JP2012138311A - Transparent conductive film substrate and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve energy conversion efficiency by reducing a driving voltage.SOLUTION: In a transparent conductive substrate 2, a metal thin wire auxiliary electrode 6 and a transparent conductive layer 8 are formed in this order on a supporting substrate 4. In the transparent conductive substrate 2, the transparent conductive layer 8 contains a conductive polymer and a hydroxyl group-containing nonconductive polymer, and the hydroxyl group-containing nonconductive polymer contains a repeating unit having a special structure in a molecule.

Description

  The present invention relates to a transparent conductive film substrate and an organic electroluminescence element, and can be suitably used particularly in various fields such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, a solar cell, an electromagnetic wave shield, electronic paper, and a touch panel. The present invention relates to a transparent conductive film substrate, and further to an organic electroluminescence element (hereinafter also referred to as organic EL element) using the transparent conductive film substrate.

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays with different display methods, the transparent electrode is an essential constituent technology. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.

  Conventionally, an ITO transparent electrode obtained by forming a composite oxide (ITO) film of indium-tin on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method has been mainly used. It was. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. On the other hand, with an increase in screen size and productivity, a technology that can reduce resistance while maintaining transparency is desired.

  In recent years, a transparent conductive film such as a conductive polymer is laminated on a thin metal wire formed in a pattern so that it can be applied to products that require such high transparency and low resistance, and the current uniformity and A transparent conductive film substrate having high conductivity has been developed (see, for example, Patent Documents 1 and 2). However, in such a configuration, it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent conductive film such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer. . Since the conductive polymer has absorption in the visible light region, there is a problem that when the film is thickened, the transparency of the transparent conductive film substrate is significantly reduced.

Moreover, the technique which laminates | stacks the mixture of a conductive polymer and an insulating polymer on a thin wire | line structure part is disclosed as making electroconductivity and transparency compatible (for example, patent document 3). However, the addition of an insulating polymer has a problem that it causes deterioration of optical performance such as haze from the viewpoint of a decrease in conductivity and compatibility with the conductive polymer.
Furthermore, as a polymer compatible with the conductive polymer, polyvinylpyrrolidone (PVP), a copolymer of poly (vinylpyridine) and poly (vinyl acetate) (PVPy-VAc), polymethacrylic acid (PMAA), poly (hydroxyethyl) A polymer or copolymer selected from the group consisting of (acrylate) and poly (methacrylic acid) copolymer (PHEA-MAA), poly (2-hydroxyethyl methacrylate), polyvinyl butyral (PVB) is disclosed (eg, Patent Document 4).
Furthermore, as a means for providing both conductivity and transparency and imparting film strength, a method using a hydroxyalkyl group-containing acrylic polymer such as poly (hydroxyethyl acrylate) as a conductive polymer is also disclosed (for example, patent document). 5).

  However, even when using a transparent conductive substrate by these techniques, the driving voltage of the organic EL element rises more than desired, and as a result, the problem of increasing the energy conversion efficiency is more It was not particularly advantageous.

JP 2005-302508 A JP 2009-87843 A JP 2009-4348 A Japanese Patent No. 3716167 US Patent Application Publication No. 2010/0255323

  Therefore, the present invention has been made in view of the above problems, and a main object of the present invention is to provide a transparent conductive film substrate capable of reducing drive voltage and improving energy conversion efficiency, and an organic EL element using the same. It is to provide.

The inventor has examined the above-mentioned problem in detail, and has devised the present invention through the following processes.
That is, in the case of providing a transparent conductive film that can suitably cope with an OLED having a large area (10 cm × 10 cm or more), a thin metal wire auxiliary electrode made of a metal material formed in a pattern is used in order to reduce sheet resistance. However, as a transparent electrode (transparent conductive film substrate) used for an OLED having a thin light emitting layer, leakage due to lack of smoothness of the edge of the pattern or the upper surface of the pattern becomes a problem. It is effective to cover the pattern of the metal thin wire auxiliary electrode with a transparent conductive layer containing a conductive polymer in order to prevent leakage and to make a surface electrode. As the film thickness increases, the transparency decreases.
For such a problem, when a hydroxyl group-containing non-conductive polymer containing a structural unit having a hydroxyl group (OH) in the repeating unit is added to the conductive polymer of the transparent conductive layer to reduce the visible region concentration, In addition to being able to suppress the decrease, it has been found that an increase in sheet resistance can be prevented.
However, by using an OH-containing polymer as a binder for the transparent conductive layer and lowering the conductive polymer concentration in the transparent electrode layer, the organic light-emitting layer adjacent to the transparent electrode layer is removed even when there is no increase in sheet resistance. LPW (lumen per watt; constant power) that may increase the resistance at the interface of the thin film layer (for example, HIL; hole injection layer) constituting the structure, resulting in an increase in the driving voltage of the organic EL element and one of the indexes of energy conversion efficiency. Brightness), and EQE (external quantum efficiency).
In view of such problems, the OH-containing polymer used for the binder of the transparent conductive layer is the polymer of the present invention (a hydroxyl group-containing non-conductive polymer containing a repeating unit having a structure represented by the formula (1) in the molecule). It has been found that the effect of improving the EQE (external quantum efficiency) can be obtained by reducing the driving voltage of the organic EL element by suppressing the resistance at the interface of the adjacent layer by switching to.

From the above viewpoint, according to one aspect of the present invention,
In the transparent conductive substrate in which the metal thin wire auxiliary electrode and the transparent conductive layer are formed in this order on the support substrate,
The transparent conductive layer contains a conductive polymer and a hydroxyl group-containing nonconductive polymer,
A transparent conductive film substrate is provided in which the hydroxyl group-containing non-conductive polymer contains a repeating unit having a structure represented by the formula (1) in the molecule.

In the formula (1), “R ¹ ” represents a hydrogen atom or a methyl group, “R ² ” and “R ³ ” represent an alkylene group, “R ⁴ ” represents a hydrogen atom, a halogen atom or an alkyl group, “X” represents a halogen atom, “m” represents 0 or 1, “n” represents 1 or 2, and “l” represents 1 or 2.

According to another aspect of the invention,
Including the transparent conductive film substrate,
An organic electroluminescent device is provided in which an organic light emitting layer and a cathode are formed in this order on the transparent conductive film substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the drive voltage of an organic EL element can be reduced and energy conversion efficiency can be improved.

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

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

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

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

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

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

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

A cathode 20 is formed on the organic light emitting layer 10.
The cathode 20 may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the cathode 20, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
The cathode 20 can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
The sheet resistance as the cathode 20 is preferably 10Ω / □ or less, more preferably 1Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

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

<< Transparent conductive film substrate (2) >>
Next, the configuration of the transparent conductive film substrate 2 will be described in detail.
(1) Support substrate 4
In the organic EL element 100, a plastic film or a glass substrate can be used as the support substrate 4.

(1.1) Plastic film From the viewpoint of lightness and flexibility, it is preferable to use a transparent plastic film.
Examples of raw materials for plastic films and plastic plates include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA, and polyvinyl chloride. , Vinyl resins such as polyvinylidene chloride, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), etc. Can be used. Of these, PET and PEN are preferred.
In the transparent conductive film substrate, the support substrate used for this is preferably one having excellent surface smoothness. Regarding the smoothness of the surface, the arithmetic average roughness Ra is preferably 5 nm or less and the maximum height Rz is preferably 50 nm or less, more preferably Ra is 2 nm or less and Rz is 30 nm or less, and Ra is 1 nm. More preferably, Rz is 20 nm or less. The surface of the support substrate may be smoothed by applying an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or a radiation curable resin, or may be smoothed by mechanical processing such as polishing. You can also
Here, the smoothness of the surface can be determined according to the surface roughness standard (JIS B 0601-2001) from measurement by an atomic force microscope (AFM) or the like.

The support substrate is preferably provided with a gas barrier layer for the purpose of blocking oxygen and moisture in the atmosphere. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used. These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having favorable barrier properties, solvent resistance, and transparency are preferable.
In addition, the barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material. The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, and more preferably 10 nm to 400 nm per layer. The gas barrier layer may be provided on at least one surface of the support substrate, and more preferably on both surfaces.
Further, the surface of the support substrate may be subjected to a protective layer treatment with a hard coat layer or the like. The hard coat layer is formed by uniformly applying a photo-radical generating material and a mixture of radical polymerizable monofunctional and / or polyfunctional monomers to a desired film thickness, and then irradiating the necessary amount of ultraviolet light with radical polymerization. It is a transparent and high-hardness polymer layer obtained by making it.

(1.2) Glass substrate It is preferable to use a transparent glass substrate from the viewpoint that the metal fine wire auxiliary electrode and the transparent conductive layer can be fired at a high temperature (150 ° C. or higher) and excellent in gas barrier properties.
There is no particular limitation on the glass substrate that can be used in the present invention. Among them, alkali-free glass is preferably used.
In addition, it is preferable to use a thin film glass having a thickness of 10 to 200 μm from the viewpoint of production suitability in roll-to-roll, flexibility of the element when used for a transparent electrode for an organic electroluminescence element, and the like.
Further, the thickness of the glass substrate is desirably 50 to 120 μm from the viewpoint of being hard to break and easy to carry the roll.
Specifically, a thin film glass as described in JP 2010-132532 A as a glass film can be used.

(2) Metal thin wire auxiliary electrode 6
(2.1) Configuration The metal thin wire auxiliary electrode is made of a metal material formed in a pattern on a support substrate. As a result, a film substrate having both a light-impermeable conductive portion made of a metal material and a light-transmissive window portion is obtained, and an electrode substrate excellent in transparency and conductivity can be produced.
The metal material is not particularly limited as long as it is excellent in conductivity. For example, the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium. In particular, from the viewpoint of ease of pattern formation as described later, the metal material is preferably a metal fine particle or metal nanowire, and the metal material is preferably silver from the viewpoint of conductivity.

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

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

The surface specific resistance of the thin wire portion of the fine metal wire auxiliary electrode is preferably 10Ω / □ or less, and more preferably 3Ω / □ or less.
The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

(2.2) Metal nanoparticles It is preferable that the metal fine line pattern is provided by printing a paste of metal particles. After printing, in order to increase conductivity, heating and baking are performed. When a PET film is used as the support substrate, the firing temperature is preferably 110 ° C. or lower.
The metal particles are preferably metal nanoparticles because high conductivity is obtained.
The metal nanoparticles refer to fine metal particles having a particle size of from atomic scale to nm size. As an average particle diameter of a metal nanoparticle, 3-300 nm is preferable and it is more preferable that it is 5-100 nm.
The metal used in the metal nanoparticles according to the present invention is preferably silver or copper from the viewpoint of conductivity, and may be silver or copper alone, or a combination of them, either silver and copper alloy, silver or copper. It may be plated with any metal. Among these, silver nanoparticles are particularly preferable.
Among these, silver nanoparticles having an average particle size of 30 nm or less are preferable.

Moreover, it is preferable that the metal fine wire auxiliary electrode formed on the support substrate is subjected to a heat baking treatment. This is particularly preferable because fusion of metal fine particles proceeds and the metal fine wire auxiliary electrode becomes highly conductive.
The temperature for heating and baking is preferably in the range of 100 to 900 ° C, more preferably in the range of 150 to 600 ° C.
The preferred range of the heat firing time varies depending on the temperature, but is preferably 1 to 60 minutes.

(3) Transparent conductive layer 8
(3.1) Configuration The transparent conductive layer contains a conductive polymer and a non-conductive polymer containing a hydroxyl group (hydroxyl group-containing non-conductive polymer) so as to cover the patterned thin metal wire auxiliary electrode. The dispersion is applied onto a support substrate and dried to form a film.
In addition to the above-mentioned printing methods such as gravure printing method, flexographic printing method, screen printing method, the application of the transparent conductive layer is performed by roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, Coating methods such as blade coating, bar coating, gravure coating, curtain coating, spray coating, doctor coating, and ink jet can be used.

The transparent conductive layer contains a conductive polymer and a hydroxyl group-containing nonconductive polymer.
The hydroxyl group-containing non-conductive polymer has the effect of enhancing the conductivity of the conductive polymer, and thereby can simultaneously satisfy high conductivity and high transparency.
By forming the transparent conductive layer of the present invention having such a laminated structure, high conductivity that cannot be obtained by the metal thin wire auxiliary electrode or the conductive polymer layer alone can be obtained uniformly in the electrode plane.

The single surface specific resistance of the transparent conductive layer is preferably 10,000 Ω / □ or less, and more preferably 2000 Ω / □ or less.
The single surface specific resistance refers to the surface specific resistance measured when only the transparent conductive layer is provided directly on the support substrate without providing the thin metal wire auxiliary electrode on the support substrate.

  The ratio of the conductive polymer and the hydroxyl group-containing non-conductive polymer in the transparent conductive layer is preferably 30 to 900 parts by mass of the hydroxyl group-containing non-conductive polymer when the conductive polymer is 100 parts by mass. From the viewpoints of preventing current leakage, enhancing the conductivity of the hydroxyl group-containing nonconductive polymer, and transparency, the hydroxyl group-containing nonconductive polymer is more preferably 100 parts by mass or more.

The dry film thickness of the transparent conductive layer is preferably 30 nm to 2000 nm. The dry film thickness of the transparent conductive layer is more preferably 100 nm or more from the viewpoint of conductivity, more preferably 200 nm or more from the viewpoint of surface smoothness of the electrode, and 1000 nm or less from the viewpoint of transparency. It is more preferable that
After applying the transparent conductive 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 at the temperature of the range which does not damage a support substrate and a transparent conductive layer. Moreover, by performing heat treatment, the crosslinking reaction of the hydroxyl group-containing nonconductive polymer can be promoted and completed. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved. In particular, in an organic EL element, effects such as reduction in driving voltage and improvement in life can be obtained. The drying step and the heat treatment step may be the same step or may be performed separately. In the case of separate processes, drying and heat treatment may be continuous, and there may be a time pause between the two processes.
There is no limitation on the conditions of the drying process and the heat treatment process. However, for example, drying can be performed at a temperature of 80 ° C. or more as a condition that moisture can be evaporated quickly, and the upper limit is a temperature that does not damage the transparent conductive layer. It is considered that it is possible to reach up to about 300 ° C. The time is preferably in the range of about 10 seconds to 10 minutes.
Further, the heat treatment is preferably performed at a temperature of 150 ° C. or higher and 300 ° C. or lower. If it is less than 150 ° C., the reaction promoting effect is small, and if it exceeds 300 ° C., the effect is small because thermal damage to the material increases. The heat treatment time is preferably 1 minute or longer. The upper limit of the treatment time is not particularly limited, but is preferably 24 hours or less from the viewpoint of productivity. However, when the heat treatment temperature exceeds 200 ° C., it is preferable to keep it within 30 minutes. The heat treatment may be performed on-line or off-line after applying and drying the transparent conductive layer. In the case of off-line, it is preferable to further perform under reduced pressure because it leads to accelerated drying of moisture.

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

(3.2) Hydroxyl group-containing nonconductive polymer The hydroxyl group-containing nonconductive polymer contains a repeating unit having a structure represented by the formula (1) in the molecule. That is, the hydroxyl group-containing non-conductive polymer is a polymer in which the structural unit represented by the formula (1) together with the structural unit containing the hydroxyl group coexists and is randomly bonded together.

In formula (1), “R ¹ ” represents a hydrogen atom or a methyl group.
“R ² ” and “R ³ ” represent an alkylene group.
“R ⁴ ” represents a hydrogen atom, a halogen atom or an alkyl group.
“X” represents a halogen atom.
“M” represents 0 or 1.
“N” represents 1 or 2.
“L” represents 1 or 2.

Preferably, in formula (1), the halogen atom of X is fluorine.
Preferably, in the formula (1), m is 0.
Preferably, in formula (1), n is 2 and l is 1.
Preferably, in formula (1), R ⁴ is fluorine.
When either of these conditions is satisfied, the effect of improving the energy conversion efficiency of the organic EL element is enhanced.

  Specific examples of the repeating unit having the structure represented by the formula (1) are as follows (1-1-1 to 1-15-2).

The method for synthesizing the hydroxyl group-containing non-conductive polymer is not particularly limited, but when producing the hydroxyl group-containing non-conductive polymer, a polymer containing a repeating unit having a structure represented by the formula (2), a formula A method obtained by a reaction with an acid anhydride having a structure represented by (3) can be preferably used.
That is, the hydroxyl group-containing non-conductive polymer is formed by esterification of a polymer in which the structure represented by the formula (2) is repeated as a minimum unit and the acid anhydride of the formula (3).

In formula (2) and formula (3), R ¹ , R ² , R ³ , R ⁴ , X, m, n, and l are the same as those defined in the description of formula (1).

As a method of obtaining a polymer containing a repeating unit having a structure represented by the formula (2) and an acid anhydride having a structure represented by the formula (3), a general alcohol compound and an acid anhydride can be used. The synthesis method of the ester compound by reaction with a product can be used.
The synthesis reaction is preferably carried out without a catalyst.
A catalyst may be used in the synthesis reaction. As the catalyst, since it is less likely to have an adverse effect such as dedoping of the conductive polymer when remaining in the transparent conductive layer, it is particularly preferable to use a catalyst having no basicity.
Although there is no limitation in the reaction solvent, the reaction may be carried out in an aqueous solution due to the solubility limitation of the polymer containing the repeating unit having the structure represented by the formula (2). In the case of the reaction in an aqueous solution, the acid anhydride having the structure represented by the formula (3) competes with the esterification reaction with the polymer containing a repeating unit having the structure represented by the formula (2). Although the hydrolysis reaction proceeds, it can be handled by using an excess amount of acid anhydride assuming a competitive reaction.
Carboxylic acid may be produced as a by-product due to the reaction, but the carboxylic acid is volatilized and removed in a heat treatment process such as a drying process or a baking process after applying or printing patterning the transparent conductive layer. There is no particular problem.

  Specific examples of the repeating unit having the structure represented by the formula (2) are as follows (from 2-A-1 to 2-C-2).

  Specific examples of the acid anhydride having a structure represented by the formula (3) are as follows (from 3-1 to 3-12).

The number average molecular weight of the hydroxyl group-containing nonconductive polymer of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably in the range of 4,000 to 500,000, and still more preferably. It is in the range of 5,000 to 100,000.
The number average molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the hydroxyl group-containing nonconductive polymer of the present invention are measured by generally known gel permeation chromatography (GPC). be able to.
The solvent to be used is not particularly limited as long as the hydroxyl group-containing non-conductive polymer dissolves, preferably THF (tetrahydrofuran), DMF (dimethylformamide), CH ₂ Cl ₂ , more preferably THF, DMF, DMF is preferred. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

(3.3) Conductive polymer The conductive polymer according to the present invention is a conductive polymer having a π-conjugated conductive polymer and a polyanion.
Such a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a poly anion described later. .

(3.3.1) π-conjugated conductive polymer The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophene, the same shall apply hereinafter), polypyrroles, poly Chain conductivity of indoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyls Polymers can be utilized. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

(3.3.2) π-conjugated system conductive polymer precursor monomer The precursor monomer used to form the π-conjugated system conductive polymer has a π-conjugated system in the molecule and acts as an appropriate oxidizing agent. Even when the polymer is polymerized by π, a π-conjugated system is formed in the main chain.
Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(3.3.3) Polyanion The polyanion used in the present invention is 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 are composed of a structural unit having an anionic group and a structural unit having no anionic group.
This poly anion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent.
The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.
The anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
It may be a polyanion further having F (fluorine atom) in the compound.
Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.
Among these, the compound having a sulfonic acid is formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more before irradiating the microwave. May be. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.
Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These poly anions have high compatibility with the hydroxy group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and an anionic group containing The method of manufacturing by superposition | polymerization of a polymerizable monomer is mentioned.
Examples of the method for producing an anionic group-containing polymerizable monomer by polymerization include a method for producing an anionic group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst.
Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.
When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion” is preferably 1: 1 to 1:20 by mass ratio. The range of 1: 2 to 1:10 is more preferable from the viewpoint of conductivity and dispersibility.
The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.
Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate half esters of alkanols such as lauryl sulfate; alkyl sulfonic acids of 1 to 20 carbons such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic (optionally) alkyl-substituted sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

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

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

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

(4) Application Examples The above transparent conductive film substrate 2 has both high conductivity and transparency, and various optoelectronics such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, and inorganic solar cells. It can be suitably used in the fields of devices, electromagnetic wave shields, touch panels and the like.
Among these, it can use especially preferably as a transparent electrode of the organic electroluminescent element (organic EL element 100) and organic thin-film solar cell element by which the smoothness of the transparent electrode surface is calculated | required severely.

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

<< Synthesis of hydroxyl group-containing non-conductive polymer >>
(1) Synthesis Example 1 (P-1 synthesis: within the present invention)
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 (5.8 g, 15 mmol, molecular weight: 116.05) and AIBN (0.8 g, 5 mmol, molecular weight: 164.11) were added, and the mixture was heated to reflux for 5 hours. Then, under reflux conditions, acid anhydride 1 (1.2 g, 4 mmol, molecular weight 309) dissolved in 30 ml of THF was added dropwise over 20 minutes, and then reflux was continued for 3 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK (methyl ethyl ketone) and stirred for 1 hour. After decantation of MEK, the precipitate 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, 5.7 g of a hydroxyl group-containing nonconductive polymer “P-1” having a number average molecular weight of 34,000 was obtained.

The molecular weight was measured by GPC (Waters 2695, manufactured by Waters).
<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) Synthesis Example 2 (P-2 synthesis: within the present invention)
In Synthesis Example 1, acid anhydride 1 was changed to acid anhydride 2 (1.0 g, 4 mmol, molecular weight 238).
Otherwise, the same operation as in Synthesis Example 1 was performed to obtain 5.3 g of a hydroxyl group-containing nonconductive polymer “P-2” having a number average molecular weight of 30000.

(3) Synthesis Example 3 (Synthesis of P-3: within the present invention)
In Synthesis Example 1, acid anhydride 1 was changed to acid anhydride 3 (1.2 g, 4 mmol, molecular weight 302).
Otherwise, the same operation as in Synthesis Example 1 was performed to obtain 5.5 g of a hydroxyl group-containing non-conductive polymer “P-3” having a number average molecular weight of 30000.

(4) Synthesis Example 4 (Synthesis of P-4: within the present invention)
In Synthesis Example 1, acid anhydride 1 was changed to acid anhydride 4 (0.7 g, 4 mmol, molecular weight 174).
Otherwise, the same operation as in Synthesis Example 1 was performed to obtain 5.0 g of a hydroxyl group-containing nonconductive polymer “P-4” having a number average molecular weight of 30000.

(5) Synthesis Example 5 (Synthesis of P-5: within the present invention)
In Synthesis Example 1, acid anhydride 1 was changed to acid anhydride 5 (0.8 g, 4 mmol, molecular weight 210).
Otherwise, the same operation as in Synthesis Example 1 was performed to obtain 5.0 g of a hydroxyl group-containing non-conductive polymer “P-5” having a number average molecular weight of 30000.

(6) Synthesis Example 6 (Synthesis of P-0: outside the present invention)
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 (5.8 g, 15 mmol, molecular weight: 116.05) and AIBN (0.8 g, 5 mmol, molecular weight: 164.11) were 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 (methyl ethyl ketone) 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, 5.2 g of a hydroxyl group-containing non-conductive polymer “P-0” which is a homopolymer of 2-hydroxyethyl acrylate having a number average molecular weight of 33700 was obtained.

<< Preparation of transparent conductive film substrate >>
(1) Formation of thin metal wire auxiliary electrode Using a thin film flexible non-alkali glass (manufactured by Nippon Electric Glass Co., Ltd.) having a thickness of 100 μm as a support substrate, silver nanoparticle ink 1 (TEC-PR-030; manufactured by InkTech) is used. Using this, printing was performed with a gravure plate engraved with a shape (pattern) having a 1 mm pitch, a width of 30 μm, and a depth of 12 μm.
The area for printing the pattern was 18 mm square.
As a printing machine, a gravure printing tester K303MULTICOATER manufactured by RK Print Coat Instruments Ltd was used.
The printed support substrate was baked at 250 ° C. for 2 minutes using an electric furnace to form a fine metal wire auxiliary electrode on the support substrate.
When the pattern of the metal thin wire auxiliary electrode was measured with a high brightness non-contact 3D surface shape roughness meter WYKO NT9100, the height of the pattern was 0.7 μm, and the average roughness Ra measured along the center line on the pattern thin line was It was 0.01 μm.

(2) Formation of transparent conductive layer A transparent conductive layer coating solution having the following composition was applied by patterning with an applicator so as to have a wet film thickness of 10 μm on the metal fine wire auxiliary electrode patterned support substrate obtained above.
The area of the pattern was 20 mm square at the position covering the thin metal wire auxiliary electrode.
The support substrate after pattern application is dried at 90 ° C. for 1 minute using a circulating thermostat, and then baked at 230 ° C. for 2 minutes using an electric furnace to form a transparent conductive layer. Obtained.
It was set as the sample of "Example 1-5, Comparative Examples 1-4" according to the presence or absence of the hydroxyl-containing nonelectroconductive polymer aqueous solution, its kind, the thickness of a transparent conductive layer, etc. (refer Table 1).

(Transparent conductive layer coating solution composition)
Conductive polymer dispersion (Clevios TH510; manufactured by HCStarck, solid content 1.7 wt%) 17.6 g
Hydroxyl group-containing non-conductive polymer aqueous solution (Table 1; adjusted to a solid content of 20 wt%) 3.5 g
Dimethyl sulfoxide 1.0g

<< Production of organic EL element >>
(1) Formation of anode In each of the produced transparent conductive film substrates, a square tile-shaped transparent pattern having a pattern side length of 20 mm was cut into a 30 mm square so as to be arranged in the center, and this was used as the first electrode (anode). Then, an organic EL element was produced by the following procedure.

(2) Formation of organic light-emitting layer The cut-out transparent pattern electrode (anode) is set in a commercially available vacuum deposition apparatus, and the constituent materials of each layer are optimal for device fabrication in each of the deposition crucibles in the vacuum deposition apparatus. The amount was filled. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

Next, an organic light emitting layer (hole transport layer, light emitting layer, electron transport layer) was formed by the following procedure.
First, after depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, the energization crucible containing the following α-NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer. Was established.
Ir-1 and Ir-14 and the following compound 1-7 were co-deposited at a deposition rate of 0.1 nm / sec so that the following Ir-1 would be 13% by mass and the following Ir-14 would be 3.7% by mass. Then, a green-red phosphorescent light emitting layer having an emission maximum wavelength of 622 nm and a thickness of 10 nm was formed.
Subsequently, E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and a blue phosphorescent light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm. Formed.
Thereafter, the following M-1 was deposited to a thickness of 5 nm to form a hole blocking layer, and CsF was co-deposited with M-1 so that the film thickness ratio was 10%. Formed.
The compounds used for forming each layer are shown below.

(3) Formation of cathode On the formed electron transport layer, an anode external lead-out terminal having a transparent conductive film substrate as an anode, and Al as a 15 mm × 15 mm cathode forming material under a vacuum of 5 × 10 ⁻⁴ Pa Then, a cathode having a thickness of 100 nm was formed by mask evaporation.

(4) Sealing Further, an adhesive was applied around the anode except for the ends so that external terminals for the cathode and anode could be formed, and Al ₂ O ₃ was vapor-deposited with a thickness of 300 nm using polyethylene terephthalate as a base material. After bonding the flexible sealing member, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

According to the type of transparent conductive film substrate (whether or not the hydroxyl group-containing non-conductive polymer aqueous solution is used and its type, the thickness of the transparent conductive layer, etc.), samples of “Examples 1 to 5 and Comparative Examples 1 to 4” were used ( (See Table 1).
In addition, in the item of “Hydroxyl group-containing non-conductive polymer” in Table 1, “PVA” in Comparative Sample 4 indicates polyvinyl alcohol (Nippon Synthetic Chemical Co., Ltd. Gohsenol GL03).

<Production of Hall-only device>
In the above description of “production of organic EL device”, the thickness of the hole transport layer is 100 nm, and the green-red phosphorescent light-emitting layer, the blue phosphorescent light-emitting layer, the hole blocking layer, and the electron transport layer are not formed. The cathode was formed directly on the hole transport layer.
In other respects, a hole-only device was produced by performing the same operation as described in “Production of organic EL device”.
According to the type of transparent conductive film substrate (whether or not the hydroxyl group-containing non-conductive polymer aqueous solution is used and its type, the thickness of the transparent conductive layer, etc.), samples of “Examples 1 to 5 and Comparative Examples 1 to 4” were used ( (See Table 1).

<Evaluation>
(1) Evaluation of transparent conductive film substrate (1.1) Surface specific resistance The surface specific resistance of each transparent conductive film substrate sample was measured by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments. The measurement results are shown in Table 1.

(1.2) Transmittance The transmittance of each transparent conductive film substrate sample was measured.
The transmittance was determined by measuring the total light transmittance using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku. The measurement results are shown in Table 1.

(1.3) Hole injection property For each hole-only device sample, the current value (mA) when a voltage of 3 V to 5 V was continuously applied was measured, and the value divided by the device area (cm ² ) It calculated | required as a current density (mA / cm < ² >). Thereafter, a plot with current density on the horizontal axis and voltage on the vertical axis was formed, and this was linearly approximated to calculate the slope (V · cm ² / mA). The calculation result was used as a hole injection resistance and used as an index of hole injection property. The evaluation results are shown in Table 1. The smaller the value of the hole injection resistance, the better the hole injection property.

(2) Evaluation of organic EL element (2.1) External extraction quantum efficiency In order to evaluate the energy conversion efficiency, the external extraction quantum efficiency (η) was determined using the equation (i).
External extraction quantum efficiency (%) = 100 × (number of photons emitted to the outside of the organic EL element) / (number of electrons sent to the organic EL element) (i)
The calculation results are shown in Table 1.
In addition, in formula (i), as "the number of photons emitted to the outside of the organic EL element", an emission spectrum measured by a spectral radiance meter CS-1000 (manufactured by Minolta) is 380 to 780 nm from the energy of photons of each wavelength. The number of photons was obtained, and the number of photons emitted from the light emitting surface was obtained based on the Lambertian assumption.
On the other hand, “the number of electrons passed through the organic EL element” was determined from the amount of current.

(2.2) Luminescence Life The organic EL element obtained was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced to half was determined.
Specifically, an organic EL device using ITO vapor-deposited glass instead of the transparent conductive film substrate of the present invention as an anode electrode was prepared by the same method as described above, and the ratio to this (= half of when using a transparent conductive film substrate) Time / half time when using ITO-deposited glass) was determined and evaluated according to the following criteria. The ratio is preferably 100% or more, and more preferably 150% or more. The evaluation results are shown in Table 1.
“◎”: 150% or more “◯”: less than 100 to 150% “△”: less than 80 to 100% “×”: less than 80%

(3) Summary As shown in Table 1, when comparing each transparent conductive film substrate sample and each hole-only element sample, the samples of Examples 1-5 have a lower surface specific resistance than the samples of Comparative Examples 1-4. The transmittance was high, the characteristics that should be inherently excellent, and the hole injection property was also excellent. And when each organic EL element sample is compared, the samples of Examples 1 to 5 have a good hole injection property, and as a result, the driving voltage decreases, and the external extraction quantum efficiency is higher than the samples of Comparative Examples 1 to 4. (The emission life was also improved).
From the above, in order to reduce the driving voltage of the organic EL element and improve the energy conversion efficiency, the transparent conductive layer of the transparent conductive film substrate contains a repeating unit having a repeating unit having the structure represented by the formula (1). It can be seen that it is useful to use a conductive polymer.

DESCRIPTION OF SYMBOLS 2 Transparent conductive film substrate 4 Support substrate 6 Metal fine wire auxiliary electrode 8 Transparent conductive layer 10 Organic light emitting layer 12 Hole transport layer 14 Light emitting layer 16 Hole block layer 18 Electron transport layer 20 Cathode 22 Anode 30 Flexible sealing member 40 Adhesive 100 Organic electroluminescence device

Claims (8)

In the transparent conductive substrate in which the metal thin wire auxiliary electrode and the transparent conductive layer are formed in this order on the support substrate,
The transparent conductive layer contains a conductive polymer and a hydroxyl group-containing nonconductive polymer,
The transparent conductive film substrate, wherein the hydroxyl group-containing nonconductive polymer contains a repeating unit having a structure represented by the formula (1) in the molecule.

In the formula (1), “R ¹ ” represents a hydrogen atom or a methyl group, “R ² ” and “R ³ ” represent an alkylene group, “R ⁴ ” represents a hydrogen atom, a halogen atom or an alkyl group, “X” represents a halogen atom, “m” represents 0 or 1, “n” represents 1 or 2, and “l” represents 1 or 2. The transparent conductive film substrate according to claim 1,
In the above formula (1), the halogen atom of X is fluorine, A transparent conductive film substrate. The transparent conductive film substrate according to claim 2,
In said Formula (1), m is 0, The transparent conductive film board | substrate characterized by the above-mentioned. The transparent conductive film substrate according to claim 3,
In the said Formula (1), n is 2, and l is 1, The transparent conductive film board | substrate characterized by the above-mentioned. The transparent conductive film substrate according to claim 4,
A transparent conductive film substrate, wherein R ⁴ is fluorine in the formula (1). The transparent conductive film substrate according to claim 1,
A polymer containing a repeating unit having a structure represented by the formula (2), wherein the repeating unit having a structure represented by the formula (1), an acid anhydride having a structure represented by the formula (3), A transparent conductive film substrate, which is a repeating unit obtained by the reaction of

In the transparent conductive film substrate according to any one of claims 1 to 6,
A transparent conductive film substrate, wherein the metal fine wire auxiliary electrode is formed by patterning metal fine particles and then firing. Including the transparent conductive film substrate according to any one of claims 1 to 7,
An organic electroluminescent element, wherein an organic light emitting layer and a cathode are formed in this order on the transparent conductive film substrate.

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