JP2011096437A - Transparent electrode, organic el element, and organic electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent electrode at low cost, wherein impurity and foreign bodies are removed, an organic EL element which can improve element lifetime by using the transparent electrode, and an organic electronic device. <P>SOLUTION: In the transparent electrode having a transparent conductive layer made of at least a conductive polymer and a binder on a transparent substrate, at least a part of the transparent conductive layer is cross-linked, and wet multistage cleaning treatment is applied to the transparent conductive layer. The organic EL element and the organic electronic device use the transparent electrode. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transparent electrode and an organic EL device using the transparent electrode, and more specifically, a transparent electrode having a transparent conductive layer comprising at least a conductive polymer and a binder on a transparent substrate, an organic EL device using the transparent electrode, and The present invention relates to an organic electronic device using a transparent electrode.

  In recent years, with increasing demand for thin TVs, various types of display technologies such as liquid crystal, plasma, organic EL, and field emission have been actively developed. The transparent electrode is an indispensable constituent technology even in various types of displays. In addition to TVs, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements. In particular, in applications such as organic EL and organic thin-film solar cells, current leakage due to unevenness on the surface of the transparent electrode and distortion of layer formation are likely to cause light emission failure and power generation failure, and the transparent electrode surface is highly smooth. Sex is required.

  Transparent electrodes used in organic electronic devices such as organic EL and organic thin-film solar cells are made of an indium-tin composite oxide (ITO) film on a substrate such as glass or transparent plastic film by vacuum deposition or sputtering. The ITO transparent electrode formed in the film is mainly used. In organic EL, before forming a functional layer such as an organic light emitting layer, a wet cleaning process is performed on a transparent electrode for the purpose of removing foreign substances and removing dirt (see, for example, Patent Documents 1 and 2). Especially for electrodes used in organic electronic devices, etc., ultra pure water or ultra pure water partially mixed with an organic solvent or surfactant is used as the cleaning liquid, but when it is used in the production process, A large amount of ultrapure water was required, which caused a huge cost for the cleaning process due to the enlargement of the equipment and the replacement of the filter.

  Further, these cleanings alone cannot sufficiently prevent the occurrence of current leakage due to irregular protrusions of the ITO transparent electrode or adhesion of foreign matters. In particular, in order to increase the area of the device, the frequency of occurrence of current leakage is increased, which is a serious problem. Therefore, it is known to form a conductive polymer layer on the ITO transparent electrode in order to improve current leakage (see, for example, Patent Document 3). Furthermore, an effect of lowering the hole injection barrier by forming a conductive polymer layer on the ITO transparent electrode can be expected (see, for example, Patent Document 4). A method of forming a layer using a conductive polymer and a binder in combination is also known (see, for example, Patent Document 5).

  However, in Patent Document 3, when a conductive polymer containing a π-conjugated conductive polymer component and a polyanion component is used, a part of the anion component diffuses into a functional layer such as a light emitting layer. There has been a problem that the lifetime of the organic electronic device is reduced. Therefore, in Patent Document 4, metal ions such as Mo are mixed with PEDOT / PSS on the ITO electrode to suppress the separation of sulfonate ions from PSS and prevent diffusion to the functional layer. When this method is used, there is a problem in that after the molybdenum oxide and the PEDOT / PSS mixed layer are formed by heating, unreacted molybdenum ions are precipitated as molybdenum oxide, and the transmittance of the transparent electrode is lowered.

  In addition, since the conductive polymer layers of Patent Documents 3 and 4 do not have a cross-linked structure or the like, when wet cleaning is performed, the smoothness is impaired due to swelling or dissolution of the conductive polymer layer. Impurities such as dust and unreacted Mo ions cannot be removed, and organic electronic devices such as organic EL elements cannot function.

  Furthermore, as in Patent Document 3, if irregular projections and foreign substances are to be filled with only the conductive polymer, the film thickness becomes thick and the absorption of the conductive polymer cannot be ignored. Therefore, there also existed a problem that the transmittance | permeability of a transparent electrode will fall.

  Patent Document 5 discloses a hole injection layer that is non-aqueous and contains an intrinsically conductive polymer, a dopant, and a synthetic polymer planarizing agent. In a transparent conductive layer that uses a combination of a conductive polymer and a synthetic polymer, the synthetic polymer has no conductivity and does not have the effect of assisting the conductivity of the conductive polymer. Resulting in. Moreover, if it is going to keep electroconductivity, the transmittance | permeability will fall by absorption of a conductive polymer. From the above, the method of Patent Document 5 has a problem that it is difficult to achieve both conductivity and transmittance. Furthermore, in the transparent conductive layer using both the conductive polymer and the synthetic polymer as described in Patent Document 5, impurities such as unreacted polymer remain in the transparent conductive layer, and the impurities cannot be removed by washing with an aqueous solvent. However, the non-aqueous solvent has a problem that a part of the film is dissolved and the surface smoothness is impaired.

JP 2001-118440 A JP 2007-242481 A JP 2003-45665 A JP 2006-286664 A JP 2008-533701 A

  An object of the present invention is to enable a transparent treatment of a transparent electrode having a transparent conductive layer composed of at least a conductive polymer and a binder on a transparent substrate, and to greatly reduce the cost of the cleaning treatment. Accordingly, it is to provide a transparent electrode from which impurities and foreign matters are removed at low cost. Furthermore, it is providing the organic EL element by which the element lifetime was improved greatly by using this transparent electrode, and the organic electronic device using this transparent electrode.

  The above object of the present invention can be achieved by the following configuration.

  1. In a transparent electrode having a transparent conductive layer comprising at least a conductive polymer and a binder on a transparent substrate, at least a part of the transparent conductive layer is cross-linked, and the transparent conductive layer is subjected to a wet multistage cleaning treatment. A transparent electrode characterized by being

  2. 2. The transparent electrode according to 1 above, wherein the conductive polymer is a conductive polymer comprising a π-conjugated conductive polymer component and a polyanion component.

  3. 3. The transparent electrode as described in 2 above, wherein the polyanion component is a polysulfonic acid group.

  4). 4. The transparent electrode according to any one of 1 to 3, wherein the binder is made of the following polymer (A).

(In the formula, X _{1 to} X ₃ each independently represent a hydrogen atom or a methyl group, and R _{1 to} R ₃ each independently represents an alkylene group having 5 or less carbon atoms. (Mol /%), 50 ≦ l + m + n ≦ 100.)
5. 5. An organic EL device using the transparent electrode according to any one of 1 to 4 above.

  6). 5. An organic electronic device using the transparent electrode according to any one of 1 to 4 above.

  According to the present invention, it is possible to impart high cleaning resistance by forming a transparent conductive layer composed of at least a conductive polymer and a binder on a transparent substrate and crosslinking the transparent conductive layer. By cleaning, the surface of the transparent conductive layer, foreign matter and impurities inside can be effectively removed, and the functional deterioration of the organic EL element due to surface smoothness and impurities can be suppressed. This also leads to longer life. Furthermore, by using a multi-stage cleaning process, high-speed and efficient processing is possible, and production costs can be greatly reduced.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

[Conductive polymer]
The conductive polymer of the present invention is a conductive polymer comprising 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. .

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

[Π-conjugated conductive polymer precursor monomer]
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. 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.

[Poly anion]
Polyanions are substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, and copolymers thereof. And a structural unit having an anionic group and a structural unit having no anionic group.

  This poly anion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  The anion group of the polyanion may be 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.

  Moreover, the poly anion which has F in a compound may be sufficient. Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.

  Among these, when a compound having a sulfonic acid is formed by applying and drying a conductive polymer-containing layer, when subjected to a heat treatment at a temperature of 100 ° C. or more and 200 ° C. or less for 5 minutes or more, It is more preferable because the cleaning 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 binder, 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, an anionic group A method of producing by polymerization of the containing polymerizable monomer may be mentioned.

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

  A commercially available material can be preferably used for such a conductive polymer.

  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.

  2nd. A water-soluble organic compound may be contained as a 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, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

[binder]
The binder of the present invention forms a transparent conductive layer together with a conductive polymer. At least a part of the transparent conductive layer according to the present invention is crosslinked. In the present invention, the phrase “at least part of the transparent conductive layer is crosslinked” means that a part of the binder takes a crosslinked structure or a binder, a conductive polymer and a crosslinked structure. In the present invention, the effects of the present invention can be achieved by either or both of them. As a result, even when wet multi-stage cleaning is performed, wet multi-stage cleaning is possible without dissolving or swelling the film, removing foreign matter on the film and impurities in the film, and using current leakage and this The lifetime of organic electronic devices is improved.

  Various resins can be used as the binder including reactive groups. For example, polyester resins, acrylic resins, polyurethane resins, acrylic urethane resins, polycarbonate resins, cellulose resins, polyvinyl acetal resins, etc. can be used alone or Used in combination, a reactive group is not limited to the following, but may have a reactive group such as a hydroxyl group, a carboxyl group, or an amide group.

  Furthermore, since the binder is at least partially and has cross-linking with the conductive polymer or the binder itself, the binder may contain a cross-linking material, is compatible with the resin, and is not particularly limited as long as it forms a cross-linked structure. For example, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a formaldehyde crosslinking agent, or the like can be used alone or in combination.

  In particular, when the anionic component of the conductive polymer is a polysulfonic acid group and the reactive group of the binder has a hydroxyl group, the anionic component of the conductive polymer and the reactive group of the binder are cross-linked to stabilize and suppress separation. It is preferable to extend the life of the organic electronic device. Furthermore, when the anionic component of the conductive polymer is a polysulfonic acid group and a conductive polymer having a structure like the polymer A is used as a binder, the polymer A has an effect of assisting the conductivity, and the conductive property of the transparent conductive layer is reduced. It does not impair the properties and transmittance. Crosslinking can be measured by a change in glass transition temperature and nanoindentation elastic modulus of the transparent conductive layer, and a change in functional group by FTIR measurement. The sulfonic acid group and the reactive group of the binder are bonded to stabilize the sulfonic acid group from being separated. As a result, it is more preferable for extending the life of the organic electronic device.

[Polymer A]
Polymer A is a monomer in which the main copolymerization component is represented by the following monomers 1 to 3, and 50 mol% or more of the copolymerization component is one of the following monomers 1 to 3, or the components of the following monomers 1 to 3 It is a copolymer having a total of 50 mol% or more. It is more preferable that the total of the components of the following monomers 1 to 3 is 80 mol% or more, and it may be a homopolymer formed from any one of the following monomers 1 to 3, and in a preferred embodiment. is there.

Monomer 1
_{CH 2 = CX 1 -O-R} 1 -OH
Monomer 2
_{CH 2 = CX 2 -COO-R} 2 -OH
Monomer 3
_{CH 2 = CX 3 -CONH-R} 3 -OH
_{Wherein, X 1, X 2, X 3} , R 1, R 2, R 3 are each of _{X 1, X 2, X 3} , R 1, R 2, R 3 as defined in the polymer (A) Represents a group.

  In the polymer (A), other monomer components may be copolymerized, but a monomer component having high hydrophilicity is more preferable.

  The polymer (A) preferably has a content of 1000 or less in the number average molecular weight of 0 to 5%. When the amount of the low molecular component is small, it is possible to further reduce the storage stability of the device and the behavior of having a barrier in the direction perpendicular to the layer when exchanging charges in the direction perpendicular to the conductive layer.

  In the number average molecular weight of the polymer (A), the content of 1000 or less is adjusted to 0 to 5% or less by reprecipitation, preparative GPC, synthesis of monodisperse polymer by living polymerization, etc. A method of removing the molecular weight component or suppressing the generation of a low molecular weight component can be used. In the reprecipitation method, the polymer is dissolved in a solvent in which the polymer can be dissolved and dropped into a solvent having a lower solubility than the solvent in which the polymer is dissolved, thereby precipitating the polymer and removing low molecular weight components such as monomers, catalysts, and oligomers. It is a method to do. In addition, preparative GPC is, for example, recycled preparative GPCLC-9100 (manufactured by Nihon Analytical Industrial Co., Ltd.), polystyrene gel column, and the polymer dissolved solution can be separated by molecular weight to cut the desired low molecular weight This is how you can do it. In the living polymerization, the generation of the starting species does not change with time, and there are few side reactions such as termination reaction, and a polymer having a uniform molecular weight can be obtained. Since the molecular weight can be adjusted by the addition amount of the monomer, for example, if a polymer having a molecular weight of 20,000 is synthesized, the formation of a low molecular weight body can be suppressed. The reprecipitation method and living polymerization are preferable from the viewpoint of production suitability.

The number average molecular weight and weight average molecular weight of the water-soluble binder of the present invention can be measured by generally known gel permeation chromatography (GPC). The molecular weight distribution can be expressed by a ratio of (weight average molecular weight / number average molecular weight). The solvent to be used is not particularly limited as long as the water-soluble binder dissolves, and THF, DMF, 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.

  The number average molecular weight of the polymer (A) 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 molecular weight distribution of the polymer (A) of the present invention is preferably from 1.01 to 1.30, more preferably from 1.01 to 1.25.

  In the distribution obtained by GPC, the content having a number average molecular weight of 1000 or less was converted by multiplying the area having a number average molecular weight of 1000 or less and dividing by the area of the entire distribution.

  The living radical polymerization solvent is inactive under the reaction conditions and is not particularly limited as long as it can dissolve the monomer and the polymer to be formed, but a mixed solvent of an alcohol solvent and water is preferable. The living radical 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 ratio of the conductive polymer to the polymer (A) is preferably 30 parts by weight to 900 parts by weight when the conductive polymer is 100 parts by weight. From the viewpoint of the property assist effect and transparency, the polymer (A) is more preferably 100 parts by mass or more.

[Transparent conductive layer]
In the present invention, the transparent conductive layer is formed by applying and drying a liquid mixture comprising at least a conductive polymer and a binder on a transparent substrate or a transparent substrate having an auxiliary electrode. The concentration of the solid content in the coating solution is preferably from 0.5% by mass to 30% by mass, and from 1% by mass to 20% by mass, the stagnation stability of the solution, the smoothness of the coating film, From the viewpoint of manifesting a leak prevention effect, it is more preferable.

  Coating methods include roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, gravure coating, curtain coating, spray coating, doctor coating, letterpress (letterpress) ) Printing method, stencil (screen) printing method, lithographic (offset) printing method, intaglio (gravure) printing method, spray printing method, inkjet printing method and the like can be used.

  The dry film thickness of the conductive polymer-containing layer is preferably 30 nm to 2000 nm. The conductive layer of the present invention preferably has a thickness of 100 nm or more because the decrease in conductivity is large in the region of less than 100 nm, and more preferably 200 nm or more from the viewpoint of further improving the leakage prevention effect. Further, it is more preferably 1000 nm or less from the viewpoint of maintaining high transmittance.

  After coating, a drying process is appropriately performed. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and a conductive polymer content layer. For example, a drying process can be performed at 80 to 150 ° C. for 10 seconds to 30 minutes.

  In particular, when the polyanion is a polyanion having a sulfonic acid, it is preferable to perform additional heat treatment for 5 minutes or more at a temperature of 100 ° C. or more and 200 ° C. or less after forming a film by coating and drying. Thereby, the washing | cleaning tolerance of a conductive polymer content layer and solvent tolerance improve remarkably. In addition, storage stability is improved. If the temperature is less than 100 ° C., the effect is small, and if the temperature exceeds 200 ° C., another reaction increases, or the effect is small. The treatment temperature is more preferably 110 ° C. or more and 160 ° C. or less, and the treatment time is more preferably 15 minutes or more. There is no particular upper limit for the treatment time, but it is preferably 120 minutes or less in view of productivity.

  Further, from the viewpoint of wettability, the transparent conductive layer may be subjected to surface treatment, and conventionally known techniques can be used for the surface treatment. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

[Transparent electrode]
In the present invention, the transparent electrode having a transparent conductive layer comprising at least a conductive polymer and a binder means that at least the electrode is formed of a single transparent conductive layer comprising the conductive polymer of the present invention and a binder, or as an auxiliary electrode. The transparent conductive layer of the present invention is laminated on other known conductive electrode layers such as ITO, ZnO, etc., or the stripe-shaped, mesh-shaped or random mesh-shaped electrodes described later are used. The transparent conductive layer may be laminated, or the transparent conductive layer of the present invention may be striped, meshed, or a random mesh electrode embedded. As long as the transparent conductive layer which becomes a conductive polymer and a binder is included at least, it will not be limited to these.

[Auxiliary electrode]
In order to cope with an increase in area, it is preferable that the electrode having the transparent conductive layer of the present invention further has an auxiliary electrode composed of a light-impermeable conductive portion and a light-transmitting window portion.

  The light-impermeable conductive portion of the auxiliary electrode is preferably a metal from the viewpoint of good conductivity, and examples of the metal material include gold, silver, copper, iron, nickel, and chromium. The metal of the conductive part may be an alloy, and the metal layer may be a single layer or a multilayer.

  The shape of the auxiliary electrode is not particularly limited. For example, the conductive portion has a stripe shape, a mesh shape, or a random mesh shape.

  There are no particular limitations on the method of forming the stripe-shaped or mesh-shaped auxiliary electrode with the conductive portion, and a conventionally known method can be used. For example, a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method. Specifically, a conductor layer is formed on the entire surface of the substrate using one or more physical or chemical forming methods such as vapor deposition, sputtering, and plating, or a metal foil is formed with an adhesive. After being laminated on the material, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used. About the method to which silver salt photography technology is applied, it can carry out with reference to 0076-0112 of Unexamined-Japanese-Patent No. 2009-140750, and an Example, for example. About the method of carrying out the gravure printing of a catalyst ink and plating, it can carry out with reference to Unexamined-Japanese-Patent No. 2007-281290, for example.

[Random network structure]
As a random network structure, for example, a method of spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles, as described in JP 2005-530005 A Can be used.

  As another method, for example, a method of forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.

  The metal nanowire refers to a fibrous structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.

  As the metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. The average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less.

  As the metal used for the metal nanowire, copper, iron, cobalt, gold, silver or the like can be used, but silver is preferable from the viewpoint of conductivity. In addition, although a single metal may be used, in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871. In particular, the above-described method for producing silver nanowires can be preferably applied because silver nanowires can be easily produced in an aqueous solution, and the conductivity of silver is maximum in metals.

[Multi-stage cleaning]
In the present invention, the cleaning is a wet multi-stage cleaning process. If there are foreign matter or impurities on the surface or inside of the transparent electrode, the performance such as the lifetime of the organic electronic device is greatly affected. Therefore, the cleaning is high in purity, and a cleaning liquid that has been subjected to filter treatment is used, which is very expensive. Since the multi-stage cleaning process has a cleaning effect equivalent to that of a normal cleaning liquid with a small amount of cleaning liquid, the cleaning cost can be greatly reduced. The wet cleaning of the present invention refers to cleaning the transparent conductive layer using an aqueous solvent cleaning liquid. By removing impurities in the transparent conductive layer and foreign matters on the transparent conductive layer, a transparent electrode with less current leakage Can be produced. Moreover, the organic electronic device using the transparent electrode which performed the washing process of this invention has a long lifetime. The aqueous solvent represents a solvent in which 50% by mass or more is water. Of course, pure water containing no other solvent may be used. Furthermore, it is desirable to use ultrapure water because there are few foreign substances in the cleaning liquid. Ultrapure water refers to water having a specific resistance of about 18 MΩ · cm and a total organic carbon TOC of less than 0.05 mg / L measured by a method according to JIS K0551 when the water temperature is 25 ° C. The component other than water in the aqueous solvent is not particularly limited as long as it is a solvent compatible with water, but an alcoholic solvent can be preferably used, and isopropyl alcohol having a boiling point relatively close to water can be used. preferable. Furthermore, in order to improve the wettability of the transparent conductive layer, the cleaning liquid may contain a surfactant. Moreover, as long as the filter component does not elute, it is preferable that the cleaning solution is passed through various filters because foreign substances in the cleaning solution are reduced.

  In addition, the multi-stage cleaning process is a process in which two or more cleaning tanks are continuous, the cleaning liquid is poured from one tank, and the cleaning liquid is sequentially overflowed into adjacent cleaning tanks. With this method, the transparent electrode can be cleaned with a small amount of cleaning liquid, rather than flowing the cleaning liquid independently for each tank. In particular, the number of cleaning tanks is preferably three or more from the viewpoint of saving water. Furthermore, from the viewpoint of productivity, a counter-current multi-stage cleaning system in which a transparent electrode flows from one of the multi-stage water tanks by a roll-to-roll system or the like and fresh cleaning water flows from the other is preferable.

[Organic electronic devices]
The substrate has a first electrode and a second electrode facing each other, and has at least one organic functional layer between the first electrode and the second electrode. In the present invention, at least one of the first electrode and the second electrode is an electrode including the transparent electrode layer of the present invention. 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.

[Transparent substrate]
The transparent substrate used for the electrode of the present invention is not particularly limited as long as it has high light transmittance. For example, a glass substrate, a resin substrate, a resin film, etc. are preferable in terms of excellent hardness as a base material and ease of forming a conductive layer on the surface, etc. It is preferable to use a transparent resin film from the viewpoint of performance and performance such as lightness and flexibility.

  There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent base material by this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin A film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more in nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

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

In addition, an inorganic or organic film or a hybrid film of both may be formed on the front or back surface of the transparent substrate, and the water vapor transmission rate (25 ± 0) measured by a method according to JIS K 7129-1992. .5 ° C., relative humidity (90 ± 2)% RH) is preferably a barrier film of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and further conforms to JIS K 7126-1987. The oxygen permeability measured by the above method is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 A high barrier film of × 10 ⁻³ g / (m ² · 24 h) or less is preferable.

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

  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.

[Synthesis example of polymer A]
<Living Radical Polymerization Using ATRP (Atom Transfer Radical Polymerization) Method>
"Synthesis of initiators"
Synthesis Example 1 (Synthesis of methoxy-capped oligoethylene glycol methacrylate 1)

  2-Bromoisobutyryl bromide (7.3 g, 35 mmol), triethylamine (2.48 g, 35 mmol) and THF (20 ml) were added to a 50 ml three-necked flask, and the internal temperature was kept at 0 ° C. with an ice bath. In this solution, 30 ml of 33% THF solution of oligoethylene glycol (10 g, 23 mmol, ethylene glycol units 7-8, manufactured by Laporte Specialties) was added dropwise. After stirring for 30 minutes, the solution was brought to room temperature and further stirred for 4 hours. After THF was removed under reduced pressure by a rotary evaporator, the residue was dissolved in diethyl ether and transferred to a minute funnel. Water was added and the ether layer was washed three times, and then the ether layer was dried with MgSO 4. Ether was distilled off under reduced pressure by a rotary evaporator to obtain 8.2 g of initiator 1 (yield 73%).

Synthesis Example 2 (Synthesis of poly (2-hydroxyethyl acrylate))
Initiator 1 (500 mg, 1.02 mmol), 2-hydroxyethyl acrylate (4.64 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 50:50 v / v% 5 ml of a methanol / water mixed solvent was put into a Schlenk tube, and the pressure was reduced. The Schlenk tube was immersed in the lower liquid nitrogen for 10 minutes. The Schlenk tube was taken out of liquid nitrogen and replaced with nitrogen after 5 minutes. After performing this operation three times, bipyridine (400 mg, 2.56 mmol) and CuBr (147 mg, 1.02 mmol) were added under nitrogen, and the mixture was stirred at 20 ° C. After 30 minutes, the reaction solution was dropped onto a 4 cm Kiriyama funnel with filter paper and silica, and the reaction solution was recovered under reduced pressure. The solvent 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, 2.60 g (yield 84%) of water-soluble binder 1 having a number average molecular weight of 13,100, a molecular weight distribution of 1.17, and a content of number average molecular weight <1000 of 0% 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>
Apparatus: Wagers 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
In the same manner, polyhydroxyethyl vinyl ether and polyhydroxyethyl acrylamide (number average molecular weight of about 20,000, number average molecular weight <1000 content 0%) were obtained.

[Transparent substrate]
A transparent gas barrier property in which three units of a low density layer, a medium density layer, a high density layer, and a medium density layer are laminated on a biaxially stretched PET film having a width of 50 mm and a length of 1000 m using an atmospheric pressure plasma discharge treatment method. A transparent substrate 1 was produced. As a result of measuring the water vapor permeability by a method based on JIS K 7129-1992, it was 10 ⁻³ g / (m ² · 24 h) or less. As a result of measuring oxygen permeability by a method based on JIS K 7126-1987, it was 10 ⁻³ ml / (m ² · 24 hr · MPa) or less.

[ITO substrate]
After patterning by photolithography on a substrate on which ITO (Indium Tin Oxide) is deposited to a thickness of 150 nm on the surface of the transparent substrate 1 without a barrier layer, the substrate is immersed in isopropyl alcohol, and an ultrasonic cleaner Bransonic An ultrasonic cleaning process was performed for 10 minutes with 3510J-MT (manufactured by Nippon Emerson) to prepare an ITO substrate.

[Silver nanowire substrate]
Further, the silver nanowire dispersion liquid is applied to the surface of the transparent substrate 1 without the barrier layer using a bar coating method so that the weight of the silver nanowires is 0.06 g / m ^2. After drying at 20 ° C. for 20 minutes, the following metal fine particle removal solution was subjected to pattern printing using screen printing, and the metal fine particle removal solution was removed by washing with water to produce a silver nanowire substrate.

  Silver nanowire dispersions are described in Adv. Mater. , 2002, 14, 833 to 837, by using PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were produced. Silver nanowires are filtered and washed using a filtration membrane, and then redispersed in an aqueous solution in which 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to silver to prepare a silver nanowire dispersion. did. Further, the metal fine particle removing liquid having the following composition was used.

<Preparation of metal fine particle removal solution>
Ethylenediaminetetraacetic acid ferric ammonium 60g
Ethylenediaminetetraacetic acid 2.0 g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5.0g
Finished to 1 L with pure water, and adjusted to pH 5.5 with sulfuric acid or ammonia water, a metal fine particle removing solution was prepared. Further, the viscosity of the metal fine particle removing liquid BF was adjusted to 10 Pa · s (10000 cP) with sodium carboxymethylcellulose (manufactured by SIGMA-ALDRICH; C5013, hereinafter abbreviated as CMC).

[Copper mesh substrate]
A copper mesh was prepared on the surface of the transparent substrate 1 without the barrier layer as an auxiliary electrode by the following method and patterned with the metal fine particle removing liquid BF to produce a copper mesh substrate.

  The catalyst ink GIPD-7 manufactured by Morimura Chemical Co. containing palladium nanoparticles is used, and the self-dispersion type carbon black solution CAB-O-JET300 manufactured by Cabot is used, and the carbon black ratio to the catalyst ink becomes 10.0% by mass. Then, Surfynol 465 (Nisshin Chemical Industry Co., Ltd.) was further added to prepare a conductive ink having a surface tension at 25 ° C. of 48 mN / m.

  Conductive ink as an ink jet recording head has pressure applying means and electric field applying means, and has a nozzle diameter of 25 μm, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi (dpi is 1 inch, that is, 2.54 cm per 2.54 cm). A grid-like conductive thin wire having a line width of 10 μm, a film thickness after drying of 0.5 μm, and a line spacing of 300 μm is loaded on the base material. After forming into parts, it was dried.

  Subsequently, using a high-speed electroless copper plating solution CU-5100 manufactured by Meltex, the substrate was immersed for 10 minutes at a temperature of 55 ° C., washed, and subjected to electroless plating treatment to produce an auxiliary electrode having a plating thickness of 3 μm. .

[Formation of transparent electrode]
Prepare the following mixed liquids A to I of conductive polymer and binder, apply the applied ITO substrate by adjusting the wire diameter so that the width is 40 mm and the dry film thickness is 300 nm using the extrusion method, and unnecessary by wiping. After wiping off the part, it was dried by heating at 120 ° C. for 20 minutes to prepare ITO electrodes (also referred to as ITO electrodes) 1 to 9, respectively.

A: Conductive polymer layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) alone B: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1 .89%) (manufactured by HC Starck) 1.59 g
Polyhydroxyethyl acrylate (Synthesis example 2, solid content 20% aqueous solution) 0.35 g
C: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
0.35 g of polyhydroxyethyl vinyl ether (molecular weight 20,000, solid content 20% aqueous solution)
D: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
0.35 g of polyhydroxyethylacrylamide (molecular weight 20,000, solid content 20% aqueous solution)
E: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
Polyhydroxyethyl acrylate (Synthesis example 2, solid content 20% aqueous solution) 0.35 g
Dimethyl sulfoxide 0.10g
F: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
Water-based polyester Vylonal MD1400 (solid content 15%) (manufactured by Toyobo)
0.47g
Dimethyl sulfoxide 0.10g
Block isocyanate (Elastolon BN-11, Daiichi Kogyo Seiyaku Co., Ltd.)
0.09g
Curing catalyst (Elastotron CAT-21, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.004 g
G: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
Polyvinyl alcohol PVA-235 (made by Kureha) Solid content 2% aqueous solution 3.50 g
Dimethyl sulfoxide 0.10g
Epoxy crosslinking agent Denacol EX-521 (Nagase ChemteX Corporation) 0.5g
H: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
Water-based polyester Vylonal MD1400 (solid content 15%) (manufactured by Toyobo)
0.47g
Dimethyl sulfoxide 0.10g
I: Conductive polymer and binder layer coating solution PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
Polyvinyl alcohol PVA-235 (made by Kureha) Solid content 2% aqueous solution 3.50 g
The above-mentioned conductive polymer and binder layer coating solutions B to E form a crosslinked structure between the polyhydroxy group in the molecule and PEDOT-PSS CLEVIOS PH510, and the film strength after heating and drying at 120 ° C. for 20 minutes. Has improved hardness compared to each single film.

  Further, in the same manner, the liquids A and B are applied to a silver nanowire substrate and a copper mesh substrate with a conductive polymer and binder mixed solution, patterned and dried, and then a silver nanowire electrode (also referred to as a silver nanowire electrode) 10 and 11 and copper mesh electrodes (also referred to as copper mesh electrodes) 12 and 13 were produced. Here, it apply | coated so that the film thickness of a conductive polymer and a binder layer might be set to 500 nm to a copper mesh board | substrate.

  The transmittance of each of the prepared electrodes was measured with a HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd. and summarized in Tables 1 to 3. From the viewpoint of light transmittance in the element, it is preferably 75% or more.

  From Tables 1 to 3, it can be seen that when the conductive polymer alone is laminated to reduce the influence of foreign matters and impurities, the transmittance is greatly reduced.

[Washing]
The ITO electrodes 1 to 9, the silver nanowire electrodes 10 to 11, and the copper mesh electrodes 12 to 13 were cleaned with a multistage cleaning apparatus consisting of three tanks. As the cleaning liquid, ultrapure water produced using a Milli-Q water production apparatus Milli-Q Advantage (Japan Millipore Corporation) was used. The transparent electrode was exposed to a cleaning tank by a roll-to-roll method and sent out at a speed of 1 m / h. The multistage cleaning was performed at a flow rate of 50 ml / h, and multistage cleaned ITO electrodes 1 to 9, silver nanowire electrodes 10 to 11, and copper mesh electrodes 12 to 13 were produced. In the above multi-stage cleaning apparatus, the cleaning liquid is introduced from the cleaning liquid introduction part installed in the cleaning tank located at the most downstream in the sample traveling direction, moves with the sample counter-currently, and the cleaning tank into which the sample is first placed. It is discharged from the cleaning liquid outlet installed in

  Moreover, the ITO electrodes 1-9, the silver nanowire electrodes 10-11, and the copper mesh electrodes 12-13 were wash | cleaned using the ultrapure water with the single tank washing | cleaning apparatus. Sending out was performed at a speed of 1 m / h, and cleaning was performed at a flow rate of 50 ml / h to produce ITO electrodes 14 to 22, silver nanowire electrodes 23 to 24, and copper mesh electrodes 25 to 26 that had been subjected to single tank cleaning. Moreover, the amount of water for washing was changed to 1 l / h, and single tank cleaning was performed to prepare ITO electrodes 27 to 35, silver nanowire electrodes 36 to 37, and copper mesh electrodes 38 to 39 that had been cleaned for a single tank. In the single tank cleaning apparatus, the cleaning liquid is introduced from the cleaning liquid introduction part installed at the lowermost part of the cleaning tank of the single tank cleaning apparatus, and is discharged from the cleaning liquid outlet installed at the upper part of the cleaning tank. The sample is exposed to the cleaning tank in a roll-to-roll manner.

  After washing, the transmittance and the film surface after washing were evaluated for all the electrodes, and the results are shown in Tables 1 to 3.

<Measurement of transmittance>
The transmittance was measured using a HAZE METER NDH5000 manufactured by Tokyo Denshoku.
<Evaluation of membrane surface after cleaning>
Whether the surface of the transparent conductive layer was disturbed by visual observation was evaluated according to the following criteria.
○: None ×: Available

  From Tables 1 to 3, it can be seen that when the transparent conductive layer does not contain a conductive polymer alone or a crosslink, the surface of the layer is disturbed, the smoothness is impaired, and the organic electronic device cannot be used.

Example 2
[Production of organic EL element]
For each transparent electrode produced in Example 1, Baytron PH510 (manufactured by HC Starck Co., Ltd.), which is a dispersion of PEDOT / PSS [poly (3,4-ethylenediothiophene) -poly (styrenesulfonate)] = 1: 2.5. ) By using a spin coater to form a conductive layer having a thickness of 30 nm, the transparent electrode was converted into a surface electrode, and an anode electrode was formed.

  Next, each of the vapor deposition crucibles in a commercially available vacuum vapor deposition apparatus was filled with the constituent material of each layer in an optimum amount for manufacturing each element. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

First, after reducing the vacuum to 1 × 10 ⁻⁴ Pa, the deposition crucible containing α-NPD was energized and heated, and deposited on the anode electrode at a deposition rate of 0.1 nm / second. A hole transport layer was provided.

  Subsequently, each light emitting layer was provided in the following procedures.

  Ir-1, Ir-2 and compound 1-1 were co-deposited at a deposition rate of 0.1 nm / second so that the concentration of Ir-1 was 13% by mass and Ir-2 was 3.7% by mass. A green-red phosphorescent light emitting layer having a maximum wavelength of 622 nm and a thickness of 10 nm was formed.

  Next, E-1 and Compound 1-1 were co-evaporated at a deposition rate of 0.1 nm / second so that E-1 was 10% by mass, and a blue phosphorescent light emitting layer having a maximum emission wavelength of 471 nm and a thickness of 15 nm was formed. Formed.

  Thereafter, M-1 is vapor-deposited to a thickness of 5 nm to form a hole blocking layer, and CsF is co-deposited with M-1 so that the film thickness ratio is 10%, and an electron transport layer having a thickness of 45 nm is formed. Formed.

  Furthermore, aluminum 110nm was vapor-deposited and the cathode was formed.

Next, using a flexible sealing member made of polyethylene terephthalate as a base material and depositing Al ₂ O ₃ with a thickness of 300 nm, the cathode electrode except for the ends so that external lead terminals of the anode electrode and the cathode electrode can be formed. After applying an adhesive around the substrate and pasting a flexible sealing member, the adhesive was cured by heat treatment to produce organic EL elements 1 to 39.
(Structure formula is affixed separately)

  Further, the electrodes 1 to 39 were formed into elements without washing, and the corresponding organic EL elements 40 to 78 were prepared and used as comparative samples.

[Evaluation of organic EL elements]
The organic EL elements 1 to 78 were evaluated as follows and are summarized in Table 4.

(leak)
A current value when a voltage of +3 V / -3 V was applied to the produced organic EL elements 1 to 39 was measured, and a rectification ratio was obtained by the following calculation formula.

Rectification ratio = current value when +3 V is applied / current value when -3 V is applied From the viewpoint of luminous efficiency, the rectification ratio is preferably 1000 or more. The rectification ratio of 10 elements manufactured by the same manufacturing procedure was measured. Table 4 shows the leakage evaluated by the following indices. In order to cope with an increase in area, it is essential that the level is 3 or more, and 4 or more is preferable.

5: 1000 or more is 8 or more in 10 4: 1000 or more is 5 or more in 10 3: 1000 or more is 3 or more in 10 2: 1000 or more is 1 or more in 10 1: 1000 or more is 0 Pieces (life)
The obtained organic EL elements 1 to 39 were allowed to emit light continuously at an initial luminance of 5000 cd / m ² , and the time until the luminance was reduced by half was determined. The ratio of the organic EL elements 40 to 78 corresponding to the respective substrates to the lifetime of the organic EL elements 40 to 78 that have not been cleaned is obtained and evaluated according to the following indices, and the lifetime is shown in Table 4. 3 or more is preferable, and 4 or more is more preferable.

5: 200% or more 4: 150% or more 3: 120% or more 2: 110% or more 1: 100% or more 0: 90% or more

  From Table 4, it can be seen that the organic EL elements 2 to 7, 11 and 13 of the present invention are excellent in leakage and have a very improved life. On the other hand, the organic EL elements 15-20, 24, and 26 produced from the electrodes 15-20, 24, and 26, which have a small amount of water and cleaned in a single tank, are electrodes 2-7, 11, and 13 that are subjected to multi-stage cleaning in a leak. As compared with the organic EL elements 2 to 7, 11 and 13 produced from the above, there are some which maintain the level 3 which is slightly inferior, but it is understood that the lifetime is not improved as compared with that before cleaning. Furthermore, the organic EL elements 28 to 33, 37 and 39 prepared from the electrodes 28 to 33, 37 and 39 which were cleaned in a single tank were actually 20 times as much as the cleaning liquid compared to the electrodes 2 to 7, 11 and 13 which were cleaned in multiple stages. It turns out that it shows the same level of performance only after washing with

  In Table 4, the column marked with-indicates light emission but almost impossible measurement, and the blank column means an element that does not emit light evenly or does not emit light because the surface of the layer is too disturbed by washing with water.

  Similarly, when an element of an organic solar cell was produced using an electrode subjected to multi-stage cleaning treatment, leakage was suppressed and improvement in power generation efficiency was confirmed.

Claims (6)

  In a transparent electrode having a transparent conductive layer comprising at least a conductive polymer and a binder on a transparent substrate, at least a part of the transparent conductive layer is cross-linked, and the transparent conductive layer is subjected to a wet multistage cleaning treatment. A transparent electrode characterized by being   The transparent electrode according to claim 1, wherein the conductive polymer is a conductive polymer including a π-conjugated conductive polymer component and a polyanion component.   The transparent electrode according to claim 2, wherein the polyanion component is a polysulfonic acid group. The said binder consists of the following polymer (A), The transparent electrode of any one of Claims 1-3 characterized by the above-mentioned.

(In the formula, X _{1 to} X ₃ each independently represent a hydrogen atom or a methyl group, and R _{1 to} R ₃ each independently represents an alkylene group having 5 or less carbon atoms. (Mol /%), 50 ≦ l + m + n ≦ 100.)   An organic EL device using the transparent electrode according to claim 1.   An organic electronic device using the transparent electrode according to claim 1.