JP5884671B2 - Transparent conductive film, organic electroluminescent element, and method for producing transparent conductive film - Google Patents

Description

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

  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, a transparent electrode made of a transparent conductive film is an essential constituent technology. Moreover, the transparent electrode which consists of a transparent conductive film is an indispensable technical element also in touch panels other than a television, a mobile telephone, electronic paper, various solar cells, various electroluminescent light control elements, etc.

  Conventionally, as a transparent electrode, an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as transparent glass or plastic film by a vacuum deposition method or a sputtering method is mainly used. I came. 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.

JP 2010-244746 A

  However, in the technique described in Patent Document 1, due to the influence of the hygroscopic dissociative group, it is insufficient to suppress moisture remaining in the film after drying, and the transparent electrode is durable for a long period of time in a high temperature and high humidity environment. It has been found that transparency, conductivity and film strength in the property test, and device performance using the transparent electrode are also adversely affected. 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 by improving the conductivity significantly, the transparency and conductivity are made compatible, and light emission uniformity using the transparent conductive film It is an object of the present invention to provide an organic EL device that is excellent in light emission, has little deterioration in light emission uniformity even under a high temperature and high humidity environment for a long period of time, and has a long light emission life, and a method for producing the transparent conductive film described above. .

  To solve the problem of the present invention, it is important to use a conductive polymer particle dispersion and a binder resin having an aspect ratio of 10 or more and 1000 or less, and that the conductive polymer particles are dispersed in an organic solvent, More specifically, the problem is solved by the following configuration.

1. A transparent base material, a conductive polymer formed on the transparent base material, having a π-conjugated conductive polymer and a polyanion, and a transparent conductive layer containing a binder resin; The conductive layer has a conductive polymer particle, which is the conductive polymer, dispersed in an organic solvent, and the dispersed conductive polymer particle has an aspect ratio of 10 or more and 1000 or less. A transparent conductive film characterized in that the conductive polymer particles are formed using a dispersion containing a conductive polymer having an average diameter of 10 to 500 nm and the binder resin.

2. 2. The transparent conductive film according to 1 above, wherein the ratio of the conductive polymer to the binder resin is 5 to 50 parts by mass of the conductive polymer when the binder resin is 100 parts by mass.

3. 3. The transparent conductive film according to 1 or 2, wherein the π-conjugated conductive polymer is polythiophene.

4). A first conductive layer formed on the transparent base material and made of a metal material, and a second conductive layer that is the transparent conductive layer, wherein the first conductive layer and the second conductive layer are The transparent conductive film according to any one of 1 to 3, which is electrically connected to each other.

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

6). A first step of forming a first conductive layer made of metal on a transparent substrate, and a second step of forming a transparent second conductive layer on the transparent substrate on which the first conductive layer is formed. And in the second step, the second conductive layer is formed using a dispersion containing conductive polymer particles having an aspect ratio of 10 or more and 1000 or less and a binder resin. Manufacturing method of electrically conductive film.

7). In the second step, the conductive polymer particles and the binder are prepared using a step of preparing a first dispersion in which the conductive polymer particles are dispersed in an organic solvent, and the first dispersion and the binder resin. The step of preparing a second dispersion containing a resin, and the step of forming the second conductive layer using the second dispersion, Production method.

  According to the present invention, a transparent conductive film having excellent transparency, conductivity, and film strength, and having little deterioration in transparency, conductivity, and film strength even in a high temperature, high humidity environment for a long time, and the transparent conductivity Organic EL device using a film, having excellent light emission uniformity, little deterioration of light emission uniformity even under long-term, high temperature and high humidity environment, and excellent light emission life, and method for producing the transparent conductive film Can be provided.

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 uses a conductive polymer and a binder resin as a transparent conductive film, and the conductive polymer is a conductive polymer particle dispersion having an aspect ratio of 10 or more and 1000 or less, and dispersed in an organic solvent. By using a conductive polymer characterized by the use of a body, 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 the water resistance and film strength of the film are also improved. It can be greatly improved. Also, in the step of applying the coating liquid (second dispersion) mixed with the binder resin on the base material, the conductive polymer particles in the dispersion liquid may have different shapes due to the specific shape of the conductive polymer particles in the dispersion. Orientation proceeds easily, and by efficiently forming a network of conductive paths, the conductivity can be greatly improved, and both transparency and conductivity can be achieved. Therefore, according to the present invention, a transparent conductive film with excellent stability having high conductivity, high transparency and good film strength can be obtained 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 is a transparent conductive layer containing 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 conductive polymer further includes: It is a conductive polymer particle dispersion having an aspect ratio of 10 or more and 1000 or less, and is formed using a dispersion dispersed in an organic solvent.

<Conductive polymer>
In the present invention, “conductivity” refers to the property of electricity flowing, 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 ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, or Nafion (manufactured by DuPont) is preferable. . These poly anions have high compatibility with the nonconductive polymer added as a 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.

  A method for producing a polyanion by polymerization of an anion group-containing polymerizable monomer is 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. Is mentioned. 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) of inorganic acids including organic acids. Salts, iron (III) salts of inorganic acids containing organic residues), hydrogen peroxide, potassium dichromate, alkali persulfates (eg potassium persulfate, sodium persulfate), ammonium, alkali perborate, permanganate It is preferable to use potassium or 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 commercially available from Nissan Chemical Company 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.

The conductive polymer obtained by the chemical oxidative polymerization and the commercially available product are both aqueous dispersions of a conductive polymer having a π-conjugated conductive polymer and a polyanion. Examples of the method for obtaining the organic solvent-dispersed conductive polymer dispersion of the present invention from the aqueous dispersion of the conductive polymer include the following methods.
(1) A method in which the aqueous dispersion of the conductive polymer is concentrated and the organic solvent is added to replace the organic solvent, thereby performing dispersion treatment.
(2) A method in which an aqueous dispersion of the conductive polymer is spray-dried, and the resulting dried solid is mixed with an organic solvent and subjected to a dispersion treatment. A dispersant may be added as appropriate.
(3) A method in which an aqueous dispersion of the above conductive polymer is freeze-dried and an organic solvent is added for dispersion treatment.
(4) A method in which a precipitant is added to the aqueous dispersion of the conductive polymer, water is removed from the obtained gel-like swollen body, and an organic solvent is added for dispersion treatment.

  In order to obtain a conductive polymer particle dispersion having an aspect ratio of 10 or more and 1000 or less according to the present invention, the freeze-drying method (3) is preferably used.

  Although there is no restriction | limiting in particular about the method of a dispersion process, For example, it can carry out using apparatuses, such as a high-speed stirrer, an ultrasonic homogenizer, and a shaker. In addition, when an advanced process is required, you may add processes, such as a high-pressure homogenizer, a bead mill, and a grindstone rotary type crusher.

  A high-pressure homogenizer is a device that grinds by shear force due to accelerated high flow velocity, rapid pressure drop (cavitation), and impact force caused by high-velocity particles colliding face-to-face within a fine orifice, and is commercially available. As the device, a nanomizer (manufactured by Nanomizer Co., Ltd.), a microfluidizer (manufactured by Microfluidics) or the like can be used. The degree of dispersion by the high-pressure homogenizer depends on the pressure fed to the high-pressure homogenizer and the number of passes (number of passes) passed through the high-pressure homogenizer.

  Examples of the bead mill include a wet vibration mill, a wet planetary vibration mill, a wet ball mill, a wet roll mill, a wet coball mill, a wet bead mill, and a wet paint shaker. Among these, for example, a wet bead mill is a device in which a metal or ceramic medium is built in a container and this is subjected to wet grinding by forcibly stirring it. A mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), a pearl mill (manufactured by Ashizawa Co., Ltd.), a dyno mill (manufactured by Shinmaru Enterprises Co., Ltd.), or the like can be used.

The grindstone rotary type crusher is a kind of colloid mill or stone mortar type crusher, for example, by rubbing a grindstone made of abrasive grains having a particle size of No. 16 to 120, and passing the dispersion through the rubbing part, It is a device to be crushed. You may perform a process in multiple times as needed. It is one of the preferred embodiments that the grindstone is appropriately changed. The grindstone rotary type crusher has both “short fiber” and “miniaturization” effects, but the effect is influenced by the grain size of the abrasive grains. For the purpose of shortening the fiber length, a # 46 or less grindstone is effective. For miniaturization purposes, a # 46 or greater grindstone is effective. No. 46 has both functions. Specific examples of the apparatus include a pure fine mill (Grinder mill) (Kurita Machinery Co., Ltd.), a serendipeater, a super mass collider, and a super grinder (above, Masuko Sangyo Co., Ltd.).
In the dispersion treatment, at least one of a surfactant and a dispersant may be added as appropriate.

(Organic solvent)
In the present invention, the conductive polymer is characterized by using a dispersion dispersed in an organic solvent. Preferred examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium triamide, acetonitrile, benzonitrile and other polar solvents, cresol, phenol, xylenol and other phenols, methanol, ethanol, propanol, butanol and other alcohols, acetone, methyl ethyl ketone, etc. Ketones, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, ethyl Chain ethers such as polyglycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutarodinitrile, methoxyacetonitrile, propio Examples include nitrile compounds such as nitrile and benzonitrile. These organic solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

(aspect ratio)
In the present invention, the aspect ratio of the conductive polymer particle dispersion is 10 or more and 1000 or less, and the aspect ratio is a ratio (length / diameter) of a long side and a short side of the conductive polymer particle. Ratio). There is no restriction | limiting in particular as a measuring method of the said aspect ratio, According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned. When measuring the aspect ratio of the conductive polymer particles with an electron microscope, it is difficult to accurately measure the aspect ratio of each of the conductive polymer particles when the aspect ratio of the conductive polymer particles is high. However, it is only necessary to confirm whether the aspect ratio of the conductive polymer particles is 10 or more and 1000 or less with one field of view of an electron microscope. Moreover, the aspect ratio of the whole conductive polymer particle can be estimated by measuring the length and diameter of the conductive polymer particle separately.

  The aspect ratio of the conductive polymer particles is not particularly limited as long as it is 10 or more and 1000 or less, and can be appropriately selected according to the purpose, but is preferably 10 or more and 500 or less. If the aspect ratio is less than 10, it is not preferable because the conductive polymer particles are not sufficiently formed into a network and the conductivity cannot be improved. In addition, when the aspect ratio exceeds 1000, the conductive polymer particles are entangled and aggregated before film formation during the formation of the conductive polymer particles or in subsequent handling, which is not preferable because a stable liquid cannot be obtained. When the aspect ratio is 500 or less, the formation of aggregates is further suppressed, and a more stable liquid can be obtained.

In the present invention, the size of the conductive polymer particles is preferably small from the viewpoint of transparency, while it is preferably large from the viewpoint of conductivity. Therefore, in the present invention, the conductive polymer particles preferably have an average length of 100 nm to 10 μm, and more preferably 500 nm to 5 μm. The average diameter is 10 nm to 500 nm , preferably 10 nm to 100 nm .

  The conductive polymer particles in the present invention are considered to function by forming a three-dimensional conductive network when the conductive polymer particles come into contact with each other in the transparent conductive layer. Therefore, a longer conductive polymer particle is advantageous for forming a conductive network. However, on the other hand, when the conductive polymer particles become long, the conductive polymer particles are entangled to form an aggregate, which may deteriorate the optical characteristics.

<Binder resin>
In the present invention, the binder resin is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer, and may be a thermosetting resin or a thermoplastic resin. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like.

  These binder resins may be dissolved in an organic solvent or may be dispersed in an organic solvent. Alternatively, the conductive polymer dispersion may be solidly added and dispersed.

  Among the binder resins, at least one of polyurethane, polyester, acrylic resin, polyamide, polyimide, and epoxy resin is preferable from the viewpoint of compatibility with the conductive polymer and transparency. Particularly preferred are polyester and acrylic resin.

(Ratio of conductive polymer to binder resin)
In the present invention, the ratio of the conductive polymer to the binder resin is preferably 5 to 50 parts by mass of the conductive polymer, more preferably 100 parts by mass of the binder resin when the binder resin is 100 parts by mass. The conductive polymer is 10 to 20 parts by mass. Here, the reason why the amount of the conductive polymer used is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the binder resin is that the amount of the conductive polymer used is 5 parts by mass or more with respect to 100 parts by mass of the binder resin. As a result, the ratio of the conductive polymer does not become too small, and a conductive network is sufficiently formed to improve the conductivity. Further, when the amount is 50 parts by mass or less, light in the visible light region is absorbed. This is because the influence of the conductive polymer is reduced and the visible light transmittance is increased. In order to improve the transmittance as much as possible and prevent a decrease in conductivity, the ratio of the conductive polymer to the binder resin is preferably in the above range.

<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 the transparent conductive film 1, the total light transmittance in the visible light wavelength region measured by a method based on JIS K 7361-1: 1997 (Plastic—Testing method of total light transmittance of transparent material) is 80%. The above is preferably used as the substrate 11.

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

  As the base material 11, for example, a resin substrate, a resin film, and the like are preferably exemplified, 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 the base material 11, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film is preferable from the viewpoint of transparency, heat resistance, ease of handling, strength and cost. 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 substance and an organic substance may be formed on the front or back surface of the film-like base material 11, and the base material 11 on which such a film is formed, Water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferably a barrier 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, water vapor permeability (25 ± It is preferable that the film has a high barrier property at 0.5 ° C. and a relative humidity (90 ± 2)% RH) of 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  As a material for forming a barrier film formed on the front or back surface of the film-like base material 11 in order to obtain a high-barrier film, a material having a function of suppressing intrusion of elements that cause deterioration of the element 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.

<First conductive layer made of a metal material>
In the present invention, the transparent conductive film 1 is formed by further providing a conductive layer 12 made of a metal material on the base material 11 on which the conductive layer 13 containing a conductive polymer and a binder resin is formed. It is more preferable. 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 to 100 nm are 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), and the following method 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>
The second conductive layer 13 used in the present invention is prepared 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 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 performance improvement 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), or a commercially available surface resistivity meter can be 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.

<Manufacturing method>
The transparent conductive film 1 includes a first step of forming a first conductive layer 12 made of metal on a transparent base material 11, and a transparent second conductive layer on the base material 11 on which the first conductive layer 12 is formed. And a second step of forming 13. Here, in the second step, the second conductive layer 13 is formed using a dispersion liquid containing conductive polymer particles having an aspect ratio of 10 or more and 1000 or less and a binder resin.

  The second step includes the step of preparing a first dispersion in which conductive polymer particles are dispersed in an organic solvent, and the conductive polymer particles and the binder resin using the first dispersion and a binder resin. The step may include a step of preparing the second dispersion liquid and a step of forming the second conductive layer 13 using the second dispersion liquid.

<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, 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 organic solvent dispersion of conductive polymer particles>
(Dispersion E-1)
An aqueous dispersion of PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) was freeze-dried with a freeze dryer FDU-2200 (manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a solid of PEDOT-PSS. Got. Ethanol was added to this solid, and this ethanol dispersion liquid was almost contacted with a grinder ("Kurita Kikai Seisakusho" KM1-10 ") between the disks rotating at 1200 rpm from the center to the outside. The operation of passing was performed 12 times (12 passes) to produce an ethanol dispersion of conductive polymer particles having a solid content of 1%. As a result of observation with an electron microscope, the particles had an average length of 330 nm, an average diameter of 30 nm, and an aspect ratio of 11.

(Dispersion E-2)
In the production of Dispersion E-1, an ethanol dispersion of conductive polymer particles having a solid content of 1% was produced in the same manner as in the production of Dispersion E-1, except that the number of passes of the grinder was changed to 8. As a result of observation by an electron microscope, the particles had an average length of 24 μm, an average diameter of 50 nm, and an aspect ratio of 480.

(Dispersion E-3)
In the production of Dispersion E-1, an ethanol dispersion of conductive polymer particles having a solid content of 1% was produced in the same manner as in the production of Dispersion E-1, except that the pass number of the grinder was changed to 2. As a result of observation with an electron microscope, the particles had an average length of 79 μm, an average diameter of 80 nm, and an aspect ratio of 988.

(Dispersion E-4)
In the production of Dispersion E-1, PEDOT-PSS was changed to Polyaniline M (solid content concentration 6.0%, TA Chemical) in the same manner as in the production of Dispersion E-1. An ethanol dispersion of conductive polymer particles was produced. As a result of observation with an electron microscope, the particles had an average length of 20 μm, an average diameter of 50 nm, and an aspect ratio of 400.

(Dispersion E-5)
In the production of Dispersion E-1, an organic solvent dispersion of conductive polymer particles having a solid content of 1% was produced in the same manner as the production of Dispersion E-1, except that the pass number of the grinder was changed to 15. As a result of observation with an electron microscope, the particles had an average length of 270 nm, an average diameter of 30 nm, and an aspect ratio of 9.

(Dispersion E-6)
In the production of Dispersion E-1, an ethanol dispersion of conductive polymer particles having a solid content of 1% was produced in the same manner as in the production of Dispersion E-1, except that the number of passes of the grinder was changed to 1. As a result of observation with an electron microscope, the particles had an average length of 88 μm, an average diameter of 80 nm, and an aspect ratio of 1100.

(Dispersion E-7)
An aqueous dispersion of conductive polymer particles having a solid content of 1% was produced in the same manner as in the production of Dispersion E-1, except that the dispersion medium was changed to water in the production of Dispersion E-1. The average length was 20 μm, the average diameter was 50 nm, and the aspect ratio was 400.

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

Subsequently, a gas barrier layer was formed on the sample provided with the smooth layer under the following conditions.
(Gas barrier layer coating solution)

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

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

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

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

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp-filled gas Xe manufactured by M.D.Com 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 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds A film substrate (base material) 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, on the surface of the barrier on the transparent electrode film substrate having a gas barrier property obtained as described above, the following coating liquid A is extruded using an extrusion method so that the dry film thickness is 300 nm. Is applied and dried by heating 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, and the obtained electrode is 8 × 8 cm. Cut out. 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)
A coating solution having the following formulation was used after stirring and mixing.
E-1 dispersion (solid content concentration 1.0%) 2.0 g
Polyester resin organic solvent solution (Polyester TP-220S30M, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 30%) 0.38 g
Dimethyl sulfoxide (DMSO) 0.2g

(Preparation of transparent electrodes TC-102 to TC-110)
The transparent electrode TC was prepared except that the dispersion E-1 of the coating liquid A was changed to the dispersion type and amount ratio shown in Table 1 (parts by weight of the conductive polymer with respect to 100 parts by weight of the binder resin) in preparation of the transparent electrode TC-101. Transparent electrodes TC-102 to TC-110 were produced in the same manner as in the production of -101.

(Preparation of comparative transparent electrodes TC-1111 to TC-113)
In the production of the transparent electrode TC-101, the transparent electrode was prepared in the same manner as in the production of the transparent electrode TC-101 except that E-1 which is the dispersion of the coating liquid A was changed to the dispersion type and amount ratio shown in Table 1. TC-1111 to TC-113 were produced.

(Preparation of transparent electrodes TC-114 and TC-115)
In the production of the transparent electrode TC-101, the binder resin solution (the polyester resin organic solvent solution) of the coating solution A was changed to the acrylic resin organic solvent solution (Acridic A-165, manufactured by DIC) (TC-114). Transparent electrode TC-114 and TC-115 were produced in the same manner as the production of the transparent electrode TC-101 except that the case was changed to polyamideimide resin (Vilomax HR-15ET) (in the case of TC-115).

<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.

  From Table 1, the transparent electrodes TC-101 to TC-110, TC-114, and TC-115 of the present invention are compared with the transparent electrodes TC-1111 to TC-113 of the comparative example even under a high temperature and high humidity environment. It turns out that there is little deterioration of electroconductivity, light transmittance, and film | membrane intensity | strength, and it is excellent in stability.

<Example 2>
(Preparation of transparent electrode TE-101)
First, the 1st conductive layer which consists of a metal material formed in the pattern form by the gravure printing shown below was formed in the surface of the barrier on the film substrate for transparent electrodes which has gas barrier property obtained as mentioned above.

  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)
E-1 dispersion (solid content concentration 1.0%) 2.0 g
Polyester resin organic solvent solution (Polyester TP-220S30M, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 30%) 0.38 g
Dimethyl sulfoxide (DMSO) 0.2g

(Preparation of transparent electrodes TE-102 to TE-110)
In preparation of transparent electrode TE-101, it is transparent except having changed E-1 which is the dispersion of coating liquid A into the dispersion kind and quantity ratio of Table 2 (binder resin mass part with respect to 100 mass parts of conductive polymers). Transparent electrodes TE-102 to TE-110 were produced in the same manner as the production of the electrode TE-101.

(Preparation of transparent electrode TE-111)
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-112)
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% by mass relative to silver (A silver nanowire dispersion was prepared by re-dispersing in an aqueous solution.)

(Preparation of comparative transparent electrodes TE-113 to TC-115)
In preparation of transparent electrode TE-101, it is transparent except having changed E-1 which is the dispersion of coating liquid A into the dispersion kind and quantity ratio of Table 2 (binder resin mass part with respect to 100 mass parts of conductive polymers). Transparent electrodes TC-113 to TC-115 were produced in the same manner as the production of the electrode TE-101.

(Preparation of transparent electrodes TE-116 and TC-117)
In the production of the transparent electrode TE-101, a binder resin solution of the coating solution A (an organic solvent solution of polyester resin) was used as an organic solvent solution of an acrylic resin (Acridic A-165, manufactured by DIC) (of TE-116). Transparent electrode TE-116 and TC-117 were produced in the same manner as the production of the transparent electrode TE-101, except that the case was changed to polyamideimide resin (Vilomax HR-15ET) (in the case of TE-117).

<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-113 to TE-115 of the comparative example, the transparent electrodes TE-101 to TE- of the present invention. It can be seen that 112, TE-116, and TE-117 are excellent in stability with little deterioration of 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-117 were produced using transparent electrodes TE-101 to TE-117, 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-117 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 the above 23 ± 3 ° C. and 55 ± 3% RH environment 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-113 to OEL-115 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 life of the EL elements OEL-101 to OEL-112, OEL-116, and OEL 117 are stable after heating and excellent in durability.

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

Claims (7)

A transparent substrate,
A transparent conductive layer comprising a conductive polymer formed on the transparent substrate, having a π-conjugated conductive polymer and a polyanion, and a binder resin;
A transparent conductive film comprising:
In the conductive layer, conductive polymer particles as the conductive polymer are dispersed in an organic solvent, and the dispersed conductive polymer particles have an aspect ratio of 10 or more and 1000 or less, and an average of the conductive polymer particles. A transparent conductive film characterized by being formed using a dispersion containing a conductive polymer having a diameter of 10 to 500 nm and the binder resin. The ratio of the said conductive polymer and binder resin is 5-50 mass parts of conductive polymers, when binder resin is 100 mass parts. The transparent conductive film of Claim 1 characterized by the above-mentioned. The transparent conductive film according to claim 1, wherein the π-conjugated conductive polymer is a polythiophene. A first conductive layer formed on the transparent substrate and made of a metal material;
A second conductive layer which is the transparent conductive layer;
With
The transparent conductive film according to any one of claims 1 to 3, wherein the first conductive layer and the second conductive layer are electrically connected to each other. An organic electroluminescence device comprising the transparent conductive film according to any one of claims 1 to 4 as a transparent electrode. A first step of forming a first conductive layer made of metal on a transparent substrate;
A second step of forming a transparent second conductive layer on the transparent substrate on which the first conductive layer is formed;
With
In the second step,
A method for producing a transparent conductive film, comprising forming the second conductive layer using a dispersion liquid containing conductive polymer particles having an aspect ratio of 10 or more and 1000 or less and a binder resin. The second step includes
Preparing a first dispersion in which the conductive polymer particles are dispersed in an organic solvent;
Preparing a second dispersion containing the conductive polymer particles and the binder resin using the first dispersion and the binder resin;
Forming the second conductive layer using the second dispersion;
The manufacturing method of the transparent conductive film of Claim 6 characterized by the above-mentioned.

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