JP5880100B2 - Manufacturing method of transparent electrode - Google Patents

Description

  The present invention relates to a method for producing a transparent electrode, a transparent electrode, and an organic electronic device used in an organic electronic device such as an organic EL (electroluminescence) or solar cell using the transparent electrode.

In recent years, organic electronic devices such as organic EL elements and organic solar cells have attracted attention, and in such devices, transparent electrodes have become an essential constituent technology.
In organic electronic devices, there is an increasing demand for an increase in area. In the case of transparent electrodes such as indium tin oxide (ITO) and conductive polymers that have been used in the past, the film formation cost is low in large area applications that require particularly low surface resistance due to surface uniformity of current. It is extremely difficult to obtain a sufficiently low surface resistance in practical use as well as a dramatic increase.

In order to achieve both transparency and conductivity, a transparent electrode in which an ITO transparent conductive film and a metal conductive layer formed in a pattern are combined is disclosed (for example, see Patent Document 1).
In order to increase the transparency of the transparent electrode in which the transparent conductive film and the metal conductive layer are combined, it is essential to refine the metal conductive layer pattern. As a means for forming a miniaturized metal conductive pattern, in recent years, a method of directly forming a metal conductive pattern miniaturized by a printing method has attracted attention. The formation of the conductive pattern by the printing method has a feature that the process is simple and can be performed at low cost.
In forming a conductive pattern by a printing method, a method of forming a conductive pattern by printing an ink containing a conductor such as a metal nano-ink on a substrate on which a conductive pattern is to be formed is used. The conductivity of the conductive pattern is improved by heating and baking at a high temperature.

  When providing flexibility (flexibility) to an organic electronic device, a film such as PET is used for the substrate, but in order not to damage the substrate, a conductive metal fine line pattern formed from metal nanoparticles is used. It is known to fire by local heating. For example, an example of firing with pulsed light is disclosed (for example, see Patent Document 2). Moreover, the example (for example, refer nonpatent literature 1) which provides a PEDOT / PSS layer on the metal fine wire pattern baked by local heating is described. By providing the conductive polymer-containing layer on the thin metal wire pattern, the smoothness of the surface of the transparent electrode is improved, and current leakage between the electrodes can be suppressed when used in an organic electronic device.

JP 2006-352073 A Special table 2008-522369

Organic PhotoVolatics, Open Innovation Program ECN-Holst Centre, Netherlands, Large-area, Organic & Printed Electronics Convention, June 2, 2010, RonneArens.

However, in the method of firing by local heating as in Patent Document 2, since the metal fine line pattern itself becomes very high temperature, the substrate is easily damaged near the interface between the metal fine line pattern and the substrate, and the substrate damage is suppressed. However, it was difficult to improve the conductivity. Neither Patent Document 2 nor Non-Patent Document 1 suggests such a problem or suggests a solution.
Therefore, the main object of the present invention is to provide a method for producing a transparent electrode capable of producing a transparent electrode having excellent conductivity while suppressing substrate damage.

  In order to solve the above problems, the present inventor forms a fine line pattern of metal nanoparticles on a protective layer of a transparent substrate having a protective layer in the process of studying the cause of the above problem, and is fired by flash light irradiation. By performing the above, it is possible to achieve both substrate damage suppression and conductivity improvement, and further, in combination with a conductive polymer-containing layer containing a π-conjugated conductive polymer and a polyanion, The present inventors have found an unexpected effect that not only the smoothness of the surface of the transparent electrode can be obtained but also the gas barrier performance of the transparent electrode, which is a characteristic suitable for use in an organic electronic device, is remarkably improved.

That is, according to the present invention,
In a method for producing a transparent electrode having a flexible transparent substrate, a protective layer, and a conductive fine metal wire pattern,
Forming the protective layer on one surface of the transparent substrate;
Forming a metal fine wire pattern with metal nanoparticles on the protective layer;
E Bei and a step of firing the flash light irradiation the fine metal wire pattern,
In the step of forming the protective layer,
A first coating liquid containing a polyfunctional monomer containing a polymerizable functional group or a polyfunctional oligomer is coated on the transparent substrate, the first coating liquid is polymerized, and a hard coat layer composed of an organic compound is Forming on a transparent substrate;
A second coating solution containing polysilazane is applied onto the hard coat layer, the second coating solution is irradiated with light having a wavelength component of 200 nm or less, and a gas barrier layer composed of an inorganic compound is formed on the hard coat layer. Forming the step,
A method for producing a transparent electrode is provided.

  Preferably, a step of forming a conductive polymer-containing layer containing at least a π-conjugated conductive polymer and a polyanion on the metal fine wire pattern after heating and firing is preferably provided.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent electrode excellent in electroconductivity can be manufactured, suppressing board | substrate damage.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

The transparent electrode according to a preferred embodiment of the present invention has at least a flexible transparent substrate, a protective layer, and a conductive fine metal wire pattern. The protective layer is formed on the transparent substrate, and the metal is formed on the protective layer. A fine line pattern is formed. In the transparent electrode, a conductive polymer layer is preferably formed on a fine metal wire pattern.
Hereinafter, the configuration, characteristics, manufacturing method, and the like of each member of the transparent electrode will be described.

[Transparent substrate]
The transparent substrate used for the transparent electrode of the present invention is not particularly limited as long as it has high light transparency, and the total light transmittance is preferably 70% or more, and preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.
As the transparent substrate of the present invention, for example, a resin substrate, a resin film, glass and the like are preferably mentioned, but it is preferable to use a transparent resin film from the viewpoint of productivity and performance such as lightness and flexibility.
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. For example, polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc. Resin films, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like. If the resin film transmittance of 80% or more in 80~780nm), can be preferably applied to a transparent resin film according to the present invention. Among them, biaxial stretching of biaxially stretched polyethylene terephthalate resin film, biaxially stretched polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. from the viewpoint of transparency, heat resistance, ease of handling, strength and cost It is preferably a polyester resin film, more preferably a biaxially stretched polyethylene terephthalate resin film or a biaxially stretched polyethylene naphthalate resin film.

[Protective layer]
In the transparent electrode of the present invention, a protective layer is formed on at least one surface of the transparent substrate. Moreover, it is preferable to laminate | stack in order of a protective layer and a metal fine wire pattern on a transparent substrate.
The protective layer of the present invention is used to suppress substrate damage due to local heating, and is preferably an inorganic protective layer. In order to be suitably used for an organic electronic device, the inorganic protective layer is a gas barrier layer. More preferred.
The protective layer of the present invention may be a combination of an organic protective layer and an inorganic protective layer. From the viewpoint of imparting sufficient durability, impact resistance and smoothness to the film, the organic protective layer is a hard coat layer. Is preferred. The protective layer is preferably formed in the order of the transparent substrate, the organic protective layer, and the inorganic protective layer.

(1) Gas barrier layer There is no restriction | limiting in particular as a gas barrier layer and its formation method in this invention, The film | membrane by inorganic compounds, such as a silica, can be formed by vacuum evaporation or CVD method. Further, after coating and drying a coating liquid containing a polysilazane compound, a gas barrier layer may be formed by oxidation treatment by ultraviolet irradiation in a nitrogen atmosphere containing oxygen and water vapor, and an inorganic or organic coating or a hybrid coating of both. May be formed.
Any appropriate method can be adopted as a method for applying the polysilazane compound. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H or the like, such as SiO ₂ , Si ₃ N _4, or an intermediate solid solution SiOxNy or the like. It is a precursor inorganic polymer.
In order not to damage the resin film substrate, it is preferable that the resin film substrate is ceramicized at a relatively low temperature and modified to silica as described in JP-A-8-112879, and is represented by the following general formula (1). What can be preferably used.

In the general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. In perhydropolysilazane, all of R ¹ , R ² , and R ³ are hydrogen atoms, and in organopolysilazane, any of R ¹ , R ² , and R ³ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, An alkylsilyl group, an alkylamino group or an alkoxy group; Perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferred because of the denseness of the resulting barrier film.
On the other hand, organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the ceramic made of polysilazane which is hard and brittle The film can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

The coated film is preferably annealed to obtain a uniform dry film from which the solvent has been removed. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 2 hours.
The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30% RH to 90% RH, more preferably 40% RH to 80% RH.

As the oxidation treatment of polysilazane, steam oxidation and / or heat treatment (including drying treatment), treatment by ultraviolet irradiation, and the like are known, and ultraviolet irradiation treatment is preferably used. By irradiating ultraviolet light in the presence of oxygen, active oxygen and ozone are generated, and the oxidation reaction can be further advanced.
Further, ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion for the shortage of reactive ozone, and introduced into the ultraviolet irradiation portion.
The wavelength of the ultraviolet light irradiated at this time is not particularly limited, but the wavelength of the ultraviolet light is preferably 100 nm to 450 nm, and more preferably irradiated with ultraviolet light of about 150 nm to 300 nm.
As the light source, a low-pressure mercury lamp, a deuterium lamp, a Xe excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. As the output of the lamp 400W～30kW, more preferably preferably ^{10mJ / cm 2 ~5000mJ / cm 2} , 100mJ / cm 2 ~2000mJ / cm 2 as ^{100mW / cm 2 ~100kW / cm 2} , irradiation energy as illuminance . Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² . By irradiating the polysilazane coating film with ultraviolet rays in an oxidizing gas atmosphere, the polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. Control is possible by irradiation time and wavelength (energy density of light), and it is possible to select appropriately such as properly using different types of lamps in order to obtain a desired film structure. In addition to continuous irradiation, multiple irradiations may be performed, and multiple irradiations may be so-called pulse irradiation in a short time.
Among these, it is preferable to perform the treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 200 nm or less having a higher photon energy. This is because if the energy is small, the effect of polysilazane is insufficient and the barrier property is lowered. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to promote a reaction (also referred to as an oxidation reaction or a conversion treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. You may select suitably the method which can maintain the smoothness of a coating film.
As temperature to heat, the range of 50 to 200 degreeC is preferable, More preferably, it is the range of 80 to 150 degreeC, As a heating time, the range of 1 second-10 hours is preferable, More preferably, it is 10 seconds-1 Heating for a range of time.

As the gas barrier layer of the present invention, one layer may be used, and two layers or three layers are preferably stacked, but four or more layers may be stacked. A stress relaxation layer may be sandwiched between the gas barrier layers.
In the case of a single layer or stacked layers, the thickness of one gas barrier layer is preferably 30 nm to 1000 nm, more preferably 30 nm to 500 nm, particularly 90 nm to 500 nm. When it is 30 nm or more, the film thickness uniformity is good and the gas barrier performance is excellent. When the thickness is 1000 nm or less, cracks due to bending rapidly become extremely small, and an increase in internal stress during film formation is suppressed to prevent generation of defects.

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

(2) Hard coat layer The film thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm to 10 μm, and most preferably 3 μm to 7 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include (meth) alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. Acrylic acid diesters; (Meth) acrylic acid of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Diesters; (meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2--2-bi {4- (acryloxy · polypropoxy) phenyl} ethylene or propylene oxide adduct (meth) acrylic acid diesters such as propane; and the like.
Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.
Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like. In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .
Two or more polyfunctional monomers may be used in combination.

It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals, Esacure (KIP100F, KB1, EB3, BP, X33, KT046) manufactured by Sartomer , KT37, KIP150, TZT) and the like.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in “Latest UV Curing Technology”, Technical Information Association, 1991, p. 159. Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried.

[Metallic fine wire pattern]
The fine metal wire pattern of the present invention is formed from metal nanoparticles. The metal material of the metal nanoparticles is not particularly limited as long as it has excellent conductivity. For example, an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium may be used. Silver is preferred from the viewpoint.
Here, the average particle size of the metal nanoparticles is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 30 nm.
The average particle diameter of the metal nanoparticles in the present invention is determined by observing 200 or more metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse at random from an electron microscope observation of the metal nanoparticles. It is obtained by determining the particle size of the nanoparticles and determining the number average value thereof. Here, the average particle diameter according to the present invention refers to the minimum distance among the distances between the outer edges of the metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. . When measuring the average particle diameter, the ones that clearly represent the side surfaces of the metal nanoparticles are not measured.

The pattern shape of the metal fine line pattern in the present invention is not particularly limited. For example, the pattern shape may be a stripe shape or a mesh shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. . An aperture ratio is the ratio which the electroconductive part which has translucency accounts to the whole. For example, when the light-impermeable metal fine line pattern 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 about 90%. The line width of the pattern is preferably 10 to 200 μm. When the line width of the thin wire is 10 μm or more, desired conductivity is obtained, and when it is 200 μm or less, sufficient transparency as a transparent electrode is obtained. The height of the fine wire is preferably 0.1 to 5 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and if it is 5 μm or less, the unevenness difference does not affect the film thickness distribution of the functional layer in the formation of the organic electronic element.
As a method of forming an electrode having a conductive portion having a stripe shape or a mesh shape, a method of printing an ink containing metal nanoparticles in a desired shape is preferable. There is no restriction | limiting in particular as a printing method, It can print and form in a desired shape with well-known printing methods, such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing.

[Conductive polymer-containing layer]
The conductive polymer-containing layer according to the present invention is formed from a conductive polymer containing at least a π-conjugated conductive polymer and a polyanion.
The dry film thickness of the conductive polymer-containing layer is preferably 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is more preferably 300 nm or more. Further, from the viewpoint of transparency, the thickness is more preferably 1000 nm or less, and further preferably 800 nm or less.
In addition to the above-described printing methods such as gravure printing, flexographic printing, and screen printing, the conductive polymer-containing layer is applied in roll coating, bar coating, dip coating, spin coating, casting, and die coating. Coating methods such as a method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.

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

(1.1) π-conjugated conductive polymer The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophene, the same shall apply hereinafter), polypyrroles, and polyindoles. A chain conductive polymer of polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazils Can be used. Of these, polythiophenes and polyanilines are preferred from the viewpoints of conductivity, transparency, stability, and the like, and ease of adsorption to metal nanoparticles. Most preferred is polyethylene dioxythiophene.

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

(1.2) Poly anion The poly anion used in the present invention is an acidic polymer in a free acid state, a polymer of a monomer having an anionic group, or a monomer having an anionic group and a monomer having no anionic group. It is a copolymer. The free acid may be in the form of a partially neutralized salt. A substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof, at least having an anionic group Is included.
This poly anion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.
The anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Further, it may be a poly anion further having F (fluorine atom) in the compound. Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.
Among these, the compound having a sulfonic acid may be formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.
Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These poly anions have high compatibility with the hydroxyl group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.

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

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

The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion” is preferably 1: 1 to 1:20 by mass ratio. The range of 1: 2 to 1:10 is more preferable from the viewpoint of conductivity and dispersibility.
The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.
Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, For example, methane or dodecanesulfonic acid; aliphatic carboxylic acids having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as sulphur Mention may be made of acids and in particular aromatic, optionally alkyl-substituted sulphonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecene sulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic acid. Furthermore, oxidation polymerization can be performed using a known oxidation catalyst.
As such a conductive polymer, a commercially available material can also be preferably used. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095, 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.

(2) Second dopant The conductive polymer-containing layer may contain a water-soluble organic compound as the second dopant. There is no restriction | limiting in particular in the water-soluble 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 hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin, and the like. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

(3) Other components and additives, etc. The conductive polymer-containing layer of the present invention has film formability and film strength in addition to a conductive polymer comprising at least a π-conjugated conductive polymer and a polyanion. In order to ensure, a transparent resin component or additive may be included. The transparent resin component 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.
Among these, it is preferable to form a binder resin or a water-soluble binder resin that can be uniformly dispersed in an aqueous solvent from the viewpoint of obtaining high surface smoothness while maintaining high transparency and conductivity.

(3.1) Binder resin that can be uniformly dispersed in an aqueous solvent The binder resin that can be uniformly dispersed in an aqueous solvent is one that can be uniformly dispersed in an aqueous solvent, and is a colloid made of a binder resin without agglomerating in the aqueous solvent. It means that the particles are dispersed. The size of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 nm).
The colloidal particles can be measured with a light scattering photometer.
The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, and a hydrophilic organic solvent. And pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, mixed solvents of water and alcohol, and the like.
The binder resin that can be uniformly dispersed in the aqueous solvent according to the present invention is preferably transparent.
The binder that can be uniformly dispersed in the aqueous solvent of the present invention is not particularly limited as long as it is a medium for forming a film. Examples of the binder that can be uniformly dispersed in the aqueous solvent include: acrylic resin emulsion, aqueous urethane resin, aqueous polyester resin, and the like.
The acrylic resin emulsion is made of vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers. In addition, the acid part is composed of a copolymer of an anionic lithium salt, sodium salt, potassium salt, ammonium salt, and a monomer having a nitrogen atom, and a cationic nitrogen atom forming a hydrochloride salt, Preferably it is anionic.
Examples of aqueous urethane resins include water-dispersed urethane resins and ionomer-type aqueous urethane resins (anionic). The water-dispersed urethane resin includes a polyether-based urethane resin and a polyester-based urethane resin, preferably a polyester-based urethane resin.
Examples of the ionomer type water-based urethane resin include polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins, and polyester-based urethane resins and polyether-based urethane resins are preferable.
The aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
The polybasic acid component is, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, etc., and these may be used alone. Two or more types may be used in combination, and as the polybasic acid component that can be used particularly preferably, terephthalic acid and isophthalic acid are industrially produced in large quantities and inexpensive. Particularly preferred.
Typical examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, bisphenol, and the like. These may be used singly or may be used in combination of two or more. The polyol component that can be particularly suitably used is inexpensive because it is industrially mass-produced, Ethylene glycol, propylene glycol, or neopentyl glycol is particularly preferable because various properties such as improvement in solvent resistance and weather resistance of the resin coating are balanced.
One or more binders that can be uniformly dispersed in the aqueous solvent can be used.
The amount of the polymer dispersible in the aqueous solvent is preferably 50 to 1000% by mass with respect to the conductive polymer from the viewpoint of transparency and conductivity, and more preferably 100 to 900% with respect to the conductive polymer. It is 200 mass%, More preferably, it is 200-800 mass% with respect to a conductive polymer.

(1.4.2) Water-soluble binder resin The water-soluble binder resin is preferably a water-soluble binder resin containing a structural unit represented by the following general formula (2).

In General Formula (2), R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, and A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) xCH ₂ CHRb—. Rb represents a hydrogen atom or an alkyl group, and x represents the average number of repeating units.

Since such a resin can be easily mixed with a conductive polymer and also has the above-mentioned second dopant effect, by using this water-soluble binder resin in combination, the conductivity and transparency are not reduced. The film thickness of the conductive polymer-containing layer can be increased.
The water-soluble binder resin is a water-soluble binder resin, and means a binder resin in which 0.001 g or more is dissolved in 100 g of water at 25 ° C. The dissolution can be measured with a haze meter or a turbidimeter.
The water-soluble binder resin is preferably transparent.
The water-soluble binder resin preferably has a structure including a structural unit represented by the general formula (2). The homopolymer represented by the general formula (2) may be used, or other components may be copolymerized. When copolymerizing other components, the structural unit represented by the general formula (2) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.
The water-soluble binder resin is preferably contained in the conductive polymer-containing layer in an amount of 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.

  In the structural unit having a hydroxyl group represented by the general formula (2), R represents a hydrogen atom or a methyl group. Q represents -C (= O) O-, -C (= O) NRa-, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxyl groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyls. Group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, aryl Rucarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl group, Lumpur oxysulfonyl group, an alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxyl group and an alkyloxy group are preferable.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.
The number of carbon atoms in the cycloalkyl group is preferably 3-20, more preferably 3-12, and even more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group may have a branch, the number of carbon atoms is preferably 1-20, more preferably 1-12, still more preferably 1-6, and 1-4 Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group.
The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1-20, more preferably 1-12, even more preferably 1-6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group.
The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.
The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
The number of carbon atoms of the heterocycloalkyl group is preferably 2 to 10, and more preferably 3 to 5. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.
The number of carbon atoms in the heteroaryl group is preferably 3-20, and more preferably 3-10. Examples of the heteroaryl group include a thienyl group and a pyridyl group.
The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group.
The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like.
The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include a methanesulfonamide group.
The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group.
The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
The acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.
The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group.
The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.
The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.
The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.
The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

In the structural unit having a hydroxyl group represented by the general formula (2), A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) x —CH ₂ CHRb—. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent described above. Rb represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with the above-mentioned substituent. Furthermore, x represents the average number of repeating units, preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.

  Hereinafter, representative specific examples of the structural unit represented by the general formula (2) are shown, but the present invention is not limited thereto.

The water-soluble binder resin of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.
The number average molecular weight of the water-soluble binder resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably 5,000 to 100,000.
The number average molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the water-soluble binder resin of the present invention can be measured by a generally known gel permeation chromatography (GPC). it can. The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, THF and DMF are more preferable, and DMF is more preferable. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

[Characteristics of transparent electrode]
The total light transmittance of the transparent electrode in the present invention is 70% or more, preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.
As the electric resistance value of the conductive portion of the transparent electrode in the present invention, the surface specific resistance is preferably 100Ω / □ or less, more preferably 20Ω / □ or less, for use in a large-area organic electronic device. 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.

[Method for producing transparent electrode]
The manufacturing method of the transparent electrode is mainly
(I) forming a protective layer on one surface of the transparent substrate;
(Ii) forming a fine metal wire pattern with metal nanoparticles on the protective layer;
(Iii) a step of heating and firing the fine metal wire pattern by flash light irradiation;
Preferably,
(Iv) It is good to provide the process of forming a conductive polymer content layer on the metal fine wire pattern after heat-firing.

In particular, with respect to the step (iii), the heating and baking by light irradiation using a flash lamp is performed in order to improve the conductivity by baking a conductive fine metal wire pattern formed from metal nanoparticles.
Xenon, helium, neon, and argon can be used as the discharge tube of the flash lamp of the present invention, but xenon is preferably used.
The preferred spectral band of the flash lamp in the present invention is preferably 240 nm to 2000 nm, since the transparent substrate of the present invention is not damaged by the flash light irradiation, such as thermal deformation.
As for the light irradiation conditions of the flash lamp of the present invention, the total light irradiation energy is preferably from 0.1 to 50 J / cm2, and more preferably from 0.5 to 10 J / cm2. The light irradiation time is preferably from 10 μsec to 100 msec, more preferably from 100 μsec to 10 msec. Further, the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1 to 50 times. By performing flash light irradiation in these preferable condition ranges, the fine metal wire pattern can be heated and fired without damaging the substrate, and high conductivity can be obtained.

When the material of the substrate is a transparent body, irradiation of the flash lamp to the substrate is basically performed from the front side on which the metal fine line pattern is printed, but may be performed from both sides.
The flash light irradiation of the present invention may be performed in the air, but can also be performed in an inert gas atmosphere such as nitrogen, argon, helium, etc., if necessary.
In addition, the substrate temperature at the time of flash light irradiation is the boiling point (vapor pressure) of the dispersion medium of the ink containing the metal nanoparticles, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the metal nanoparticles, What is necessary is just to determine in consideration of the film thickness of a conductive polymer content layer, the heat-resistant temperature of a base material, etc., It is preferable to carry out at room temperature or more and 150 degrees C or less. Note that the substrate on which the fine metal wire pattern has been formed may be subjected to heat treatment in advance before performing the flash light irradiation.
The light irradiation device of the flash lamp may be any device that satisfies the above irradiation energy and irradiation time.

[Organic electronic devices]
The organic electronic device in the present invention has a transparent electrode and an organic functional layer produced by the method of the present invention.
For example, the transparent electrode formed by the method of the present invention is used as a first electrode portion, an organic functional layer is formed on the first electrode portion, and a second electrode portion is formed on the organic functional layer as a counter electrode. By forming it, an organic electronic device can be obtained.
Examples of the organic functional layer include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like, without any particular limitation. This is particularly effective in the case of an organic photoelectric conversion layer.
Hereinafter, the component in case the organic electronic element of this invention is an organic EL element and an organic photoelectric conversion element is demonstrated.

(1) Organic EL element (1.1) Organic functional layer structure (organic light emitting layer)
In the present invention, an organic EL device having an organic light emitting layer as an organic functional layer includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, an electron block layer, etc. in addition to the organic light emitting layer. A layer for controlling the light emission may be used in combination with the organic light emitting layer.
Since the conductive polymer layer on the transparent electrode of the present invention can also serve as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.

Although the preferable specific example of a structure is shown below, this invention is not limited to these.
(I) (first electrode part) / light emitting layer / electron transport layer / (second electrode part)
(Ii) (first electrode part) / hole transport layer / light emitting layer / electron transport layer / (second electrode part)
(Iii) (first electrode part) / hole transport layer / light emitting layer / hole block layer / electron transport layer / (second electrode part)
(Iv) (first electrode part) / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (second electrode part)
(V) (first electrode part) / anode buffer layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (second electrode part)

Here, the light emitting layer may be a monochromatic light emitting layer having a light emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm, respectively. A white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL device of the present invention is preferably a white light emitting layer.
In addition, as the light emitting material or doping material that can be used in the organic light emitting layer in the present invention, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, 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 and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material.
The organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.

(1.2) Electrode The transparent electrode of the present invention is used in the first or second electrode portion described above. In a preferred embodiment, the first electrode portion is an anode and the second electrode portion is a cathode.
The second electrode portion may be a single conductive material layer, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the second electrode portion, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.
If a metal material is used as the conductive material of the second electrode part, the light coming to the second electrode side is reflected and returns to the first electrode part side. By using a metal material as the conductive material of the second electrode portion, this light can be reused and the extraction efficiency is further improved.

(2) Organic photoelectric conversion element The organic photoelectric conversion element includes a first electrode part, a photoelectric conversion layer having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer) (hereinafter also referred to as a bulk heterojunction layer), and a second electrode. It is preferable to have a structure in which the portions are laminated.
The transparent electrode of the present invention is used at least on the incident light side.
An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the second electrode portion.

(2.1) Photoelectric conversion layer The photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. It is preferable. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons as in the case of an electrode, but donates or accepts electrons by a photoreaction.

Examples of the p-type semiconductor material include various condensed polycyclic aromatic compounds and conjugated compounds.
As the condensed polycyclic aromatic compound, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.
Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.
In particular, among polythiophene and oligomers thereof, thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.

Other examples of the polymer p-type semiconductor include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. Substituted-unsubstituted alternating copolymer polythiophenes such as JP-A-2006-36755, JP-A-2007-51289, JP-A-2005-76030, J. Org. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, etc., polymers having a condensed ring thiophene structure, WO2008 / 000664, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.
Furthermore, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiotetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes of C60, C70, C76, C78, C84, fullerenes such as SWNT, carbon nanotubes such as SWNT, merocyanine dyes, dyes such as hemicyanine dyes, and σ-conjugated polymers such as polysilane and polygermane Organic / inorganic hybrid materials described in Kai 2000-260999 can also be used.

Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.
Examples of pentacenes include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216, and the like. A pentacene derivative described in U.S. Patent Application Publication No. 2003/136964 and the like; Amer. Chem. Soc. , Vol127. Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.
Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable. Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, 2706 and the like, and acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in U.S. Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.

Among these, the latter precursor type can be preferably used.
This is because the precursor type is insolubilized after conversion, so when forming the hole transport layer, electron transport layer, hole block layer, electron block layer, etc. on the bulk hetero junction layer by solution process, bulk hetero junction This is because the layer does not dissolve and the material constituting the layer and the material forming the bulk heterojunction layer are not mixed, and further improvement in efficiency and life can be achieved. .
The p-type semiconductor material is a compound that has undergone a chemical structural change by a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material. Preferably there is. Among them, compounds that cause a scientific structural change by heat are preferred.
Examples of n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic acid Examples thereof include polymer compounds containing an anhydride, an aromatic carboxylic acid anhydride such as perylenetetracarboxylic acid diimide, or an imidized product thereof as a skeleton.
Among these, fullerene-containing polymer compounds are preferable. Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton. As the fullerene-containing polymer compound, a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.
The fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. Are preferred.
This is not because fullerene is contained in the main chain because the polymer does not have a branched structure, so that it can be packed with high density when solidified, resulting in high mobility. It is estimated that.
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).

As a form which uses the photoelectric conversion element of this invention as photoelectric conversion devices, such as a solar cell, a photoelectric conversion element may be utilized by a single layer and may be laminated | stacked and utilized (tandem type).
In addition, since the photoelectric conversion device is not deteriorated by oxygen, moisture, or the like in the environment, the photoelectric conversion device is preferably sealed by a known method.

According to the above embodiment, it is possible to provide a method for producing a transparent electrode excellent in transparency, conductivity, and gas barrier properties, a transparent electrode produced by the production method, and an organic electronic device using the transparent electrode. it can.
The expression mechanism or action mechanism of the effect of the present invention is presumed as follows.
In the present embodiment, a fine metal wire pattern is formed on the protective layer, and is heated and fired by flash light irradiation. Even when the metal fine line pattern itself becomes very high temperature, the presence of the protective layer can improve the conductivity without damaging the substrate.
In this embodiment, by providing a conductive polymer-containing layer on the fine metal wire pattern, it becomes possible to supply electricity to the window (opening) where the fine metal wire pattern does not exist, and function as a planar electrode. ing. In addition, the conductive polymer-containing layer becomes a reinforcing film for the transparent electrode, and the strength against deformation and cracking of the substrate due to bending, heat, etc. is improved. Furthermore, even when a fine crack is generated on the substrate, the conductive polymer-containing layer is contained. It is considered that the layer itself becomes a hygroscopic layer and expresses a desiccant (drying agent) -like effect, and the gas barrier performance is remarkably improved.

  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 "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

(1) Production of transparent substrate with protective layer (1.1) Formation of hard coat layer Acrylic / urethane resin (Unidic 17-806 manufactured by Dainippon Ink & Chemicals) 100 as a hard coat layer forming material 5 parts of hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was added to the part to prepare a toluene solution diluted to a concentration of 30% by mass.
The material for forming the hard coat layer was applied to one surface of a polyethylene terephthalate (PET) film having a thickness of 100 μm and a size of 180 mm × 180 mm, and dried at 100 ° C. for 3 minutes. Immediately thereafter, ultraviolet rays were irradiated with two ozone type high pressure mercury lamps (energy density 80 W / cm ² , 15 cm condensing type) to form a hard coat layer having a thickness of 5 μm.

(1.2) Formation of gas barrier layer (1.2.1) coating (average) film after drying a 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS, AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) It apply | coated on the hard-coat layer formed above so that thickness might be set to 0.3 micrometer, and the transparent substrate with a protective layer was obtained.

(1.2.2) Drying and dehumidification (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.

(1.2.3) Reformation (reforming process)
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)
An excimer irradiation apparatus (MODEL: MECL-M-1-200, wavelength 172 nm, lamp sealed gas Xe) manufactured by M.D.Com Co., Ltd. was used.
A sample was fixed on the operation stage, and the sample was modified 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

(2) Preparation of transparent electrode (sample) (2.1) Preparation of transparent electrode TCF-1 (comparative example)
ITO was sputter-deposited with an average film thickness of 150 nm on an area of 150 mm × 150 mm on the protective layer forming surface side of the transparent substrate with a protective layer produced above, to produce “transparent electrode TCF-1”.

(2.2) Production of transparent electrode TCF-2 (comparative example)
Using the silver nanoparticle ink 1 (TEC-PA-010; manufactured by InkTech) on the protective layer-forming surface side of the transparent substrate with a protective layer produced above, a screen plate pattern having a square grid shape of 50 μm width and 1 mm pitch Then, a fine metal line pattern was printed by a screen printing method so that the height of the fine line after firing was 800 nm. A small thick film semi-automatic printing machine STF-150IP (manufactured by Tokai Shoji Co., Ltd.) was used as a printing apparatus. The area of the pattern printing area was 150 mm × 150 mm. After printing, heat treatment was performed on a hot plate at 150 ° C. for 30 minutes to produce “transparent electrode TCF-2”.

(2.3) Production of transparent electrode TCF-3 (Example)
In the production of TCF-2, instead of performing a heat treatment at 150 ° C. for 30 minutes with a hot plate, after printing a fine metal wire pattern, a xenon flash lamp 2400WS (made by COMET) equipped with a short wavelength cut filter of 250 nm or less was used. Then, irradiation was performed once from the printing surface side with an irradiation energy of 1.5 J / cm ² and an irradiation time of 2 milliseconds. Other than that was carried out similarly to preparation of TCF-2, and produced "transparent electrode TCF-3".

(2.4) Production of transparent electrode TCF-4 (comparative example)
In the production of TCF-3, a metal fine line pattern was printed on the side opposite to the protective layer forming surface of the transparent substrate with a protective layer. Other than that was carried out similarly to preparation of TCF-3, and produced "transparent electrode TCF-4".

(2.5) Production of transparent electrode TCF-5 (comparative example)
In preparation of TCF-4, the flash lamp irradiation conditions were performed once with an irradiation energy of 100 mJ / cm ² and an irradiation time of 2 milliseconds. Otherwise, “transparent electrode TCF-5” was produced in the same manner as TCF-4.

(2.6) Production of transparent electrode TCF-6 (Example)
In the production of TCF-3, the polyethylene terephthalate (PET) film was changed to a polyethylene naphthalate (PEN) film.
In production of TCF-3, PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5 as a conductive polymer in accordance with the printing width of the thin metal wire pattern on the fine metal wire pattern after flash lamp irradiation. BONCOAT AN-155E (manufactured by Dainippon Ink Co., Ltd., solid content concentration 55%) which is a binder resin that can be uniformly dispersed in an aqueous solvent. The conductive polymer liquid CP-1 added to 233% by mass with respect to the solid content of the conductive polymer was used as a conductive polymer-containing layer using an applicator having a coating width of 150 mm, and the dry average film thickness was It apply | coated so that it might become 500 nm, and the unnecessary peripheral part was wiped off so that it might become the same as the printing area | region of a metal fine wire pattern.
Other than that was carried out similarly to preparation of TCF-3, and produced "transparent electrode TCF-6".

(2.7) Production of transparent electrode TCF-7 (Example)
In the production of TCF-6, the conductive polymer liquid CP-1 was replaced with bondic 1940NE (manufactured by Dainippon Ink Co., Ltd., solid content concentration 50%) as a binder resin that can be uniformly dispersed in an aqueous solvent. CP-2 was used. Otherwise, “transparent electrode TCF-7” was produced in the same manner as in the production of TCF-6.

(2.8) Production of transparent electrode TCF-8 (Example)
In the production of TCF-6, a conductive polymer liquid obtained by replacing the binder resin of the conductive polymer liquid CP-1 that can be uniformly dispersed in an aqueous solvent with Bondic 2210 (Dainippon Ink Co., Ltd., solid content concentration 40%). CP-3 was used. Other than that was carried out similarly to preparation of TCF-6, and produced "transparent electrode TCF-8".

(2.9) Production of transparent electrode TCF-9 (Example)
In the production of TCF-6, the binder resin that can be uniformly dispersed in the aqueous solvent of the conductive polymer liquid CP-1 was replaced with Hydran AP-40 (F) (Dainippon Ink Co., Ltd., solid content concentration 22%). Conductive polymer liquid CP-4 was used. Other than that was carried out similarly to TCF-6, and produced "transparent electrode TCF-9."

(2.10) Production of transparent electrode TCF-10 (Example)
In the production of TCF-6, the conductive polymer liquid CP-1 was replaced with a positive coat Z-561 (manufactured by Kyoyo Chemical Industry Co., Ltd., solid content concentration: 25%). Polymer solution CP-5 was used. Other than that was carried out similarly to TCF-6, and produced "transparent electrode TCF-10."

(2.11) Production of transparent electrode TCF-11 (Example)
In the production of TCF-10, the flash lamp irradiation conditions were performed once with an irradiation energy of 1.8 J / cm ² and an irradiation time of 500 μsec. Other than that was carried out similarly to preparation of TCF-10, and produced "transparent electrode TCF-11."

(2.12) Preparation of transparent electrode TCF-12 (Example)
In the production of TCF-10, the flash lamp was irradiated three times with an irradiation energy of 1.0 J / cm ² and an irradiation time of 2 milliseconds. Other than that was carried out similarly to preparation of TCF-10, and produced "transparent electrode TCF-12."

(2.13) Preparation of transparent electrode TCF-13 (comparative example)
In the production of TCF-10, printing of a metal fine line pattern and irradiation with a flash lamp were not performed. Other than that was carried out similarly to preparation of TCF-10, and produced "transparent electrode TCF-13."

(2.14) Preparation of transparent electrode TCF-14 (Example)
In the production of TCF-6, the conductive polymer liquid CP-1 was replaced with a water-soluble binder resin 1 aqueous solution prepared by synthesizing Boncoat AN-155E, which is a binder resin that can be uniformly dispersed in an aqueous solvent. Conductive polymer liquid CP-6 was used. Other than that was carried out similarly to preparation of TCF-6, and produced "transparent electrode TCF-14."

<Synthesis of water-soluble binder resin 1>
After adding 200 ml of THF to a 300 ml three-necked flask and heating to reflux for 10 minutes, it was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (10.0 g, 86.2 mmol, molecular weight 116.12) and AIBN (2.8 g, 17.2 mmol, molecular weight 164.11) were added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 2000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed three times with 100 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 9.0 g (yield 90%) of water-soluble binder resin 1 having a number average molecular weight of 22100 and a molecular weight distribution of 1.42 was obtained.
The structure and molecular weight were measured by 1H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.
<GPC measurement conditions>
Device: Waters 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
The obtained water-soluble binder resin 1 was dissolved in pure water to prepare a water-soluble binder resin 1 aqueous solution having a solid content of 20%.

(2.15) Production of transparent electrode TCF-15 (Example)
In the production of TCF-14, a conductive polymer liquid CP-7 was used in which the aqueous solution of the water-soluble binder resin 1 in the conductive polymer liquid CP-6 was replaced with the aqueous solution of the water-soluble binder resin 2 prepared by synthesis as follows. did. Other than that was carried out similarly to preparation of TCF-14, and produced "transparent electrode TCF-15."

<Synthesis of water-soluble binder resin 2>
In the synthesis of the water-soluble binder resin 1, 2-hydroxyethyl acrylate was changed to 3-hydroxypropyl acrylate (11.2 g, molecular weight 130.14), and the purification solvent was changed from MEK to normal heptane. Other than that, 9.5 g (yield 85%) of water-soluble binder resin 2 having a number average molecular weight of 25,500 and a molecular weight distribution of 1.53 was obtained by carrying out the same operation as the synthesis of water-soluble binder resin 1.
The obtained water-soluble binder resin 2 was dissolved in pure water to prepare a water-soluble binder resin 2 aqueous solution having a solid content of 20%.

(2.16) Production of transparent electrode TCF-16 (Example)
In the production of TCF-14, the conductive polymer liquid CP-8 was used in which the aqueous solution of the water-soluble binder resin 1 in the conductive polymer liquid CP-6 was replaced with the aqueous solution of the water-soluble binder resin 3 prepared as follows. did. Other than that was carried out similarly to preparation of TCF-14, and produced "transparent electrode TCF-16."

<Synthesis of water-soluble binder resin 3>
In the synthesis of the water-soluble binder resin 1, 2-hydroxyethyl acrylate was changed to 4-hydroxybutyl acrylate (12.4 g, molecular weight 144.17), and the purification solvent was changed from MEK to normal heptane. Other than that, 10.2 g (yield 82%) of water-soluble binder resin 3 having a number average molecular weight of 21,700 and a molecular weight distribution of 1.36 was obtained by carrying out the same operation as the synthesis of water-soluble binder resin 1.
The obtained water-soluble binder resin 3 was dissolved in pure water to prepare a water-soluble binder resin 3 aqueous solution having a solid content of 20%.

(2.17) Production of transparent electrode TCF-17 (Example)
In the production of TCF-14, a conductive polymer liquid CP-9 was used in which the aqueous solution of the water-soluble binder resin 1 in the conductive polymer liquid CP-6 was replaced with the aqueous solution of the water-soluble binder resin 4 prepared by synthesis as follows. did. Otherwise, “transparent electrode TCF-17” was produced in the same manner as in the production of TCF-14.

<Synthesis of water-soluble binder resin 4>
In the synthesis of the water-soluble binder resin 1, 2-hydroxyethyl acrylate was changed to 2-hydroxyethyl acrylamide (9.9 g, molecular weight 115.15), and the purification solvent was changed from MEK to diisopropyl ether. Other than that, 7.9 g (yield 80%) of water-soluble binder resin 4 having a number average molecular weight of 28300 and a molecular weight distribution of 1.48 was obtained by carrying out the same operation as the synthesis of water-soluble binder resin 1.
The obtained water-soluble binder resin 4 was dissolved in pure water to prepare a water-soluble binder resin 4 aqueous solution having a solid content of 20%.

(3) Measurement and evaluation of transparent electrode The SEM observation of the cross section of each transparent electrode is performed by the following method, and the transmittance, surface specific resistance, and water vapor transmission rate of the conductive portion of each transparent electrode are measured to obtain transparency and conductivity. And gas barrier property was evaluated.

(3.1) SEM observation About each produced transparent electrode, after processing with the focused ion beam processing apparatus (FIB: Hitachi, FB-2000), exposing the cross section of a metal fine wire pattern, the cross section is scanned. When observed with a scanning electron microscope (SEM: manufactured by Hitachi, Ltd., S-5000H, acceleration voltage 1.0 kV, magnification 50,000 times), the transparent electrodes according to the examples of the present invention are all silver nanowires with a fine metal wire pattern. The particles were fused with high density, and no substrate damage was observed.
On the other hand, TCF-2 has incomplete fusion of silver nanoparticles with a metal fine line pattern. In TCF-4, the silver nanoparticles of the metal fine line pattern were fused with high density, but the surface of the substrate in contact with the metal fine line pattern was dissolved in a bowl shape along the metal fine line pattern. confirmed. As for TCF-5, silver nanoparticles having a metal fine line pattern were hardly fused.

(3.2) Transmittance The transmittance was determined by measuring the total light transmittance of the transparent electrode using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.
(3.3) Surface specific resistance The surface specific resistance measured the surface specific resistance of the transparent electrode by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.
(3.4) Water vapor transmission rate Various methods have been proposed for measuring the water vapor transmission rate according to the above-mentioned JIS K 7129B method. For example, the cup method, the wet and dry sensor method (Lassy method), and the infrared sensor method (mocon method) can be cited as representatives. The following method has also been proposed. The method for measuring the water vapor transmission rate is not particularly limited, but here, evaluation by the Ca method was performed.

<Water vapor permeability measurement method other than the above>
Ca method: a method in which metal Ca is vapor-deposited on a gas barrier film and the phenomenon that the metal Ca is corroded by moisture that has passed through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.
Method proposed by MORESCO Co., Ltd. (December 8, 2009, NewsRelease); a method of passing through a cold water vapor trap between a sample space under atmospheric pressure and a mass spectrometer in ultra-high vacuum.
HTO method (General Atomics, USA); a method for calculating water vapor transmission rate using tritium.
Method proposed by A-Star (Singapore) (WO05 / 95924); using a material whose electrical resistance is changed by water vapor or oxygen (for example, Ca, Mg) as a sensor, from the electrical resistance change and the inherent 1 / f fluctuation component Method for calculating water vapor transmission rate.

<Ca method used for this evaluation>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)

<Production of water vapor barrier property evaluation cell>
On the electrode surface of each transparent electrode, using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), other than the portion to be vapor deposited (12 mm × 12 mm 9 positions) was masked to deposit metal calcium. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of the metal calcium deposition side. After the aluminum vapor deposition, the vacuum state is released, and immediately in a dry nitrogen gas atmosphere, a quartz glass with a thickness of 0.2 mm is faced to the aluminum sealing side via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). The cell for evaluation was produced by irradiating with ultraviolet rays.
The prepared evaluation cell was stored at 60 ° C. and 90% RH under high temperature and high humidity for 100 hours, and based on the method described in JP-A-2005-283561, the amount of moisture permeated into the cell from the corrosion amount of metallic calcium Was calculated.
In addition, in order to confirm that there is no permeation | transmission of the water vapor | steam from members other than a transparent electrode, the cell for evaluation produced using the quartz glass plate of thickness 0.2mm as a comparative sample is similarly 60 degreeC and 90%. It was stored under high temperature and high humidity of RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.
The results of measurement and evaluation are shown in Table 3.

(4) Summary As shown in Table 3, the transparent electrode according to the example of the present invention is excellent in transparency, conductivity and gas barrier properties without damaging the substrate, and forms a conductive polymer-containing layer. This shows that the gas barrier performance is higher. From the above, when manufacturing transparent electrodes with excellent electrical conductivity while suppressing substrate damage, a protective layer is formed on the transparent substrate, and a fine pattern of metal nanoparticles is formed on the protective layer, and flash light irradiation is performed. It can be seen that it is useful to perform baking with heating.

(1) Preparation of organic EL element (sample) Using the transparent electrodes TCF-1, TCF-10, and TCF-14 prepared in Example 1 as the first electrode (anode), "organic EL elements OLED-1 to OLED" -3 "was prepared by the following procedure.

  In the transparent electrode TCF-1, on the first electrode, PEDOT-PSS CLEVIOS P AI 4083 (solid content 15%) (manufactured by Heraeus) is used, and the dry film thickness becomes 30 nm using an applicator with a coating width of 150 mm. It was applied on the protective layer, and unnecessary peripheral portions were wiped off so as to have an area of 150 mm × 150 mm, and then dried (the transparent electrodes TCF-10 and TCF-14 were not subjected to such treatment). .

  Next, each transparent electrode was set in a commercially available vacuum deposition apparatus, and each of the deposition materials in the vacuum deposition apparatus was filled with the constituent material of each layer in an optimum amount for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

Subsequently, each organic compound layer was provided in the following procedures.
First, after depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, the energization crucible containing the following α-NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer. Was provided.
Ir-1, Ir-14 and the following compound 1-7 were co-deposited at a deposition rate of 0.1 nm / sec so that the following Ir-1 would be 13% by mass and the following Ir-14 would be 3.7% by mass. Then, a green-red phosphorescent light emitting layer having an emission maximum wavelength of 622 nm and a thickness of 10 nm was formed.
Subsequently, E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and a blue phosphorescent light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm. Formed.
Thereafter, the following M-1 was vapor-deposited to a thickness of 5 nm to form a hole blocking layer, and CsF was co-deposited with M-1 so that the film thickness ratio was 10%, and an electron transport layer having a thickness of 45 nm. Formed.
The compounds used for forming each layer are shown below.

On the formed electron transport layer, Al was mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as a material for forming an external lead terminal for the first electrode and a second electrode (cathode) of 150 mm × 150 mm. A 100 nm second electrode was formed.
Further, an adhesive is applied to the periphery of the second electrode except for the end portions so that external lead terminals of the first electrode and the second electrode can be formed, and a polyethylene terephthalate resin film is used as a substrate to form Al ₂ O ₃ with a thickness of 300 nm. After bonding the vapor-deposited flexible sealing member, the adhesive was cured by heat treatment to form a sealing film, and an organic EL element having a light emitting area of 150 mm × 150 mm was produced.
As the adhesive, a two-component epoxy compounded resin (manufactured by Three Bond Co., Ltd.) 2016B and 2103 was blended at a ratio of 100: 3.

(2) Measurement and Evaluation of Samples By the following method, the uneven light emission measurement and the storage stability test of each organic EL device produced as described above were performed, and the light emission uniformity and durability of the organic EL device were evaluated.

(2.1) Light emission unevenness Using a KEITHLEY source measure unit type 2400, a direct current voltage was applied to each organic EL element to emit light so that the luminance became 1000 cd / m ² , and the light emission state was visually evaluated according to the following criteria. . The evaluation results are shown in Table 4.
○: Almost uniform light emission, no problem Δ: Some light emission unevenness is partially observed, but practically acceptable ×: Light emission unevenness is observed over the entire surface, and is not acceptable

(2.2) Storage stability test Each organic EL element is stored in a thermostat at 85 ° C., taken out from the thermostat every 12 hours, applied with a voltage for emitting light at 1000 cd / m ² , and brightness at that time (initial (Luminance) was measured, and the time until the initial luminance was halved was measured and used as the storage time. The luminance half time of OLED-1 was set to 100, and the relative value was evaluated. 120 or more is a practically good range. The evaluation results are shown in Table 4.

(3) Summary As shown in Table 4, it can be seen that the organic EL elements OLED-2 and OLED-3 using the transparent electrode according to the examples of the present invention emit light uniformly even in a large area and have high durability.

Claims (7)

In a method for producing a transparent electrode having a flexible transparent substrate, a protective layer, and a conductive fine metal wire pattern,
Forming the protective layer on one surface of the transparent substrate;
Forming a metal fine wire pattern with metal nanoparticles on the protective layer;
E Bei and a step of firing the flash light irradiation the fine metal wire pattern,
In the step of forming the protective layer,
A first coating liquid containing a polyfunctional monomer containing a polymerizable functional group or a polyfunctional oligomer is coated on the transparent substrate, the first coating liquid is polymerized, and a hard coat layer composed of an organic compound is Forming on a transparent substrate;
A second coating solution containing polysilazane is applied onto the hard coat layer, the second coating solution is irradiated with light having a wavelength component of 200 nm or less, and a gas barrier layer composed of an inorganic compound is formed on the hard coat layer. Forming the step,
The manufacturing method of the transparent electrode characterized by having . In the manufacturing method of the transparent electrode of Claim 1,
A method for producing a transparent electrode, comprising a step of forming a conductive polymer-containing layer containing at least a π-conjugated conductive polymer and a polyanion on the metal wire pattern after heating and firing. In the manufacturing method of the transparent electrode of Claim 1 or 2,
A method for producing a transparent electrode, wherein the transparent substrate is composed of a transparent substrate having a total light transmittance of 70% or more. In the manufacturing method of the transparent electrode of Claim 1 or 2,
A method for producing a transparent electrode, wherein the transparent substrate is composed of a transparent substrate having a total light transmittance of 80% or more. In the manufacturing method of the transparent electrode of Claim 1 or 2,
A method for producing a transparent electrode, wherein the transparent substrate is composed of a biaxially stretched polyester resin film. In the manufacturing method of the transparent electrode as described in any one of Claims 1-5 ,
In the step of forming the fine metal wire pattern, an aperture ratio of the fine metal wire pattern is set to 80% or more. In the manufacturing method of the transparent electrode as described in any one of Claims 1-5 ,
In the step of forming the fine metal wire pattern, an aperture ratio of the fine metal wire pattern is set to 90% or more.