JP5834954B2 - Transparent conductive film and organic electroluminescence device - Google Patents

Description

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

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

  Conventionally, as the transparent electrode, an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method is mainly used. It has been. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. Also, roll-to-roll production technology using a flexible substrate has been desired along with an increase in display screen and productivity.

  In recent years, a transparent electrode such as a conductive polymer has been laminated on a thin metal wire formed in a pattern so that it can be used for products that require such a large area and low resistance. A transparent conductive film having both properties has been developed (see, for example, Patent Documents 1 and 2).

  However, in such a configuration, it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent electrode such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer. However, since the conductive polymer has absorption in the visible light region, there is a problem that the transparency of the transparent electrode is remarkably lowered when the film is thickened.

  As a method for achieving both conductivity and transparency, a technique of laminating a conductive polymer on a thin wire structure (for example, see Patent Document 3), a binder that can be uniformly dispersed in a conductive polymer and an aqueous solvent on a conductive fiber. A technique using a resin (for example, see Patent Document 4) and a technique for laminating a conductive polymer and a binder on a conductive layer are disclosed (for example, see Patent Document 5).

Polymer films are widely used from the viewpoint of handling in roll-to-roll production technology using flexible substrates. When a polymer film is used, drying at a low temperature and in a short time is desired. As a method for reducing the drying load, it is required that the water-soluble polymer content in the material constituting the transparent electrode is low, and as the conductive material having a low water-soluble polymer content, a conductive polymer , a conductive composition (for example, Patent Documents 5 and 6), polythiophene dispersions (for example, see Patent Document 7), and the like are known.

JP 2005-302508 A JP 2009-87843 A JP 2009-4348 A JP 2010-244746 A JP 2011-96437 A JP 2009-230885 A Japanese Patent Application Laid-Open No. 07-90060

  However, even with the techniques described in Patent Documents 3 and 4, sufficient sheet resistance and transmittance cannot be obtained, and there is a problem that it is difficult to achieve both physical properties. In addition, in the technique described in Patent Document 5, a high drying temperature and a long drying time are required to sufficiently advance the crosslinking reaction, which not only increases the process load, There was a problem that the reaction-derived desorbents adversely affected the transparent electrode and the organic EL device during storage, and the desired storage performance could not be obtained. Furthermore, when a polymer having a low glass transition temperature is used as the material constituting the transparent electrode, the surface smoothness of the transparent electrode cannot be obtained, and the performance of the transparent electrode and the organic EL element after the environmental test is deteriorated. there were.

  In addition, the materials described in Patent Documents 5 to 7 have insufficient compatibility, and the haze and surface roughness performance of the transparent conductive film cannot be obtained, or the performance of the organic EL element is deteriorated due to poor drying. was there.

  The present invention has been made in view of the above problems, and is excellent in transparency, conductivity and film strength, and also has a transparent conductive film with little deterioration in transparency, conductivity and film strength even under high temperature and high humidity environments, Another object of the present invention is to provide an organic EL element that uses the conductive film and has excellent light emission uniformity, little deterioration in light emission uniformity even in a high temperature and high humidity environment, and excellent light emission life.

The above-described problems of the present invention are solved by the following configuration.
1. A transparent conductive film comprising a transparent base material and a transparent organic compound layer formed on the base material, wherein the organic compound layer is a conductive material having a cationic π-conjugated conductive polymer and a polyanion. A weight ratio of the polyanion to the cationic π-conjugated conductive polymer in the conductive polymer compound is formed using a dispersion containing a polymer compound and a dissociable group-containing self-dispersing polymer. Is 0.5 or more and less than 2.5.

2. 2. The transparent conductive film according to 1 above, wherein the weight ratio is 0.8 or more and 1.2 or less.

3. A first conductive layer made of a metal material formed in a pattern on the substrate, and a transparent layer made of the organic compound layer formed on the substrate and electrically connected to the first conductive layer. The transparent conductive film according to 1 or 2, further comprising a second conductive layer.

4). 4. The transparent conductive film according to any one of 1 to 3, wherein the dissociable group-containing self-dispersing polymer has a glass transition temperature of 25 ° C. or higher and 80 ° C. or lower.

5. An organic electroluminescence device comprising the transparent conductive film according to any one of 1 to 4 as an electrode.

6). A step of producing a dispersion containing a cationic π-conjugated conductive polymer and a conductive polymer compound having a polyanion and a dissociable group-containing self-dispersing polymer, and using the produced dispersion, Forming a transparent organic compound layer on a transparent substrate, and the weight ratio of the polyanion to the cationic π-conjugated conductive polymer in the conductive polymer compound is 0.5 or more and 2.5 The manufacturing method of the transparent conductive film characterized by being less than.

  According to the present invention, the transparency, conductivity and film strength are excellent, and the transparent conductive film with little deterioration of transparency, conductivity and film strength even under high temperature and high humidity environment, and the transparent conductive film, It is possible to provide an organic EL element that is excellent in light emission uniformity, has little deterioration in light emission uniformity even under a high temperature and high humidity environment, and has an excellent light emission lifetime.

It is the schematic which shows an example of the transparent conductive film which concerns on embodiment of this invention, (a) is a top view, (b) is X arrow sectional drawing of (a).

  Conventionally, as a coating liquid for forming a transparent conductive film, a water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) and a binder resin are used in order to achieve both conductivity and transmittance. Containing compositions have been developed.

  Here, as the binder resin, a hydrophilic binder resin has been studied from the viewpoint of compatibility with the water-dispersible conductive polymer. However, the demand for flexibility increases as the transparent substrate, and when a resin film such as polyethylene terephthalate is used, the drying temperature is lower than that of the glass substrate from the viewpoint of avoiding film deformation. In addition, the hydroxyl group-containing binder resin that is known to be compatible with PEDOT / PSS undergoes a dehydration reaction under acidic conditions and crosslinks between polymer chains. As a result, the cross-linking reaction progressed during storage to generate water, and the performance of the transparent electrode and the device using the transparent electrode was significantly deteriorated due to the influence of residual water in the film. In order to solve this problem, it was necessary to reduce the interaction between the main skeleton of the binder and water, and further reduce or eliminate the number of hydroxyl groups in the binder resin. In addition, when a dispersion liquid in which a hydrophobic polymer is uniformly dispersed in an aqueous solvent using a surfactant is used, the device performance using the transparent conductive film and the transparent conductive film is adversely affected. In order to improve the storage stability of the organic EL device, it is necessary not only to increase the hydrophobicity of the binder, but also to reduce the water-soluble polymer in the conductive composition. In water-dispersible conductive polymers, polyanions having the functions of dopants, dispersion stabilizers, and film-formability improvers are widely used. It was difficult to release water and had the problem of deteriorating the performance of the transparent conductive film and the organic EL element.

  As a result of intensive studies to improve these phenomena, the present inventors have used a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent (a self-dispersing polymer containing a dissociable group), and has a conductive property. In the conductive polymer compound, the weight ratio of the polyanion to the cationic conductive polymer is 0.5 or more and less than 2.5.

  That is, the object of the present invention is to use a dissociable group-containing self-dispersing polymer as a binder resin to be mixed with a conductive polymer, and in the conductive polymer compound, the weight ratio of the polyanion to the cationic conductive polymer is It became clear that it can be solved by setting it as 0.5 or more and less than 2.5, and came to this invention.

  The present invention uses a dissociable group-containing self-dispersing polymer as a binder resin, and in the conductive polymer compound, the weight ratio of the polyanion to the cationic conductive polymer is 0.5 or more and less than 2.5. By combining the transparency and conductivity of the transparent conductive film, the film has excellent film strength, and also has high conductivity, transparency and good film strength even after environmental tests in high temperature and high humidity environments. It has been found that by suppressing the generation of water derived from water, a transparent conductive film having excellent stability and a long-life organic EL element using the transparent conductive film can be obtained.

  Hereinafter, embodiments of the present invention will be described. 1A and 1B are schematic views illustrating an example of a transparent conductive film according to an embodiment of the present invention, in which FIG. 1A is a top view and FIG. 1B is a cross-sectional view taken along the arrow X in FIG.

  As shown in FIG. 1, the transparent conductive film 1 according to the embodiment of the present invention includes a base material 11, a first conductive layer 12, and a second conductive layer 13. The first conductive layer 12 is made of a metal material formed in a pattern, and the second conductive layer 13 contains a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent. A feature of the present invention is that the second conductive layer 13 contains a conductive polymer compound having a weight ratio of polyanion to cationic conductive polymer of 0.5 to less than 2.0.

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

  In the present invention, the conductive polymer compound is 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 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-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(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. Polyester and any of these copolymers, which are 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 in a solvent. The anion group of the polyanion functions as a dopant for the cationic π-conjugated conductive polymer, and improves the conductivity and heat resistance of the cationic π-conjugated conductive polymer. In addition, by using an excessive amount of polyanion with respect to the cationic π-conjugated polymer compound, there is also a function of improving the dispersibility and film-forming property of the conductive polymer compound particles comprising the cationic π-conjugated polymer compound and the polyanion. Have.

  The anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the π-conjugated conductive polymer. Such an anion group is preferably a mono-substituted sulfate group, a mono-substituted phosphate group, a phosphate group, a carboxy group, a sulfo group, etc. 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 π-conjugated conductive polymer.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Examples include acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . 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 is used as a polyanion, after forming a conductive polymer-containing layer by coating and drying, it is further subjected to a heating and drying treatment at 100 to 120 ° C. for 5 minutes or more, and then the microanion. You may irradiate a wave, near infrared light, etc. In some cases, the heat drying treatment 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, polyethyl acrylate sulfonic acid, or polybutyl acrylate sulfonate is preferable.

  The degree of polymerization 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 the viewpoint of solvent solubility and conductivity, it is preferably 50 to 10,000. A range is more preferred.

  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 an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer.

When the obtained polymer is a salt of a polyanion, it is preferably transformed into a polyanion acid. Examples of the method for transforming into polyanionic acid include ion exchange method using ion exchange resin, dialysis method, ultrafiltration method and the like. Among these, ultrafiltration method is preferable from the viewpoint of easy work.
The ratio between the cationic π-conjugated conductive polymer contained in the conductive polymer compound and the polyanion constituting the conductive polymer compound, and the weight ratio of the polyanion to the cationic π-conjugated conductive polymer are determined by conductivity and dispersion. From a viewpoint of property, Preferably it is 0.5 or more and less than 2.5, More preferably, it is 0.8 or more and 1.2 or less.

  When the weight ratio of the polyanion to the cationic π-conjugated conductive polymer is 2.5 or more, the amount of water retained by the hydrophilic polyanion or the conductive polymer compound increases, and the transparent conductive film and The storage stability of an organic electroluminescence element or the like using a transparent conductive film is deteriorated. Further, if the weight ratio is less than 0.5, not only the resistance of the conductive polymer compound increases with the decrease in dopant, but the effect of the polyanion acting as a protective colloid is weakened and the stability of the particles is deteriorated. The particle size increases. From the viewpoint of storage properties such as conductivity, particle stability, a transparent conductive film and an organic electroluminescent device using the transparent conductive film, the weight ratio of the polyanion to the more preferable cationic π-conjugated conductive polymer is 0.8. It is 1.2 or less.

  Examples of a method for setting the weight 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 during the synthesis of the conductive polymer compound. In this method, when the polyanion amount is 1.0 or less by weight with respect to the cationic π-conjugated conductive polymer, the conductive polymer compound particles tend to be large. These polymer compounds can be used in combination. The polymer compound that can be used in combination is not particularly limited as long as the conductive compound particles are stabilized and the transmittance and conductivity are not deteriorated, but polyacryl such as 2-hydroxyethyl acrylate, self-dispersing containing a dissociable group An aqueous dispersion polymer such as a mold polymer is preferred. Also, water in commercially available PEDOT / PSS is removed by drying, azeotropic removal with toluene, or powdered by a known method such as freeze-drying, then washed with water, PSS is removed by ultrafiltration, and PSS is removed by ultrafiltration. However, a method of replacing with water can be used.

The oxidizing agent used when the precursor monomer that forms the cationic π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J . Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. Such oxidants include, for practical reasons, cheap 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, tetrafluoride). It is preferable to use copper borate). 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 the iron (III) salt of an inorganic acid containing an organic residue include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms (for example, lauryl sulfate), alkyl sulfonic acids having 1 to 20 carbon atoms. (For example, methane, dodecanesulfonic acid), carboxylic acid having 1 to 20 aliphatic carbon atoms (for example, 2-ethylhexylcarboxylic acid), aliphatic perfluorocarboxylic acid (for example, trifluoroacetic acid, perfluorooctanoic acid), aliphatic dicarboxylic acid Acids (eg oxalic acid), in particular aromatic, optionally alkyl substituted sulfonic acids having 1 to 20 carbon atoms (eg Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid) Is mentioned.

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

  The size (average particle size) of the conductive polymer before dispersion treatment in the conductive polymer compound-containing dispersion used in the present invention is 1 to 500 nm, preferably 3 to 300 nm, and more preferably 5 ~ 100 nm. When the colloidal particles of the conductive polymer compound are large (when larger than 500 nm), the haze of the second conductive layer (transparent conductive layer) 13 generated by applying the dispersion to the substrate 11 and Smoothness (surface roughness (Ra)) deteriorates. Further, when the colloidal particles of the conductive polymer compound are extremely small (smaller than 1 nm), the particles are aggregated to reduce the dispersibility of the dispersion liquid. As a result, the second conductive layer ( The haze and smoothness (surface roughness (Ra)) of the transparent conductive layer 13 are deteriorated. In order to improve the smoothness at the time of film formation, the size of the colloidal particles is more preferably 3 to 300 nm, and further preferably 5 to 100 nm. The size of the colloidal particles can be measured with a light scattering photometer.

  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, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

[Dissociable group-containing self-dispersing polymer]
In the present invention, the dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent does not contain a surfactant or an emulsifier that assists micelle formation, and can be dispersed in an aqueous solvent by itself. In the present invention, “dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration. The size (average particle diameter) of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 μm). The size (average particle diameter) of the dissociable group-containing self-dispersing polymer colloidal particles before the dispersion treatment is preferably 1 to 500 nm, more preferably 5 to 300 nm, like the colloidal particles of the conductive polymer compound. More preferably, it is 5-100 nm. When the colloidal particles of the dissociable group-containing self-dispersing polymer are large (when larger than 500 nm), the second conductive layer (transparent conductive layer) 13 generated by applying the dispersion to the substrate 11 is used. Haze and smoothness (surface roughness (Ra)) deteriorate. Further, when the colloidal particles of the dissociative group-containing self-dispersing polymer are extremely small (smaller than 1 nm), the particles are aggregated to reduce the dispersibility of the dispersion liquid. The haze and smoothness (surface roughness (Ra)) of the conductive layer (transparent conductive layer) 13 are deteriorated. In order to improve the smoothness at the time of film formation, the size of the colloidal particles is more preferably 3 to 300 nm, and further preferably 5 to 100 nm. 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.

  The dissociable group-containing self-dispersing polymer according to the present invention is preferably transparent. The dissociable group-containing self-dispersing polymer is not particularly limited as long as it is a medium that forms a film. In addition, there is no particular limitation as long as there is no problem in the bleed out to the surface of the transparent conductive film 1 and the element performance when the organic EL element is laminated, but the polymer dispersion controls the surfactant (emulsifier) and the film forming temperature. It is preferable not to contain a plasticizer or the like.

  The average particle diameter of the dissociable group-containing self-dispersing polymer according to the present invention is 5 to 100 nm.

  The glass transition temperature (Tg) of the dissociable group-containing self-dispersing polymer according to the present invention is preferably 25 to 150 ° C, more preferably 50 to 80 ° C. When Tg is less than 25 ° C., the surface smoothness of the transparent conductive film 1 tends to deteriorate, and the performance after the environmental test of the organic EL element including the transparent conductive film 1 and the transparent conductive film 1 deteriorates. Cheap. When Tg is 50 to 80 ° C., melting of the dissociable group-containing self-dispersing polymer particles sufficiently proceeds at the drying temperature when the transparent conductive film 1 is produced. When Tg exceeds 80 ° C., the melting of the dissociable group-containing self-dispersing polymer particles does not proceed sufficiently at the drying temperature during the production of the transparent conductive film 1, but the surface after drying is not rough and the organic electroluminescence If the desired performance is obtained without causing leakage when the elements are laminated, the particle shape of the dissociable group-containing self-dispersing polymer may be maintained. Further, in order to increase the Tg of the dissociable group-containing self-dispersing polymer above 150 ° C., it is necessary to make the skeleton rigid, increase the molecular weight, etc., and disperse these polymers in the dispersion by making the polymer less than 100 nm. It is difficult to do. The glass transition temperature Tg can be measured according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a temperature rising rate of 20 ° C./min.

  The pH of the dispersion of the dissociable group-containing self-dispersing polymer used in the production of the transparent conductive film 1 is compatible with the conductive polymer compound solution to be separately compatible, the dissociable group-containing self-dispersing polymer and the conductive high From the viewpoint of the conductivity of the liquid mixture with the molecular compound, it is preferably 0.1 to 11.0, more preferably 3.0 to 9.0, and still more preferably 4.0 to 7.0. .

  Examples of the dissociable group used in the self-dispersing polymer containing a dissociable group include an anionic group (sulfonic acid and its salt, carboxylic acid and its salt, phosphoric acid and its salt, etc.), and a cationic group (ammonium salt, etc.). Etc. 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 self-dispersing polymer can be dispersed in the aqueous solvent, and is preferably as small as possible because the drying load is reduced in a suitable manner in the process. In addition, the counter species used for the anionic group and the cationic group are not particularly limited, but from the viewpoint of performance when the organic EL element including the transparent conductive film 1 and the transparent conductive film 1 is laminated, it is hydrophobic and has a small amount. It is preferable that

  The main skeleton of the dissociable group-containing self-dispersing polymer includes polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyolefin copolymer, polyamide (nylon), Polyvinylidene chloride, polyester, polyacrylate, polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone-poly Acrylate, polyvinylidene fluoride-polyacrylate, polyfluoroolefin-polyvinyl ether, etc. It is. Further, based on these skeletons, copolymerization using another monomer may be the main skeleton. Among these, a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, and a polyethylene resin emulsion having an ethylene skeleton are preferable.

  As commercial products, Polysol FP3000 (polyester resin, anion, core: acrylic, shell: polyester, manufactured by Showa Denko KK), Vironal MD1480 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Vironal MD1245 (polyester resin, anion, Toyobo Co., Ltd.) ), Bironal MD1500 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD2000 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD1930 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Plus Coat RZ105 (polyester resin, anion) , Manufactured by Mutual Chemical Co., Ltd.), Plus Coat RZ570 (polyester resin, anion, manufactured by Interactive Chemical Co., Ltd.) Itec S-9242 (polyethylene resin, anion, manufactured by Toho Chemical Co., Ltd.), Movinyl 7720 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.), Movinyl 7820 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used. . Further, the dissociable group-containing self-dispersing polymer may contain one kind of those described above, or may contain a plurality of kinds.

[Dispersion made of conductive polymer compound and self-dispersing polymer containing dissociable group]
The dispersion comprising the conductive polymer compound and the dissociable group-containing self-dispersing polymer according to the present invention comprises a conductive polymer compound dispersed in an aqueous solvent and a dissociable group-containing self-dispersible type dispersible in the aqueous solvent. It consists of a polymer. 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.

  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 bleed out to the surface of the transparent conductive film 1 and the element performance when the organic EL element is laminated. It is preferable not to include a plasticizer or the like for controlling the film temperature.

  The pH of the dispersion according to the present invention is not particularly problematic as long as desired conductivity is obtained, but is preferably 0.1 to 7.0, and more preferably 0.3 to 5.0.

  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.

  The size (average particle size) after the dispersion treatment of the conductive polymer compound and the dissociable group-containing self-dispersing polymer after the dispersion treatment contained in the dispersion according to the present invention is preferably 1 to 100 nm. More preferably, it is 3-80 nm, More preferably, it is 5-50 nm. When the particles in the dispersion are large (when larger than 100 nm), the haze and smoothness of the second conductive layer (transparent conductive layer) 13 generated by applying the dispersion to the substrate 11 ( The surface roughness (Ra)) is deteriorated, and further, the performance of the organic electroluminescence element is deteriorated. When the particles in the dispersion are extremely small (smaller than 1 nm), the particles are aggregated and the dispersibility of the dispersion is lowered. As a result, the second conductive layer (transparent conductive layer) 13 haze and smoothness (surface roughness (Ra)) deteriorate. 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. Even if the average particle size is controlled, if the film-forming temperature of the dissociable group-containing self-dispersing polymer 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 forming temperature.

  Examples of a method for setting the average particle size of the dispersion to a desired range include a homogenizer, an ultrasonic disperser (US disperser), a dispersion technique using a ball mill, a reverse osmosis membrane, an ultrafiltration membrane, and a microfiltration membrane. The classification of the used particles can be used. 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 ° C to 50 ° C. It is below, More preferably, it is higher than 0 degreeC and less than 30 degreeC. In the case of a dispersion operation with a large shearing force that cuts the polymer, the temperature of the dispersion tends to be high, and the conjugated system of the conductive polymer is broken by heat, causing performance deterioration. When the temperature exceeds 50 ° C., the particle size tends to be small, but the sheet resistance of the second conductive layer (transparent conductive layer) 13 generated by the dispersion increases. In addition, when an organic solvent is contained in the 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 is evaporated and the dispersion concentration is likely to fluctuate. As a result, the performance of the transparent conductive film 13 may be affected. Classification is not particularly limited as long as a membrane to be used is selected as necessary.

  The dissociable group-containing self-dispersing polymer particles and the conductive polymer particles in the dispersion according to the present invention are in a state in which each particle is dispersed independently and the particle size is the sum of the particle sizes. The particles having different compositions may be aggregated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.

  The use amount (solid content) of the dissociable group-containing self-dispersing polymer is preferably 50 to 1000% by mass, more preferably 100 to 900% by mass, and still more preferably based on the solid content of the conductive polymer. Is 200 to 800% by weight. Here, the reason why the use amount of the dissociable group-containing self-dispersing polymer is more preferably 50 to 1000% by mass with respect to the conductive polymer is that when the amount is less than 50% by mass, the transmittance is improved. (The conductive polymer absorbs light in the visible light region, so in order to improve the transmittance, we want to reduce the conductive polymer as much as possible without reducing the conductivity.) This is because the ratio of the conductive polymer becomes too small and the conductivity is lowered. In order to obtain a transmittance improvement effect and prevent a decrease in conductivity, the amount of polymer dispersible in an aqueous solvent is more preferably 100 to 900% by mass with respect to the conductive polymer. More preferably, it is 200 to 800 mass% with respect to the polymer.

  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. The self-dispersing polymer particles and conductive polymer particles containing a dissociable group do not use a surfactant, and the particle size becomes unstable by dilution, so that the measurement can be performed without dilution with a solvent. A concentrated particle size measuring device is preferable, and examples of the concentrated particle size measuring device include a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), the Zetasizer Nano series (manufactured by Malvern), and the like.

(Metal material)
As shown in FIG. 1, a transparent conductive film 1 according to an embodiment of the present invention includes a conductive layer containing a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent (first in FIG. 1). In addition to the two conductive layers 13), a metal material-containing conductive layer (first conductive layer 12 in FIG. 1) formed in a pattern on the substrate 11 is provided.

  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 transparent conductive film 1, the first conductive layer 12 according to the present invention is formed on the base material 11 so as to exhibit a pattern shape having the opening 12a. The opening part 12a is a part which does not have a metal material on the base material 11, 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 opening 12a to the entire surface of the transparent 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 light-impermeable conductive portion to the whole. 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 10 to 200 μm from the viewpoint of transparency and conductivity. If the line width of the fine line is less than 10 μm, desired conductivity cannot be obtained, and if the line width of the fine line exceeds 200 μm, the transparency is lowered. The height of the thin wire is preferably 0.1 to 10 μm. If the height of the fine line is less than 0.1 μm, the desired conductivity cannot be obtained, and if the height of the fine line exceeds 10 μm, the cause of current leakage and poor distribution of the thickness of the functional layer in the formation of organic electronic devices It becomes.

  There is no restriction | limiting in particular as a method of forming the stripe-shaped or mesh-shaped 1st conductive layer 12, 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 substrate 11 and subjecting the metal layer to a known photolithography method. Specifically, a metal layer is formed on the entire surface of the substrate 11 using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, or the like, or a metal foil is used as an adhesive. The first conductive layer 12 processed into a desired stripe shape or mesh shape can be obtained by laminating the substrate 11 on the substrate 11 and then 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 in a desired shape by gravure printing or an inkjet method, or a plating process, or A method using silver salt photography technology is mentioned.

  A technique using silver salt photography technology can be implemented with reference to, for example, [0076]-[0112] of Japanese Patent Application Laid-Open No. 2009-140750 and Examples. Further, a method for carrying out a plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, Japanese Patent Application Laid-Open No. 2007-281290.

  In addition, as a random network structure, for example, as described in JP 2005-530005 A, 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 method, 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 a 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 3 to 500 μm. When the length of the metal nanowire exceeds 500 μm, one wire does not spread well and bends and overlaps. As a result, the film thickness of the first conductive layer 12 becomes thick, which hinders thinning and transmittance. Cause deterioration. When the length of the metal nanowire is less than 3 μm, the number of contacts between the metal wires is reduced, and it is necessary to increase the amount of addition in order to obtain a desired sheet resistance. When the amount of addition is increased, the transmittance decreases. . In addition, the relative standard deviation of the length is preferably 40% or less. This is because when the relative standard deviation of the length exceeds 40%, the film thickness unevenness of the first conductive layer 12 and the uniformity of the sheet resistance may be reduced. 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 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. This is because when the relative standard deviation of the minor axis exceeds 20%, the film thickness unevenness of the first conductive layer 12 may occur, and the brightness unevenness of the organic electroluminescence element may occur. The basis weight of the metal nanowire is preferably 0.02 to 0.5 g / m ² . When the basis weight of the metal nanowire is less than 0.02 g / m ² , a desired sheet resistance cannot be obtained, and when the basis weight exceeds 0.5 g / m ² , the sheet resistance is low. The transmittance decreases. The weight of the metal nanowire 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 (sulfurization resistance, oxidation resistance, and migration resistance of metal nanowires), the metal as the main component and one or more other types are used. These 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.

  In addition, the surface specific resistance of the thin wire portion (first conductive layer 12) made of 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.

  Moreover, it is preferable that the thin wire | line part (1st conductive layer 12) which consists of metal materials is heat-processed in the range which does not damage the base material 11. FIG. As a result, fusion between the metal fine particles and the metal nanowires proceeds, and the thin wire portion made of the metal material becomes highly conductive.

(Base material)
The base material 11 is a plate-like body that can carry the conductive layers 12 and 13, and in order to obtain the transparent conductive film 1, JIS K 7361-1: 1997 (Testing method of total light transmittance of plastic-transparent material) ) Having a total light transmittance of 80% or more in the visible light wavelength region measured by a method in accordance with (1) is preferably used.

  As the substrate 11, a material that is excellent in flexibility, has a sufficiently low dielectric loss coefficient, and is a material that absorbs microwaves smaller than the conductive layers 12 and 13 is preferably used.

  As the base material 11, for example, a resin substrate, a resin film, and the like are preferably exemplified. However, it is preferable to use a transparent resin film from the viewpoints of productivity and performance such as lightness and flexibility. The transparent resin film is a film having a total light transmittance of 50% or more measured in a visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (a test method for total light transmittance of plastic-transparent material). Say.

  There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. Examples of such transparent resin films 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 olefin resins. Polyolefin resin films such as polyvinyl chloride, polyvinyl resin such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate ( PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. .

  If it is a resin film whose above-mentioned total light transmittance is 80% or more, it is preferably used as a film board | substrate used as the base material 11 of this invention. The film substrate is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film from the viewpoint of transparency, heat resistance, ease of handling, strength and cost. An axially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.

  The base material 11 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). A conventionally well-known technique can be used about surface treatment and an easily bonding layer.

  For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

  Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

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

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

(Coating, heating, drying)
The second conductive layer 13 of the present invention has a coating liquid (dispersion) containing the above-described conductive polymer compound and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent on the substrate 11. It is formed by applying, heating and drying. When the transparent conductive film 1 has a fine wire portion made of a metal material as the first conductive layer 11, the above-described coating solution is applied onto the substrate 11 on which the thin wire portion made of the metal material is formed, and is heated and dried. Thus, the second conductive layer 13 is formed. Here, the second conductive layer 13 only needs to be electrically connected to the thin metal wire portion that is the first conductive layer 12, and may completely cover the patterned thin metal wire portion. A part of the part may be covered, or may be in contact with the fine metal wire part.

  In addition to printing methods such as a gravure printing method, a flexographic printing method, a screen printing method, etc., a coating liquid composed of a conductive polymer compound and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent can be applied to a roll Coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, ink jet method, etc. Any of the methods can be used.

  In addition, the second conductive layer 13 containing a conductive polymer compound and a dissociable group-containing self-dispersing polymer that can be dispersed in an aqueous solvent covers or contacts a part of the thin metal wire portion (first conductive layer 12). As a method for producing the transparent conductive film 1, the first conductive layer 12 is formed on the transfer film by the above-described method, and a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent are used. A method of transferring the laminated second conductive layer 13 contained by the method described later to the above-described base material 11 is exemplified.

  In addition, as a method for producing the transparent conductive film 1, a self-dispersing group containing a dissociable group dispersible in a conductive polymer and an aqueous solvent by a known method such as an inkjet method on a non-conductive portion (opening portion 12a) of a thin metal wire portion. And a method of forming the second conductive layer 13 containing a mold polymer.

  In the second conductive layer 13 containing a conductive polymer compound and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent, the weight ratio of the polyanion to the cationic π-conjugated polymer is 0.5-2. It is characterized by containing less than 5 conductive polymer compounds. Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength can be obtained.

  By forming the conductive layers 12 and 13 of the present invention having such a structure, the surface of the transparent conductive film 1 has high conductivity that cannot be obtained by a metal or metal oxide fine wire or a conductive polymer layer alone. Can be obtained uniformly in the inside.

  In the second conductive layer 13 containing a conductive polymer compound and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent, the dissociable group-containing self-dispersible dispersible in the conductive polymer compound and the aqueous solvent. The ratio to the type polymer is preferably such that the dissociable group-containing non-conductive polymer is 30 to 900 parts by mass when the conductive polymer compound is 100 parts by mass. From the viewpoint of enhancing the conductivity of the conductive polymer compound and transparency, the dissociable group-containing non-conductive polymer is more preferably 100 parts by mass or more.

  The dry film thickness of the second conductive layer 13 is preferably 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, it is more preferably 200 nm or more. The dry film thickness of the second conductive layer 13 is more preferably 1000 nm or less from the viewpoint of transparency.

  After applying a coating liquid (dispersion liquid) containing a conductive polymer compound and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent, the second conductive layer 13 is formed by performing a drying treatment. . Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range in which the base material 11 and the conductive layers 12 and 13 are not damaged. For example, the drying process can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes. Thereby, the washing | cleaning tolerance and solvent tolerance of the transparent conductive film 1 improve remarkably, and element performance improves further. In particular, in an organic EL element provided with the transparent conductive film 1, effects such as reduction in driving voltage and improvement in life can be obtained.

  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 second conductive layer 13 that is a transparent conductive layer are Ry = maximum height (the difference in height between the top and bottom of the surface) and Ra = arithmetic mean roughness. This is a value according to the surface roughness specified in JIS B601 (1994). In the transparent conductive film 1 according to the present invention, the smoothness of the surface of the second conductive layer 13 which is a transparent conductive layer is Ry ≦ 50 nm and the second conductive is a transparent conductive layer from the viewpoint of improving the conductivity. The smoothness of the surface of the layer 13 is preferably 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, it can be measured by the following method.

  Using an SPI 3800N probe station manufactured by Seiko Instruments Inc. and a SPA400 multifunctional unit as the AFM, set a sample cut to a size of about 1 cm square on a horizontal sample table on a piezo scanner, and place the cantilever on the sample surface. When approaching and reaching the region where the atomic force works, 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 Seiko Instruments Inc., 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 transparent 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. Moreover, as an electrical resistance value of the 2nd conductive layer 13 which is a transparent conductive layer in the transparent conductive film 1 of this invention, it is preferable that it is 1000 ohm / square or less as a surface resistivity from a viewpoint of a performance improvement, and it is 100 ohm / square. The following is more preferable. Furthermore, in order to apply the transparent conductive film 1 to a current-driven optoelectronic device, the surface resistivity may be 50Ω / □ or less from the viewpoint of improving the performance when applied to a current-driven optoelectronic device. Preferably, it is 10Ω / □ or less. That is, it is preferable that the surface resistivity is 10 ³ Ω / □ or less because the transparent conductive film 1 can suitably function as an electrode in various optoelectronic devices. The above-mentioned surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method by conductive probe four-probe method) or the like, or using a commercially available surface resistivity meter. It can be easily measured.

  There is no restriction | limiting in particular in the thickness of the transparent conductive 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 a softness | flexibility are so thin that thickness is thin. It is more preferable because it improves.

<Organic EL device>
An organic EL device according to an embodiment of the present invention includes a transparent conductive film 1 as an electrode, and includes an organic layer including an organic light emitting layer and the transparent conductive film 1. The organic EL element according to the embodiment of the present invention preferably includes the transparent 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 the organic EL element. Things can be used.

  The element configuration of the organic EL element is as follows: 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 / 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. it can.

  In the present invention, the light emitting material or doping material that can be used for 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, quinacridone Rubrene, distyrylbenzene derivatives, di still arylene derivatives, various fluorescent dyes, rare earth metal complex, but phosphorescent material and the like, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material. 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 transparent conductive film 1 according to the embodiment of the present invention has both high conductivity and transparency, and various optical options such as a liquid crystal display device, an organic light emitting device, an inorganic electroluminescent device, electronic paper, an organic solar cell, and an inorganic solar cell. It can be suitably used in the fields of electronics devices, electromagnetic wave shields, touch panels and the like. Among them, it can be particularly preferably used as a transparent electrode of an organic EL device or an organic thin film solar cell device in which the smoothness of the transparent electrode surface is strictly required.

  Moreover, since the organic EL element according to the present invention can emit light uniformly and without unevenness, it is preferably used for lighting applications, and can be used for self-luminous displays, liquid crystal backlights, lighting, and the like. .

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

<Synthesis of Conductive Polymer Compound of the Present Invention>
Examples of the synthesis of the conductive polymer compound according to the present invention and the comparative conductive polymer compound are shown below.

Synthesis example 1
Synthesis of conductive polymer compound CP-1 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 2.4 (mass ratio)) (invention)
Polystyrene sulfonic acid (PSS) (2.7 g, 2.6 mmol; monomer equivalent, monomer molecular weight 184.02) was added to an 18% aqueous solution, and potassium persulfate (0.46 g, 1.7 mmol, molecular weight 270.32, Kanto) Chemical) and iron sulfate (III) n hydrate (2.6 mg, 4.5 × 10 ⁻³ mmol (purity 70% equivalent), molecular weight 399.88, manufactured by Kanto Chemical Co., Inc.), 68 ml of pure water Added and dissolved. A homogenizer (main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was installed and operated under the surface of the solution, and then 3.4-ethylenedioxythiophene ( 0.2 g, 1.4 mmol, molecular weight 142.18, manufactured by Aldrich) was added and polymerized at room temperature for 24 hours. Subsequently, 5.0 g of an anion exchanger (Bayer AG Lewatit MP62) and 5.0 g of a cation exchanger (Bayer AG Lewatit S100) were added to the solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, 5 to 10 ° C., and the conductive polymer compound CP according to the present invention. -1 was obtained (solid content concentration: 0.97%).

Synthesis example 2
Synthesis of conductive polymer compound CP-2 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 1.5 (mass ratio)) (present invention)
Synthetic Example 1 except that the amount of polystyrene sulfonic acid (PSS) (1.7 g, 1.7 mmol; monomer conversion, monomer molecular weight 184.02) was changed in Synthesis Example 1 and the pure water to be added was changed to 50 ml. Similarly, the conductive polymer compound CP-2 according to the present invention was obtained (solid content concentration: 0.96%).

Synthesis example 3
Synthesis of conductive polymer compound CP-3 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 1.0 (mass ratio)) (present invention)
Synthetic Example 1 is the same as Synthetic Example 1 except that the amount of polystyrene sulfonic acid (PSS) (1.1 g, 1.1 mmol; monomer conversion, monomer molecular weight 184.02) was changed and the amount of pure water added was changed to 40 ml. In the same manner, a conductive polymer compound CP-3 according to the present invention was obtained (solid content concentration: 0.97%).

Synthesis example 4
Synthesis of conductive polymer compound CP-4 (PEDOT (polyethylenedioxythiophene) / PSS / binder (polyester), PEDOT / PSS = 1.0 / 0.5 (mass ratio)) (invention)
In Synthesis Example 1, the same procedure as in Synthesis Example 1 except that the amount of polystyrene sulfonic acid (PSS) (0.6 g, 0.6 mmol; monomer conversion, monomer molecular weight 184.02) and pure water to be added were changed to 30 ml. Thus, a conductive polymer compound CP-4 according to the present invention was obtained (solid content concentration: 0.97%).

Synthesis example 5
Synthesis of conductive polymer compound CP-5 (PANI (polyaniline) / PSS, PANI / PSS = 1.0 / 2.0 (mass ratio)) (invention)
50 ml of 20% aqueous polystyrene sulfonate solution (PS5 manufactured by Tosoh Corporation, molecular weight: 50,000 to 100,000) is diluted with 1 L of distilled water, treated with an H-type cation exchange resin (Dowex 50W X12) packed in a column, and polystyrene. A solution containing sulfonic acid was obtained. This solution was concentrated with a rotary evaporator to obtain a 20% aqueous polystyrene sulfonic acid solution.
0.366 g (1.5 mmol) of ammonium dichromate was dissolved in 20 ml of distilled water. Separately, 80 g of distilled water and 3.73 g (4 mmol) of the above 20% polystyrene sulfonic acid solution are added to a 300 ml beaker, and a homogenizer (main body: UltraTex T-25, shaft generator: S25N-10G (manufactured by IKA) )) Was placed and operated under the surface of the solution, and 0.373 g (4 mmol) of aniline was added to the solution. While maintaining the internal temperature at 5 ° C., the aqueous ammonium dichromate solution was added dropwise over 30 minutes. After a few minutes, the reaction solution turned green. After dropwise addition of the aqueous ammonium dichromate solution, the reaction solution was stirred for 1 hour. Subsequently, 5.0 g of an anion exchanger (Bayer AG Lewatit MP62) and 5.0 g of a cation exchanger (Bayer AG Lewatit S100) were added to the black-green solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, 5 to 10 ° C., and the conductive polymer compound CP according to the present invention. -5 was obtained (solid content concentration: 1.3%).

Synthesis Example 6
Synthesis of conductive polymer compound CP-6 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 3.0 (mass ratio)) (Comparative compound)
Synthetic Example 1 except that the amount of polystyrene sulfonic acid (PSS) (3.3 g, 3.2 mmol; monomer conversion, monomer molecular weight 184.02) was changed and the pure water added was changed to 80 ml in Synthesis Example 1. Similarly, the conductive polymer compound CP-6 according to the present invention was obtained (solid content concentration: 0.96%).

Synthesis example 7
Synthesis of conductive polymer compound CP-7 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 0.3 (mass ratio)) (present invention)
Synthesis Example 1 is the same as Synthesis Example 1 except that the amount of polystyrene sulfonic acid (PSS) (0.3 g, 0.3 mmol; monomer conversion, monomer molecular weight 184.02) was changed, and the pure water added was changed to 26 ml. Similarly, the conductive polymer compound CP-7 according to the present invention was obtained (solid content concentration: 0.98%).

Synthesis example 8
Synthesis of conductive polymer compound CP-8 (PANI (polyaniline) / PSS, PANI / PSS = 1.0 / 10.0 (mass ratio)) (Comparative compound)
The conductivity according to the present invention was the same as in Synthesis Example 1 except that the amount of 20% polystyrene sulfonic acid (PSS) (18.6 g, 20 mmol; monomer equivalent, monomer molecular weight 184.02) was changed in Synthesis Example 5. A polymer compound CP-8 was obtained (solid content concentration: 4.1%).

Synthesis Example 9
Synthesis of binder resin P-1: Comparative compound [synthesis of poly-2-hydroxyethyl acrylate (P-1)]
In a 300 ml eggplant flask, 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g (43.1 mmol, Fw 116.12), 2,2′-azobis (2-methylisopropionitrile) 0.7 g (4.3 mmol, Fw164.21) and 100 ml of tetrahydrofuran were added, and the mixture was heated to reflux for 8 hours. The solution was then cooled to room temperature and added dropwise into 2.0 L of vigorously stirred methyl ethyl ketone. After stirring the reaction solution for 1 hour, methyl ethyl ketone was decanted and the polymer adhering to the wall surface was washed three times with 100 ml of methyl ethyl ketone. The polymer was dissolved in 100 ml of tetrahydrofuran, transferred to a 200 ml flask, and tetrahydrofuran was distilled off under reduced pressure using a rotary evaporator. Then, the remaining THF was distilled off by reducing the pressure at 80 ° C. for 3 hours, and 4.1 g (yield 82%) of P-1 having a number average molecular weight of 57,800 and a molecular weight distribution of 1.24 was obtained.

The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively. Further, the obtained P-14.0 g was dissolved in 16.0 g of pure water to prepare a 20% aqueous solution of P-1.

<GPC measurement conditions>
Device: Waters 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (containing 20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C

<Production of substrate>
A UV curable organic / inorganic hybrid hard coat material: OPSTAR Z7501 manufactured by JSR Co., Ltd. was applied to a non-undercoated surface of a polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm, and dried. After coating with a wire bar so that the average film thickness becomes 4 μm, after drying at 80 ° C. for 3 minutes, curing is performed under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere, and a smooth layer Formed.

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

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

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

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

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

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com

  The sample fixed on the operation stage was modified under the following conditions.

(Reforming treatment conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds A film substrate (base material 11) for a transparent electrode (transparent conductive film 1) having gas barrier properties was produced as described above.

<Example 1>
<Preparation of transparent electrode>
<Preparation of transparent electrode TC-101>
Adjust the slit gap of the extrusion head to a dry film thickness of 300 nm on the non-barrier surface of the transparent electrode film substrate having gas barrier properties, using the extrusion method, so that the dry film thickness is 300 nm. Then, it was heated and dried at 110 ° C. for 5 minutes to form a second conductive layer made of a binder resin dispersible in a conductive polymer and an aqueous solvent, and the obtained electrode was cut out to 8 × 8 cm. Transparent electrode TC-101 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive composition CPC-1.
Conductive polymer compound: CP-1 20.0 g
Binder: Pluscoat Z561 (solid content concentration 25%) 4.4 g
1.0 g of dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass)

(Preparation of transparent electrodes TC-102 to TC-110)
In the production of the transparent electrode TC-101, the conductive polymer compound and binder of the coating liquid A were changed as shown in Table 1, and the conductive polymer compound and binder added to the coating liquid A had a solid content of 19 each. Transparent electrodes TC-102 to TC-110 were produced in the same manner as the production of the transparent electrode TC-101 except that the addition amount was changed to 2 mg and 110 mg.

(Preparation of comparative transparent electrodes TC-1111 to TC-116)
The transparent electrode of Comparative Example was prepared in the same manner as the transparent electrode TC-101 except that the conductive polymer compound and the binder of the coating liquid A were changed as shown in Table 1 in the production of the transparent electrode TC-101. TC-1111 to TC-116 were produced.
Note that LX433C and LX435, which are binders used in TC-113 and TC-114, are not dissociable group-containing self-dispersing polymers according to the present invention, and a surfactant is used for dispersion.

<Evaluation of transparent electrode>
The glass transition temperature (Tg) of the binder resin was measured as follows. The film shape, transparency, surface resistance (conductivity), surface roughness and film strength of the obtained transparent electrode were evaluated as follows. In addition, in order to evaluate the stability of the transparent electrode, the film shape, transparency, surface resistance, surface roughness and film strength of the transparent electrode sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 10 days are evaluated. Went.

(Particle size measurement)
Using a particle size measuring machine (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.), it was measured with the solution as it was without dilution.

(Measurement of Tg)
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), the temperature was measured at a heating rate of 10 ° C./min, and the value was obtained according to JIS K7121 (1987).

(transparency)
Based on JIS K 7361-1: 1997, total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. Since it is used for an organic electronic device, it is preferably 75% or more.
A: 80% or more B: 75% to less than 80% B: 70% to less than 75% X: Less than 70% Evaluation criteria: Samples evaluated as A and B pass as the present invention.

(Surface resistance)
The surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.) in accordance with JIS K 7194: 1994. The surface resistance is preferably 100Ω / □ or less, and preferably 30Ω / □ or less in order to increase the area of the organic electronic device.
Evaluation criteria: Samples evaluated as 30Ω / □ or less after forced deterioration pass the present invention.

(Surface roughness (Ra, Ry))
Using an AFM (Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit) and using a sample cut to a size of about 1 cm square, the surface roughness specified in the above method (JIS B601 (1994)). ).
Evaluation criteria: Samples evaluated as Ry ≦ 50 nm and Ra ≦ 10 nm passed the present invention.

(Membrane strength)
The strength of the conductive layer film was evaluated by a tape peeling method.
Crimping / peeling was repeated 10 times on the conductive layer using a Scotch tape manufactured by Sumitomo 3M Co., and the dropping of the conductive layer was visually observed and evaluated according to the following criteria.
◎: No change after 5 times of pressure bonding / peeling ○: No change after 3 times of pressure peeling / bonding △: Peeling is observed after 1 time of pressure peeling, but more than 80% pattern remains ×: 1 time of pressure peeling Peeling was observed, and the remaining pattern was less than 80% Evaluation criteria: Samples evaluated as ◎, ○ passed the present invention

  The evaluation results are shown in Table 1.

  From Table 1, with respect to the transparent electrodes TC-1111 to TC-116 of the comparative example, the transparent electrodes TC-101 to 110 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, and at a high temperature. It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.

<Example 2>
<Preparation of transparent electrode>
<Formation of first conductive layer>
The 1st conductive layer was formed with the following method in the surface without the barrier on the film substrate (base material 11) for transparent electrodes (transparent conductive film 1) which has the gas barrier property obtained above.

(Thin wire grid)
The fine wire lattice (metal material) was produced by gravure printing or silver nanowire as shown below.
(Gravure printing)
Silver nanoparticle paste 1 (M-Dot SLP: manufactured by Mitsuboshi Belting Co., Ltd.) was printed on a fine wire grid having a line width of 50 μm, a height of 1.5 μm, and an interval of 1.0 mm using a gravure printing tester K303MULTICATOR manufactured by RK Print Coat Instruments Ltd. Thereafter, a drying process was performed at 110 ° C. for 5 minutes.

<Preparation of transparent electrode TC-201>
The following coating liquid A is extruded on the transparent electrode in which the first conductive layer is formed by gravure printing on the film substrate for the transparent electrode having gas barrier properties, using an extrusion method so as to have a dry film thickness of 300 nm. The slit gap was adjusted and applied, dried by heating at 110 ° C. for 5 minutes to form a second conductive layer composed of a conductive polymer and a binder resin dispersible in an aqueous solvent, and the obtained electrode was 8 × 8 cm. Cut out. Transparent electrode TC-201 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

<Formation of Second Conductive Layer 13>
(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive composition CPC-1.
Conductive polymer compound: CP-1 20.0 g
Binder: Pluscoat Z561 (solid content concentration 25%) 4.4 g
1.0 g of dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass)

(Production of transparent electrodes TC-202 to TC-207)
In the production of the transparent electrode TC-201, the conductive polymer compound and binder of the coating liquid A were changed as shown in Table 2, and the conductive polymer compound and binder added to the coating liquid A had a solid content of 19 each. Transparent electrodes TC-202 to TC-210 were produced in the same manner as the production of the transparent electrode TC-201 except that the addition amount was changed to 2 mg and 110 mg.

(Preparation of transparent electrode TC-211)
(Random network structure)
Silver nanowire dispersions are described in Adv. Mater. , 2002, 14, 833 to 837, by using PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were produced. Silver nanowires are filtered and washed using a filtration membrane, and then redispersed in an aqueous solution in which 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to silver to prepare a silver nanowire dispersion. did.
The random network structure was prepared using silver nanowires as shown below.
The silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m ² , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced.
A second conductive layer is formed on a transparent electrode in which a random network structure is formed by silver nanowires, using the same coating liquid A (CPC-3) as TC-203 and by the same method as the production of transparent electrode TC-201 And cut into 8 × 8 cm. The obtained electrode was heated at 110 ° C. for 30 minutes using an oven to prepare a transparent electrode TC-211.

(Preparation of transparent electrode TC-212)
(Copper mesh substrate)
A copper mesh was produced on the substrate as an auxiliary electrode by the following method, and patterned with a metal fine particle removing liquid BF to produce a copper mesh substrate.
The catalyst ink GIPD-7 manufactured by Morimura Chemical Co. containing palladium nanoparticles is used, and the CAB-O-JET300, a self-dispersing carbon black solution manufactured by Cabot, has a carbon black ratio of 10.0% by mass with respect to the catalyst ink. 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, that is, 2.54 cm. A grid-like conductive thin wire having a line width of 10 μm, a film thickness after drying of 0.5 μm, and a line spacing of 300 μm is loaded on the base material. After forming into parts, it was dried.
Subsequently, using a high-speed electroless copper plating solution CU-5100 manufactured by Meltex, the substrate was immersed for 10 minutes at a temperature of 55 ° C., washed, and subjected to electroless plating treatment to produce an auxiliary electrode having a plating thickness of 3 μm. .
On the transparent electrode on which the copper mesh is formed, the second conductive layer is formed by the same method as the production of the transparent electrode TC-203 using the same coating liquid A (CPC-3) as TC-203, and 8 × 8 cm Cut out. Transparent electrode TC-212 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

(Preparation of comparative transparent electrodes TC-213 to TC-218)
The transparent electrode of Comparative Example was prepared in the same manner as the transparent electrode TC-201 except that the conductive polymer compound and the binder of the coating liquid A were changed as shown in Table 2 in the production of the transparent electrode TC-201. TC-213 to TC-218 were produced.
Note that LX433C and LX435, which are binders used in TC-215 and TC-216, are not dissociable group-containing self-dispersing polymers according to the present invention, and a surfactant is used for dispersion.

<Evaluation of transparent electrode>
The obtained transparent electrode was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2.

  From Table 2, with respect to the transparent electrodes TC-213 to TC-218 of the comparative examples, the transparent electrodes TC-201 to 212 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, and at a high temperature. It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.

<Example 3>
<Production of organic EL device>
After the transparent electrode substrate produced in Example 2 was washed with ultrapure water, it was cut into a 30 mm square so that one square tile-shaped transparent pattern with a pattern side length of 20 mm was placed in the center, and used for the anode electrode. The organic EL device was produced respectively. The hole transport layer and subsequent layers were formed by vapor deposition. Organic EL elements OEL-301 to OEL-318 were produced using transparent electrodes TC-201 to TC-218, respectively.
Each crucible for vapor deposition in a commercially available vacuum vapor deposition apparatus was filled with a constituent material of each layer in a necessary amount for device production. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
First, an organic EL layer including a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.

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

<Formation of organic light emitting layer>
Next, each light emitting layer was provided in the following procedures.
Compound 2, Compound 3 and Compound 5 are deposited on the formed hole transport layer so that Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass. Co-evaporation was performed in the same region as the hole transport layer at a speed of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
Next, compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass. Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.

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

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

＜カソード電極の形成＞
形成した電子輸送層の上に、透明電極を陽極として陽極外部取り出し端子及び１５ｍｍ×１５ｍｍの陰極形成用材料としてＡｌを５×１０^−４Ｐａの真空下にてマスク蒸着し、厚さ１００ｎｍの陽極を形成した。
さらに、陰極及び陽極の外部取り出し端子が形成できるように、端部を除き陽極の周囲に接着剤を塗り、ポリエチレンテレフタレートを基材としＡｌ_２Ｏ_３を厚さ３００ｎｍで蒸着した可撓性封止部材を貼合した後、熱処理で接着剤を硬化させ封止膜を形成し、発光エリア１５ｍｍ×１５ｍｍの有機ＥＬ素子を作製した。

<Formation of cathode electrode>
On the formed electron transport layer, a transparent electrode is used as an anode and an anode external takeout terminal and Al as a 15 mm × 15 mm cathode forming material are mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa, and a 100 nm thick anode Formed.
Further, a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al ₂ O ₃ is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed. After pasting the members, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

<Evaluation of organic EL element>
About the obtained organic EL element, the light emission nonuniformity and lifetime were evaluated as follows.

(Emission uniformity)
For light emission uniformity, a KEITHLEY source measure unit 2400 type was used to apply a DC voltage to the organic EL element to emit light. Regarding the organic EL elements OEL-201 to OEL-218 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. Further, the organic EL elements OEL-201 to OEL-218 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. Thereafter, 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: Samples evaluated as ◎, ○ after forced deterioration pass the present invention ”

(lifespan)
The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL 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. 100% or more is preferable, and 150% or more is more preferable.
◎: 150% or more ○: 100 to less than 150% △: less than 80 to 100% ×: less than 80% Evaluation criteria: After forced deterioration ◎, samples evaluated as ○ pass as the present invention.

  Table 3 shows the evaluation results. In Table 3, “Invention” in the remarks indicates that it corresponds to an example of the present invention, and “Comparison” indicates that it is a comparative example.

表３から、比較の有機ＥＬ素子ＯＥＬ−３１３〜ＯＥＬ−３１８は６０％ＲＨ、８０℃２時間の加熱後、発光均一性が著しく劣化するのに対し、本発明の有機ＥＬ素子ＯＥＬ−３０１〜ＯＥＬ−３０１２の発光均一性は加熱後でも安定しており耐久性に優れることが分かる。

From Table 3, the comparative organic EL elements OEL-313 to OEL-318 are significantly deteriorated in light emission uniformity after heating at 60% RH and 80 ° C. for 2 hours, whereas the organic EL elements OEL-301 to 301 of the present invention are deteriorated. It can be seen that the light emission uniformity of OEL-3012 is stable after heating and excellent in durability.

DESCRIPTION OF SYMBOLS 1 Transparent conductive film 11 Base material 12 1st conductive layer 13 2nd conductive layer

Claims (6)

A transparent conductive film comprising a transparent substrate and a transparent organic compound layer formed on the substrate,
The organic compound layer is formed using a dispersion containing a cationic high molecular weight conjugated conductive polymer and a conductive polymer compound having a polyanion, and a dissociable group-containing self-dispersing polymer.
The transparent conductive film, wherein a weight ratio of the polyanion to the cationic π-conjugated conductive polymer in the conductive polymer compound is 0.5 or more and less than 2.5. The transparent conductive film according to claim 1, wherein the weight ratio is 0.8 or more and 1.2 or less. A first conductive layer made of a metal material formed in a pattern on the substrate;
A transparent second conductive layer made of the organic compound layer formed on the substrate and electrically connected to the first conductive layer;
The transparent conductive film according to claim 1, further comprising: 4. The transparent conductive film according to claim 1, wherein a glass transition temperature of the dissociable group-containing self-dispersing polymer is 25 ° C. or more and 80 ° C. or less. An organic electroluminescence element comprising the transparent conductive film according to any one of claims 1 to 4 as an electrode. Producing a dispersion containing a cationic π-conjugated conductive polymer and a conductive polymer compound having a polyanion, and a dissociable group-containing self-dispersing polymer;
Forming a transparent organic compound layer on a transparent substrate using the produced dispersion;
Including
The method for producing a transparent conductive film, wherein a weight ratio of the polyanion to the cationic π-conjugated conductive polymer in the conductive polymer compound is 0.5 or more and less than 2.5.

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