JP2013187090A - Transparent conductive film and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film in which moisture volatility in a film while drying is improved significantly, and waterproofness of a film is also improved significantly, and degradation of transparency, conductivity and film strength is little even after the transparent conductive film is placed under a high temperature, high humidity environment for a long period.SOLUTION: A transparent conductive film 1 includes a transparent conductive layer 13 containing a conductive polymer and a binder resin and formed on a transparent substrate 11. The binder resin is composed of composite particles of an organic resin and an inorganic material. The conductive layer 13 is formed using a fluid dispersion containing a conductive polymer and a binder resin.

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, with increasing demand for flat-screen televisions, various types of display technologies such as liquid crystal, plasma, organic electroluminescence (EL), field emission, and the like have been developed. In any of these displays having different display methods, an electrode made of a transparent conductive film, that is, a 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, Patent Document 1 discloses a transparent electrode using a binder resin that can be uniformly dispersed in a conductive polymer and an aqueous solvent on a conductive fiber so that it can be used for products requiring such a large area and a low resistance value. The technology is disclosed. Patent Document 2 proposes a coating material containing conductive polymer, resin particles and inorganic particles, and a binder resin in order to improve water resistance and scratch resistance.

JP 2010-244746 A JP 2011-116860 A

  However, in the techniques described in Patent Documents 1 and 2, moisture in the film after drying is caused by the influence of the hygroscopic dissociative groups of the binder resin and the resin particles and the non-uniformity of the resin particles and the inorganic particles. Insufficient suppression of residuals, adverse effects on transparency, conductivity, film strength, and device performance using transparent electrodes in durability tests under high-temperature, high-humidity environments for long periods Was found to affect.

  The present invention has been made in view of the above-described circumstances, and greatly improves the water volatility in the film during drying, and also greatly improves the water resistance of the film. Even if there is a transparent conductive film with little deterioration in transparency, conductivity and film strength, and using the transparent conductive film, the conductivity is greatly improved, so that both transparency and conductivity are achieved, and light emission is uniform. It is an object of the present invention to provide an organic EL element that is excellent in lightness, has little deterioration in light emission uniformity even under long-term, high-temperature, and high-humidity environments, and has an excellent light emission lifetime.

  To solve the problems of the present invention, there is provided a binder resin comprising a conductive polymer and a binder resin, and the binder resin is composed of composite particles of an organic resin and an inorganic material dispersible in an aqueous solvent. It is important to use, and more specifically, the problem is solved by the following configuration.

1. A transparent conductive film in which a transparent conductive layer containing a conductive polymer and a binder resin is formed on a transparent substrate, wherein the binder resin is composed of composite particles of an organic resin and an inorganic material, The said conductive layer is formed using the dispersion liquid containing the said conductive polymer and the said binder resin, The transparent conductive film characterized by the above-mentioned.

2. 2. The transparent conductive film according to 1 above, wherein the composite particles are particles in which inorganic particles are bonded to the surface of organic resin particles.

3. 3. The transparent conductive film according to 2 above, wherein the inorganic particles are silica particles.

4). The ratio between the conductive polymer and the binder resin is such that the binder resin is 100 to 900 parts by mass when the conductive polymer is 100 parts by mass. film.

5. The conductive layer made of a metal material, wherein the transparent conductive layer containing the conductive polymer and the binder resin is electrically connected to the conductive layer made of the metal material. The transparent conductive film according to claim 4.

6). An organic electroluminescence device comprising the transparent conductive film according to any one of 1 to 5 as a transparent electrode.

  According to the present invention, a transparent conductive film which is excellent in transparency, conductivity and film strength, and has little deterioration in transparency, conductivity and film strength even under a high temperature and high humidity environment for a long time, and the transparent conductive film It is possible to provide an organic EL element that uses a film and has excellent light emission uniformity, little deterioration in light emission uniformity even under long-term high temperature and high humidity environments, and excellent light emission life.

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

  Hereinafter, modes for carrying out the present invention will be described. The present invention provides a binder resin characterized in that a conductive polymer and a binder resin are used as a transparent conductive film, and the binder resin is composed of composite particles of an organic resin and an inorganic material that can be dispersed in an aqueous solvent. By using it, the water volatility at the time of drying can be greatly improved, the residual moisture in the film after drying can be suppressed as much as possible, and at the same time the water resistance and film strength of the film can be greatly improved. Moreover, a dry load can be reduced by containing the inorganic component which does not have a volatile component. Furthermore, the conductivity can be greatly improved by the efficient formation of the conductive path, and both transparency and conductivity can be achieved. Therefore, it is possible to obtain a transparent conductive film with excellent stability, which has high conductivity, high transparency and good film strength even after an environmental test under a high temperature and high humidity environment. Furthermore, it has been found that a long-life organic EL element using the transparent conductive film as a transparent electrode 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.

  As shown in FIG. 1, the transparent conductive film 1 according to the embodiment of the present invention may include a base material 11, a first conductive layer 12, and a second conductive layer 13, and the first conductive layer 12. May be omitted, and only the substrate 11 and the second conductive layer 13 may be configured. The first conductive layer 12 is preferably made of a metal material formed in a pattern, and the second conductive layer 13 contains a conductive polymer and a binder resin. That is, in a preferred embodiment of the present invention, the first conductive layer 12 includes a conductive layer formed of a metal material, and the second conductive layer 13 includes a conductive polymer and a binder resin, and the binder resin is an organic material. The conductive layer is composed of composite particles of a resin and an inorganic material, and the conductive layer is formed using a dispersion liquid containing the conductive polymer and the binder resin.

<Binder resin>
The present invention relates to a transparent conductive film having a conductive polymer and a binder resin, and an organic EL device provided with the transparent conductive film, wherein the binder resin is composed of composite particles of an organic resin and an inorganic material that can be dispersed in an aqueous solvent. It is characterized by that.

  In the present invention, the binder resin is a composite particle of an organic resin and an inorganic material dispersible in an aqueous solvent (also referred to as an aqueous solvent). In the present invention, “dispersible in an aqueous solvent” means “organic in an aqueous solvent”. In a situation where composite particles of resin and inorganic material are in the state of primary particles and / or secondary particles, suitable particle sizes are selected and dispersed according to conditions such as the material constituting the particles and the solvent used. This means that a suspension that is substantially uniformly dispersed in an aqueous solvent can be formed by ordinary dispersion means such as stirring. In the present invention, 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. is there. Examples of the organic solvent include alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as diethylene glycol, propylene glycol, and glycerin; derivatives of polyhydric alcohols such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; Ethers such as propyl ether, dioxane, tetrahydropyran and tetrahydrofuran, acetals, ketones such as acetone, diacetone alcohol and methyl ethyl ketone, esters such as butyrolactone, amines such as ethylamine and propylamine, N, N-dimethylformamide And pyrrolidones such as 2-pyrrolidone and N-methyl-pyrrolidone, and a mixed solvent of water and the organic solvent.

  Subsequently, composite particles of an organic resin and an inorganic material that can be dispersed in an aqueous solvent in the present invention will be described.

<Composite particles of organic resin and inorganic material>
The composite particles of organic resin and inorganic material in the present invention (hereinafter also referred to as organic-inorganic composite particles) are particles of a composite of an inorganic material and an organic resin. The composite form is not particularly limited. For example, an aspect in which an inorganic material is dispersed and contained in resin particles, an aspect in which the surface of particles made of an inorganic material is coated with an organic resin (including a core-shell structure), and vice versa A mode in which the surface of the organic resin particles is coated with an inorganic material (including a core-shell structure), a mode in which the inorganic particles are bonded on the surface of the organic resin particles, and an organic resin in the inorganic particles having a pore structure Examples include a mode of entering, and a mode of entering inorganic particles in the entangled structure of the organic resin. Each particle shape may be any particle shape such as a spherical shape, a needle shape, a plate shape, a scale shape, and a crushed shape, and is not particularly limited, but a spherical shape or a shape close to a spherical shape is preferable.

  The form of bonding between the inorganic material and the organic resin may be a form that is physically or chemically fixed. Physically fixed means, for example, a state where organic resin particles are fixed in inorganic particles having a pore structure. The term “chemically fixed” refers to, for example, a state where organic resin particles and inorganic particles are fixed by chemical bonding.

  In the present invention, chemically fixed composite particles are preferable in terms of strength, and organic-inorganic composite particles having a structure in which inorganic particles are bonded to the surface of organic resin particles are particularly preferable. The reason for this is estimated as follows. That is, when the organic resin component of the organic / inorganic composite particles exerts a film forming action, partial inhibition of film formation occurs due to the inorganic component. This spreads evenly over the entire conductive layer, so that a fine pore network structure can be formed. The present inventors presume that the composite particles more advantageous for forming the pore network structure are organic-inorganic composite particles having a structure in which inorganic particles are bonded to the surface of the resin particles.

  This network of pores secures the route of water volatilization from the inside to the film surface during film formation, greatly improves the water volatility during dry film formation, and the water resistance of the resin film and the film due to the effects of inorganic substances. Strength is greatly improved. Furthermore, the present inventors presume that the network structured pores are filled with the conductive polymer at the same time as the drying proceeds to form a network structure of the conductive path. .

  Thus, the present inventors presume that an efficient conductive path can be formed with the minimum amount of conductive polymer, and both improved conductivity and transparency can be achieved. On the other hand, when inorganic particles and organic binder resin particles are added separately and used, the inorganic particles are biased and a uniform network structure cannot be formed, and the improvement in volatility and conductivity is not sufficient. The inventors have estimated.

Examples of the inorganic material of the organic-inorganic composite particles in the present invention include, for example, silicon oxide, calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, sodium silicate, aluminum oxide, iron oxide, zirconium oxide, barium sulfate, and oxidation. Titanium, tin oxide, antimony trioxide, carbon black, and molybdenum disulfide can be used.
Of these, silicon oxide is particularly preferred. The inorganic material is preferably in the form of particles, and the inorganic particles are preferably inorganic particles having a primary particle size of 100 nm or less and a secondary particle size of 500 nm or less. For example, JP-A-1-97678 JP-A-2-275510, JP-A-3-281383, JP-A-3-285814, JP-A-3-285815, JP-A-4-92183, JP-A-4-267180, Pseudo boehmite sol which is an alumina hydrate disclosed in Kaihei 4-27517, etc., JP-A-60-219083, JP-A-61-19389, JP-A-61-188183, Colloidal silica as described in JP-A-63-178074, JP-A-5-51470, etc., Japanese Patent Publication No. 4-19037 And silica / alumina hybrid sol as described in JP-A-62-2286787, gas phase process silica as described in JP-A-10-119423 and JP-A-10-217601 Silica sol dispersed with a high-speed homogenizer, and other smectite clays such as hectite and montmorillonite (JP-A-7-81210), zirconia sol, chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, antimony oxide sol, etc. Can be cited as representative. Among these, colloidal silica can be suitably used as the inorganic particles.

  The colloidal silica preferably used in the present invention is a modified colloidal silica in which the silica surface is coated with ions or compounds such as calcium and alumina to change the behavior with respect to ionicity or pH fluctuation, in addition to conventional non-modified colloidal silica. Either can be used.

  The colloidal silica that can be suitably used in the present invention may be a commercially available product. Examples of commercially available colloidal silica include Nihon Chemical Industry, such as Snowtex 20, Snowtex 40, Snowtex N, Snowtex O, Snowtex S, Snowtex 20L, Snowtex AK, Snowtex UP, etc., manufactured by Nissan Chemical Industries. Silica doll 20, silica doll 20A, silica doll 20G, silica doll 20P, etc., Adelite AT-20, Adelite AT-20N, Adelite AT-30A, Adelite AT-20Q, etc. manufactured by Asahi Denka Kogyo, etc. HS-30, Ludox LS, Ludox SM-30, Ludox AS, Ludox AM, etc. are mentioned.

  The average particle diameter of the inorganic particles is preferably in the range of 2 to 100 nm, more preferably in the range of 5 to 50 nm. When the average particle diameter of the inorganic particles is smaller than 2 nm, the production of the organic-inorganic composite particles is limited. When the average particle diameter of the inorganic particles is larger than 100 nm, the surface roughness of the transparent conductive film 1 is increased and the performance is improved. There is a risk of adverse effects. In addition, when the average particle size of the inorganic particles is 5 nm or more, partial film formation inhibition by the inorganic component works effectively, the pore network is sufficiently formed, and the performance of the transparent conductive film 1 is improved. Is done. Moreover, in order to suppress the surface roughness of the transparent conductive film 1 and improve performance, the average particle diameter of the inorganic particles is more preferably 50 nm or less.

  The organic resin of the organic-inorganic composite particles in the present invention is preferably a polymer from the viewpoint of coating film adhesion, and the molecular weight, shape, composition, presence or absence of a functional group, etc. are not particularly limited, and any polymer can be used. Can be used.

  Examples of organic resins include acrylic resins, styrene-acrylic copolymers, styrene-butadiene copolymers, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate-vinyl chloride copolymers. A coalescence, polyethylene resin, polypropylene resin, polyester resin, urethane resin, silicone resin, fluorine resin, benzoguanamine resin, phenoxy resin, phenol resin, nylon resin, butyral resin, or the like can be used. Of these, acrylic resins, polyester resins and polyethylene resins are particularly preferred as the organic resin.

  The glass transition temperature (Tg) of the resin in the present invention is preferably in the range of 30 to 120 ° C. When Tg of resin is less than 30 degreeC, the water resistance of a resin film falls and there exists a possibility that the transparency after a hot-water process may deteriorate. In addition, when the Tg of the resin exceeds 120 ° C., a high temperature is required to form a resin film. Therefore, if a resin base material having poor heat resistance such as PET is used, deformation may occur during film formation. There is. Moreover, it becomes a resin film inferior in blocking resistance, for example, when the film coated with the resin film is taken up, the operability may be deteriorated such that the coat film is blocked.

  The organic resin is preferably in the form of resin particles, and the preferred particle size of the resin particles is preferably 20 nm to 500 nm, particularly preferably 50 nm to 200 nm. If the average particle diameter of the resin particles is smaller than 20 nm, the production of the organic-inorganic composite particles is limited. If the average particle diameter of the resin particles is larger than 500 nm, the surface roughness of the transparent conductive film 1 is increased and the performance is adversely affected. May cause effects. In addition, when the average particle diameter of the resin particles is 50 nm or more, the film forming action between the organic resin particles and the partial film formation inhibition by the inorganic component are balanced, and the pore network is sufficiently formed. Thus, the performance of the transparent conductive film 1 is improved. Moreover, in order to suppress the surface roughness of the transparent conductive film 1 and improve the performance, the average particle diameter of the resin particles is more preferably 200 nm or less.

  The organic-inorganic composite particles are preferably used in a dispersion solution. Examples of the method for producing the dispersion solution include the following production methods.

(1) In the process of producing a copolymerizable monomer, a monomer having a polymerizable unsaturated double bond and an alkoxysilane group in the molecule, vinyl silane, colloidal silica, and emulsion polymerizing the polymer component Incorporating an inorganic material on the resin particle surface to obtain composite particles, for example, JP-A-10-237348, JP-A-7-304999, International Publication WO2005 / 116120, JP-A-59-71316, A method disclosed in JP-A-60-127371 and JP-T 2009-520867.

(2) Using a hydrolyzable alkoxysilane that is incompatible with water, such as ethyl orthosilicate, a silica component is deposited on the surface of the resin particles that are formed in advance and fixed to obtain composite particles. For example, International Symposium on The method described in Polymeric Microspheres Prints, 1991, 181.

(3) Silica particles are fixed on the surface of polyester resin particles by uniformly mixing an aqueous nanosilica dispersion composed of fumed nanosilica with vinyldiethoxysilyl polyester and a nonionic surfactant in a high-speed dispersion container. For example, the method disclosed in JP-T-2009-520867.

(4) Silane coupling or the like is bonded to the divinylbenzene polymer particles, and a specific metal alkoxide, colloidal metal oxide, or colloidal silica is reacted therewith to at least a part of the inside and the surface of the polymer particles. A method disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-204355, in which a metalloxane bond-containing part, a metal compound part composed of a metal oxide particle part, and the like are formed to obtain composite particles.

(5) A composite particle in which silica is encapsulated in a polymer matrix is obtained by (co) polymerizing a polymerizable organic (co) monomer in the presence of silica in a fine state. For example, it is disclosed in JP-A-5-117772. Way.

(6) Composite particles in which cationic polymer particles are encapsulated inside pores of silica particles having a pore structure are obtained by mixing tetramethoxysilane and bistriethoxysilylethane into an aqueous solution in a suspension of cationic polymer particles. For example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-263171.

  Further, the dispersion method of the organic-inorganic composite particles in an aqueous solvent will be described in detail. The carboxyl group at the terminal of the resin component of the composite particles is neutralized at least partially or entirely using a basic compound. Thus, it can be produced by a method of dispersing in an aqueous medium. Specifically, the carboxyl anion is generated by neutralizing the carboxyl group, and the composite particles are stably dispersed without agglomeration due to the electric repulsion between the anions.

  In addition to the above-described production method, for example, an aqueous dispersion can be produced without using a basic compound by using a resin having a sulfonate group as a resin or using a surfactant as a dispersant. Is possible.

  The dispersion solution of the organic / inorganic composite particles includes a curing agent, various additives, a compound having a protective colloid action, water, an organic solvent, a dye, and an aqueous resin (aqueous polyester resin, aqueous urethane resin, aqueous olefin resin, if necessary. , Aqueous acrylic resin and the like) can be used.

  The water used for dispersion is not particularly limited, and examples thereof include distilled water, ion exchange water, city water, and industrial water, but it is preferable to use distilled water or ion exchange water.

  The size of the organic-inorganic composite particles is preferably 22 to 600 nm, more preferably 55 to 250 nm. When the average particle diameter of the organic / inorganic composite particles is smaller than 22 nm, the production of the organic / inorganic composite particles is limited. When the organic / inorganic composite particles are larger than 600 nm, the surface roughness of the transparent conductive film 1 increases and the performance is improved. There is a risk of adverse effects. In addition, when the average particle diameter of the resin particles is 55 nm or more, the film forming action between the organic resin particles and the partial film forming inhibition by the inorganic component are balanced, and the pore network is sufficiently formed. Thus, the performance of the transparent conductive film 1 is improved. Moreover, in order to suppress the surface roughness of the transparent conductive film 1 and improve performance, it is more preferable that the average particle diameter of the organic-inorganic composite particles is 250 nm or less. The size of the colloidal particles can be measured with a light scattering photometer.

  The mass ratio of the inorganic component and the organic resin particles (inorganic component / resin component) is preferably 10/90 to 70/30, and more preferably 20/80 to 60/40. When the mass ratio (inorganic component / resin component) is 70/30 or less, a uniform and flexible resin layer can be formed, and when the mass ratio is 10/90 or more, the pore network structure can be formed. Can be formed. Moreover, the flexibility of the transparent conductive film 1 is suitably ensured by being 60/40 or less, and winding becomes easy, and by being 20/80 or more, the network structure of the pores is more suitable by an inorganic component. Can be formed.

  As the aqueous dispersion of the organic-inorganic composite particles in the present invention, a commercially available product can be used. As a commercial product of the aqueous dispersion of composite particles in which colloidal silica particles are bonded to the surface of the resin particles, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Emulsion “mobile” series, for example, mobile vinyl 8055A, 8030, etc. can be preferably used.

  These aqueous dispersions of organic / inorganic composite particles may be used alone or in combination.

  In this invention, the usage-amount of the binder resin comprised from an organic inorganic composite particle becomes like this. Preferably it is 50-1000 mass% with respect to a conductive polymer, More preferably, it is 100-900 mass with respect to a conductive polymer. %. Here, the reason why the amount of the binder resin used is preferably 50 to 1000% by mass with respect to the conductive polymer is that when the amount is less than 50% by mass, the effect of improving the transmittance becomes insufficient (conductivity). Since the polymer absorbs light in the visible light region, it is desirable to reduce the conductive polymer as much as possible without reducing the conductivity in order to improve the transmittance.) If it exceeds 1000% by mass, the ratio of the conductive polymer This is because the conductivity becomes too small and the conductivity is lowered. In order to obtain the effect of improving the transmittance and prevent a decrease in conductivity, the amount of the binder resin used is more preferably 100 to 900% by mass with respect to the conductive polymer.

<Conductive polymer>
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 is a conductive polymer having a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily obtained by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a poly anion described later. Can be manufactured.

(Π-conjugated conductive polymer)
In the present invention, the π-conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, or polythiazyl chain conductive polymers can be used. Among these, polythiophenes or polyanilines are preferable from the viewpoint of conductivity, transparency, stability, and the like, and polyethylenedioxythiophene is most preferable.

(Π-conjugated conductive polymer precursor monomer)
In the present invention, a precursor monomer used for forming a π-conjugated conductive polymer has a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, A π-conjugated system is formed. 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.

(Poly anion)
In the present invention, the poly anion used for the conductive polymer 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 poly anion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  The anion group of the polyanion may be 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. In particular, a sulfonic acid group and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. Further, the polyanion may be a homopolymer of these, or two or more kinds of copolymers.

  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, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like. .

  Among these, when a compound having a sulfonic acid as a polyanion is used, after forming a conductive polymer-containing layer by coating and drying, it is further subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more. The microwaves may be irradiated. Such heat drying treatment is preferable from the viewpoint that the crosslinking reaction is accelerated and the washing resistance and solvent resistance of the coating film are remarkably improved.

  Furthermore, among the compounds having sulfonic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, or Nafion is preferable. These poly anions have high compatibility with the nonconductive polymer added as the binder resin, and can further increase the conductivity of the obtained conductive polymer.

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

  Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And the like, 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.

  The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

  When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for 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.

  Ratio of π-conjugated conductive polymer and polyanion contained in conductive polymer, “π-conjugated conductive polymer”: “poly anion” is preferably a mass ratio from the viewpoint of conductivity and dispersibility Is in the range of 1: 1 to 20, and more preferably in the range of 1: 2 to 10 in terms of mass ratio.

  The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. Such oxidants include, for practical reasons, inexpensive and easy-to-handle oxidants such as iron (III) salts (eg FeCl 3, Fe (ClO 4) 3, iron (III) salts of inorganic acids including organic acids, Iron (III) salts of inorganic acids containing organic residues), hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate), ammonium, alkali perborate, potassium permanganate, Alternatively, it is preferable to use a copper salt (for example, copper tetrafluoroborate). 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 persulfates, iron (III) salts containing organic acids, or iron (III) salts of inorganic acids containing organic residues has great application advantages because they are not corrosive.

  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.

  As such a conductive polymer, a commercially available material can also be preferably used. For example, a conductive polymer (abbreviated as PEDOT-PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is H.264. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095, 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.

  The conductive polymer 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.

<Base material>
The base material 11 in the present invention is a transparent plate-like body that can carry a conductive polymer and a binder resin, and is also called a substrate. In order to obtain a transparent conductive film, the total light transmittance in the visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (a test method for the total light transmittance of plastic-transparent material) is 80% or more. Is preferably used as the substrate 11.
As the base material, 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, but a transparent resin film is preferably used from the viewpoint 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 used more preferably as the base material 11 which concerns on this invention. As such a substrate, from the viewpoints of transparency, heat resistance, ease of handling, strength and cost, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film is preferable. A biaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.

  In order to ensure the wettability and adhesiveness of the coating liquid, the substrate 11 according to the present invention can be subjected to a surface treatment or an easy adhesion layer. 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 an inorganic material and an organic material may be formed on the front surface or the back surface of the film-shaped substrate, and the substrate on which such a film is formed is JIS K. Barrier property of water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method based on 7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less The film is preferably a film. Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and the water vapor permeability (25 ± 0. 5 ° C. and relative humidity (90 ± 2)% RH) is preferably a high barrier film having 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-like base material in order to obtain a high barrier film, it is a material having a function of suppressing intrusion although it causes deterioration of elements such as moisture and oxygen. 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 | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

<Conductive layer and transparent conductive film>
In the present invention, the conductive layer 13 and the transparent conductive film 1 including the conductive layer 13 are coated on the base material 11 with a coating liquid which is a dispersion containing the conductive polymer and the binder resin. It is formed by heating and drying.

  In addition to printing methods such as gravure printing, flexographic printing, and screen printing, the application of a coating solution composed of a conductive polymer and a binder resin is a roll coating method, a bar coating method, a dip coating method, and a spin coating method. Any of coating methods such as casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and inkjet method can be used.

  After applying a coating solution containing a conductive polymer and a binder resin, a drying treatment can be appropriately performed. Although there is no restriction | limiting in particular as conditions for a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and a conductive layer. For example, a drying process can be performed at 80 to 150 ° C. for 10 seconds to 15 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 including the transparent conductive film 1, effects such as a reduction in driving voltage and an improvement in lifetime can be obtained.

  Furthermore, from the viewpoint of improving workability such as coating properties, the coating solution described above is a solvent (for example, water, organic solvents (alcohols, glycols, cellosolves, ketones, esters, ethers, amides, carbonized). Hydrogens, etc.).

  In the present invention, the value of Ry representing the smoothness of the surface of the conductive layer 13 of the transparent conductive film 1 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 of the conductive layer 13 of the transparent conductive film 1 is more preferably 10 nm or less, and further preferably 5 nm or less.

  The dry film thickness of the conductive layer 13 of the present invention is preferably 30 to 2000 nm from the viewpoint of surface smoothness and transparency, more preferably 100 nm or more from the viewpoint of conductivity, and the transparent conductive film 1. From the viewpoint of the surface smoothness, it is more preferably 200 nm or more. The dry film thickness of the conductive layer 13 is more preferably 1000 nm or less from the viewpoint of transparency.

  In the present invention, Ry and Ra representing the smoothness of the surface of the conductive layer 13 mean Ry = maximum height (the difference in height between the crest and trough of the surface) and Ra = arithmetic mean roughness, JIS B601. It is a value according to the surface roughness specified in (1994). In the present invention, a commercially available atomic force microscope (AFM) can be used to measure Ry and Ra.

  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 particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. In addition, the electrical resistance value of the transparent conductive layer 13 in the transparent conductive film 1 of the present invention is 1000Ω / □ or less as the surface resistivity from the viewpoint of improving the performance when applied to a current-driven optoelectronic device. Preferably, it is 100Ω / □ or less. Furthermore, in order to apply the transparent conductive film 1 to a current-driven optoelectronic device, the electrical resistance value of the transparent conductive layer 13 is the surface from the viewpoint of performance improvement when applied to a current-driven optoelectronic device. The resistivity is preferably 50Ω / □ or less, and more preferably 10Ω / □ or less. In particular, it is preferably 1000Ω / □ or less because it can function suitably as a transparent 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 using a conductive plastic four-probe method), and a commercially available surface resistivity meter is used. And can be measured easily.

  There is no restriction | limiting in particular in the thickness of the transparent conductive film 1 of 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 improve, so that thickness becomes thin. Therefore, it is more preferable.

  As shown in FIG. 1, the transparent conductive film 1 according to the embodiment of the present invention preferably includes a base material 11, a first conductive layer 12, and a second conductive layer 13, and the first conductive layer 12. Is preferably made of a metal material formed in a pattern, and the second conductive layer 13 contains a conductive polymer and a binder resin. That is, in a preferred embodiment of the present invention, the first conductive layer 12 includes a conductive layer formed of a metal material, and the second conductive layer 13 includes a conductive polymer and a binder resin, and the binder resin is an aqueous solvent. It is to use a binder resin characterized by being composed of composite particles of an organic resin and an inorganic material that can be dispersed in the resin. Below, the 1st conductive layer 12, the 2nd conductive layer 13, and the transparent conductive film 1 are demonstrated.

<First conductive layer made of a metal material>
In the present invention, a transparent electrode is formed by providing a conductive layer 12 made of a metal material on the transparent conductive film 1 in which a conductive layer 13 containing a conductive polymer and a binder resin is formed on the base material 11 described above. More preferably. The conductive layer 12 made of a metal material according to the present invention is preferably made of a metal material formed in a pattern.

  As shown in FIG. 1, a transparent conductive film 1 according to the present invention includes a first conductive layer 12 (hereinafter also referred to as a metal pattern conductive layer 12) made of a metal material formed in a pattern on a substrate 11. It is preferable to have. In particular, the first conductive layer 12 is preferably formed using metal particles because it is advantageous for ease of pattern formation, stability over time, and densification of the metal pattern.

(Metal particles)
The metal of the metal particles is not particularly limited as long as it has excellent conductivity, and examples thereof include alloys in addition to metals such as gold, silver, copper, iron, nickel, and chromium. From the viewpoint of conductivity, silver or copper is preferable, and silver or copper may be used alone or in combination, or an alloy of silver and copper, or silver or copper may be plated with the other metal.

  The average particle size of the metal particles is preferably in the range of atomic scale to 1000 nm. The smaller the average particle size of the metal particles is, the more advantageous is the densification (improvement of electrical conductivity) of the fine metal wires and the surface smoothness. Also become. From this viewpoint, in the present invention, those having an average particle diameter of 3 to 300 nm are particularly preferred, and those having a mean particle diameter of 5 to 100 nm are more preferably used. Among those described above, silver nanoparticles having an average particle diameter of 3 nm to 100 nm are particularly preferable.

  The aspect ratio (major axis length / minor axis length) of the metal particles is preferably a metal particle close to a sphere of 2.0 or less from the viewpoint of improving the surface smoothness and densifying the metal pattern. In the present invention, the average particle diameter can be easily measured using a commercially available measuring apparatus using a light scattering method. Specifically, it is a value measured using a Zetasizer 1000 (manufactured by Malvern Co., Ltd.) by a laser Doppler method at S25 ° C. and a sample dilution amount of 1 ml.

(Metal pattern conductive layer)
The metal pattern conductive layer 12 preferably used in the present invention is a layer containing metal, and is a layer formed in a pattern so as to have an opening 12a on the transparent substrate 11.

  The opening part 12a is a part which does not have the metal pattern conductive layer 12 among the transparent base materials 11, and is a translucent part of a metal pattern. The shape of the pattern is not particularly limited, but for example, a stripe shape, a lattice shape, a honeycomb shape or the like is preferable. 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.

  For example, when the metal pattern conductive layer 12 has a stripe shape, the aperture ratio of the stripe pattern having a line width of 100 μm and a line interval of 1 mm is approximately 90%. The line width of the pattern is preferably 10 to 200 μm from the viewpoint of transparency and conductivity. In the stripe-like or lattice-like pattern, the distance between the fine lines of the metal pattern conductive layer 12 is preferably 0.5 to 4 mm from the viewpoint of transparency and conductivity. In the honeycomb pattern, the length of one side of the metal pattern conductive layer 12 is preferably 0.5 to 4 mm from the viewpoint of transparency and conductivity. In the metal pattern conductive layer 12, the height of the thin line is preferably 0.1 to 3.0 μm from the viewpoint of conductivity and current link prevention.

(Method for producing metal pattern conductive layer)
The metal pattern conductive layer 12 according to the present invention can be obtained by forming a pattern on the substrate 11 by printing a coating liquid for metal pattern conductive layer containing metal particles. The coating liquid for metal pattern conductive layers containing metal particles is a metal particle dispersion containing metal particles described later. The metal particle dispersion contains metal particles in a solvent such as water and alcohol, but may contain a binder, a dispersant for dispersing the metal, and the like as necessary. Using the metal particle dispersion, the metal pattern conductive layer 12 can be formed on the substrate 11 by a printing method such as a gravure printing method, a flexographic printing method, a screen printing method, or an ink jet printing method.

  For each printing method, a method generally used for forming an electrode pattern is applicable to the present invention. As specific examples, as for the gravure printing method, the methods described in JP 2009-295980 A, JP 2009-259826 A, JP 2009-96189 A, JP 2009-90662 A, and the like can be used. Regarding the printing method, methods described in JP-A Nos. 2004-268319 and 2003-168560 are disclosed, and regarding the screen printing method, JP-A 2010-34161, JP-A 2010-10245, and JP-A 2009. An example is the method described in Japanese Patent No. -30345.

Moreover, it is preferable that the metal pattern conductive layer 12 is heat-treated within a range that does not damage the film-like substrate 11. Thereby, fusion and densification of the metal particles proceed, and the metal pattern conductive layer 12 becomes highly conductive.
(Surface specific resistance of metal pattern conductive layer)

  The surface specific resistance of the thin wire portion of the metal pattern conductive layer 12 is preferably 100Ω / □ or less, more preferably 10Ω / □ or less, and further 5Ω / □ or less from the viewpoint of increasing the area. It is more preferable. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

(Roughness Ra of the surface of the metal pattern conductive layer)
In the present invention, the surface roughness Ra of the metal pattern conductive layer 12 is preferably 20 nm or less. The value of Ra can be measured in accordance with, for example, JIS, B601 (1994), etc., and the following method is used using a commercially available atomic force microscope (AFM) as described below. Can be measured. As the AFM, use the Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit, set it on the horizontal sample stage on the piezo scanner, approach the cantilever to the sample surface, and reach the region where atomic force works Then, scanning is performed in the XY directions, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. As the piezo scanner, a scanner capable of scanning XY20150 μm and Z25 μm is used. As the cantilever, a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc. having a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 30 nm is used, and Ra is measured in a DFM mode (Dynamic Force Mode). For measurement, use a CCD camera to adjust the tip of the probe to the center in the width direction of the thin line so that the fine line of the metal pattern and the measurement area are parallel or perpendicular to each other. 10 × 10 μm was performed at a scanning frequency of 0.1 Hz. After the measurement, 10 lines with a length of 10 μm are drawn at intervals of 0.9 μm parallel to the thin line, Ra on the line is calculated, and the average value is taken as the value of Ra.

<Second conductive layer and transparent conductive film>
The second conductive layer 13 preferably used in the present invention is obtained by applying the coating liquid containing the conductive polymer and the binder resin onto the base material 11 on which the metal pattern conductive layer 12 is formed. It is formed by coating on the conductive layer 12, heating and drying. Here, the second conductive layer 13 only needs to be electrically connected to the metal pattern conductive layer 12, and may completely cover the metal pattern conductive layer 12, or a part of the metal pattern conductive layer 12 may be covered. The metal pattern conductive layer 12 may be covered.
In addition to printing methods such as gravure printing, flexographic printing, and screen printing, the application of a coating solution composed of a conductive polymer and a binder resin is a roll coating method, a bar coating method, a dip coating method, and a spin coating method. Any of coating methods such as casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and inkjet method can be used.

  Moreover, as a method of manufacturing the transparent conductive film 1 in which a part of the metal pattern conductive layer (first conductive layer) 12 is covered or in contact with the second conductive layer 13 containing a conductive polymer and a binder resin. Is obtained by forming the first conductive layer 12 on the transfer film by the method described above, and further laminating the second conductive layer 13 containing a conductive polymer and a binder resin on the transfer film by the method described above. A method of transferring to the base material 11, and a non-conductive portion of the base material 11 on which the metal pattern conductive layer (first conductive layer) 12 is formed by a known method such as an ink jet method or the like, containing a conductive polymer and a binder resin. The method of forming the 2 conductive layer 13 is mentioned.

  By having the first conductive layer 12 and the second conductive layer 13, the transparent conductive film 1 of the present invention has high conductivity that cannot be obtained by a metal thin wire or a conductive polymer layer alone, and is in the plane of the transparent conductive film 1. Can be obtained uniformly.

  The dry film thickness of the second conductive layer 13 is preferably 30 to 2000 nm from the viewpoint of surface smoothness and transparency, more preferably 100 nm or more from the viewpoint of conductivity, and the surface of the transparent electrode 1. From the viewpoint of smoothness, the thickness 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 solution containing a conductive polymer and a binder resin, a drying treatment can be appropriately performed. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range in which the base material 11 and the conductive layers 12 and 13 are not damaged. For example, a drying process can be performed at 80 to 150 ° C. for 10 seconds to 15 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 including the transparent conductive film 1, effects such as a reduction in driving voltage and an improvement in lifetime can be obtained.

  Furthermore, from the viewpoint of improving workability such as coating properties, the coating solution described above is a solvent (for example, water, organic solvents (alcohols, glycols, cellosolves, ketones, esters, ethers, amides, carbonized). Hydrogens, etc.).

  In the present invention, the value of Ry representing the smoothness of the surface of the second conductive layer 13 which is a transparent conductive layer is more preferably 50 nm or less, and further preferably 40 nm or less, from the viewpoint of improving conductivity. preferable. Similarly, the value of Ra of the second conductive layer 13 which is a transparent conductive layer is more preferably 10 nm or less, and further preferably 5 nm or less.

  In the present invention, Ry and Ra representing the smoothness of the surface of the second conductive layer 13 mean Ry = maximum height (the difference in height between the top and bottom of the surface) and Ra = arithmetic mean roughness, It is a value according to the surface roughness specified in JIS B601 (1994). In the transparent electrode 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 smoothness of the surface of the second conductive layer 13 which is a transparent conductive layer is Ra ≦ 10 nm. It is preferable that In the present invention, a commercially available atomic force microscope (AFM) can be used for the measurement of Ry and Ra as described above.

  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 particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. In addition, the electrical resistance value of the second conductive layer 13 which is the transparent conductive layer in the transparent conductive film 1 of the present invention is 1000 Ω / as the surface resistivity from the viewpoint of improving the performance when applied to a current-driven optoelectronic device. □ or less is preferable, and 100 Ω / □ or less is more preferable. Furthermore, in order to apply the transparent conductive film 1 to a current-driven optoelectronic device, the electrical resistance value of the second conductive layer 13 that is a transparent conductive layer is a performance when applied to a current-driven optoelectronic device. From the viewpoint of improvement, the surface resistivity is preferably 50Ω / □ or less, more preferably 10Ω / □ or less. In particular, it is preferably 1,000Ω / □ or less because it can function as a transparent 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 using a conductive plastic four-probe method), and a commercially available surface resistivity meter is used. And can be measured easily.

  There is no restriction | limiting in particular in the thickness of the transparent conductive film 1 of 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 improve, so that thickness becomes thin. Therefore, it is more preferable.

<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 present invention has both high conductivity and transparency, and is used in various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, and inorganic solar cells. In addition, it can be suitably used in fields such as an electromagnetic wave shield and a touch panel. Among them, it can be particularly preferably used as an 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.

<Production of aqueous dispersion of organic-inorganic composite particles>
(Aqueous dispersion E-1)
A four-necked flask equipped with a stirrer, thermometer, condenser and dropping funnel is charged with 100 parts of ion-exchanged water, 3 parts of sodium dioctylsulfosuccinate and 20 parts of colloidal silica having an average particle size of 20 nm, and stirred uniformly. The temperature was raised to 60 ° C. while dispersing. While dropwise adding a mixture of 20 parts of methyl methacrylate, 30 parts of 2-ethylhexyl acrylate, 30 parts of styrene and 0.3 part of potassium persulfate, the mixture was allowed to react at 60 to 70 ° C. until the monomer disappeared. A 49% aqueous dispersion of organic-inorganic composite particles was produced. The average particle size of the composite particles was 80 nm. As a result of observation by an electron microscope, the composite particles were in a form in which colloidal silica particles were dispersed and combined inside the resin particles.

(Aqueous dispersion E-2)
An organic-inorganic composite particle aqueous dispersion having a solid content of 49% is produced in the same manner as in the production of the aqueous dispersion E-1, except that the colloidal silica is changed to nano zirconium oxide particles in the production of the aqueous dispersion E-1. did. The average particle size of the composite particles was 80 nm. As a result of observation by an electron microscope, this composite particle was in a form in which zirconium oxide fine particles were dispersed and compounded inside the resin particle.

(Aqueous dispersion E-3)
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube and a dropping funnel, 100 parts of ion-exchanged water and 3 parts of sodium dioctylsulfosuccinate were charged and stirred, and the temperature was raised to 60 ° C. while uniformly dispersing. The monomer disappears at 60-70 ° C. while dropping a mixture of 15 parts of methyl methacrylate, 30 parts of 2-ethylhexyl acrylate, 30 parts of styrene, 5 parts of vinyltrimethoxysilane and 0.3 part of potassium persulfate. Then, 20 parts of colloidal silica having an average particle diameter of 20 nm was added to produce an organic-inorganic composite particle aqueous dispersion having a solid content of 49%. The average particle size of the composite particles was 90 nm. As a result of observation by an electron microscope, the composite particles were in a form in which colloidal silica particles were combined and combined with the surface of the acrylic resin particles.

(Aqueous dispersion E-4)
According to Production Example 1 of Japanese Patent Laid-Open No. 5-115772, an organic-inorganic composite particle aqueous dispersion having a solid content of 10% using silica powder (BET specific surface area: 200 m @ 2 / g; average primary particle diameter: 12 nm) Manufactured. The average particle size of the composite particles was 80 nm. As a result of observation with an electron microscope and particle analysis, the composite particles were in a form in which silica core particles were coated with an acrylic resin mainly composed of polyethyl acrylate.

(Aqueous dispersion E-5)
An organic-inorganic composite particle aqueous dispersion having a solid content of 10% was produced according to Example 5 of JP-A-2000-204355. The average particle size of the composite particles was 180 nm. As a result of observation with an electron microscope and particle analysis, the composite particles were in a form in which core particles mainly composed of a styrene-methacrylic acid copolymer were coated with silicon oxide to form a composite.

(Aqueous dispersion E-6)
According to Example 1 of JP-A-2009-263171, an organic-inorganic composite particle aqueous dispersion having a solid content of 10% was produced using silica particles having a pore structure. The average particle size of the composite particles was 450 nm. As a result of observation with an electron microscope, the composite particles were in a form in which a cationic polymer entered the pores of silica particles having a pore structure and was fixed and combined.

(Aqueous dispersion E-7)
According to Example 4 of JP-T-2009-520867, an organic-inorganic composite particle aqueous dispersion having a solid content of 48% was obtained using silica particles and vinyldiethoxysilyl polyester. The average particle size of the composite particles was 650 nm. As a result of observation with an electron microscope, the composite particles were in a form in which silica particles were bonded to the surface of the polyester resin particles to form a composite.

<Preparation of base material>
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 100 μm thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) 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 is formed. Formed.

  Subsequently, a gas barrier layer was formed on the base material (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 modification 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 Co., Ltd. The sample fixed on the operating stage was subjected to a modification treatment under the following conditions.

(Reforming treatment conditions)
Excimer light intensity 60mW / cm2 (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds

  A film substrate (base material) for a transparent electrode (transparent conductive film) having gas barrier properties was produced as described above.

<Example 1>
(Preparation of transparent electrode TC-101)
First of all, the following coating solution A is extruded to a dry film thickness of 300 nm on the non-barrier surface on the transparent electrode film substrate having gas barrier properties obtained as described above. Adjust the slit gap of the head, apply and heat dry at 110 ° C. for 5 minutes to form a conductive layer (only the second conductive layer in FIG. 1) made of a conductive polymer and a binder resin. Cut into 8 × 8 cm. Furthermore, transparent electrode TC-101 was produced by heat-processing the obtained electrode using an oven for 30 minutes at 110 degreeC.

(Coating liquid A)
Conductive polymer dispersion: PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
Organic inorganic composite particle aqueous dispersion: E-1 0.14 g (solid content 70 mg)
Dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass) 0.16 g

(Preparation of transparent electrodes TC-102 to TC-114)
In the production of the transparent electrode TC-101, E-1 which is the organic-inorganic composite particle aqueous dispersion of the coating liquid A is used as the kind and amount ratio of the organic-inorganic composite particle aqueous dispersion shown in Table 1 (binder for 100 parts by mass of the conductive polymer) Transparent electrodes TC-102 to TC-114 were produced in the same manner as the production of the transparent electrode TC-101 except that it was changed to resin mass parts).

(Preparation of transparent electrode TC-115)
In preparation of transparent electrode TC-101, except that PEDOT-PSS of coating liquid A was changed to 0.5 g of polyaniline M (solid content concentration 6.0%, TA Chemical) Similarly, a transparent electrode TC-115 was produced.

(Preparation of comparative transparent electrodes TC-116 to TC-118)
In the production of the transparent electrode TC-101, E-1 which is an organic-inorganic composite particle aqueous dispersion of the coating liquid A is added to inorganic particles alone, organic resin particles alone, inorganic particles and organic resin particles individually listed in Table 1. Transparent electrodes TC-116 to TC-118 were produced in the same manner as the production of the transparent electrode TC-101 except for the change.

<Evaluation of transparent electrode>
The transparency, surface resistance (conductivity) and film strength of the obtained transparent electrode were evaluated as described below. Further, in order to evaluate the stability of the transparent electrode, the transparency, surface resistance, and film strength of the transparent electrode sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 6 days were evaluated.

(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.
○: 80% or more Δ: 75% or more and less than 80% ×: less than 75% Evaluation criteria: Samples evaluated as ○ or Δ after the forced deterioration test passed 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.

(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.
○: Affected part is 5% or less △: Affected part exceeds 5% but 30% or less ×: Affected part exceeds 30% Evaluation criteria: After forced degradation test Table 1 shows the results of passing evaluation of the samples evaluated as ○ and △ as the present invention. In Table 1, “present invention” in the remarks represents that it corresponds to an example of the present invention, and “comparison” represents a comparative example.

Mobile 8055A: Nippon Synthetic Chemical Industry Co., Ltd. acrylic resin / colloidal silica particle composite emulsion Mobile 8030: Nihon Synthetic Chemical Industry Co., Ltd. acrylic resin / colloidal silica particle composite emulsion Snowtex 40: Nissan Chemical Industries Co., Ltd. colloidal silica dispersion Bon Coat AN -155E: DIC acrylic resin emulsion

  From Table 1, compared with the transparent electrodes TC-116 to TC-118 of the comparative example, the transparent electrodes TC-101 to TC-115 of the present invention are conductive, light transmissive and film even under high temperature and high humidity environment. It can be seen that there is little deterioration in strength and excellent stability.

<Example 2>
(Preparation of transparent electrode TE-101)
First, a first conductive layer made of a metal material formed in a pattern by gravure printing shown below on a non-barrier surface on the transparent electrode film substrate having gas barrier properties obtained as described above. Formed.

  A silver nanoparticle paste (M-Dot SLP: manufactured by Mitsuboshi Belting Co., Ltd., average particle diameter 20 nm, aspect ratio when 50 particles were observed was 1.5 or less), a gravure printing tester K303MULTICOATER manufactured by RK Print Coat Instruments Ltd. After printing a thin wire grid having a line width of 50 μm, a height of 1.5 μm, and an interval of 1.0 mm, a drying process was performed at 110 ° C. for 5 minutes to form a first conductive layer (see FIG. 1).

  Next, the following coating liquid A is applied onto the transparent electrode on which the first conductive layer has been formed by adjusting the slit gap of the extrusion head so as to have a dry film thickness of 300 nm using an extrusion method. The mixture was heat-dried for 2 minutes to form a second conductive layer (see FIG. 1) composed of a conductive polymer and a binder resin, and the obtained electrode was cut into 8 × 8 cm. Furthermore, transparent electrode TE-101 was produced by heat-processing the obtained electrode using an oven at 110 degreeC for 30 minutes.

(Coating liquid A)
Conductive polymer dispersion: PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
Organic inorganic composite particle aqueous dispersion: E-1 0.14 g (solid content 70 mg)
Dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass) 0.16 g

(Preparation of transparent electrodes TE-102 to TE-114)
In the production of the transparent electrode TE-101, E-1 which is the organic-inorganic composite particle aqueous dispersion of the coating liquid A is used as the organic-inorganic composite particle aqueous dispersion type and amount ratio described in Table 2 (binder for 100 parts by mass of the conductive polymer). Transparent electrodes TE-102 to TE-114 were produced in the same manner as the production of the transparent electrode TE-101 except that the resin electrode was changed to resin mass parts).

(Preparation of transparent electrode TE-115)
In the production of the transparent electrode TE-101, PEDOT-PSS CLEVIOS PH510 (solid content: 1.89%, manufactured by HC Starck) of the coating solution A was added to polyaniline M (solid content concentration: 6.0%, TAE Chemical). ) A transparent electrode TE-115 was produced in the same manner as the production of the transparent electrode TE-101 except that it was changed to 0.5 g.

(Preparation of transparent electrode TE-116)
In the production of the transparent electrode TE-101, TE- except that the first conductive layer (see FIG. 1) made of a metal material formed in a pattern using a copper nanoparticle paste instead of the silver nanoparticle paste was formed. A transparent electrode TE-116 was produced in the same manner as the production of 101. (The copper nanoparticle paste is prepared by dissolving 0.28 g of polyvinyl pyrrolidone having an average molecular weight of 10,000 (manufactured by Tokyo Chemical Industry Co., Ltd.) in 0.72 g of ethylene glycol, glycerin, diethylene glycol, and 2,3-butanediol. Copper nanoparticles (manufactured by Sigma-Aldrich) 4.0 g, three rolls and a mixer were used for kneading and the aspect ratio when observing 50 particles with an electron microscope was 2.0 or less.)

(Preparation of transparent electrode TE-117)
In the production of the transparent electrode TE-101, TE- except that the first conductive layer (see FIG. 1) made of a metal material formed in a pattern using a silver nanowire dispersion instead of the silver nanoparticle paste was formed. A transparent electrode TE-117 was produced in the same manner as the production of 101. (The silver nanowire dispersion was prepared by referring to the method described in Adv. Mater., 2002, 14, 833-837, using PVP K30 (molecular weight 50,000; manufactured by ISP), and having an average minor axis of 75 nm, Silver nanowires with an average length of 35 μm were prepared, and after silver nanowires were filtered and washed using an ultrafiltration membrane, hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 25 mass% with respect to silver. (A silver nanowire dispersion was prepared by re-dispersing in an aqueous solution.)

(Preparation of comparative transparent electrodes TE-118 to TC-120)
In the production of the transparent electrode TE-101, E-1 which is the organic-inorganic composite particle aqueous dispersion of the coating liquid A is added to the inorganic particles alone, the organic resin particles alone, the inorganic particles and the organic resin particles individually listed in Table 2. Transparent electrodes TC-118 to TC-120 were produced in the same manner as the production of the transparent electrode TE-101 except for the change.

<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. In Table 2, “present invention” in the remarks indicates that it corresponds to an example of the present invention, and “comparison” indicates that it is a comparative example.

  From Table 2, the conductivity is remarkably improved by having a conductive layer made of a metal material, and compared with the transparent electrodes TE-118 to TE-120 of the comparative example, the transparent electrodes TE-101 to TE- of the present invention. It can be seen that 117 is excellent in stability with little deterioration in electrical conductivity, light transmission and film strength even under high temperature and high humidity environment.

<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-101 to OEL-120 were produced using transparent electrodes TE-101 to TE-120, 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.
Subsequently, 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. 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.

(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 sealing member in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a substrate to deposit Al ₂ O ₃ with a thickness of 300 nm so that external terminals for the cathode and the anode can be formed. After bonding, 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>
The obtained organic EL device was evaluated for light emission unevenness and lifetime 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-101 to OEL-120 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. In addition, after heating the organic EL element in an oven at 80 ° C. and 60% RH for 3 hours and then adjusting the humidity again at 23 ± 3 ° C. and 55 ± 3% RH for 1 hour or more, the same The emission uniformity was observed.
○: Completely uniform light emission Δ: Partial emission unevenness is observed ×: Light emission unevenness is observed over the entire surface Evaluation criteria: After the forced deterioration test, samples evaluated as ○ and Δ 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.
◎: 150% or more ○: 100 or more and less than 150% △: 80 or more and less than 100% ×: less than 80% Evaluation criteria: After the forced deterioration test, samples evaluated as ◎, ○, △ passed 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.

  From Table 3, the organic EL elements OEL-118 to OEL-120 of the comparative examples are deteriorated in light emission uniformity and life after heating for 3 hours in an environment of 80 ° C. and 60% RH, whereas the organic EL elements of the present invention are deteriorated. It can be seen that the light emission uniformity and lifetime of the EL elements OEL-101 to OEL-117 are stable even after heating and have excellent 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 in which a transparent conductive layer containing a conductive polymer and a binder resin is formed on a transparent substrate,
The binder resin is composed of composite particles of an organic resin and an inorganic material,
The said conductive layer is formed using the dispersion liquid containing the said conductive polymer and the said binder resin. The transparent conductive film characterized by the above-mentioned. The transparent conductive film according to claim 1, wherein the composite particles are particles in which inorganic particles are bonded to the surface of organic resin particles. The transparent conductive film according to claim 2, wherein the inorganic particles are silica particles. 4. The ratio of the conductive polymer to the binder resin is 100 to 900 parts by mass of the binder resin when the conductive polymer is 100 parts by mass. 5. The transparent conductive film as described in 2. Provided with a conductive layer made of a metal material,
5. The transparent conductive layer containing the conductive polymer and the binder resin is electrically connected to the conductive layer made of the metal material. 5. The transparent conductive film as described in the item. An organic electroluminescence element comprising the transparent conductive film according to any one of claims 1 to 5 as a transparent electrode.

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