1) Porosity of porous layer After forming the porous layer on the substrate, before forming the metal wire pattern, use a lens reflectometer (model number: USPM-RU, Olympus Corporation) The porosity of the porous layer was measured using 550 nm light.
As a result, all of the transparent electrodes 2 to 19 had a porosity of 90% or less, and it was confirmed that a desired porous layer could be formed.
(2) Layer thickness of porous layer After forming a porous layer on a substrate, a part of the porous layer was shaved, and the level difference was measured using a high brightness non-contact three-dimensional surface shape roughness meter WYKO NT9100.
The measurement was performed at 10 arbitrary points, and the average value was obtained.
(3) Average line width of fine metal wire pattern Using CNC image evaluation system NEXIV VMR-1515 (manufactured by NIKON), the line width at any 100 locations of the fine metal wire pattern of each transparent electrode was measured to obtain the average value. .
(4) Thickness of fine metal wire pattern After forming a porous layer on the substrate, forming a fine metal wire pattern, firing, and then using high brightness non-contact three-dimensional surface shape roughness meter WYKO NT9100 The shape of the fine line pattern was measured.
Based on this data, the height from the upper surface of the porous layer at the center of the line width was measured.
The measurement was performed at 10 arbitrary locations, and the average value was obtained. The value obtained by adding the height of the porous layer used in (2) to this value was the thickness of the fine metal wire pattern.

(5) Sheet resistance About each transparent electrode, the silver electrode was vapor-deposited on the both ends of a metal fine wire so that a metal fine wire part might become a square, the resistance of the both ends of a silver electrode was measured, and the surface resistance of the transparent electrode was measured.
At this time, the thickness of the silver electrode portion was adjusted so as to be 1/10 or less of the resistance of the metal thin wire portion. The sheet resistance is preferably 5Ω / □ or less, and more preferably 1Ω / □ or less, in order to increase the area of the organic electronic device.
“◎”: 1Ω / □ or less “○”: greater than 1Ω / □, 5Ω / □ or less “△”: greater than 5Ω / □, 10Ω / □ or less “×”: greater than 10Ω / □ (6) Winding Sheet resistance after treatment For each transparent electrode, the sheet resistance was measured in the same manner as in (5) above after being wound around a cylindrical rod having a diameter of 3 cm. Evaluated whether it was growing.
“◎”: The variation range of the sheet resistance value is 20% or less “O”: The variation range of the sheet resistance value is greater than 10% and 50% or less “△”: The variation range of the sheet resistance value is greater than 50% and 100% or less “×”: The fluctuation range of the sheet resistance value is larger than 100%. (7) Presence / absence of peeling of the fine metal wire pattern after the winding process A test piece of an appropriate size is wound by the same method as in (6). The number of peeled portions of the thin metal wire pattern in an area of 20 mm (vertical) × 20 mm (horizontal) was counted using an electron microscope Miniscope TM-1000 (manufactured by Hitachi, Ltd.) and classified as follows.
“◎”: When there is no peeling part “○”: When there are 1 to 3 peeling parts “△”: When there are 3 to 10 or more peeling parts “×”: When almost peeling (8) Winding Presence / absence of cracks in the porous layer after the staking treatment A test piece having an appropriate size is cut out by the same method as in (6), and a porous material having an area of 20 mm (vertical) × 20 mm (horizontal) is obtained. Whether or not the layer was cracked was evaluated using an optical microscope as follows.
“◯”: No cracks “Δ”: When there are 1 to 3 cracks “X”: When there are 3 or more cracks (9) Measurement of transmittance For each transparent electrode, HAZE manufactured by Tokyo Denshoku Co., Ltd. Using METER NDH5000, the total light transmittance was measured and evaluated according to the following criteria.
In order to use a transparent electrode for an organic electronic device, the transmittance is preferably 75% or more, and more preferably 80% or more.
“◎”: 80% or more “◯”: 75% to less than 80% “△”: 70% to less than 75% “X”: 0% to less than 70%

<< Production of organic EL devices 1-19 (sample) >>

(1) Production of Transparent Film Substrate with Barrier Layer A 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS, AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) has an average film thickness after drying of 0.3 μm. After applying to one side of a polyethylene naphthalate (PEN) film having a thickness of 110 μm and a size of 80 mm (length) × 80 mm (width) provided with a hard coat layer on both sides, the temperature is 85 ° C. and the humidity is 55% RH. The sample was kept for 1 minute in the atmosphere and dried, and further dehumidified by being kept for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.).
The sample subjected to the dehumidification treatment was subjected to a modification treatment under the following conditions to produce a transparent film substrate with a barrier layer. The dew point temperature during the reforming process was -8 ° C.

<Modification processing equipment>
An excimer irradiation apparatus (MODEL: MECL-M-1-200, wavelength 172 nm, lamp-filled gas Xe) manufactured by M.D.Com Co., Ltd. was used. A sample was fixed on the operation stage, and the sample was modified under the following conditions.
<Reforming treatment conditions>
Excimer light intensity 60mW / cm2 (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds When the water vapor permeability of the produced transparent film substrate with a barrier layer was evaluated by the Ca method, it was 2 × 10 ⁻⁵ (g · m ² · day).
In forming the fine metal wire pattern of Example 1, the ink used was changed to a silver complex ink (TEC-IJ-010; manufactured by InkTec).
Other than that, when a sample was prepared and evaluated in the same manner as in Example 1, the same result as in Example 1 was obtained.

(2) Formation of Organic EL Layer, etc. The 5 cm square transparent film substrate with a barrier layer prepared above was immersed in 2-propanol, further immersed in ultrapure water, and dried at 120 ° C. for 30 minutes.
An ITO (indium tin oxide) film having a thickness of 150 nm is formed on the cleaned film substrate by a sputtering method, an ITO substrate is prepared, and a film substrate (an anode electrode portion (central portion: 30 mm) having ITO as an extraction electrode by a photolithography method. × 30 mm) without ITO was prepared and further dried at 120 ° C. for 1 day.
Thereafter, transparent electrodes 1 to 19 are formed as anode electrodes on the film substrate having ITO as an extraction electrode, and an organic EL layer (a hole transport layer, an organic light emitting layer, a hole blocking layer and an electron) is formed on the anode electrode. The “transport layer” and the cathode electrode were formed by the following procedure, and “organic EL devices 1 to 19” were produced.
The take-out electrode ITO and a part of the metal fine line pattern were formed to have contacts. Further, when forming the porous layer, after the porous layer was applied and formed, unnecessary portions were wiped off and patterned before curing.

The layers after the hole transport layer of the organic EL layer were formed by vapor deposition.
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.
(2.1) Formation of organic EL layer First, an organic EL layer composed of a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer is formed on the transparent electrodes 1 to 19 with respect to the transparent electrodes 1 to 19. It formed in order in the range of 30 mm x 33 mm of a part.
(2.1.1) Formation of hole transport layer After depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, the deposition crucible containing Compound 1 was energized and heated, and the deposition rate was 0.1 nm / second. Evaporation was performed to provide a hole transport layer having a thickness of 30 nm.
(2.1.2) 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.
(2.1.3) Formation of hole blocking layer Furthermore, the hole blocking layer was formed by vapor-depositing the compound 6 in a film thickness of 5 nm in the same region as the formed organic light emitting layer.
(2.1.4) Formation of Electron Transport Layer Subsequently, CsF was co-evaporated with Compound 6 so as to have a film thickness ratio of 10% in the same region as the formed hole blocking layer, and a 45 nm thick electron transport layer was formed. A layer was formed.

(2.2) Formation of cathode electrode On the electron transport layer of the formed organic EL layer, Al was deposited as a cathode forming material under a vacuum of 5 × 10 ⁻⁴ Pa under a vacuum of 100 nm thickness. A 30 mm × 42 mm cathode was formed.
Finally, an adhesive is applied to the periphery of the anode excluding the ends so that the cathode and anode external lead terminals can be formed, and Al ₂ O ₃ is vapor-deposited with a thickness of 300 nm using polyethylene terephthalate as a substrate. After the sealing member was bonded, the adhesive was cured by heat treatment to form a sealing film, and “organic EL devices 1 to 19” having a light emitting area of 30 mm × 30 mm were produced.
The heat treatment was carried out with a heater using a stage that was molded in the part where the adhesive was applied so that only the surrounding adhesive was heated.

≪Evaluation of organic EL devices 1 to 19 (sample) ≫
For each of the obtained organic EL devices 1 to 19, the rectification ratio was calculated according to the following formula, and the evaluation results are summarized in Table 2.
"Rectification ratio" = (Current value when + 4V is applied) / (Current value when -4V is applied)
From the viewpoint of luminous efficiency, the rectification ratio is preferably 1000 or more.
The rectification ratio of 10 devices manufactured by the same manufacturing procedure was measured, and the average value was obtained.
The rectification ratio was evaluated using the following indicators.
In the following rank, it is essential that the level is 1 or more from the viewpoint of current leakage, and 2 or more is preferable from the viewpoint of increasing the area.
“4”: Rectification ratio is 1.0 × 10 ⁴ or more “3”: Rectification ratio is 1.0 × 10 ³ to less than 1.0 × 10 ⁴ “2”: Rectification ratio is 1.0 × 10 ² to 1 Less than 0 × 10 ³ “1”: Rectification ratio is less than 5.0 × 10 ¹ to less than 1.0 × 10 ² “0”: Rectification ratio is less than 5.0 × 10 ¹

≪Summary≫
As shown in Table 1 and Table 2, it can be seen from the results of the transparent electrode 1 that if the porous layer is not formed on the transparent resin substrate, the fine metal wire pattern is peeled off by winding.
From the result of the transparent electrode 6, when the thickness of the thin metal wire pattern is as small as 0.2 μm, the amount of adhesion of silver itself is small and the sheet resistance is increased. For example, when it is used for a large organic EL device, it can emit light uniformly. Can not.
From the results of the transparent electrodes 5, 17 and 18, when the thickness of the fine metal wire pattern is larger than 3.0 μm, a part of the fine metal wire pattern is peeled off or the porous layer is cracked by winding. It can be seen that the sheet resistance increases.
In particular, from the results of the organic EL devices 17 and 18, when the thickness of the fine metal wire pattern is larger than 3.0 μm, it becomes difficult to completely cover the irregularities of the porous layer with the transparent conductive protective layer. When used in an organic EL device, the rectification ratio was poor.
In addition, it can be seen from the results of the organic EL devices 5, 15, 16, and 18 that if the porous layer is too thick, the porous layer is cracked by winding, while the results of the organic EL device 9 indicate that the porous layer is porous. It can be seen that if the layer is too thin, the fine metal wire pattern peels off by winding.
Since the transparent electrode 19 uses paper for the substrate, cracks did not occur in the porous layer, but the organic EL device 19 produced using the transparent electrode 19 did not emit light, and the rectification ratio was low. . This shows that IJ paper cannot be used for the organic EL device.

On the other hand, from the results of the transparent electrodes 2 to 4, 7 to 8, and 10 to 14, the thickness of the porous layer is in the range of 5 to 40% with respect to the thickness of the fine metal wire pattern, When the thickness of the fine metal wire pattern is in the range of 0.3 to 3.0 μm, the sheet resistance is excellent, and even when wound, there is no increase in the sheet resistance or peeling of the fine metal wire pattern. A transparent electrode in which the transparent resin substrate and the fine metal wire pattern were in close contact with each other without cracks was obtained. Furthermore, from the results of the organic EL electronic devices 2 to 4, 7 to 8, and 10 to 14, the organic EL device using the devices could produce a device having an excellent rectification ratio and no current leakage.
From the above, in order to suppress at least peeling of the fine metal wire pattern and cracking of the porous layer, the thickness of the porous layer with respect to the fine metal wire pattern is in the range of 5 to 40% and the thickness of the fine metal wire pattern is It can be seen that it is useful to be within the range of 0.3 to 3.0 μm.

≪Preparation of transparent electrodes 21 to 25 and organic EL devices 21 to 25 (samples) ≫
Examples 1 and 6 to 11 (described in JP2010-132485A) were formed on one side of a PEN film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides. With reference to paragraphs 0050 and 0055 to 0060) and comparative examples 4 to 6 (paragraphs 0064 to 0066), a porous layer having a porosity of the values shown in Table 3 and a thickness of 0.2 μm was formed. .

Specifically, in the formation of the porous layer 21 used for the transparent electrode 21 and the organic EL device 21, 1.21 g (0.088 mol) of n-hexadecyltrimethylammonium chloride (manufactured by Kanto Chemical Co., Ltd.) is added to 40 g of hydrochloric acid (0.01 N) at pH 2. / L), and block copolymer HO (C ₂ H ₄ O) _106- (C ₃ H ₆ O) _70- (C ₂ H ₄ O) ₁₀₆ H (trade name “Pluronic F127”, Sigma-Aldrich) 2.41 g (0.0043 mol / L) was added and stirred at 25 ° C for 1 hour, tetraethoxysilane (manufactured by Kanto Chemical Co., Inc.) 4.00 g (0.45 mol / L) was added, and the mixture was stirred at 25 ° C for 1 hour. 3.94 g (1.51 mol / L) of mass% ammonia water was added to adjust the pH to 10.6, and the mixture was stirred at 25 ° C. for 0.5 hour. Thereafter, the obtained surfactant-mesoporous silica nanoparticle composite solution was applied to one side of a PEN film having a thickness of 110 μm and a size of 180 mm (length) × 180 mm (width) provided with a hard coat layer on both sides. After applying by spin coating and drying at 80 ° C. for 0.5 hour, 1.6 W / cm ² ultraviolet ray was irradiated for 1 minute to form a mesoporous silica porous film. For the ultraviolet irradiation treatment, a UV lamp device (model number: F300S, light source: D type electrodeless lamp bulb, manufactured by Fusion Ubui Systems Japan Co., Ltd.) was used.
In the formation of the porous layer 22 used for the transparent electrode 22 and the organic EL device 22, the porous layer 21 was baked at 150 ° C. for 48 hours in an air atmosphere instead of the ultraviolet irradiation when forming the porous layer 21.
In the formation of the porous layer 23 used for the transparent electrode 23 and the organic EL device 23, a plasma cleaner (model number: PDC210, manufactured by Yamato Scientific Co., Ltd.) is used instead of the ultraviolet irradiation at the time of forming the porous layer 21, and 15 Pa Under reduced pressure, plasma was discharged for 10 minutes at a power density of 0.7 W / cm ² and a power frequency of 13.56 MHz while supplying oxygen at 80 mL / min.
In the formation of the porous layer 24 used for the transparent electrode 24 and the organic EL device 24, the ultraviolet irradiation time when forming the porous layer 21 was set to 2 minutes.
In the formation of the porous layer 25 used for the transparent electrode 25 and the organic EL device 25, the ultraviolet irradiation time when forming the porous layer 21 was 3 minutes.

On the film in which each porous material was formed, the metal fine line pattern was printed in the same manner as the transparent electrode 1 in the same manner as the metal fine line patterns 6 to 18 so that the dry film pressure was 2.0 μm.
Thereafter, for each substrate, using a xenon flash lamp 2400WS (made by COMET) equipped with a short-wavelength cut filter of 250 nm or less, flash light with an irradiation energy of 2.5 J / cm ^{2 is} applied to the thin metal wire pattern after printing. Were fired and fired once from the metal fine line pattern printing surface side with an irradiation time of 2 milliseconds to produce metal fine line patterns 21 to 25.
Then, the transparent electrodes 21 to 25 and the organic EL devices 21 to 25 were produced by the same method as the production of the transparent electrodes 1 to 19 and the organic EL devices 1 to 19.

≪Evaluation of transparent electrodes 21-25 and organic EL devices 21-25 (sample) ≫
For the transparent electrodes 21 to 25, the porosity of the porous layer was measured by the same method as in Example 1, and the presence or absence of peeling of the fine metal wire pattern was performed by the same method as in Example 1 without performing the winding process. Evaluated.
For the organic EL devices 21 to 25, the rectification ratio was measured in the same manner as in Example 1.
The above evaluation results are summarized in Table 3.

≪Summary≫
As shown in Table 3, from the results of the transparent electrodes 21 to 25, when the porosity of the porous layer is 30% or more and 77% or less, a transparent resin can be obtained even by heating with flash light irradiation due to sufficient adhesion. It can be seen that a low-resistance transparent electrode can be formed without peeling off the fine metal wire pattern from the substrate.
In particular, the results of the transparent electrodes 22 to 24 show that the effect is great when the porosity is 55 to 75%.
From the above, it can be seen that it is useful that the porosity of the porous layer is in the range of 30 to 77% in order to suppress the peeling of the fine metal wire pattern.

≪Change of water-soluble binder≫
The water-soluble binder 1 of the coating liquid 1 for forming a transparent conductive protective layer used in Example 1 was changed from polyhydroxyethyl acrylate (PHEA) to polyhydroxyethyl acrylamide (PHEAA), polyhydroxyethyl acrylate and polyhydroxyethyl acrylamide. To a copolymer (PHEA / PHEAA) and an aqueous dispersion polymer (described later).
Other than that, when a sample (transparent electrode and organic EL device) was prepared and evaluated in the same manner as in Example 1, the same result as in Example 1 was obtained.

<Synthesis of Polyhydroxyethylacrylamide (PHEAA) (I-19)>
In the synthesis of polyhydroxyethyl acrylate, hydroxyethyl acrylamide was used as a monomer.
Otherwise, polyhydroxyethylacrylamide was obtained by the same method as the synthesis of polyhydroxyethyl acrylate.

<Synthesis of polyhydroxyethyl acrylate and polyhydroxyethylacrylamide copolymer (PHEA / PHEAA)>
After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (4.1 g, 35 mmol, molecular weight: 116.05), hydroxyethylacrylamide (I-19) (1.7 g, 15 mmol, molecular weight: 115.15), AIBN (0.8 g, 5 mmol, molecular weight) 164.11) was added and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed 3 times with 100 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF 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, 10.3 g (yield 90%) of “copolymer of polyhydroxyethyl acrylate and polyhydroxyethyl acrylamide” having a number average molecular weight of 33700 and a molecular weight distribution of 2.4 was obtained.

<Water-dispersed polymer>
The following two types of water-dispersed polymers were used.
Polyester resin plus coat Z-561 (Keio Chemical Industry Co., Ltd.)
Acrylic resin Movinyl 5450 (Nippon Synthetic Chemical Industry Co., Ltd.)

≪Change of conductive polymer≫
Instead of 15.9 g of PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by Heraeus) as the conductive polymer 1 of the coating solution 1 for forming a transparent conductive protective layer used in Example 1, a conductive material Polyaniline dispersion ORMECON (registered trademark) INK (conductive polymer dispersion liquid ink) (solid content concentration 2.5%, manufactured by Nissan Chemical Co., Ltd.) was changed to 12.0 g.
Other than that, when a sample (transparent electrode and organic EL device) was prepared and evaluated in the same manner as in Example 1, the same result as in Example 1 was obtained.

The present invention is a transparent electrode having a fine metal wire pattern with good adhesion to a substrate, and the porous fine electrode pattern is peeled off when wound up or irradiated with flash light, or when the transparent electrode is bent. It can be particularly suitably used to suppress the occurrence of cracks in the quality layer.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 10 Transparent resin substrate 20 Porous layer 22 Thickness 30 Metal fine wire pattern 32 Thickness 40 Transparent conductive protective layer

Claims

It has a transparent resin substrate, a porous layer, a metal fine wire pattern and a transparent conductive protective layer, and the porous layer and the metal fine wire pattern are formed on the transparent resin substrate, and the porous layer and the metal fine wire pattern In the transparent electrode on which the transparent conductive protective layer is formed,
The transparent layer characterized in that the thickness of the porous layer with respect to the fine metal wire pattern is in the range of 5 to 40%, and the thickness of the fine metal wire pattern is in the range of 0.3 to 3.0 μm. electrode.
The transparent electrode according to claim 1,
A transparent electrode, wherein the porosity of the porous layer is in the range of 30 to 77%.
The transparent electrode according to claim 2,
A transparent electrode, wherein the porosity of the porous layer is in the range of 55 to 75%.
The transparent electrode according to any one of claims 1 to 3,
The transparent conductive protective layer contains at least a conductive polymer and an aqueous dispersion binder or a water-soluble binder.
Forming a porous layer on the transparent resin substrate;
Forming a fine metal wire pattern on the porous layer;
Forming a transparent conductive protective layer on the porous layer and the fine metal wire pattern,
In the step of forming the porous layer, the thickness of the porous layer with respect to the metal fine line pattern is set within a range of 5 to 40%,
In the step of forming the fine metal wire pattern, a thickness of the fine metal wire pattern is set within a range of 0.3 to 3.0 μm.
In the manufacturing method of the transparent electrode according to claim 5,
The forming process of the metal fine line pattern,
Printing the metal nanoparticle dispersion or metal complex solution on the surface of the transparent resin substrate on which the porous layer is formed;
Baking the metal nanoparticle dispersion or the metal complex solution after printing;
The manufacturing method of the transparent electrode characterized by having.
In the manufacturing method of the transparent electrode according to claim 6,
In the method of printing the metal nanoparticle dispersion or the metal complex solution, ink jet printing is performed.
In the manufacturing method of the transparent electrode according to claim 6,
In the step of firing the metal nanoparticle dispersion or the metal complex solution, a method for producing a transparent electrode is characterized by irradiating flash light.
The transparent electrode according to any one of claims 1 to 4,
A second electrode disposed at a position facing the transparent electrode;
An organic functional layer provided between the transparent electrode and the second electrode;
An organic electronic device comprising:
The organic electronic device according to claim 9, wherein
An organic electronic device characterized by being an organic electroluminescence device.