WO2015093342A1

WO2015093342A1 - Method for producing conductive film, conductive film, organic electronic element and touch panel

Info

Publication number: WO2015093342A1
Application number: PCT/JP2014/082514
Authority: WO
Inventors: 中村　和明; 松村　智之
Original assignee: コニカミノルタ株式会社
Priority date: 2013-12-16
Filing date: 2014-12-09
Publication date: 2015-06-25
Also published as: JPWO2015093342A1

Abstract

An objective of the present invention is to provide: a method for producing a conductive film that is suppressed in deformation of a base and has excellent transparency, electrical conductivity and surface roughness; and a conductive film. Another objective of the present invention is to provide an organic electronic element and a touch panel, each of which is provided with a conductive film that is produced by the above-described production method. A method for producing a conductive film according to the present invention is characterized by comprising at least a step (A) and a step (B), and is also characterized by a polyester resin which contains, as a constituent, a dicarboxylic acid that contains an aromatic dicarboxylic acid having at least a sulfonic acid group at a ratio within the range of 1-15% by mole. This method for producing a conductive film is further characterized in that irradiation of infrared light, which has a ratio of the spectral radiance of the wavelength of 5.8 μm relative to the spectral radiance of the wavelength of 3.0 μm of 5% or less, is carried out in the step (B).

Description

Manufacturing method of conductive film, conductive film, organic electronic device, and touch panel

The present invention relates to a method for producing a conductive film and a conductive film. In addition, the present invention relates to an organic electronic element, a touch panel, and the like that are provided with a conductive film manufactured by the manufacturing method. More specifically, the present invention relates to a method for producing a conductive film that suppresses substrate deformation and is excellent in transparency, conductivity, and surface roughness, a conductive film, an organic electronic device, and a touch panel.

In recent years, with increasing demand for thin TVs, various types of display technologies such as liquid crystal, plasma, organic electroluminescence (hereinafter also referred to as “organic EL”), field emission, and the like have been developed. In any of these displays having different display methods, the transparent electrode is an essential constituent technology. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.
Conventionally, a transparent electrode has been formed by forming a complex oxide of indium-tin (hereinafter also referred to as “ITO”) on a transparent resin film substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method. Filmed ITO transparent electrodes have been mainly used. However, since indium used in ITO is a rare metal and its price has been rising in recent years, a de-ITO transparent electrode is desired. In addition, with the increase in display screen size and productivity, a roll-to-roll production technology using a flexible substrate (flexible transparent substrate) such as a resin substrate is desired. Therefore, a de-ITO transparent electrode is desired.

In manufacturing a transparent electrode that replaces the ITO transparent electrode, a manufacturing method using a wet coating method has been studied in place of a dry coating method with low productivity such as a vacuum deposition method and a sputtering method that have been conventionally used. For example, as described in Patent Document 1, a dispersion containing a conductive material such as a conductive polymer compound represented by 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) is used as a transparent resin. A method has been developed in which a transparent electrode is produced by a wet coating method in which a conductive layer is formed by directly coating on a film substrate and drying by heating.
However, when a transparent electrode using this conductive polymer compound is applied to an organic electronic device (organic EL device, organic solar cell, etc.), residual moisture in the conductive layer due to insufficient drying, The moisture contained in the substrate PET (polyethylene terephthalate) may cause deterioration of the performance of the organic electronic device, for example, generation of dark spots at the time of light emission of the organic EL device, deterioration of device lifetime, and the like.

On the other hand, with the increase in area and productivity of organic electronic devices, a transparent electrode production technique using the roll-to-roll method described above is desired. In particular, when a transparent electrode using a conductive polymer compound on a resin film is applied to an organic electronic device, the substrate is deformed during heat drying (low heat resistance in the resin film itself) and the performance of the device is deteriorated. From the above problem, a new drying method for the applied conductive polymer compound is desired.
As a drying method other than heat drying, after applying an electrode material paste kneaded with an electrode material, a binder resin (for example, PVDF (polyvinylidene fluoride)), a conductive agent, and a solvent on a metal sheet such as aluminum or copper, A method of using a near-infrared heater in which the far-infrared region of 3.5 μm or more is cut is proposed for solvent drying (see, for example, Patent Document 2).
However, in the method described in Patent Document 1, the conductive layer formed on PET is dried under a heating condition of 140 ° C. for 1 minute at which the base material (transparent resin film base material) is not deformed. There was a problem that the performance of the transparent electrode deteriorated. This is because the solution used for the coating solution is insufficiently dried and moisture remains in the polymer conductive layer, causing deterioration of performance as a transparent electrode. In addition, due to the influence of moisture contained in these polymer conductive layers and PET, when organic EL elements are produced using these electrodes, significant performance degradation such as increase in electrode surface resistance (sheet resistance value) and current leakage is caused. There is also the problem of bringing about.

In addition, the method described in Patent Document 2 focuses on efficiently drying the solvent in the coating film, and does not consider prevention of deformation due to infrared absorption of the substrate itself, No mention is made of infrared drying when a transparent resin film substrate is used. Further, Patent Document 2 does not mention the relationship between the polyester resin contained in the electrode material paste and the solvent as an infrared irradiation effect.
From the above, in a transparent electrode using a conductive polymer compound on a resin film, a technique capable of removing water in the conductive layer without damaging the substrate has been strongly desired. .

Moreover, in a conventional conductive film, as a coating liquid for forming a conductive layer on a substrate, a water dispersible conductive polymer compound such as PEDOT / PSS and a polyester resin are used in order to achieve both conductivity and transmittance. Compositions containing have been developed.
As the binder resin, a hydrophilic binder resin has been studied from the viewpoint of compatibility with the water-dispersible conductive polymer compound. In recent years, since it is desired that the base material has high flexibility, a resin film such as PET has been used as the base material.

However, when a resin film is used as a base material, it is necessary to lower the drying temperature as compared with the case where a glass substrate is used as a base material from the viewpoint of avoiding deformation of the film. In addition, the hydroxy group-containing binder resin known to be compatible with PEDOT / PSS undergoes a dehydration reaction and crosslinks between polymer chains under acidic conditions, but crosslinks when dried at low temperatures. Defects occur. As a result, not only does the crosslinking reaction proceed during storage and water is generated, but also the transparency, conductivity and arithmetic average roughness (hereinafter referred to as “surface”) of the conductive film and the conductive film due to the water remaining in the film. There is a concern that the performance (emission uniformity, emission lifetime, etc.) of the device using the conductive film is significantly deteriorated.

JP 2009-178897 A Japanese Patent No. 4790092

The present invention has been made in view of the above-described problems and situations, and the problem to be solved is a method for producing a conductive film that suppresses deformation of the substrate and is excellent in transparency, conductivity, and surface roughness, and conductivity. Is to provide a film. Moreover, it is providing the organic electronic element and touch panel excellent in the light emission uniformity and lifetime by providing an organic electronic element and a touch panel with the electroconductive film produced with the said manufacturing method.

In order to solve the above-mentioned problems, the present inventor uses, as a constituent component, a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio within a predetermined range in the process of examining the cause of the above-described problem. If a polymer conductive layer is formed by using a polyester resin and irradiating infrared rays having a ratio of the spectral radiance of wavelength 5.8 μm to the spectral radiance of wavelength 3.0 μm being a predetermined value or less, The inventors have found that it is possible to obtain a conductive film that suppresses deformation and is excellent in transparency, conductivity, and surface roughness, and has reached the present invention.
That is, the said subject which concerns on this invention is solved by the following means.

1. A method for producing a conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate,
At least the following steps (A) and (B):
The polyester resin contains a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio within a range of 1 to 15 mol%, and further,
In the following step (B), the method for producing a conductive film is characterized by performing infrared irradiation in which the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm is 5% or less.
Step (A): A step of applying an aqueous dispersion containing the conductive polymer compound and the polyester resin on the transparent resin film substrate Step (B): The step of applying on the transparent resin film substrate Forming the polymer conductive layer by irradiating the aqueous dispersion with the infrared rays;

2. The method for producing a conductive film according to item 1, wherein at least a gas barrier layer is provided in advance on the transparent resin film substrate.

3. A conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate,
The polyester resin is produced through at least the following steps (A) and (B), and comprises a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio in the range of 1 to 15 mol%. Ingredients, and
In the step (B), a conductive film characterized by being irradiated with infrared rays having a ratio of the spectral radiance of a wavelength of 5.8 μm to the spectral radiance of a wavelength of 3.0 μm of 5% or less.
Step (A): A step of applying an aqueous dispersion containing the conductive polymer compound and the polyester resin on the transparent resin film substrate Step (B): The step of applying on the transparent resin film substrate Forming the polymer conductive layer by irradiating the aqueous dispersion with the infrared rays;

4. An organic electronic device comprising a conductive film manufactured by the method for manufacturing a conductive film according to

Item

1 or 2 or an electrode of the conductive film according to Item 3.

5. A touch panel comprising a conductive film manufactured by the method for manufacturing a conductive film according to

Item

1 or 2 or the conductive film according to Item 3 as an electrode.

By the above-mentioned means of the present invention, it is possible to provide a method for producing a conductive film and a conductive film that are excellent in transparency, conductivity, and surface roughness while suppressing deformation of the substrate. Moreover, the organic electronic element and touch panel which were excellent in the light emission uniformity and lifetime can be provided by providing an organic electronic element and a touch panel with the electroconductive film produced with the said manufacturing method.

The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

In order to solve the above problem, the present inventor speculated that in the conventional conductive film, it is necessary to reduce the interaction between the main skeleton of the binder resin and water.
A polymer emulsion is known as a binder resin having a small interaction with a solvent such as water. Among the polymer emulsions, polyester emulsions, acrylic emulsions, polyurethane emulsions, etc. are not only introduced with many ester groups and urethane groups, which are hydrophilic sites, in the polymer main chain and side chains, but also in solvents such as water. In order to enhance dispersibility, hydrophilic groups such as sulfonic acid, carboxylic acid, hydroxy group, and ammonium are present. Since the hydrophilic group in the polymer is hydrogen-bonded to a water-bondable solvent such as water or a polar solvent, the present inventor hardly releases water by heat drying at a low temperature for a short time. It was ascertained that the performance of the employed conductive film and the organic electronic device using the conductive film deteriorated. That is, in order to improve the drying property of the conductive film at a low temperature and in a short time, the present inventor directly imparts energy to a hydrogen-bondable solvent such as water or a polar solvent, and the hydrophilic group in the polymer. It has been found that it is indispensable to impart energy capable of breaking the hydrogen bond between the solvent and the solvent capable of hydrogen bonding.

However, conventionally, heat drying is performed in which the coating liquid is dried by heat conduction from the surface of the conductive film at a temperature at which the transparent resin film substrate does not deform. In this heat drying, it is difficult to rigorously remove the hydrogen-bondable solvent such as water and polar solvent that is hydrated and adsorbed from the conductive film, and as a result, the solvent remains in the conductive film, As a result, the problem that the performance of the electroconductive film and the organic electronic element using the said electroconductive film and a touch panel will deteriorate will arise.

As a result of further diligent studies to solve the above-described problems of the prior art, the present inventor constructed a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio within the range of 1 to 15 mol%. A polyester resin as a component was employed, and further, a polymer conductive layer was formed by irradiating infrared rays having a spectral radiance ratio of 5.8 μm with respect to a spectral radiance of wavelength 3.0 μm of 5% or less. As a result, it has been found that energy can be directly applied to a hydrogen bondable solvent (aqueous solvent) such as water or polar solvent, unlike heat drying in which the coating liquid is dried by heat conduction from the surface of the conductive film. As a result, it is possible to suitably remove the aqueous solvent present in the hydrophilic group portion of the conductive polymer, which could not be realized by conventional low-temperature heat drying in which a resin base material such as transparent plastic is not deformed. The present invention has been reached.

That is, according to the present invention, by having the above-described configuration, the hydration and adsorbing solvent capable of hydrogen bonding can be separated from the polymer.
Thereby, the conductive film manufactured by the manufacturing method of the present invention is compatible with both transparency and conductivity of the conductive film without deformation of the base material, and excellent in surface roughness, and further at high temperature, high Even after an environmental test in a humidity environment, it can have both high conductivity, transparency and good surface roughness. Moreover, the manufacturing method of the electroconductive film of this invention is excellent in the light emission uniformity and lifetime with which the electroconductive film excellent in stability and the said electroconductive film were equipped by suppressing generation | occurrence | production of the water derived from a polyester resin. An organic electronic device and a touch panel can be provided.

Sectional drawing which shows schematic structure of an electroconductive film The top view which shows an example of the pattern shape of the metal conductive layer of an electroconductive film The top view which shows another example of the pattern shape of the metal conductive layer of an electroconductive film The top view which shows another example of the pattern shape of the metal conductive layer of an electroconductive film The top view which shows another example of the pattern shape of the metal conductive layer of an electroconductive film Sectional drawing which shows schematic structure of wavelength control infrared heater Sectional drawing which shows the modification of the wavelength control infrared heater of FIG. Sectional drawing which shows schematic structure of organic EL element Schematic top view which shows a transparent resin film base material for demonstrating an example of the manufacturing method of an organic EL element Schematic plan view illustrating a process for forming a metal conductive layer in an example of a method for manufacturing an organic EL element Schematic plan view for explaining the process of forming a polymer conductive layer as an example of a method for producing an organic EL element Schematic plan view illustrating an organic functional layer forming step in an example of a method for manufacturing an organic EL element Schematic plan view illustrating a process of forming a counter electrode in an example of a method for manufacturing an organic EL element Schematic plan view for explaining a sealing process by a sealing member in an example of a method for manufacturing an organic EL element Graph showing infrared transmittance of quartz glass filter Graph showing spectral radiance with and without quartz glass filter Cross section of an example of a touch panel

The method for producing a conductive film of the present invention is a method for producing a conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate, wherein at least the above steps (A) and step (B), and the polyester resin contains at least a dicarboxylic acid having an aromatic dicarboxylic acid having a sulfonic acid group in a ratio within the range of 1 to 15 mol% as a constituent component. Furthermore, in the step (B), infrared irradiation is performed in which the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm is 5% or less.
This feature is a technical feature common to the inventions according to claims 1 to 5.

As an embodiment of the present invention, it is preferable that at least a gas barrier layer is provided on the transparent resin film substrate in advance from the viewpoint of manifesting the effects of the present invention. Thereby, the effect which prevents a water | moisture content and oxygen from diffusing inside a conductive film through a transparent resin film base material is acquired.

Furthermore, the conductive film of the present invention is a conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate, and at least the step (A). And the polyester resin, which is produced through the step (B), contains a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio in the range of 1 to 15 mol%. Further, the step (B) is characterized in that infrared radiation is performed such that the ratio of the spectral radiance of the wavelength 5.8 μm to the spectral radiance of the wavelength 3.0 μm is 5% or less. preferable. Thereby, while suppressing a base-material deformation | transformation, the electroconductive film excellent in transparency, electroconductivity, and surface roughness can be provided.

The conductive film produced by the production method of the present invention can be suitably used as an electrode for a touch panel and an organic electronic element. Thereby, the touch panel and organic electronic element which were excellent in the light emission uniformity and lifetime can be provided.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

(Method for producing conductive film)
The method for producing a conductive film of the present invention has at least the following steps (A) and (B), and the polyester resin contains 1 to 15 mol% of an aromatic dicarboxylic acid having at least a sulfonic acid group. In the following step (B), the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm is 5%. The following infrared irradiation is performed.

Step (A): A step of applying an aqueous dispersion containing the conductive polymer compound and the polyester resin on the transparent resin film substrate Step (B): The step of applying on the transparent resin film substrate Forming the polymer conductive layer by irradiating the aqueous dispersion with the infrared rays;

Below, the typical example of the manufacturing method of the electroconductive film of this embodiment is demonstrated.
The method for producing a conductive film of this embodiment is preferably a production method having an aspect mainly including the steps shown in the following steps 1 to 4. The constituent elements and methods used in the steps 1 to 4 will be described in detail later.

(Process 1: Polyester resin manufacturing process)
In the polyester resin production process, first, an aromatic dicarboxylic acid component having at least a sulfonic acid group, an alcohol component, and a catalyst (for example, potassium titanium oxalate) are prepared and put into a reactor to prepare a solution. The transesterification reaction is completed by raising the temperature of this solution while stirring and mixing in an atmospheric pressure and nitrogen atmosphere.
Next, after gradually reducing the pressure of this solution, the polycondensation reaction is advanced by maintaining this reduced pressure state to obtain a polyester resin. At this time, the molecular weight of the polyester resin is controlled by increasing the degree of vacuum as necessary.
The extent to which the dicarboxylic acid constituting the obtained polyester resin contains at least an aromatic dicarboxylic acid having a sulfonic acid group is determined based on the polyester resin, for example, ICP (Inductively Coupled Plasma) emission analyzer. Or by ion chromatography or by measuring the acid value or the like.

The obtained polyester resin, water and organic solvent (for example, isopropyl alcohol) can be dispersed in an aqueous solvent by placing them in a container and keeping them at a temperature in the range of 80 to 95 ° C. with stirring. Can be obtained.

(Step 2: Preparation of polymer conductive layer forming composition)
In the preparation process of this composition for forming a polymer conductive layer, a conductive polymer compound and a polyester resin are mixed, and after mixing a non-conductive polymer compound with this mixture, water is added to the polymer conductive layer. A forming composition is prepared.

(Process 3: Polymer conductive layer coating process)
The coating process of the polymer conductive layer is a step (step (A)) in which an aqueous dispersion containing a conductive polymer compound and a polyester resin is applied on the transparent resin film substrate.
In step (A), specifically, a polymer conductive layer is coated on the transparent resin film substrate having gas barrier properties using the above-described composition for forming a polymer conductive layer (see FIG. 6C).
In addition, the coating process of a polymer conductive layer may form the metal conductive layer which consists of a metal fine wire pattern on a transparent resin film base material, and may coat a polymer conductive layer on it (FIG. 6B). reference).

(Process 4: Drying process)
This drying process is a step (step (B)) in which the polymer conductive layer is formed by irradiating the aqueous dispersion applied on the transparent resin film substrate with infrared rays.
In step (B), specifically, drying is performed by irradiating with infrared rays having a ratio of the spectral radiance of wavelength 5.8 μm to the spectral radiance of wavelength 3.0 μm of 5% or less.
Thereby, a polymer conductive layer can be formed and a conductive film having a polymer conductive layer can be formed.

Next, each component and method used in the method for producing a conductive film of the present invention will be described in detail.

[Conductive film]
The conductive film has a polymer conductive layer containing at least a conductive polymer compound and a polyester resin. Such a conductive film is produced by applying a dispersion containing a conductive polymer compound and a polyester resin onto a transparent resin film substrate and drying it.
As shown in FIG. 1, the conductive film 1 includes a transparent resin film substrate 2, a metal conductive layer 4, and a polymer conductive layer 3, and can be used as a transparent electrode.

The metal conductive layer 4 is a fine line pattern of metal particles formed on the transparent resin film substrate 2. The thin line pattern in the metal conductive layer 4 may be formed in a stripe shape as shown in FIGS. 2A to 2C, or may be formed in a mesh shape (lattice, mesh shape) as shown in FIG. 2D.

The polymer conductive layer 3 is formed on the transparent resin film substrate 2 on which the metal conductive layer 4 is formed. The polymer conductive layer 3 is formed flush and covers the surface of the metal conductive layer 4 and the surface of the transparent resin film substrate 2 exposed from between the metal conductive layers 4.

The conductive film 1 may have a configuration in which the metal conductive layer 4 is omitted. However, as described above, the conductive film 1 includes the metal conductive layer 4 and is laminated by laminating the polymer conductive layer 3 on the metal conductive layer 4. It has resistance and uniform sheet resistance.

[Polyester resin]
The polymer conductive layer of the present invention contains at least a polyester resin.
The polyester resin contains a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a proportion within the range of 1 to 15 mol% (hereinafter also referred to as “ratio of aromatic dicarboxylic acid”). Further, it can be dispersed in an aqueous solvent.

Here, in the present embodiment, “dispersible in an aqueous solvent” means a state in which colloidal particles made of a polyester resin are dispersed without being aggregated in the aqueous solvent. The size (average particle diameter) of the colloidal particles is generally in the range of 0.001 to 1 μm (1 to 1000 nm). The size (average particle diameter) of the colloidal particles of the polymer dispersible in the aqueous solvent is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 300 nm, like the colloidal particles of the conductive polymer compound. More preferably, it is in the range of 5 to 100 nm.

When the particle size of the colloidal particles of the polyester resin dispersible in the aqueous solvent is 500 nm or less, the haze and smoothness (surface roughness) of the polymer conductive layer 3 produced by applying the dispersion to the transparent resin film substrate 2 are obtained. (Ra)) is improved.

Further, when the colloidal particle of the polyester resin dispersible in the aqueous solvent is 1 nm or more, the aggregation of the colloidal particles of the polyester resin can be suppressed, so that the dispersibility of the dispersion does not deteriorate. As a result, the polymer conductive layer 3 Haze and smoothness (surface roughness (Ra)) are improved. In order to improve the smoothness when the polymer conductive layer 3 is formed, the size of the colloidal particles is more preferably in the range of 3 to 300 nm, and still more preferably in the range of 5 to 100 nm. . When the average particle size of the particles is 5 nm or more, the particles are prevented from aggregating with each other, so that the dispersion stability does not deteriorate, and as a result, the concern that the coated surface becomes non-uniform can be avoided.

Further, when the thickness is 100 nm or less, not only the compatibility with the conductive polymer compound can be prevented from being deteriorated, but also the haze of the coating film can be improved, and the fear of causing the performance deterioration as an optical film can be avoided. The size of 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, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

Generally, a polyester resin dispersible in an aqueous solvent can be stably dispersed in an aqueous solvent. Therefore, an anionic substituent such as a sulfonic acid or a carboxylic acid, a nonionic substituent such as a hydroxy group, an ammonium salt in a polymer. Contains a dissociative group of a hydrophilic group such as a cationic substituent of the structure. These dissociable groups are introduced in order to maintain dispersion stability in an aqueous solvent.
However, since these dissociable groups are hydrophilic and disadvantageous for drying, it is necessary to minimize the introduction rate.

In this embodiment, if the ratio of the aromatic dicarboxylic acid is larger than 15 mol%, moisture in the coating film cannot be sufficiently removed in drying after the coating film is formed, and as a result, the water resistance of the resin coating film is reduced. Not only does it significantly reduce performance as a conductive film, but also increases the electrode surface resistance and dark spots when manufacturing organic electroluminescent devices (organic EL devices) using these conductive films. , Resulting in significant performance degradation such as current leakage.

Further, when the ratio of the aromatic dicarboxylic acid is less than 1 mol%, the hydrophilicity of the polyester is lowered, and as a result, the dispersion of the polyester resin in water is lowered, and the particle size of the colloidal particles of the polyester resin is increased. . When the particle size of the colloidal particles is large, the haze of the conductive film is increased as described above, so that the optical performance and the surface roughness are deteriorated. As a result, the performance of the organic EL element or touch panel provided with the conductive film Becomes a factor of deterioration. From the viewpoint of drying properties and dispersibility in water, the ratio of the aromatic dicarboxylic acid is more preferably in the range of 2 to 10 mol%, and still more preferably in the range of 3 to 5 mol%.

Examples of the aromatic dicarboxylic acid component having at least a sulfonic acid group according to the present invention include 5-sodium sulfoisophthalic acid (SIPA-Na), 5-sodium sulfoterephthalic acid (STPA-Na), and 5-potassium sulfoisophthalic acid (SIPA). -K), 5-potassium sulfoterephthalic acid (STPA-K), 5-lithium sulfoisophthalic acid (SIPA-Li), 5-lithium sulfoterephthalic acid (STPA-Li), 3,5-di (carbo-β- Hydroxyethoxy) benzene sulfonate sodium (SIPG-Na), 2,5-di (carbo-β-hydroxyethoxy) benzene sulfonate sodium (STPG-Na), 3,5-di (carbo-β-hydroxyethoxy) benzene Potassium sulfonate (SIPG-K), 3,5-di (carbo-) -Hydroxyethoxy) lithium benzenesulfonate (SIPGLi), dimethyl 5-sodium sulfoisophthalate (SIMM-Na), dimethyl 5-sodium sulfoterephthalate (STPM-Na), dimethyl 5-potassium sulfoisophthalate (SIMM-K) Dimethyl 5-lithium sulfoisophthalate (SIPM-Li), sodium 5-sulfonate dimethylisophthalate and the like.

In the aqueous dispersion of the polyester resin according to the present invention, the addition amount of the monomer of the aromatic dicarboxylic acid component having a sulfonic acid group as an acid component constituting the polyester resin should be suppressed as much as possible. Addition of various additives such as an emulsifier for emulsifying and dispersing the powder should be avoided.

It is preferable that at least 50 mol% or more of the acid component of the polyester resin is an aromatic dicarboxylic acid component among all the acid components. When the aromatic dicarboxylic acid component is 50 mol% or more, the concern that the water resistance of the resin film is lowered can be avoided. In addition, in a polyester resin having a large proportion of the aromatic dicarboxylic acid component, hardness, solvent resistance, workability and the like are improved in addition to water resistance.

Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 3-tert-butylisophthalic acid, diphenic acid, and the like. These aromatic dicarboxylic acid components may be used alone or in combination of two or more.
Particularly preferred aromatic dicarboxylic acid components are industrially produced in large quantities and inexpensive, so terephthalic acid (for example, dimethyl terephthalic acid) and isophthalic acid (for example, dimethyl isophthalic acid). .).

As a constituent component of the polyester resin according to the present invention, a saturated aliphatic dicarboxylic acid component (oxalic acid, oxalic acid, as long as the ratio of the aromatic dicarboxylic acid component described above is satisfied, and the glass transition temperature is within the above range. Succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, aicosane diacid, hydrogenated dimer acid, etc.), unsaturated aliphatic dicarboxylic acid components (fumaric acid, maleic acid, maleic anhydride, itacone) Acid, itaconic anhydride, citraconic acid, citraconic anhydride, dimer acid, etc.), alicyclic dicarboxylic acid components (1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2 , 5-norbornene dicarboxylic acid or their anhydride, tetrahydrophthalic acid or its anhydride, etc.) It is used. Also, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydro) Trifunctional or higher carboxylic acid components such as 1,2,3,4-butanetetracarboxylic acid can also be used as a component of the polyester resin.

The alcohol component for synthesizing the polyester resin according to the present invention is not particularly limited. For example, an aliphatic glycol component (ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol) 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1, 9-nonanediol, 2-ethyl-2-butylpropanediol, etc.), alicyclic glycol components (1,4-cyclohexanedimethanol, etc.), ethylene oxide adducts of bisphenols (bisphenol A) (diethylene glycol, triethylene glycol, Dipropylene Coal, 2,2-bis [4- (hydroxyethoxy) phenyl] propane), ethylene oxide adducts of bisphenols (bisphenol S) (bis [4- (hydroxyethoxy) phenyl] sulfone, etc.), ether bond-containing glycol components (Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.). Also, trifunctional or higher functional alcohol components such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol can be used.

As an alcohol component that is particularly suitably used, ethylene glycol is inexpensive because it is industrially mass-produced, and has various balances of performance such as improved solvent resistance and weather resistance of the resin coating. , Diethylene glycol, triethylene glycol, neopentyl glycol, 1,6-hexanediol.

The constituent components of the polyester resin according to the present invention may be copolymerized with a monocarboxylic acid component, a monoalcohol component, a hydroxycarboxylic acid component, etc., for example, lauric acid, myristic acid, palmitic acid, stearin Acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, stearyl alcohol, 2-phenoxyethanol, ε-caprolactone, lactic acid, β-hydroxybutyric acid or and ethylene oxide adducts of p-hydroxybenzoic acid. Further, a tri- or higher functional polyoxycarboxylic acid component may be copolymerized, and examples thereof include malic acid, glyceric acid, citric acid, and tartaric acid.

Subsequently, a method for producing a polyester resin will be described. The polyester resin that can be dispersed in the aqueous solvent in the present invention is prepared by first producing a polyester resin, and then using this polyester to make an aqueous solvent dispersion. As a method for producing a polyester resin, for example, it can be produced by polycondensing one or more of the above-described acid components and one or more of the alcohol components by a known method. All the monomer components or their low polymers are reacted in an inert atmosphere within a range of 180 to 260 ° C. and 2.5 to 10 hours to carry out an esterification reaction, followed by 130 Pa or less in the presence of a condensation polymerization catalyst. And a method of obtaining a polyester resin by proceeding a condensation polymerization reaction at a temperature in the range of 220 to 280 ° C. under reduced pressure until a desired molecular weight is reached.

The polycondensation catalyst for polyester is not particularly limited, and known compounds such as zinc acetate and antimony trioxide are used.
Examples of a method for imparting a desired acid value to the polyester resin include a method in which an acid component is further added after the above condensation polymerization reaction and a depolymerization reaction is performed in an inert atmosphere.
In addition, as a method for imparting a desired acid value to the polyester resin, a method in which an acid component of an anhydride is further added after the above-described polycondensation reaction and an addition reaction is performed with the hydroxy group of the polyester resin in an inert atmosphere is used. However, in such a method, the melt viscosity during production becomes very high, and the polyester resin may not be discharged, so care must be taken.

As the acid component used in the depolymerization reaction or addition reaction, the above-described trifunctional or higher carboxylic acid is preferable. By using a trifunctional or higher functional carboxylic acid, a desired acid value can be imparted while suppressing a decrease in the molecular weight of the polyester resin due to depolymerization. As the trifunctional or higher functional carboxylic acid, aromatic carboxylic acid components trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride are particularly preferable.

In addition, when the number average molecular weight of the polyester resin is 10,000 or more, it is possible to avoid the concern that the resin film does not become brittle and the adhesion to the base material and the durability are insufficient. For this reason, in order to further improve the adhesion and durability of the resin coating to the substrate, the number average molecular weight of the polyester resin is more preferably 10,000 or more. Moreover, the number average molecular weight of the polyester resin is preferably 100,000 or less, more preferably 20000 or less, from the viewpoint of ease of production.

Subsequently, a method for producing a polyester resin dispersed in an aqueous solvent from the polyester resin (hereinafter also referred to as “polyester resin aqueous dispersion”) will be described.
In the present invention, the polyester resin aqueous dispersion is a liquid material in which the above-described polyester resin is dispersed in an aqueous medium. Here, the aqueous medium is a medium composed of a liquid containing water, and may contain additives such as an organic solvent, an antiseptic, an antifoaming agent, and a basic compound.

In the present embodiment, the content of the polyester resin in the aqueous polyester resin dispersion is preferably in the range of 5 to 50% by mass, and more preferably in the range of 15 to 40% by mass. When the content of the polyester resin is within 50% by mass, aggregation of the dispersed polyester resin can be suppressed, and the dispersion stability of the polyester resin tends to be improved.
In addition, the content rate of the practical polyester resin in this embodiment is 5 mass% or more. In order to improve the dispersion stability of the polyester resin and practically exhibit the curing of the polyester, the polyester resin content in the aqueous polyester resin dispersion is more preferably 15 to 40% by mass.

In the present invention, the pH of the aqueous polyester resin dispersion is not particularly limited, but is preferably 5 or more and less than 8 at room temperature. When the pH is less than 8, there is no concern that the polyester resin aqueous dispersion aggregates due to mixing with the conductive polymer compound that exhibits acidity, and the concern that the uniform aqueous dispersion cannot be obtained can be avoided.
The water is not particularly limited and includes distilled water, ion exchange water, city water, industrial water, and the like, but it is preferable to use distilled water or ion exchange water.

As the method for producing the polyester resin aqueous dispersion in the present invention, the polyester resin is charged into an aqueous solvent and heated and stirred. The carboxy group at the terminal of the polyester resin is at least partially or entirely using a basic compound. Examples thereof include a method of dispersing in an aqueous medium by neutralization and a method of using a surfactant as a dispersant. In addition, the production method includes a step of dissolving a polyester resin in an organic solvent (dissolution step), and a step of dispersing a resin solution (solution) dissolved in the organic solvent in water (phase inversion emulsification). Step), and further, a method (“phase inversion emulsification”) of performing the three steps of removing the organic solvent (desolvation step) from the obtained contents (dispersion).
In the phase inversion emulsification, from the viewpoint of process suitability, a method of adding to an aqueous solvent and stirring with heating is preferably used.

[Infrared irradiation]
In the step of forming the polymer conductive layer by irradiating the aqueous dispersion applied on the transparent resin film substrate with the infrared rays, the present invention provides a wavelength 5 for a spectral radiance of 3.0 μm. Irradiation with an infrared ray having a spectral radiance ratio of 8 μm is 5% or less.
In general, infrared refers to light radiation that is longer than the wavelength of visible radiation.
In the present embodiment, the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm is preferably 3% or less, more preferably 1% or less, and even more preferably 0. .5% or less.

The aqueous solvent preferably used in the liquid composition for forming the polymer conductive layer of the present invention has a strong absorption wavelength due to OH stretching vibration in the vicinity of about 3.0 μm, and is preferably used for the transparent resin film substrate of the present invention. The obtained polyester resin film has almost no absorption wavelength in the infrared wavelength region near 3.0 μm, but preferably has a strong absorption wavelength in the infrared wavelength region of 5.8 μm or more.
By adopting such an aqueous solvent and a transparent resin film substrate and irradiating infrared rays according to the present invention, it is possible to further suppress damage to the transparent resin film substrate, and more efficiently polymer conductive. It is possible to dry the layer. That is, it becomes possible to more efficiently remove water and a solvent or additive having a hydroxy group from the polymer conductive layer. As a result, it is possible to obtain a polymer conductive layer having high conductivity, transparency and good surface roughness even after an environmental test under a high humidity environment. Furthermore, by using the transparent electrode manufactured by the manufacturing method of the present invention for an organic EL element or a touch panel, an effect of improving the light emission uniformity and life of the organic EL element and suppressing a decrease in resistance value over time of the touch panel is obtained. Can do.

Although there is no limitation in particular about the method of infrared irradiation in this invention, It is preferable to carry out with an infrared heater. As the infrared heater, for example, an infrared heater as described in Japanese Patent No. 4790092 can be preferably used.
Below, the infrared heater preferably used for this invention is demonstrated.

(Infrared heater)
FIG. 3 is a cross-sectional view showing a schematic configuration of the wavelength control infrared heater. FIG. 4 is a cross-sectional view showing a modification of the wavelength control infrared heater of FIG.
The external appearance of the infrared heater 20 has a cylindrical shape, and as shown in FIG. 3, the filament 22, the protective tube 24, and the

filters

26 and 28 are mainly arranged concentrically in this order. The

filters

26 and 28 have a function of absorbing infrared rays having a wavelength of 3.5 μm or more, and the materials of the

filters

26 and 28 include quartz glass and borosilicate crown glass, from the viewpoint of heat resistance and thermal shock resistance. Quartz glass is preferred.

The infrared heater 20 has a function of absorbing infrared rays having a wavelength of 3.5 μm or more. Specifically, the

filters

26 and 28 themselves absorb infrared rays having a wavelength of 3.5 μm or more, and are heated by the filament 22 to become a high temperature. Therefore, the

filters

26 and 28 themselves become infrared radiators and emit long-wave infrared rays.
However, in the infrared heater 20, a refrigerant (for example, cooling air) flows through the hollow portion 30 between the

filters

26, 28, and the cooling function reduces the surface temperature of the

filters

26, 28. , 28 can suppress secondary radiation.
As a result, infrared radiation having a wavelength of 3.5 μm or more is reduced, and far infrared radiation having a wavelength of 5.8 μm or more, which mainly has an absorption region in the transparent resin film substrate 2, can be significantly reduced. Then, the polymer conductive layer can be dried without deforming the transparent resin film substrate 2 by selectively irradiating the object to be dried with infrared rays having a wavelength of 3.0 μm which is an absorption region of the aqueous solvent. .

The thickness and the number of the

filters

26 and 28 can be appropriately selected and changed according to the necessary infrared spectrum.
As a cooling function, as above-mentioned, it can cool by making a filter into a hollow double or multiple lamination, and letting air flow through the hollow part in between.
As described above, the shape of the

filters

26 and 28 may cover the entire columnar filament 22 concentrically. As shown in FIG. 4, the reflection plate 32 covers the three directions of the filament 22 (and the protective tube 24). The

filters

26 and 28 may be arranged in parallel plates on the infrared radiation surface side.

In the case of a multiple structure in which another filter is arranged in addition to the

filters

26 and 28, it is preferable from the viewpoint of cooling efficiency that cooling air is allowed to flow in opposite directions between the hollow portions between the filters. Further, the cooling air on the discharge side may be discharged out of the system, or may be used as part of hot air used in the drying process.

The temperature of the filament 22 of the infrared heater 20 is preferably 800 ° C. or more, and preferably 3000 ° C. or less from the viewpoint of heat resistance of the filament 22 from the viewpoint of achieving both drying properties and prevention of deformation of the substrate. Depending on the filament temperature, the radiation energy in the wavelength region corresponding to the absorption of these aqueous solvents can be increased, and the filament temperature can be appropriately selected and changed depending on the desired coating and drying conditions. The filament temperature can be measured, for example, using a radiation thermometer.

The surface temperature of the outermost filter 28 disposed on the object to be dried is preferably 200 ° C. or less, and more preferably 150 ° C. or less, from the viewpoint of suppressing secondary radiation due to its own infrared absorption. This can be adjusted by flowing air between the filters stacked in layers.

Further, in the drying step, the drying zone is composed (covered) with a material having high infrared reflectivity, whereby infrared rays that are not absorbed by the object to be dried can be used with high efficiency.
As shown in FIGS. 3 and 4, the wavelength control infrared heater 20 is connected to a cooling mechanism 40 for circulating (circulating) the refrigerant in the hollow portion 30, and the cooling mechanism 40 and the filament 22 are connected to a control device. 45 is connected. In such a control circuit, the control device 45 controls the amount of refrigerant flowing into the hollow portion 30 by the cooling mechanism 40, the heat generation temperature of the filament 22, and the like.

Moreover, if it is a grade which does not produce the deformation | transformation of the transparent resin film base material of this invention, you may have a preheating process separately before the infrared irradiation process of this invention.
The preheating treatment method is not particularly limited, and examples thereof include an electric furnace such as a hot plate, a box furnace, and a conveyor furnace, a near infrared heater, a middle infrared heater, a far infrared heater, hot air, hot air, and microwaves. These may be used alone or in combination.

In the infrared ray according to the present invention, the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm can be obtained, for example, by the following method.

2005 Survey and Research Report on Methods for Easily Evaluating Radiant Energy of Far Infrared Heaters (Japan Machinery Federation, Far Infrared Association), FTIR TALK LETTER vol. 13 (Shimadzu Corporation), etc., referring to the radiation output from the infrared heater and the radiation output from the standard blackbody furnace at the same temperature as the filament temperature of the infrared heater. The spectral emissivity of the infrared heater is determined by measuring with a Fourier transform infrared spectrophotometer.

Next, the spectral radiation spectrum of the infrared heater can be obtained by multiplying the black body radiation spectrum calculated according to Planck's radiation law by the spectral emissivity of the infrared heater. A spectral radiance value at a wavelength of 3.0 μm and a spectral radiance value at a wavelength of 5.8 μm are read from the obtained spectral radiance spectrum, and a spectral radiance of a wavelength of 5.8 μm with respect to a spectral radiance of a wavelength of 3.0 μm is read. The ratio can be calculated as a percentage.

[Conductive polymer compound]
In the present invention, “conductive” refers to a state in which electricity flows, and a sheet resistance value measured by a method in accordance with JIS K 7194 “Resistivity Test Method by 4-Probe Method of Conductive Plastic” is 1 ×. It means lower than 10 ⁸ Ω / □.

In the present invention, the conductive polymer compound that is a polymer having conductivity is preferably a conductive polymer compound having a cationic π-conjugated conductive polymer and a polyanion. Such a conductive polymer compound can be easily obtained by chemical oxidative polymerization of a precursor monomer that forms a cationic π-conjugated conductive polymer, which will be described later, in the presence of an appropriate oxidizing agent and an oxidation catalyst, and a polyanion, which will be described later. Can be manufactured.

(Cationic π-conjugated conductive polymer)
In the present invention, the cationic π-conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, and polyacetylenes. A chain conductive polymer compound of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes or polythiazyl compounds can be used. As the cationic π-conjugated conductive polymer, polythiophenes or polyanilines are preferable, and polyethylenedioxythiophene is more preferable from the viewpoints of conductivity, transparency, stability, and the like.

(Cationic π-conjugated conductive polymer precursor monomer)
In the present invention, a precursor monomer used for forming a cationic π-conjugated conductive polymer has a π-conjugated system in the molecule, and the main monomer even when polymerized by the action of an appropriate oxidizing agent. A π-conjugated system is formed in the chain. Examples of such precursor monomers 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-hexyl Offene, 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-diethoxythio , 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyl Oxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3- Methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3- Isobutylaniline, 2-anilinesulfonic acid, 3-anili Sulfonic acid and the like.

(Polyanion)
In the present invention, the polyanion used in the conductive polymer compound is substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted. It is desirable that the polyester or any of these copolymers be composed of a structural unit having an anionic group and a structural unit having no anionic group.

This polyanion is a solubilized polymer that solubilizes a cationic π-conjugated conductive polymer compound in a solvent. The anion group of the polyanion functions as a dopant for the cationic π-conjugated conductive polymer compound, and improves the conductivity and heat resistance of the cationic π-conjugated conductive polymer compound. In addition, the polyanion is used in an excess amount with respect to the cationic π-conjugated conductive polymer compound, so that the dispersibility of the conductive polymer compound particles composed of the cationic π-conjugated conductive polymer compound and the polyanion and It also has a function of improving film formability.

The anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the cationic π-conjugated conductive polymer compound. As such an anion group, a mono-substituted sulfate group, a mono-substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable from the viewpoint of ease of production and stability. Further, the anionic group is more preferably a sulfo group, a monosubstituted sulfate group or a carboxy group from the viewpoint of the doping effect of the functional group on the cationic π-conjugated conductive polymer compound.

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

Further, the polyanion may further have F (fluorine atom) in the compound. Specific examples of such a polyanion include Nafion (manufactured by Dupont) containing a perfluorosulfonic acid group, and Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group.

Among these, when a compound having a sulfonic acid group is used as the polyanion, after the polymer conductive layer 3 is formed by coating and drying by an infrared heater, the mixture is further heated and dried within a range of 100 to 120 ° C. for 5 minutes or more. You may irradiate a microwave, near-infrared light, etc., after processing. In some cases, heat drying may be omitted, and only irradiation with microwaves, near infrared light, or the like may be performed.

Furthermore, among the compounds having sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid or polyacrylic acid butylsulfonic acid is preferable.
The polymerization degree of the polyanion is preferably in the range of 10 to 100,000 monomer units from the viewpoint of dispersibility of the conductive polymer compound, and from 50 to 10,000 from the viewpoint of solvent solubility and conductivity. The range of is more preferable.

Examples of the polyanion production method 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 polymerizable monomer. And the like.

Examples of the method for producing a polyanion by polymerization of an anion group-containing polymerizable monomer include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidation polymerization or radical polymerization in the presence of an oxidizing agent or a polymerization catalyst. .
Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, and this is kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent or a polymerization catalyst is dissolved in the solvent is added to the solvent in advance. React. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent.

In this production method, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer.
Further, when the obtained polymer is a salt of a polyanion, it is preferably transformed into a polyanion acid. Examples of methods for transforming polyanion salts into polyanionic acids include ion exchange methods using ion exchange resins, dialysis methods, ultrafiltration methods, etc. Among these, ultrafiltration is used because it is easy to work with. The method is preferred.

The ratio of the cationic π-conjugated conductive polymer contained in the conductive polymer compound to the polyanion constituting the conductive polymer compound, that is, the value of the mass ratio of the polyanion to the cationic π-conjugated conductive polymer is From the viewpoint of conductivity and dispersibility, the range of 0.5 to 25 is preferable.

If the value of the mass ratio of the polyanion to the cationic π-conjugated conductive polymer is 25 or less, in addition to improving the conductivity, moisture retained by the hydrophilic polyanion or the conductive polymer compound The amount is reduced, and the storage stability of the conductive film and the organic EL element using the conductive film is improved.

In addition, if the mass ratio is 0.5 or more, the resistance of the conductive polymer compound decreases as the dopant increases, and the effect of the polyanion acting as a protective colloid becomes stronger. Stability is improved and particle size is suppressed.
As described above, from the viewpoint of preservability of the electroconductivity, particle stability, conductive film, and organic electroluminescence device using the conductive film, the mass ratio of the polyanion to the cationic π-conjugated conductive polymer is 0. Within the range of 5 to 25 is preferable.

Examples of a method for adjusting the mass ratio of the polyanion to the cationic π-conjugated conductive polymer to a desired value include a method of adjusting the amount of polyanion used when the conductive polymer compound is synthesized.
In this method, if the amount of polyanion is a value of a mass ratio of 1.0 or less with respect to the cationic π-conjugated conductive polymer, the conductive polymer compound particles tend to be large. Other polymer compounds can be used in combination during compound synthesis. The polymer compound that can be used in combination is not particularly limited as long as the conductive polymer compound particles are stabilized and the transmittance and conductivity are not deteriorated, but polyacrylic such as 2-hydroxyethyl acrylate or an aqueous solvent may be used. An aqueous dispersion polymer such as a dispersible polymer is preferred.
In addition, water in commercially available PEDOT / PSS is removed by drying, azeotropic removal with toluene or pulverized by a known method such as freeze-drying, and then washed with water to remove PSS, while removing PSS by ultrafiltration. A method of replacing with water can be used.

As an oxidizing agent used for obtaining a conductive polymer compound according to the present invention by chemically oxidatively polymerizing a precursor monomer that forms a cationic π-conjugated conductive polymer in the presence of a polyanion, For example, J. et al. Am. Soc. 85, 454 (1963), and any oxidizing agent suitable for oxidative polymerization of pyrrole.
Such oxidants include, for practical reasons, inexpensive and easy-to-handle oxidants such as iron (III) salts (eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and inorganic acids containing organic residues). Iron (III) salt), hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate), ammonium, alkali perborate, potassium permanganate or copper salts (eg boron tetrafluoride) It is preferable to use (acid copper). In addition, air or oxygen in the presence of catalytic amounts of metal ions (for example, iron ions, cobalt ions, nickel ions, molybdenum ions, vanadium ions) can be used as an oxidizing agent. Among these, the use of persulfate, iron (III) salts of inorganic acids including organic acids, or iron (III) salts of inorganic acids including organic residues has great application advantages.

Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of sulfuric acid half esters of alkanols within the range of 1 to 20 carbon atoms (eg lauryl sulfate), 1 to 20 carbon atoms. Alkyl sulfonic acids within the range (eg methane, dodecane sulfonic acid), carboxylic acids with an aliphatic carbon number in the range of 1-20 (eg 2-ethylhexyl carboxylic acid), aliphatic perfluorocarboxylic acids (eg trifluoroacetic acid, Fluorooctanoic acid), aliphatic dicarboxylic acids (eg oxalic acid), especially aromatic, optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms (eg benzenecene sulfonic acid, p-toluenesulfonic acid, dodecylbenzene) Fe (III) salt of sulfonic acid).

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

The conductive polymer compound may contain an organic compound 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, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable.

Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone, and the like. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. 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.

[Aqueous dispersion containing conductive polymer compound and polyester resin]
The aqueous dispersion containing the conductive polymer compound and the polyester resin according to the present invention is a liquid in which the conductive polymer compound and the polyester resin dispersible in the aqueous solvent are dispersed in the aqueous solvent.

The dispersion according to the present invention is preferably transparent, and is not particularly limited as long as it is a medium for forming a film. In addition, there is no particular limitation as long as there is no problem in the device performance when the bleed-out to the surface of the transparent conductive film 1 and the organic electronic device are laminated, but the dispersion may be a surfactant (emulsifier) or It is preferable not to contain a plasticizer or the like that controls the film formation temperature.

The pH of the dispersion according to the present invention at room temperature is not particularly problematic as long as desired conductivity is obtained, but is preferably in the range of 0.1 to 7.0, more preferably in the range of 0.3 to 5.0. Is within. When the pH of the dispersion is 0.1 or more, more preferably 0.3 or more, the polymer can be suitably prevented from being decomposed during drying. Further, if the pH of the dispersion is 7.0 or less, more preferably 5.0 or less, the sheet resistance value of the conductive film is deteriorated due to a decrease in the function of the dopant by preventing neutralization of PEDOT / PSS. It can prevent suitably.

The pH at room temperature of the dispersion of the polyester resin dispersible in the aqueous solvent used for the production of the conductive film 1 of the present invention is the compatibility with the conductive polymer compound solution to be separately compatible, the polyester dispersible in the aqueous solvent From the viewpoint of the conductivity of the mixed liquid (dispersion) of the resin and the conductive polymer compound, it is preferably in the range of 0.1 to 11.0, more preferably in the range of 3.0 to 9.0. More preferably, it is within the range of 4.0 to 7.0.

In order to control the surface tension of the dispersion according to the present invention, an organic solvent may be added to the dispersion.
The organic solvent is not particularly limited as long as a desired surface tension can be obtained, but a monovalent, divalent or polyvalent alcohol solvent is preferable. The boiling point of the organic solvent is preferably 200 ° C. or lower, more preferably 150 ° C. or lower. If the boiling point of the organic solvent is 200 ° C. or lower, more preferably 150 ° C. or lower, the residual solvent in the film can be suitably reduced in short-time drying.

The size (average particle size) of the conductive polymer compound and the polyester resin after the dispersion treatment contained in the dispersion according to the present invention is preferably in the range of 1 to 100 nm, more preferably 3 to 80 nm. Within the range, more preferably within the range of 5 to 50 nm.

If the size of the conductive polymer compound and polyester resin particles in the dispersion is 100 nm or less, haze and smoothness of the polymer conductive layer 3 produced by applying the dispersion to the transparent resin film substrate 2. (Surface roughness (Ra)) is improved, and further the performance of the organic EL element is improved. If the size of the particles in the dispersion is 1 nm or more, the occurrence of aggregation between the particles is suppressed and the dispersibility of the dispersion is improved. As a result, the haze and smoothness of the polymer conductive layer 3 are improved. To do.
In order to improve the smoothness during film formation, the size of the particles in the dispersion is more preferably 3 to 80 nm, and further preferably 5 to 50 nm.
Moreover, even if the average particle size is controlled, if the film forming temperature of the polyester resin that can be dispersed in the aqueous solvent used is too high, the film shape remains without being formed within the drying temperature, and the average roughness of the film surface remains. Therefore, it is desirable to control the film formation temperature.

(Preparation of dispersion containing conductive polymer compound and polyester resin)
Preparation of a dispersion having an average particle size within a desired range is performed by mixing a conductive polymer compound and a polyester resin, and then adding the mixture to an aqueous solvent, and using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, or the like. It can be carried out by using a dispersion technique, a reverse osmosis membrane, an ultrafiltration membrane, a particle classification using a microfiltration membrane, or the like. Dispersion techniques using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, etc. all tend to increase particles at high temperatures. Therefore, the temperature during the dispersion operation is preferably −10 to 50 ° C. It is within the range, and more preferably within the range of 0 to 30 ° C.

In the case of a dispersion operation with a large shearing force that cuts the polymer, the temperature of the dispersion liquid tends to be high, and there is a concern that the conjugated system of the conductive polymer compound is broken by heat and causes performance deterioration. As a result, when the temperature exceeds 50 ° C., the particle diameter tends to be small, but there is a concern that the sheet resistance value of the polymer conductive layer 3 generated by the dispersion liquid increases. Further, when an organic solvent is contained in an aqueous solvent, even when the temperature is 0 ° C. or lower (for example, −10 ° C. or higher and 0 ° C. or lower), the dispersion operation can be suitably performed as long as the solvent does not solidify. It is. Further, since the dispersion is water-rich, the viscosity increases at 0 ° C. or lower, and a load is applied to the stirring. Further, if the temperature is 30 degrees or more, the solvent evaporates, and the dispersion concentration tends to fluctuate. As a result, there is a concern that the performance of the conductive film 1 is affected. Classification is not particularly limited as long as a membrane to be used is selected as necessary.

The polyester resin particles and the conductive polymer compound particles dispersible in the aqueous solvent in the dispersion according to the present invention are in a state in which the respective particles are dispersed independently, and the particle sizes are the respective particle sizes. Or particles having different compositions may be agglomerated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.

The amount (solid content) of the polyester resin dispersible in the aqueous solvent according to the present invention is preferably in the range of 50 to 5000% by mass, more preferably 100 to 5000%, based on the solid content of the conductive polymer compound. It is within the range of 3500% by mass, and more preferably within the range of 200 to 2000% by mass.
Here, the reason why the amount of the polyester resin dispersible in the aqueous solvent is preferably in the range of 50 to 5000% by mass with respect to the conductive polymer compound is that the transmittance is 50% by mass or more. (The conductive polymer compound absorbs light in the visible light region, so in order to improve the transmittance, the conductive polymer compound should be reduced as much as possible within a range that does not decrease the conductivity.) 5000 This is because if the content is less than or equal to mass%, suitable conductivity can be obtained without the ratio of the conductive polymer compound becoming too small.
As described above, in order to obtain the effect of improving the transmittance and prevent the decrease in conductivity, the amount of the polyester resin dispersible in the aqueous solvent is within the range of 100 to 3500 mass% with respect to the conductive polymer compound. More preferably, it is more preferably in the range of 200 to 2000 mass% with respect to the conductive polymer compound.

The particle size measurement method of the dispersion according to the present invention is not particularly limited, but is preferably a dynamic light scattering method, a laser diffraction method or an image imaging method, and more preferably a dynamic light scattering method. Since the particle diameter of the polyester resin particles and the conductive polymer compound particles that can be dispersed in an aqueous solvent becomes unstable due to dilution, a concentrated particle size measuring machine that can be measured as it is without diluting the solvent is preferable. . Examples of such a thick particle size analyzer include a thick particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), a zeta sizer nano series (manufactured by Malvern) and the like.

Fine particles may be added to the dispersion according to the present invention. Such fine particles are preferably used by replacing a polyester resin dispersible in an aqueous solvent constituting the polymer conductive layer from the viewpoint of reducing the drying load and suppressing the thickness of the polymer conductive layer. The amount of the fine particles used is preferably in the range of 25 to 75% by mass with respect to the polyester resin dispersible in the aqueous solvent, more preferably 30 to 60% by mass with respect to the conductive polymer compound. Is within the range.
Here, the reason that the amount of the polymer dispersible in the aqueous solvent is preferably in the range of 25 to 75% by mass with respect to the conductive polymer is that the drying load can be reduced if the amount is 25% by mass or more. This is because the film physical properties of the polymer conductive layer are improved if it is sufficient and 75% by mass or less. As described above, in order to obtain a drying load reduction effect and prevent a decrease in film physical properties of the polymer conductive layer, the amount of fine particles used is 25 to 75% by mass in terms of solid content with respect to the polyester resin dispersible in an aqueous solvent. More preferably within the range.

The dispersion liquid may contain a polymer dispersible in an aqueous solvent in addition to the conductive polymer compound and the polyester resin. Examples of dissociable groups used in polymers dispersible in aqueous solvents include anionic groups (sulfonic acid and its salts, carboxylic acid and its salts, phosphoric acid and its salts, etc.), cationic groups (ammonium salts, etc.), etc. Is mentioned. The dissociable group is not particularly limited, but an anionic group is preferable from the viewpoint of compatibility with the conductive polymer solution. The amount of the dissociable group is not particularly limited as long as the polymer dispersible in the aqueous solvent is dispersible in the aqueous solvent, and is preferably as small as possible because the drying load is reduced appropriately in the process.
In addition, the counter species (cation, anion) used for the anionic group and the cationic group are not particularly limited, but the performance of the organic EL device including the conductive film 1 and the conductive film 1 is laminated. From the viewpoint, it is preferably hydrophobic and in a small amount.

The main skeletons of polymers dispersible in aqueous solvents are polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polyethylene-polyacrylic acid, polyethylene-polymethacrylic acid, polybutadiene, polybutadiene-polystyrene, polyolefin Copolymer, polyamide (nylon), polyvinylidene chloride, polyester, polyester-urethane, polyester-acrylate, polyacrylate, polyacrylate copolymer, polymethacrylate, polymethacrylate copolymer, polyacrylate-polyester, polyacrylate-polystyrene , Polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane Polyacrylates, polyamides, polyacrylic - silica, polyacrylic - polystyrene - silica, silicone, silicone - polyurethane, silicone - polyacrylate, polyvinylidene fluoride - polyacrylates, fluoroolefin - polyvinyl ether. Of these, the main skeleton having no absorption at 2.5 to 3.0 μm can be converted into a polymer having an absorption at 2.5 to 3.0 μm by means of copolymerization, block or grafting. Of these, polyurethane-polycarbonate, polyamide, polyester-urethane, and polyacryl-polystyrene-silica are preferred.

Commercially available products include Superflex 130 (polyurethane-polyether, manufactured by Daiichi Kogyo Seiyaku), Superflex 210, Superflex 620 (polyurethane-polyester, manufactured by Daiichi Kogyo Seiyaku), Superflex 126, Superflex 150, Superflex 170, Superflex 300 (polyurethane-polyester-polyether, manufactured by Daiichi Kogyo Seiyaku), Superflex 420, Superflex 460, Superflex 470, Superflex 650 (Polyurethane-polycarbonate, manufactured by Daiichi Kogyo Seiyaku) Pesresin WAC-14, WAC-17XC (urethane-modified polyester, manufactured by Takamatsu Yushi Co., Ltd.) Mobile 8020, Mobile 8030 (acrylic modified colloidal silica, It can be used styrene-modified colloidal silica, manufactured by Nippon Synthetic Chemical Industry Co.) - manufactured by the Gosei Kagaku Co.), Mowinyl 8055A (acrylic. In addition, the polymer dispersible in the aqueous solvent may contain one kind of those described above, or may contain a plurality of kinds.

(Polar solvent)
The aqueous dispersion for forming the polymer conductive layer contains a polar solvent, so that the composition can be stably maintained without impairing the dispersion stability of the polymer that can be dispersed in the aqueous solvent, and stable by the ink jet method. Discharged.
As the polar solvent, those having a dielectric constant of 25 or more, preferably 30 or more, more preferably 40 or more can be used. Examples of such polar solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, glycerin, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and the like. be able to. Propylene glycol, ethylene glycol, and dimethyl sulfoxide are particularly preferable from the viewpoints of dry removal by an infrared heater, stability of the composition, dischargeability in ink jet printing, and conductivity of the polymer conductive layer.
The addition amount of the polar solvent can be determined from the viewpoint of the stability of the composition, and is preferably in the range of 5 to 40% with respect to the total mass of the composition. If it is 5% or more, the stabilizing effect of the composition is improved, and if it is 40% or less, the surface tension of the composition is not too high and the wettability to the substrate is improved.
The dielectric constant of the solvent can be measured, for example, using a liquid dielectric constant meter Model-871 (manufactured by Nippon Luft).

(Transparent resin base material)
The transparent resin film substrate 2 in the present embodiment is a plate-like body that can carry the polymer conductive layer 3 and the metal conductive layer 4 (hereinafter collectively referred to as “

conductive layers

3 and 4”), and is conductive. In order to obtain the conductive film 1, the total light transmittance in the visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (Plastics—Testing method of total light transmittance of transparent material) is 80% or more. Are preferably used.

The transparent resin film substrate 2 is preferably made of a material that is excellent in flexibility, has a sufficiently low dielectric loss coefficient, and has a microwave absorption smaller than that of the

conductive layers

3 and 4.
Moreover, as a transparent resin film base material 2, although a resin substrate, a resin film, etc. are mentioned suitably, it is preferable to use a transparent resin film base material from a viewpoint of performance, such as lightness and a softness | flexibility, and productivity. preferable. In the present invention, the transparent resin film substrate means a total light transmittance in a visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (a test method for the total light transmittance of a plastic-transparent material). It means 50% or more.

The transparent resin film substrate 2 that can be preferably used is not particularly limited, and the material, shape, structure, thickness, and the like can be appropriately selected from known materials. Examples of the transparent resin film substrate include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, and cyclic olefins. Polyolefin resin films such as polyvinyl resins, 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, Examples include polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. Kill.

Any resin film having a total light transmittance of 80% or more is preferably used as a film substrate used as the transparent resin film substrate 2 of the present invention. As such a film substrate, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film is preferable. A biaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.

The transparent resin film substrate 2 used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to ensure wettability and adhesion of the coating liquid (dispersion).
For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

In addition, an inorganic coating, an organic coating, or a hybrid coating of both may be formed on the front or back surface of the transparent resin film substrate. The transparent resin film substrate on which such a coating is formed has a water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 of 1 ×. The gas barrier film is preferably 10 ⁻³ g / (m ² · 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / High gas barrier property with m ² · 24h · atm or less, water vapor transmission rate (25 ± 0.5 ° C, relative humidity (90 ± 2)% RH) 1x10 ^-3 g / (m ² · 24h) or less A film is preferred.

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

《Gas barrier layer》
An organic electronic device (see below) such as an organic EL device easily deteriorates in performance when a small amount of moisture or oxygen is present inside the device. In order to prevent moisture and oxygen from diffusing inside the device through the transparent resin film substrate, it is effective to form a gas barrier layer having a high shielding ability against moisture and oxygen on the transparent resin film substrate. It is.

There is no particular limitation on the composition and structure of the gas barrier layer and the formation method thereof, and a film made of an inorganic compound such as silica can be formed by vacuum deposition or CVD. Alternatively, the gas barrier layer can be formed by applying and drying a coating solution containing a polysilazane compound and then oxidizing (modifying) it by ultraviolet irradiation in a nitrogen atmosphere containing oxygen and water vapor.

Any appropriate method can be selected as a method for applying the polysilazane compound. For example, as a coating method, flow coating method, cast film forming method, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, curtain coating method, spray coating method In addition to various printing methods such as a doctor coating method, various coating 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.
When it is preferable to form the gas barrier layer in a pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, or an ink jet printing method.

The polysilazane used in the present embodiment is a polymer having a silicon-nitrogen bond, such as SiO _{2 made of} Si—N, Si—H, N—H, etc., Si ₃ N ₄ and both intermediate solid solutions SiOxNy, etc. It is a ceramic precursor inorganic polymer.
When using a resin substrate, as described in JP-A-8-112879, it is preferable that the resin substrate is ceramicized at a relatively low temperature to be modified to silica, and the one represented by the following general formula (1) is preferable. Can be used.

In the general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
In perhydropolysilazane, all of R ¹ , R ² , and R ³ are hydrogen atoms, and in organopolysilazane, any of R ¹ , R ² , and R ³ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, An alkylsilyl group, an alkylamino group or an alkoxy group; Perhydropolysilazane, in which all of R ¹ , R ² , and R ³ are hydrogen atoms, is particularly preferred because of the denseness of the resulting gas barrier film.

The gas barrier layer may be a single layer or may have a laminated structure of two or more layers. When it has a laminated structure, it may be a laminated structure of an inorganic compound, or may be formed as a hybrid film of an inorganic compound and an organic compound. A stress relaxation layer may be sandwiched between the gas barrier layers.
Whether it is a single layer or a laminated layer, the thickness of one gas barrier layer is preferably in the range of 30 to 1000 nm, more preferably in the range of 30 to 500 nm, and particularly preferably in the range of 90 to 500 nm. When the thickness is 30 nm or more, the uniformity of the layer thickness is improved, and excellent gas barrier performance is obtained. When the thickness is 1000 nm or less, cracks due to bending are rarely abruptly entered, and an increase in internal stress during film formation can be suppressed, and generation of defects can be prevented.

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

Before the gas barrier layer is formed, the surface of the transparent resin film substrate can be pretreated with a silane coupling agent or the like in order to improve the adhesion with the transparent resin film substrate.

(Metal conductive layer)
As shown in FIG. 1, a conductive film 1 according to an embodiment of the present invention is a conductive layer (polymer conductive layer 3 in FIG. 1) containing a conductive polymer compound and a polymer dispersible in an aqueous solvent. In addition, it has a conductive layer (metal conductive layer 4 in FIG. 1) containing a metal material formed in a pattern on the transparent resin film substrate 2.

The metal material is not particularly limited as long as it has conductivity, and may be an alloy in addition to a metal such as gold, silver, copper, iron, nickel, or chromium. In particular, from the viewpoint of ease of pattern formation as described later, the shape of the metal material is preferably metal fine particles or metal nanowires, and the metal material is preferably silver from the viewpoint of conductivity.

In order to constitute the conductive film 1, the metal conductive layer 4 according to the present invention is formed on the transparent resin film substrate 2 so as to exhibit a pattern shape having an opening. An opening is a part which does not have a metal material on the transparent resin film base material 2, and is a translucent window part. Although there is no restriction | limiting in particular in a pattern shape, For example, it is preferable that they are stripe shape, mesh shape, or random mesh shape.
The ratio of the openings to the entire surface of the conductive film 1, that is, the opening ratio is preferably 80% or more from the viewpoint of transparency.

The aperture ratio is the ratio of the entire portion of the surface of the transparent resin film substrate 2 excluding the light-impermeable conductive portion (metal conductive layer 4). For example, when the light-impermeable conductive portion is striped or meshed, the aperture ratio of the striped pattern having a line width of 100 μm and a line interval of 1 mm is about 90%.

The line width of the pattern is preferably within the range of 10 to 200 μm from the viewpoint of transparency and conductivity.
If the line width of the pattern is 10 μm or more, desired conductivity is obtained, and if the line width of the pattern is 200 μm or less, desired transparency is obtained.
The pattern height is preferably in the range of 0.1 to 10 μm. If the pattern height is 0.1 μm or more, desired conductivity can be obtained, and if the height of the thin line is 10 μm or less, current leakage and functional layer thickness distribution in the formation of an organic electronic device. Defects are prevented.

There is no restriction | limiting in particular as a method of forming the stripe-shaped or mesh-shaped metal conductive layer 4, A conventionally well-known method can be utilized. For example, it can be formed by forming a metal layer on the entire surface of the transparent resin film substrate 2 and subjecting the metal layer to a known photolithography method.
Specifically, a metal layer is formed on the entire surface of the transparent resin film substrate 2 using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, or the like, or a metal foil After being laminated on the transparent resin film substrate 2 with an adhesive, the metal conductive layer 4 processed into a desired stripe shape or mesh shape can be obtained by etching using a known photolithography method.
The metal species is not particularly limited as long as it can be energized, and copper, iron, cobalt, gold, silver, and the like can be used. From the viewpoint of conductivity, silver or copper is preferable, and silver is more preferable. It is.

As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, a method of applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, or a plating treatment, or a silver salt A method using photographic technology can be listed.
A technique using silver salt photographic technology can be implemented with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and examples. Further, a method for performing a plating process by gravure printing of the catalyst ink can be implemented with reference to, for example, Japanese Patent Application Laid-Open No. 2007-281290.

Further, as a random network structure, for example, as described in JP-T-2005-530005, a random network structure of conductive fine particles is spontaneously formed by coating and drying a liquid containing metal fine particles. Techniques for forming can be used.

As another technique, for example, as described in JP-T-2009-505358, a coating solution (dispersion) containing metal nanowires is applied and dried to form a random network structure of metal nanowires. Techniques to form are available.
The metal nanowire refers to a fibrous structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.

As the metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, and more preferably in the range of 3 to 500 μm.
If the length of the metal nanowire is 500 μm or less, one wire spreads well and is arranged without overlapping with other wires, and as a result, the thickness of the metal conductive layer 4 is suppressed, and a thin film is achieved. And the transmittance is improved.
Moreover, if the length of metal nanowire is 3 micrometers or more, the contact of metal nanowire will increase and desired sheet resistance value and transmittance | permeability will be obtained, suppressing the addition amount of metal nanowire.
In addition, the relative standard deviation of the length is preferably 40% or less. This is because if the relative standard deviation of the length is 40% or less, the sheet resistance value of the metal conductive layer 4 is prevented from being reduced in uniformity and film thickness unevenness.

Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint.
Therefore, the average minor axis of the metal nanowire is preferably in the range of 10 to 300 nm, and more preferably in the range of 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. This is because if the relative standard deviation of the minor axis is 20% or less, the occurrence of unevenness in the thickness of the metal conductive layer 4 can be suppressed, and the occurrence of uneven brightness in the organic EL element can be suppressed.

The basis weight of the metal nanowire is preferably in the range of 0.02 to 0.5 g / m ² . If the basis weight of the metal nanowire is 0.02 g / m ² or more, a desired sheet resistance value is obtained, and if the basis weight is 0.5 g / m ² or less, a desired sheet resistance value and transmittance are obtained. It is done. The basis weight of the metal nanowires is more preferably 0.03 to 0.2 g / m ² from the viewpoint of sheet resistance and transmittance.

Examples of the metal used for the metal nanowire include copper, iron, cobalt, gold, silver and the like, and silver is preferable from the viewpoint of conductivity. In addition, although a single metal may be used, in order to achieve both conductivity and stability (sulfuration resistance, oxidation resistance and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.
There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known methods, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.
For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745, a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871.
In particular, the method for producing silver nanowires disclosed in the above-mentioned literature can easily produce silver nanowires in an aqueous solution, and the electrical conductivity of silver is the highest among metals, so it is preferably applied to the present invention. can do.

Further, the surface specific resistance of the thin wire portion (metal conductive layer 4) formed from a metal material is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less from the viewpoint of increasing the area.
The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

Further, it is preferable that the thin wire portion (metal conductive layer 4) formed from a metal material is subjected to heat treatment within a range that does not damage the transparent resin film substrate 2. As a result, fusion between the metal fine particles and the metal nanowires proceeds, and the fine wire portion formed from the metal material becomes highly conductive.

(Application of aqueous dispersion, heating, drying)
The method for producing the conductive film of the present invention includes at least
Step (A): Step of applying an aqueous dispersion containing a conductive polymer compound and a polyester resin on a transparent resin film substrate Step (B): For the aqueous dispersion applied on the transparent resin film substrate And forming a polymer conductive layer by performing infrared irradiation.
Specifically, in the method for producing a conductive film of the present invention, an aqueous dispersion containing the above-described conductive polymer compound and a polyester resin is applied onto the transparent resin film substrate 2 and heated and dried. Formed by. When the conductive film 1 has a fine line pattern formed from a metal material as the metal conductive layer 4, the above-described coating solution is applied onto the transparent resin film substrate 2 on which the fine line pattern formed from the metal material is formed. Then, the polymer conductive layer 3 is formed by heating and drying using an infrared heater. Here, the polymer conductive layer 3 only needs to be electrically connected to the metal fine line pattern which is the metal conductive layer 4, and may completely cover the patterned metal fine line pattern. A part thereof may be covered or may be in contact with the fine metal wire pattern.

Application of an aqueous dispersion (coating liquid) containing a conductive polymer compound and a polyester resin is not limited to printing methods such as gravure printing, flexographic printing, and screen printing, but also roll coating, bar coating, Use any of the coating methods such as dip coating, spin coating, casting, die coating, blade coating, bar coating, gravure coating, curtain coating, spray coating, doctor coating, and inkjet. Can do.

In addition, as a method for producing a conductive film 1 in which a part of the metal conductive layer 4 is coated or in contact with a polymer conductive layer 3 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent, The above-mentioned transparent resin film is formed by forming the metal conductive layer 4 on the film by the method described above, and further forming the polymer conductive layer 3 containing the conductive polymer compound and the polyester resin by the method described later and laminating them. The method of transferring to the base material 2 is mentioned.

In addition, as a method for producing the conductive film 1, the non-conductive portion (opening portion) of the fine metal wire pattern contains a conductive polymer compound and a polymer dispersible in an aqueous solvent by a known method such as an inkjet method. Examples thereof include a method for forming the polymer conductive layer 3.
The polymer conductive layer 3 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent contains a conductive polymer compound having a polyanion mass ratio of 0.5 to 25 to the cationic π-conjugated polymer. Is preferred. Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength can be obtained.

By forming the polymer conductive layer 3 and the metal conductive layer 4 of the present invention having such a structure, high conductivity that cannot be obtained when a metal or metal oxide fine wire pattern or polymer conductive layer is used alone. Can be obtained uniformly in the plane of the conductive film 1.

The dry layer thickness of the polymer conductive layer 3 is preferably in the range of 30 to 2000 nm from the viewpoint of surface smoothness and transparency, and more preferably 100 nm or more from the viewpoint of conductivity. From the viewpoint of surface smoothness of 1, the thickness is more preferably 200 nm or more. In addition, the thickness of the polymer conductive layer after drying is more preferably 1000 nm or less from the viewpoint of transparency.

[Formation of polymer conductive layer]
The polymer conductive layer 3 is formed by applying an aqueous dispersion (coating liquid) containing a conductive polymer compound and a polyester resin, and then applying infrared irradiation.
Here, in addition to the drying process by infrared irradiation, other drying processes can be performed. Although there is no restriction | limiting in particular as conditions of the drying process used together with infrared irradiation, The heat drying process in the temperature of the range which does not damage the transparent resin film base material 2 and the

conductive layers

3 and 4 can be used together, for example, 80 Heat drying treatment can be performed within a range of ˜120 ° C. for 10 seconds to 10 minutes. This heat drying treatment may be performed before or after the drying treatment by infrared irradiation.

The coating liquid described above contains, as additives, plasticizers, stabilizers (antioxidants, antioxidants, etc.), surfactants, dissolution accelerators, polymerization inhibitors, colorants (dyes, pigments, etc.) and the like. May be. Furthermore, from the viewpoint of improving workability such as coating properties, the coating liquid described above is a solvent (for example, water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons). Or other organic solvents).

In the present invention, Ry and Ra representing the smoothness of the surface of the polymer conductive layer 3 which is a conductive layer are Ry = the maximum height of the roughness curve (the difference in height between the top and bottom of the surface) and Ra = It means the arithmetic mean roughness of the roughness curve, and is a value according to the surface roughness specified in JIS B601 (1994). From the viewpoint of improving conductivity, the conductive film 1 according to the present invention has a surface smoothness of the polymer conductive layer 3 that is a conductive layer of Ry ≦ 50 nm, and the surface of the polymer conductive layer 3 that is a conductive layer. It is preferable that the smoothness of Ra ≦ 10 nm. In the present invention, a commercially available atomic force microscope (AFM) can be used for the measurement of Ry and Ra. For example, the measurement can be performed by the following method.

Using an AFM SPI3800N probe station and SPA400 multifunctional unit as the AFM, set the sample cut to a size of about 1 cm square on a horizontal sample stage on the piezo scanner, and place the cantilever on the sample surface. When the region where the atomic force works is reached, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Hitachi High-Tech Science Co., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 1 Hz.

In the present invention, the value of Ry is more preferably 50 nm or less, and further preferably 40 nm or less, from the viewpoint of improving conductivity. Similarly, the value of Ra is more preferably 10 nm or less, and further preferably 5 nm or less, from the viewpoint of improving conductivity.

In the present invention, the conductive film 1 preferably has a total light transmittance of 60% or more, more preferably 70% or more, and further preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.
In addition, the electrical resistance value of the polymer conductive layer 3 which is a conductive layer in the conductive film 1 of the present invention is preferably 1000Ω / □ or less as a sheet resistance value from the viewpoint of performance improvement, and is 100Ω / □ or less. More preferably. Furthermore, in order to apply the conductive film 1 to a current-driven optoelectronic device, the sheet resistance value may be 50Ω / □ or less from the viewpoint of performance improvement when applied to a current-driven optoelectronic device. Preferably, it is 10Ω / □ or less. That is, when the sheet resistance value is 10 ³ Ω / □ or less, the conductive film 1 can preferably function as an electrode in various optoelectronic devices.

The sheet resistance value described above can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method using conductive plastic 4-probe method) or the like, and using a commercially available surface resistivity meter. It can be easily measured.
There is no restriction | limiting in particular in the thickness of the electroconductive film 1 which concerns on this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and flexibility are so thin that thickness is thin. It is more preferable because of improved properties.

<Organic EL device>
An organic EL device according to an embodiment of the present invention is characterized by including a conductive film 1 as an electrode, and includes an organic layer including an organic light emitting layer and a conductive film 1. The organic EL device according to the embodiment of the present invention preferably includes the conductive film 1 as an anode, and the organic light-emitting layer and the cathode are arbitrarily selected from materials, configurations, and the like generally used for organic EL devices. Things can be used.

As an element structure of the organic EL element, anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / electron transport layer / cathode, anode / hole injection layer / hole transport layer / organic light emitting layer / Various configurations such as electron transport layer / cathode, anode / hole injection layer / organic light emitting layer / electron transport layer / electron injection layer / cathode, anode / hole injection layer / organic light emitting layer / electron injection layer / cathode, etc. Things can be mentioned.

In the present invention, the light emitting material or doping material that can be used in the organic light emitting layer includes anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, 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, pyran, quinaclide , Rubrene, distyrylbenzene derivatives, di still arylene derivatives, various fluorescent dyes, rare earth metal complex, but such phosphorescent materials include, but are not limited thereto. Further, it is preferable to contain 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. An organic light emitting layer is manufactured by well-known methods, such as vapor deposition, application | coating, transcription | transfer, using the above-mentioned material. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm and more preferably 0.5 to 200 nm from the viewpoint of light emission efficiency.

The organic EL element of the present invention can be used for a self-luminous display, a liquid crystal backlight, illumination, and the like. Since the organic EL device of the present invention can uniformly emit light without unevenness, it is preferably used for illumination.

The conductive film 1 of the present invention has both high conductivity and transparency, and various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, and electromagnetic waves. It can be suitably used in fields such as shields and touch panels. Among these, it can use especially preferably as a transparent electrode of the organic EL element and organic thin-film solar cell element by which the smoothness of the surface of an electroconductive film is calculated | required severely.

<< Configuration of Organic EL Element and Manufacturing Method Thereof >>
As shown in FIG. 5, the organic EL element 50 includes a conductive film 51 (transparent electrode) including a transparent resin film substrate 52, a metal conductive layer 54, and a polymer conductive layer 55.
An extraction electrode 53 is formed on the side edge of the transparent resin film substrate 52 of the conductive film 51.
The extraction electrode 53 is in contact with the metal conductive layer 54 and the polymer conductive layer 55, and is electrically connected to these members. An organic functional layer 56 is formed on the polymer conductive layer 55 of the conductive film 51. The organic functional layer 56 includes a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like. A counter electrode 57 is formed on the organic functional layer 56. The counter electrode 57 is an electrode facing the conductive film 51 and has a polarity opposite to that of the conductive film 51.

The organic EL element 50 is sealed by a sealing member 58 with a part of the extraction electrode 53 exposed, and the sealing member 58 covers and protects the conductive film 51 and the organic functional layer 56.

6A to 6F are schematic plan views for explaining a method of manufacturing an organic EL element.
Next, a method for manufacturing the organic EL element 50 will be described with reference to FIGS. 6A to 6F.
First, a fine line pattern of metal particles is formed on a transparent resin film substrate 52 (FIG. 6A) to form a metal conductive layer 54 (FIG. 6B).
Thereafter, a certain composition containing an aqueous dispersion containing a conductive polymer compound and a polyester resin is prepared, and the composition is ink-jet printed on the metal conductive layer 54 and dried with infrared rays of the present invention. Then, the polymer conductive layer 55 is formed, and the metal conductive layer 54 is covered with the polymer conductive layer 55 (FIG. 6C).

Thereafter, an organic functional layer 56 including a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like is formed on the polymer conductive layer 55 (conductive film 51) (FIG. 6D).
Thereafter, the counter electrode 57 is formed so as to cover the extraction electrode 53 and the organic functional layer 56 (FIG. 6E), and these are sealed by the sealing member 58 so as to completely cover the conductive film 51 and the organic functional layer 56. The member is sealed (FIG. 6F).
The organic EL element 50 is manufactured through the above steps.

The conductive film according to the embodiment of the present invention has both high conductivity and transparency, and various optoelectronics such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, electronic paper, an organic solar cell, and an inorganic solar cell. 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 an electroconductive film of the organic EL element and organic thin-film solar cell element by which the smoothness of the surface of an electroconductive film is calculated | required severely.

Moreover, since the organic electronic element (for example, organic EL element) which concerns on this invention can be made to light-emit uniformly, it is preferable to use it for an illumination use, a self-light-emitting display, a backlight for liquid crystals, It can be used for lighting or the like.
In addition, since the touch panel according to the present invention is flexible and has low resistance, it can be used for curved surface and large area applications, such as ATMs of financial institutions such as banks, vending machines and ticket vending machines. It can be used in a wide variety of fields, mainly for digital information devices such as mobile phones, personal digital assistants (PDAs), digital audio players, portable game machines, copiers, fax machines, car navigation systems, etc. .

Note that embodiments to which the present invention can be applied are not limited to the above-described embodiments, and can be appropriately changed without departing from the spirit of the present invention.

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

<Manufacture of polyester resin, etc.>
A method for producing a binder resin such as a polyester resin described in Table 1 and Table 2 used in this example will be described.

(Polyester resin P-1 dispersible in aqueous solvent)
138.6 parts of dimethyl terephthalic acid, 26.0 parts of dimethylisophthalic acid, 46.9 parts of sodium dimethylisophthalic acid, 99.3 parts of ethylene glycol, 21.2 parts of diethylene glycol, 23.1,6-hexanediol. 6 parts and 0.1 part of a catalyst (potassium titanium oxalate) were prepared.

These solutions were put into a reactor to prepare a solution. This solution was heated to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere, and then the reaction temperature was gradually raised to 260 ° C. over 4 hours to complete the transesterification reaction. Next, this solution was gradually depressurized at a temperature of 260 ° C., and the polycondensation reaction was advanced by maintaining for 2 hours under the conditions of 260 ° C. and 0.67 hPa (0.5 mmHg) to obtain a polyester resin. . When the obtained polyester resin was analyzed with an ICP emission spectrometer, the polyester resin had a ratio of 15 mol% of aromatic dicarboxylic acid having at least a sulfonic acid group (the ratio is shown in Tables 1 and 2 as “ It was confirmed that the dicarboxylic acid contained in “the ratio” is used as a constituent component.

100 parts of this polyester resin, 260 parts of water and 40 parts of isopropyl alcohol are put in a container and kept at a temperature in the range of 80 to 95 ° C. for 2 hours with stirring, so that the polyester resin concentration is 25%. A polyester resin P-1 dispersible in an aqueous solvent was obtained.

(Polyester resin P-2 dispersible in aqueous solvent)
A polyester resin that can be dispersed in the aqueous solvent, except that it is changed to 146.7 parts of dimethylterephthalic acid, 27.5 parts of dimethylisophthalic acid, and 31.2 parts of sodium dimethylisophthalic acid 5-sulfonate, which are charged as acid components. A polyester resin P-2 dispersible in an aqueous solvent was obtained in the same manner as P-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin contains a dicarboxylic acid containing at least 10 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-3 dispersible in aqueous solvent)
A polyester resin that can be dispersed in the aqueous solvent, except for changing to 153.2 parts of dimethylterephthalic acid, 28.7 parts of dimethylisophthalic acid, and 18.7 parts of sodium dimethylisophthalic acid 5-sulfonate charged as acid components. A polyester resin P-3 dispersible in an aqueous solvent was obtained in the same manner as P-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin had a dicarboxylic acid containing at least a 6 mol% aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-4 dispersible in aqueous solvent)
A polyester resin that can be dispersed in the aqueous solvent, except that it is changed to 154.9 parts of dimethyl terephthalic acid, 29.0 parts of dimethyl isophthalic acid, and 15.6 parts of sodium dimethylisophthalic acid 5-sulfonate which are charged as acid components. A polyester resin P-4 dispersible in an aqueous solvent was obtained in the same manner as P-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin had a dicarboxylic acid containing at least 5 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-5 dispersible in aqueous solvent)
A polyester resin that can be dispersed in the aqueous solvent, except for changing to 158.1 parts of dimethyl terephthalic acid, 29.6 parts of dimethyl isophthalic acid, and 9.4 parts of sodium dimethylisophthalic acid 5-sulfonate charged as acid components A polyester resin P-5 dispersible in an aqueous solvent was obtained in the same manner as P-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin had a dicarboxylic acid containing at least 3 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-6 dispersible in aqueous solvent)
A polyester resin that can be dispersed in the aqueous solvent, except that 159.7 parts of dimethylterephthalic acid, 30.0 parts of dimethylisophthalic acid, and 6.2 parts of sodium dimethylisophthalic acid are added as acid components. A polyester resin P-6 dispersible in an aqueous solvent was obtained in the same manner as P-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin contains a dicarboxylic acid containing at least 2 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-7 dispersible in aqueous solvent)
The polyester resin P dispersible in the aqueous solvent, except for changing to 161.4 parts of dimethyl terephthalic acid, 30.3 parts of dimethyl isophthalic acid, and 3.1 parts of sodium dimethylisophthalic acid, which are charged as acid components. A polyester resin P-7 dispersible in an aqueous solvent was obtained in the same manner as in Example-1. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin contains a dicarboxylic acid containing at least 1 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-8 dispersible in aqueous solvent): Comparison Changed to 130.4 parts of dimethyl terephthalic acid, 24.5 parts of dimethyl isophthalic acid, and 62.5 parts of sodium dimethylisophthalic acid 5-sulfonate, which are charged as acid components Except that, polyester resin P-8 dispersible in aqueous solvent was obtained in the same manner as polyester resin P-1 dispersible in aqueous solvent. When the obtained polyester resin was analyzed by an ICP emission analyzer, it was confirmed that the polyester resin had a dicarboxylic acid containing at least 20 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. .

(Polyester resin P-9 dispersible in aqueous solvent): Comparison To 161.7 parts of dimethyl terephthalic acid, 30.3 parts of dimethyl isophthalic acid and 2.5 parts of sodium dimethyl isophthalic acid 5-sulfonate charged as acid components, respectively A polyester resin P-9 dispersible in an aqueous solvent was obtained in the same manner as the polyester resin P-1 dispersible in an aqueous solvent, except for the change. When the polyester resin was analyzed by an ICP emission analyzer of the obtained polyester resin, the polyester resin has a dicarboxylic acid containing at least 0.8 mol% of an aromatic dicarboxylic acid having a sulfonic acid group as a constituent component. It was confirmed.

(Polyester resin P-10 dispersible in aqueous solvent): Comparison Sodium 2,2-bishydroxymethylpropionate was synthesized with reference to republished patent WO2007 / 40208.
163.0 parts dimethylterephthalic acid, 30.6 parts dimethylisophthalic acid, 99.3 parts ethylene glycol, 21.2 parts diethylene glycol, 23.6 parts sodium 2,2-bishydroxymethylpropionate, catalyst (potassium titanium oxalate) ) 0.1 part was prepared.

These raw materials were put into a reactor to prepare a solution. This solution was heated to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere, and then the reaction temperature was gradually raised to 260 ° C. over 4 hours to complete the transesterification reaction. Next, this solution was gradually depressurized at a temperature of 260 ° C., and the polycondensation reaction was advanced by maintaining for 2 hours under the conditions of 260 ° C. and 0.67 hPa (0.5 mmHg) to obtain a polyester resin. . According to ¹ H-NMR (proton nuclear magnetic resonance) of the obtained polyester resin, the polyester resin is composed of a dicarboxylic acid containing at least 0 mol% of an aromatic dicarboxylic acid having a sulfonic acid group. It was confirmed.

100 parts of this polyester resin, 260 parts of water and 40 parts of isopropyl alcohol are put in a container and kept at a temperature in the range of 80 to 95 ° C. for 2 hours with stirring, so that the polyester resin concentration is 25%. A polyester resin P-10 dispersible in an aqueous solvent was obtained.

(Water-soluble polyacrylic resin P-11): Comparative 500 parts of MeOH was added to the reaction vessel, heated to reflux for 10 minutes, and then cooled to room temperature under nitrogen. 200 parts of acrylamide, 34.3 parts of sodium acrylate, and 5.1 parts of AIBN were added and heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was added dropwise to 3000 parts of methyl ethyl ketone and stirred for 1 hour. After decantation of methyl ethyl ketone, the polymer was washed with 100 parts of methyl ethyl ketone three times, dissolved in pure water, and transferred to a volumetric flask. Water-soluble polyacrylic resin P-11 was obtained by adding pure water to a concentration of 25%.

In Tables 1 and 2, the abbreviations for the binder resins are as follows.
R-150: Poly (ethylene oxide) Alcox R-150 (manufactured by Meisei Chemical Co., Ltd., does not contain sulfonic acid)

[Example 1]
<Method for producing conductive film>
A conductive film was produced by the following procedure.

(11) Production of transparent resin film substrate (11.1) Formation of smooth layer JSR Corporation on the surface of 100 μm thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) UV curable organic / inorganic hybrid hard coating material: OPSTAR Z7501 was coated with a wire bar so that the average thickness after coating and drying was 4 μm, then dried at 80 ° C. for 3 minutes, and then in an air atmosphere Curing was performed under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp to form a smooth layer.

(11.2) Formation of Gas Barrier Layer Next, a gas barrier layer was formed on the sample substrate provided with the smooth layer under the following conditions.

(11.2.1) Application of gas barrier layer coating solution Average thickness after drying a 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS, AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) with a wire bar However, it apply | coated so that it might become 0.30 micrometer, and the application | coating sample was obtained.

(11.2.2) Drying and dehumidifying treatment <First step; Drying treatment>
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.
<Second step; dehumidification treatment>
The dried sample was further dehumidified by being held for 10 minutes in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.).

(11.2.3) Modification Treatment The sample subjected to the dehumidification treatment was subjected to a modification treatment using the following apparatus under the following conditions to form a gas barrier layer. The dew point temperature during the reforming process was -8 ° C.
<Modification processing equipment>
Excimer irradiation equipment MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe
<Reforming treatment conditions>
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds A transparent resin film substrate having gas barrier properties was produced as described above.

(12) Formation of Polymer Conductive Layer (12.1) Preparation of Polymer Conductive Layer-Forming Composition Transparent Conductive Polymer Compound Clevios PH510 (1.89% solution manufactured by Heraeus) and Table 1 and Table 2 Various types of binder resins were mixed at a solid content mass ratio of 15:85, and after mixing 70 parts by mass of this mixture with 15 parts by mass of propylene glycol and 12 parts by mass of ethylene glycol monobutyl ether, 100 parts by mass of water was added. A polymer conductive layer forming composition was prepared.

(12.2) Coating of polymer conductive layer and drying treatment On the transparent resin film substrate having gas barrier properties, the polymer conductive layer was coated by inkjet printing using the above-described composition for forming a polymer conductive layer. (See FIG. 6C).
This was dried by the drying method and drying time described in Table 1 and Table 2 to form a polymer conductive layer, and the “conductive film samples 101 to 155 (TCs in Tables 1 and 2) having the polymer conductive layer. −101 to TC-155) ”.
Inkjet printing was controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta) using a desktop robot Shotmaster-300 (manufactured by Musashi Engineering) equipped with an ink jet head (manufactured by Konica Minolta).

The drying methods in Tables 1 and 2 are as follows.
HP: Conductive heat transfer drying with hot plate (MH-180CS, manufactured by ASONE CORPORATION)
IR-1: Radiant heat transfer drying with an infrared heater (1000 W / color temperature 2500 K, manufactured by USHIO INC.)
IR-2: Radiation heat transfer drying with an infrared heater (the IR irradiation device IR-1 has an air cooling mechanism in a quartz glass double tube with reference to Japanese Patent No. 4790092, see FIG. 3)
The distance between the sample and the infrared heaters IR-1 and IR-2 was 100 mm.
The HP temperature in Tables 1 and 2 is the heating temperature (set temperature) of the hot plate.
The filament temperatures in Tables 1 and 2 were measured with a non-contact thermometer (IR-AHS manufactured by Chino Co., Ltd.) with the emissivity of the tungsten filament being 0.39. The output of the infrared heater was adjusted so that

The infrared transmittance of the quartz glass filter is shown in FIG.
FIG. 8 shows the spectral radiance with and without the quartz glass filter.
In FIG. 8, the dotted line indicates the spectral radiance without the filter, and the solid line indicates the spectral radiance with the filter. The spectral radiance from the wavelength of 1 μm to almost 3 μm is the same regardless of the presence or absence of the filter. .

The ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm in Table 1 and Table 2 was determined by the following method.
The temperature of the standard blackbody furnace (M390, manufactured by Mikron) was adjusted to the measured filament temperature of the infrared heater, and FT-IR (FT / IR-4100, manufactured by JASCO Corporation) was used. The radiation output of the infrared heater was measured at a measurement wave number of 7800 to 350 cm ⁻¹ , a resolution of 4 cm ⁻¹ , and the number of integrations of 32 times to obtain the spectral emissivity of the infrared heater.
Next, according to Planck's radiometry, a black body radiation spectrum at the same temperature as that of the standard black body furnace was obtained and multiplied by the spectral emissivity of the infrared heater to obtain a spectral radiation spectrum of the infrared heater.
The spectral radiance value at a wavelength of 3.0 μm and the spectral radiance value at a wavelength of 5.8 μm are read from the spectral radiation spectrum of the obtained infrared heater, and the wavelength of 5.8 μm with respect to the spectral radiance of a wavelength of 3.0 μm is read. The ratio of spectral radiance was calculated as a percentage.

(13) Evaluation of Sample The characteristics (drying property, substrate stability, transparency, sheet resistance value, surface roughness) of the conductive films TC-101 to 155 were evaluated for each sample as follows. The results are shown in Tables 3 and 4.

(13.1) Drying property Regarding the drying property of the coating film of the polymer conductive layer, the surface of the coating film was palpated and evaluated according to the following criteria.
○: There is no stickiness, and it is dry. △: There is stickiness. ×: The coating film is peeled off and the solvent remains. Evaluation criteria: A sample evaluated as ○ passes the present invention.

(13.2) Base material deformation (base material stability)
As a damage evaluation of the transparent resin film substrate due to the drying treatment, the substrate deformation was evaluated according to the following criteria.
○: No deformation Δ: Slightly warped, but the substrate can be bent freely ×: Strong warp, and the substrate does not bend at the warped portion Evaluation criteria: A sample evaluated as ○ passes the present invention.

(13.3) Transparency Based on JIS K 7361-1: 1997, the total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. In order to use a conductive film as an organic electronic device, it is preferably 80% or more.
○: 80% or more Δ: 75% or more and less than 80% ×: 70% or more and less than 75% Evaluation criteria: A sample evaluated as ○ after the forced deterioration treatment passes the present invention.

(13.4) Sheet resistance value (surface resistance)
Based on JIS K 7194: 1994, the sheet resistance value was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The sheet resistance value is preferably 1000 Ω / □ or less after the forced deterioration treatment. In order to increase the area of the organic electronic device, the sheet resistance value is preferably 30 Ω / □ or less after the forced deterioration treatment.
Evaluation criteria: Samples evaluated as 1000Ω / □ or less after forced deterioration treatment pass the present invention.

(13.5) Surface roughness (Ra)
Using an AFM (SPI3800N probe station and SPA400 multifunctional unit manufactured by Hitachi High-Tech Science Co., Ltd.) and using a sample cut into a size of about 1 cm square, the surface roughness defined in the above method (JIS B601 (1994)). (According to the arithmetic average roughness of the roughness curve).
Evaluation criteria: After forced deterioration treatment, a sample evaluated as Ra ≦ 10 nm passed the present invention.

The above-described transparency, sheet resistance value, and surface roughness were evaluated before and after the following forced deterioration treatment.

(Forced deterioration processing)
As a forced deterioration treatment, TC-101 to TC-155 were heated at 90 ° C. for 14 days in an environment of 80% RH.

(14) Summary As shown in Tables 3 and 4, conductive film samples TC-127 to TC-129, TC-132 to TC-134, TC-137 to TC dried using infrared rays of the present invention. -144, TC-150 to TC-152 and TC-155 are comparative samples TC-101 to TC-126, TC-130, TC-131, TC-135, TC-136, TC-145 to TC- 149, TC-153 and TC-154 were all excellent in coating film drying properties, substrate deformation (substrate stability), transparency, sheet resistance and surface roughness.

[Example 2]
In the method for producing a conductive film of Example 1, a metal conductive layer is formed on a gas barrier surface on a transparent resin film substrate having gas barrier properties by the following method, and a polymer conductive layer is formed on the metal conductive layer. Except for the formation of, conductive films TC-201 to TC-256 having a metal conductive layer were manufactured in the same manner as the conductive film manufacturing method of Example 1. In the production of the conductive films TC-201 to TC-256, the binder resin, conductive polymer compound, metal conductive layer, drying method, HP temperature, filament temperature, spectral radiance ratio and drying time are shown in Table 5 and Table 6 was used.

(21) Formation of metal conductive layer [Silver (Ag) fine wire]
Using a gravure printing tester K303MULTICOATER (manufactured by RK Print Coat Instruments Ltd) on the surface of the transparent resin film base without a gas barrier layer, silver nano ink (TEC-PR-030: manufactured by Inktec) is 50 μm wide, 1 mm pitch The metal conductive layer (Ag thin line of Table 5 and Table 6) which consists of a metal fine line pattern was formed (refer FIG. 6B). This was heat-treated at 120 ° C. for 30 minutes.

[Copper mesh substrate]
On the surface of the transparent resin film substrate without the gas barrier layer, a copper mesh is prepared as a metal conductive layer by the following method, and patterned with a metal fine particle removing liquid BF, which will be described later, to form a copper (copper) mesh substrate. Produced.
The catalyst ink JISD-7 manufactured by Morimura Chemical Co. containing palladium nanoparticles is used, and the CAB-O-JET300 self-dispersion type carbon black solution manufactured by Cabot is used, and the carbon black ratio to the catalyst ink becomes 10.0% by mass. Then, Surfynol 465 (Nisshin Chemical Industry Co., Ltd.) was further added to prepare a conductive ink having a surface tension at 25 ° C. of 48 mN / m.
Conductive ink as an ink jet recording head has a pressure applying means and an electric field applying means, and has a nozzle diameter of 25 μm, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi (dpi is 1 inch, ie, 2.54 cm After a grid-shaped conductive mesh having a line width of 10 μm, a dried film thickness of 0.5 μm, and a line interval of 300 μm is formed on the base material , Dried.
Next, using a high-speed electroless copper plating solution CU-5100 manufactured by Meltex, soaked at a temperature of 55 ° C. for 10 minutes, washed and electroless-plated to produce a metal conductive layer having a plating thickness of 3 μm. did.

<Preparation of metal fine particle removal liquid BF>
Ethylenediaminetetraacetic acid ferric ammonium 60g
Ethylenediaminetetraacetic acid 2g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5g
After finishing to 1 L with pure water and adjusting the pH to 5.5 (room temperature) with sulfuric acid or ammonia water, the viscosity is adjusted to 10 Pa · s (10000 cP) with sodium carboxymethylcellulose (manufactured by SIGMA-ALDRICH; C5013) A fine particle removing liquid BF was prepared.

(22) Evaluation of sample The conductive films TC-201 to TC-256 have characteristics (drying property, base material deformation (base material stability), transparency, sheet resistance value, and surface roughness) as in Example 1. Evaluation was made in the same manner. The results are shown in Tables 7 and 8.

(23) Summary As shown in Tables 7 and 8, conductive film samples TC-227 to TC-229, TC-232 to TC-234, and TC-237 to TC dried using infrared rays of the present invention. -246, TC-252 to TC-254 are comparative samples TC-201 to TC-226, TC-230, TC-231, TC-235, TC-236, TC-247 to TC-251, TC- With respect to 255 and TC-256, all of the drying property, substrate stability, transparency, sheet resistance value, and surface roughness of the coating film were excellent.

Example 3
Organic EL elements OEL-301 to OEL-356 were manufactured as organic electronic elements as described below.
(31) Production of Organic EL Element (Sample) Using the conductive films TC-201 to TC-256 produced in Example 2, the corresponding organic EL element samples OEL-301 to OEL- 356 was produced.

(31.1) Formation of organic functional layer On the transparent electrode, an organic functional layer (a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer) was formed as follows.
The organic functional layer was formed by vapor deposition. Each of the vapor deposition crucibles in a commercially available vacuum vapor deposition apparatus was filled with the optimum amount of the constituent material of each layer for device fabrication. As the evaporation crucible, a crucible made of a resistance heating material made of molybdenum or tungsten was used.

(31.1.1) Formation of hole transport layer After reducing the pressure to 1 × 10 ⁻⁴ Pa, the deposition crucible containing the following compound 1 was energized and heated, and the deposition rate was 0.1 nm / second. Was deposited on the transparent electrode to provide a hole transport layer having a thickness of 30 nm (see FIG. 6D).

(31.1.2) Formation of light emitting layer Next, the light emitting layer was provided in the following procedure.
On the formed hole transport layer, Compound 2, Compound 3 and Compound 2 so that the following Compound 2 has a concentration of 13% by mass, the following Compound 3 is 3.7% by mass, and the following Compound 5 is 83.3% by mass. 5 was co-evaporated at a deposition rate of 0.1 nm / second to form a green-red phosphorescent layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm (see FIG. 6D).
Subsequently, the compound 4 and the compound 5 were co-deposited at a deposition rate of 0.1 nm / second so that the following compound 4 had a concentration of 10.0% by mass and the compound 5 had a concentration of 90.0% by mass, and the emission maximum wavelength was 471 nm. A blue phosphorescent layer having a thickness of 15 nm was formed (see FIG. 6D).

(31.1.3) Formation of hole blocking layer Furthermore, the following compound 6 was vapor-deposited on the formed light emitting layer to form a hole blocking layer having a thickness of 5 nm (see FIG. 6D).

(31.1.4) Formation of Electron Transport Layer Subsequently, CsF was co-deposited with Compound 6 so that the layer thickness ratio was 10% on the formed hole blocking layer, and an electron transport layer having a thickness of 45 nm was formed. Formed (see FIG. 6D).

(31.2) Formation of cathode On the formed electron transport layer, Al was vacuum-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as an external lead-out terminal for the anode part and a cathode forming material, and the thickness was 100 nm. The cathode part was formed.
(31.3) Formation of sealing film Adhesive is applied to the periphery of the cathode portion except for the ends so that the external lead terminals of the anode portion and the cathode portion can be formed, and Al ₂ O ₃ is coated on the polyethylene terephthalate resin film. After bonding a flexible sealing member deposited to a thickness of 300 nm, the adhesive was cured by heat treatment to form a sealing film, and organic EL elements OEL-301 to OEL-356 were produced.
As the adhesive, a two-component epoxy compounded resin (manufactured by Three Bond Co., Ltd.) 2016B and 2103 was blended at a ratio of 100: 3.

The formed electron transport layer was sealed with a flexible sealing member in which polyethylene terephthalate was used as a base material and Al ₂ O ₃ was deposited in a thickness of 300 nm (see FIG. 6F). Specifically, after applying an adhesive and pasting a flexible sealing member, the adhesive was cured by heat treatment and sealed. “Organic EL elements OEL-301 to OEL-356” were prepared by using the polymer conductive layer and Al that had come out of the sealing member as external extraction terminals of the transparent electrode (anode, anode) and cathode (cathode), respectively.

(32) Evaluation of organic EL elements OEL-301 to OEL-356 As characteristics of the organic EL elements OEL-301 to OEL-356, the light emission uniformity (light emission unevenness) and the light emission lifetime were evaluated as follows.

(32.1) Luminescence uniformity The luminescence uniformity was obtained by applying a direct current voltage to the organic EL element using a KEITHLEY source measure unit 2400 type. Regarding the organic EL elements OEL-301 to OEL-356 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. In addition, the organic EL elements OEL-301 to OEL-356 were heated in an oven at 60% RH and 80 ° C. for 2 hours, and then conditioned again in the environment of 23 ± 3 ° C. and 55 ± 3% RH for 1 hour or more. After (forced deterioration treatment), the emission uniformity was observed in the same manner.
A: Completely uniform light emission, satisfactory O: Almost uniform light emission, no problem Δ: Some light emission unevenness is observed partially, but acceptable X: Light emission unevenness is observed over the entire surface, not acceptable Evaluation criteria: After forced deterioration treatment, samples evaluated as ◎ and ○ pass as the present invention.

(32.2) Luminous lifetime The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL element having an anode electrode made of ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. The light emission lifetime is preferably 100% or more, and more preferably 150% or more.
◎: 150% or more ○: 100% or more and less than 150% △: 80% or more and less than 100% ×: less than 80%

Evaluation results are shown in Table 9 and Table 10. In Tables 9 and 10, “present invention” in the remarks indicates that it corresponds to an example of the present invention, and “comparison” indicates that it is a comparative example. Further, the conditions for forced deterioration processing in the third embodiment are the same as those in the first and second embodiments.

(33) Summary From Tables 9 and 10, organic EL elements OEL-301 to OEL-326, OEL-330, OEL-331, OEL-335, OEL-336, OEL-347 to OEL-351, OEL of comparative examples are shown. -355 and OEL-356, after the forced deterioration treatment, the light emission uniformity is significantly deteriorated and the lifetime is short, whereas the organic EL elements OEL-327 to OEL-329, OEL-332 to OEL-334 of the present invention, It can be seen that OEL-337 to OEL-346 and OEL-352 to OEL-354 have stable emission uniformity and excellent durability (high life) even after heating.

Example 4
<Production of touch panel>
Using the conductive films TC-101 to TC-155 and TC-201 to TC-256 produced in Examples 1 and 2, the touch panel 101 shown in FIG. 9 was assembled by the following method.

<Assembly method of touch panel>
As illustrated in FIG. 9, the touch panel 101 includes a lower electrode 110, an upper electrode 120, and a thermosetting type dot spacer 130 provided therebetween. The lower electrode 110 is a touch panel glass ITO (sputtering film product), and includes a touch panel glass 111 and an ITO film 112 provided on the touch panel glass 111. The upper electrode 120 has any one of the conductive films TC-101 to TC-155 and TC-201 to TC-256 in the above-described embodiments, and includes a transparent resin film substrate 121, a polymer conductive layer 122, . Then, the touch panel 101 is assembled by making the ITO film 112 of the lower electrode 110 and the polymer conductive layer 122 of the upper electrode 120 face each other and interposing a thermosetting type dot spacer 130 to form a panel with an interval of 7 μm. It was.

The resistance measuring machine was attached to the upper electrode 120 and the lower electrode 110 of the assembled touch panel 101, the center of the touch panel 101 was pushed by hand, and the resistance value was measured 1000 times. As a result, the conductive films TC-127 to TC-129, TC-132 to TC-134, TC-137 to TC-144, TC-150 to TC-152, TC-227 to TC-229, TC of the present invention. Compared to the touch panel 101 having -232 to TC-234, TC-237 to TC-246, and TC-252 to TC-254, the conductive films TC-101 to TC-126, TC-130, TC-131, TC-135, TC-136, TC-145 to TC-149, TC-153, TC-154, TC-201 to TC-226, TC-230, TC-231, TC-235, TC-236, TC- It was confirmed that the resistance value of the touch panel 101 having 247 to TC-251, TC-255, and TC-256 is greatly decreased over time.

As described above, the present invention is suitable for providing a method for producing a conductive film and a conductive film that are excellent in transparency, conductivity, and surface roughness while suppressing deformation of the substrate.
Moreover, this invention is suitable for providing the organic electronic element and touch panel which were excellent in the light emission uniformity and lifetime by providing an organic electronic element and a touch panel with the electroconductive film produced with the said manufacturing method.

DESCRIPTION OF SYMBOLS 1 Conductive film 2 Transparent resin film base material 3 Polymer conductive layer 4 Metal conductive layer 20 Infrared heater 22 Filament 24

Protection tube

26, 28 Filter 30 Hollow part 32 Reflector 40 Cooling mechanism 45 Control device 50 Element 51 Conductive film 52 Transparent Resin film substrate 53 Extraction electrode 54 Metal conductive layer 55 Polymer conductive layer 56 Organic functional layer 57 Counter electrode 101 Touch panel 110 Lower electrode 112 ITO film 120 Upper electrode 121 Transparent resin film substrate 122 Polymer conductive layer

Claims

A method for producing a conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate,
At least the following steps (A) and (B):
The polyester resin contains a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio within a range of 1 to 15 mol%, and further,
In the following step (B), the method for producing a conductive film is characterized by performing infrared irradiation in which the ratio of the spectral radiance at a wavelength of 5.8 μm to the spectral radiance at a wavelength of 3.0 μm is 5% or less.
Step (A): A step of applying an aqueous dispersion containing the conductive polymer compound and the polyester resin on the transparent resin film substrate Step (B): The step of applying on the transparent resin film substrate Forming the polymer conductive layer by irradiating the aqueous dispersion with the infrared rays;
The method for producing a conductive film according to claim 1, wherein at least a gas barrier layer is provided in advance on the transparent resin film substrate.
A conductive film having a polymer conductive layer containing at least a conductive polymer compound and a polyester resin on a transparent resin film substrate,
The polyester resin is produced through at least the following steps (A) and (B), and comprises a dicarboxylic acid containing at least an aromatic dicarboxylic acid having a sulfonic acid group in a ratio in the range of 1 to 15 mol%. Ingredients, and
In the step (B), a conductive film characterized by being irradiated with infrared rays having a ratio of the spectral radiance of a wavelength of 5.8 μm to the spectral radiance of a wavelength of 3.0 μm of 5% or less.
Step (A): A step of applying an aqueous dispersion containing the conductive polymer compound and the polyester resin on the transparent resin film substrate Step (B): The step of applying on the transparent resin film substrate Forming the polymer conductive layer by irradiating the aqueous dispersion with the infrared rays;
An organic electronic device comprising a conductive film produced by the method for producing a conductive film according to claim 1 or 2 or the conductive film according to claim 3 as an electrode.
A touch panel comprising a conductive film produced by the method for producing a conductive film according to claim 1 or 2 or the conductive film according to claim 3 as an electrode.