JP5609307B2 - Transparent conductive support - Google Patents

Description

  The present invention relates to a transparent conductive support used for organic electronic elements such as organic electroluminescence elements (hereinafter referred to as organic EL elements) and organic solar cells, and in particular, transparent conductive having a transparent conductive layer provided on a transparent support. The present invention relates to a transparent conductive support that can improve device performance such as driving voltage, efficiency, and life of an organic electronic device.

  In recent years, organic electronic elements such as organic EL elements and organic solar cells have attracted attention, and in such elements, a transparent conductive support provided with a transparent conductive layer on a transparent support has become an essential constituent technology. Yes.

  Conventionally, a transparent conductive support is an ITO transparent conductive support in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as glass or a transparent plastic film by vacuum deposition or sputtering. However, it has been mainly used from the viewpoint of performance such as conductivity and transparency. However, transparent conductive supports using a vacuum deposition method or a sputtering method are problematic in that they are inferior in productivity and are expensive to manufacture, and because they are inferior in flexibility, they cannot be applied to device applications that require flexibility. there were.

  In contrast, there is a method of forming a transparent conductor layer by coating or printing using a coating solution in which a conductive polymer typified by a π-conjugated polymer is dissolved or dispersed in an appropriate solvent (see, for example, Patent Document 1). Proposed. However, compared to a metal oxide transparent conductive film such as ITO formed by a vacuum film formation method, there is a problem that both transparency and conductivity are remarkably lowered. Furthermore, when an organic electronic device such as an organic EL device is formed using this, in addition to the low conductivity of the transparent conductive layer itself, a behavior that is considered to have a high interface resistance with the functional layer provided on the transparent conductive layer ( For example, in an organic electroluminescence (EL) element, an increase in driving voltage was observed, and there was a problem that the performance as an element was lowered.

  On the other hand, a transparent conductive film has been proposed in which a metal film is bonded to the surface of a plastic substrate via an adhesive, and then a fine metal wire pattern is formed using a photolithography technique (see, for example, Patent Document 2).

  However, in the production of such a transparent conductive film, there is a problem that it is difficult to perform production at high speed using a so-called roll-to-roll technique.

  Further, as a means for forming a fine metal wire pattern on a transparent support, a conductive paste containing silver particles or the like is used, and a conductive polymer is applied so as to cover the fine metal wire pattern after using a printing technique such as screen printing. There has been proposed a transparent conductive layer that has been applied and developed to exhibit conductivity on the entire surface (see, for example, Patent Documents 3 and 4). However, in these examples, there is no means for ensuring the adhesion between the support and the fine metal wire pattern and the adhesion between the support and the conductive polymer layer. When an organic EL element is formed using a transparent conductive layer formed on a substrate, if a bending force is applied, the interface between the substrate and the transparent conductive layer peels off, resulting in a partial light emission failure. there were.

  In addition, with respect to a silane coupling agent that is known to exhibit an adhesive action under specific conditions, an example of using it as a binder matrix material of a transparent conductor layer (Patent Document 3), or other on a transparent conductive layer Although the example (patent document 5) used as an easily bonding layer at the time of laminating | stacking a layer is known, using as an effective means for adhere | attaching a transparent conductive layer and a base-material surface was not known.

JP-A-6-273964 JP 2000-98912 A JP 2008-130449 A JP 2009-231194 A JP 2007-140282 A

  The object of the present invention has been made in view of the above circumstances, has both high conductivity and transparency, can be produced at high speed, and is an organic electron such as a flexible organic electroluminescence (EL) element or organic solar cell. An object of the present invention is to provide a transparent conductive support capable of reducing the fear of causing a light emission failure due to bending when an element is formed.

  The above object of the present invention is achieved by the following means.

（式中、Ｘ _１ 〜Ｘ _３ はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ _１ 〜Ｒ _３ はそれぞれ独立に、炭素数５以下のアルキレン基を表す。ｌ、ｍ、ｎは構成率（ｍｏｌ％）を表し、５０≦ｌ＋ｍ＋ｎ≦１００である。） 1. A first conductive layer made of fine metal wires formed in a pattern on a substrate, a second conductive layer covering the first conductive layer and containing a conductive polymer and a hydroxyl group-containing nonconductive polymer; The hydroxyl group-containing nonconductive polymer is a polymer (A) having the following structure, and has a subbing layer formed by applying a silane coupling agent to the substrate surface. A transparent conductive support characterized by comprising:

(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%), and 50 ≦ l + m + n ≦ 100.)

  2. 2. The transparent conductive support according to 1 above, wherein at least a part of the silane coupling agent is a compound having either a mercapto group or an amino group in the molecule.

3. 3. The transparent conductive material according to 1 or 2 above, wherein the hydroxyl group-containing nonconductive polymer contained in the second conductive layer is a polyhydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 5 or less carbon atoms . Support.

  4). 4. The transparent conductive support according to 3 above, wherein the conductive polymer contained in the second conductive layer is a polythiophene derivative doped with polysulfonic acid.

  5. 5. The transparent conductive support according to any one of 1 to 4, wherein an undercoat layer is formed by applying a silane coupling agent after the substrate surface is subjected to excimer treatment.

  6). 6. The transparent conductive support according to any one of 1 to 5, wherein the substrate is a resin film provided with a barrier layer that blocks moisture and oxygen on the surface.

  7). Any one of 1 to 6 above, wherein the first conductive layer is a fine line electrode formed by patterning and baking a paste made of silver fine particles into a fine line shape by a printing method. The transparent conductive support described.

  8). 8. The transparent conductive support according to 7 above, wherein the silver fine particles are silver nanoparticles having an average particle size of 30 nm or less.

  According to the present invention, a transparent conductive support that has both high conductivity and transparency and can be produced at high speed can be provided. When an organic electronic device such as a flexible organic EL device or an organic solar cell is formed, it is bent. As a result, it was possible to reduce the fear of causing light emission defects.

It is a figure which shows the representative example of the metal fine wire pattern of a 1st conductive layer. It is sectional drawing of an organic electronic element.

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

<substrate>
In the present invention, a plastic film, a plastic plate, glass or the like can be used as the substrate, and a transparent plastic film is preferably used from the viewpoint of lightness and flexibility.

  Examples of raw materials for plastic films and plastic plates include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA, and polyvinyl chloride. , Vinyl resins such as polyvinylidene chloride, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), etc. Can be used. Of these, PET and PEN are preferred.

  In the transparent conductive support, the substrate used for this is preferably one having excellent surface smoothness. The smoothness of the surface is preferably an arithmetic average roughness Ra of 5 nm or less and a maximum height Rz of 50 nm or less, more preferably Ra of 2 nm or less and Rz of 30 nm or less, and still more preferably Ra of 1 nm or less. Rz is 20 nm or less. The surface of the substrate may be smoothed by applying an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or a radiation curable resin, or may be smoothed by mechanical processing such as polishing. You can also. Here, the smoothness of the surface can be determined according to the surface roughness standard (JIS B 0601-2001) from measurement by an atomic force microscope (AFM) or the like.

  The substrate is preferably provided with a gas barrier layer for the purpose of blocking oxygen and moisture in the atmosphere. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used. These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having favorable barrier properties, solvent resistance, and transparency are preferable.

  In addition, the barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material. The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, more preferably 10 nm to 400 nm per layer. The gas barrier layer is provided on at least one surface of the substrate, and more preferably on both surfaces.

  Further, the surface of the substrate may be subjected to a protective layer treatment with a hard coat layer or the like. The hard coat layer is formed by uniformly applying a photo-radical generating material and a mixture of radical polymerizable monofunctional and / or polyfunctional monomers to a desired film thickness, and then irradiating the necessary amount of ultraviolet light with radical polymerization. It is a transparent and high-hardness polymer layer obtained by making it.

Moreover, in this invention, it is preferable to perform an excimer process before apply | coating a silane coupling material as a subbing layer to a board | substrate. As the light source used for the excimer treatment, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. The output of the lamp ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, preferably 10~5000mJ / cm ² as irradiation energy, 100 to 2000 mJ / cm ² is more preferable. The illuminance at the time of ultraviolet irradiation is preferably 1 mW to 10 W / cm ² .

<Underlayer>
The transparent conductive support of the present invention has an undercoat layer formed by applying a silane coupling agent to the substrate surface.

  Examples of the silane coupling agent that can be used for the undercoat layer include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and β- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ -Glycidoxypropyltrimethoxysilane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane , Ok Tadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane and the like can be mentioned. Of these, those having either a mercapto group or a dialkylamino group in the molecule are preferred. Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyl are preferred. Methyldimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane / hydrochloride, γ-mercaptopropyltrimethoxysilane and the like are particularly preferable.

  In order to form an undercoat layer using a silane coupling agent, the silane coupling agent is dissolved in water, an organic solvent, or the like, applied, and then dried.

  The solvent not only dissolves the silane coupling agent but also affects the developability and wettability on the inorganic substrate. In the case of using water, in the case of aminosilane, it is easy to dissolve and pH adjustment is not necessary, but other silane coupling agents are preferably used in the vicinity of pH 4.

  Drying is preferably performed at a temperature of room temperature to 100 ° C. for about 2 to 30 minutes. By drying, a chemical reaction occurs between the silane coupling agent and the substrate, the organic functional group of the silane coupling agent is oriented outside the substrate surface, and a first conductive layer made of fine metal wires formed in a pattern on the substrate, It is considered that the adhesiveness is improved by interacting with the second conductive layer containing a conductive polymer that is in contact with the undercoat layer at the opening portion of the pattern formed by the first conductive layer.

<Conductive layer>
The conductive layer in the present invention is composed of a first conductive layer made of a metal fine line pattern (hereinafter, a thin line or a fine line pattern) and a second conductive layer made of a conductive polymer.

  As a method for forming the conductive layer, it is preferable that the first conductive layer is formed by printing and baking a fine line pattern with a paste of metal particles on the substrate having the undercoat layer by a printing method. By applying a coating solution for the second conductive layer so as to cover the substrate and the first conductive layer formed on the substrate, the electrode is developed even between the thin line patterns without the first conductive layer. I can do it.

(First conductive layer)
First, a fine metal wire pattern is formed as a first conductive layer on a support.

  FIG. 1 shows some examples of the fine metal wire pattern of the first conductive layer formed on the substrate in the transparent conductive support of the present invention as seen from the normal direction of the electrode surface. The pattern is not particularly limited, and there is no particular limitation such as a stripe shape, a mesh shape, or a random mesh shape as shown in the figure. An arbitrary repeating pattern having a line width of 10 to 400 μm and a pitch of 200 μm to 3000 μm, or a random pattern having an average pitch having the above values may be used.

  The fine line pattern can be formed by a printing method such as a gravure printing method, a flexographic printing method, and a screen printing method using a dispersion of metal particles. For each printing method, a method generally used for electrode pattern formation can be applied to the present invention. Specific examples of the gravure printing method include the methods described in JP2009-295980, JP2009-259826, JP2009-96189, and JP2009-90662, and the gravure printing method is special. Examples of the methods described in JP-A-2004-268319 and JP-A-2003-168560 and the like, and examples of the screen printing method include methods described in JP-A 2010-34161, JP-A 2010-10245, and JP-A 2009-302345. Can be mentioned.

  Although the line | wire width of the thin wire | line in a 1st conductive layer is arbitrary, 10-400 micrometers is preferable, 20-200 micrometers is more preferable, 30-120 micrometers is more preferable. The height (thickness) of the fine wire is preferably 0.2 to 2.0 μm, and more preferably 0.5 to 1.5 μm.

  The surface specific resistance of the thin wire portion of the first conductive layer is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. 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.

(Metal nanoparticles)
The metal fine line pattern is preferably provided by printing a paste of metal particles. After printing, in order to increase conductivity, heating and baking are performed. When a PET film is used as the substrate, the firing temperature is preferably 110 ° C. or lower. The metal particles are preferably metal nanoparticles because high conductivity is obtained.

  The metal nanoparticles refer to fine metal particles having a particle size of from atomic scale to nm size. As an average particle diameter of a metal nanoparticle, 3-300 nm is preferable and it is more preferable that it is 5-100 nm. The metal used in the metal nanoparticles according to the present invention is preferably silver or copper from the viewpoint of conductivity, and may be silver or copper alone, or a combination of them, either silver and copper alloy, silver or copper. It may be plated with any metal. Among these, silver nanoparticles are particularly preferable. Among these, silver nanoparticles having an average particle size of 30 nm or less are preferable.

(Second conductive layer)
Further, as the second conductive layer, a dispersion liquid made of a conductive polymer is applied and dried so as to cover the patterned first conductive layer, thereby forming a film. In addition to the above-mentioned printing methods such as gravure printing method, flexographic printing method, screen printing method, the application of the second conductive layer is performed by roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method. A coating method such as a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, or an inkjet method can be used.

The second conductive layer further contains a polymer (A) as a hydroxyl group-containing non-conductive polymer having a conductivity enhancing effect of the conductive polymer. Thereby, high electroconductivity, high transparency, and water resistance can be satisfy | filled simultaneously.

  By forming the conductive layer of the present invention having such a laminated structure, high conductivity that cannot be obtained by a metal thin wire or a conductive polymer layer alone can be obtained uniformly in the electrode plane.

  The ratio of the conductive polymer of the second conductive layer to the hydroxyl group-containing non-conductive polymer is preferably 30 to 900 parts by mass of the hydroxyl group-containing non-conductive polymer when the conductive polymer is 100 parts by mass. From the viewpoints of preventing current leakage, enhancing the conductivity of the hydroxyl group-containing non-conductive polymer, and transparency, the hydroxyl group-containing non-conductive polymer is more preferably 100 parts by mass or more.

  The dry film thickness of the second conductive layer is preferably 30 nm 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 further preferably 200 nm or more. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.

  After apply | coating a 2nd conductive layer, a drying process can be given suitably. 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 or a conductive layer. For example, a drying process can be performed at 80 to 150 ° C. for 10 seconds to 10 minutes. In the present invention, after the completion of drying, the crosslinking reaction of the hydroxyl group-containing nonconductive polymer can be promoted and completed by further heat treatment. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved. In particular, in an organic EL element, effects such as reduction in driving voltage and improvement in life can be obtained.

  The heat treatment is preferably performed at a temperature of 50 ° C. or higher and 200 ° C. or lower for 30 minutes or longer. If it is less than 50 ° C., the reaction promoting effect is small, and if it exceeds 200 ° C., thermal damage to the material increases, or the effect is small. The treatment temperature is more preferably 80 ° C. or more and 150 ° C. or less, and the treatment time is more preferably 1 hour or more. The upper limit of the treatment time is not particularly limited, but is preferably 24 hours or less from the viewpoint of productivity. The heat treatment may be performed on-line or off-line after applying and drying the conductive layer. In the case of off-line, it is preferable to further perform under reduced pressure because it leads to accelerated drying of moisture.

  In the present invention, the crosslinking reaction of the hydroxyl group-containing nonconductive polymer can be promoted and completed using an acid catalyst. As the acid catalyst, hydrochloric acid, sulfuric acid or ammonium sulfate can be used. Moreover, in the polyanion used as a dopant for a conductive polymer, a dopant and a catalyst can be used together by using a sulfo group-containing polyanion. In addition, the heat treatment described above can be performed in combination with the use of an acid catalyst, which is preferable because it shortens the treatment time.

<Conductive polymer>
The conductive polymer of the present invention is preferably a conductive polymer comprising a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemically oxidatively polymerizing 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 polyanion described later.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer used in the present invention is not particularly limited, and examples thereof include polythiophenes (including basic polythiophene, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, and polyacetylenes. A chain conductive polymer such as polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, and polythiazyl compounds 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.

(Polyanion)
The polyanion is 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. It consists of a structural unit having an anionic group and a structural unit having no anionic group.

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

  The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a 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 the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene. Polysulfonic acid such as 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 Examples thereof include polycarboxylic acids such as acids.

  These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient. Moreover, the polyanion which has a fluorine 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 the compound having a sulfo group is formed by coating and drying the conductive polymer-containing layer, the coating film is washed when heat treatment is performed at a temperature of 100 ° C. or more and 200 ° C. or less. Since resistance and solvent tolerance improve remarkably, it is more preferable. Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive polymer.

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

  Examples of methods for producing polyanions include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And a method of production by polymerization of a functional monomer.

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

  A water-soluble organic compound may be contained as the second dopant. There is no restriction | limiting in particular in this water-soluble organic compound, 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.

  For the second conductive layer, it is preferable to use an aqueous solvent for the preparation of the coating liquid from the solubility characteristics of the conductive polymer and the hydroxyl group-containing non-conductive polymer.

<Hydroxyl-containing non-conductive polymer>
As the hydroxyl group-containing non-conductive polymer in the present invention, polymer (A) is used .

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. l, m, and n represent the composition ratio (mol%), and 50 ≦ l + m + n ≦ 100. )
The main copolymerization component of the polymer (A) is composed of the following monomers M1, M2, and M3, and the copolymer component is a copolymer polymer in which 50 mol% or more of the copolymer components are any of the monomers or the total is 50 mol% or more. The total of the monomer components is more preferably 80 mol% or more, and it may be a homopolymer formed from any single monomer, which is a preferred embodiment.

Monomer _{M1 CH 2 = C (X 1} ) O-R 1 -OH
Monomer _{M2 CH 2 = C (X 2} ) COO-R 2 -OH
Monomer _{M3 CH 2 = C (X 3} ) CONH-R 3 -OH
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.

Among these, a polymer of the monomer M1 is particularly preferable. More specifically, in the monomer M1, X ₁ is preferably a hydrogen atom. R ₁ is particularly preferably an ethylene group.

  In the polymer (A), other monomer components may be copolymerized as long as they are soluble in an aqueous solvent, but a monomer component having high hydrophilicity is more preferable. The polymer (A) preferably has a number average molecular weight of 1000 or less in a content of 0 to 5%. When there are few low molecular components, the preservation | save property of an element and the behavior which has a barrier in the electroconductivity perpendicular | vertical with respect to a conductive layer can be reduced more.

  As a method for adjusting the content of the polymer (A) having a number average molecular weight of 1000 or less to 0 to 5%, a low molecular weight component is obtained by synthesizing a monodisperse polymer by living polymerization in a reprecipitation method or preparative GPC. A method of removing or suppressing the generation of low molecular weight components 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 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.

  In the present invention, 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. 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. This is advantageous for the smoothness of the film to be formed.

  The dispersion containing the conductive polymer of the present invention and the hydroxyl group-containing non-conductive polymer further contains other transparent non-conductive polymers and additives as long as the conductivity, transparency and smoothness of the conductive layer are simultaneously satisfied. May be.

  As the transparent non-conductive polymer, a natural polymer resin or a synthetic polymer resin can be widely selected and used, and a water-soluble polymer or an aqueous polymer emulsion is particularly preferable. Examples of water-soluble polymers include natural polymers such as starch, gelatin, and agar, semi-synthetic polymers such as hydroxypropylmethylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, cellulose derivatives, synthetic polymers such as polyvinyl alcohol, and polyacrylic acid polymers. , Polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc., and aqueous polymer emulsions include acrylic resins (acrylic silicone modified resins, fluorine modified acrylic resins, urethane modified acrylic resins, epoxy modified acrylic resins, etc.), polyester resins, urethanes Resin, vinyl acetate resin and the like can be used.

  In addition, the synthetic polymer resin of the aqueous polymer emulsion may be a transparent thermoplastic resin (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene). , Vinylidene fluoride) and transparent curable resins that are cured by heat, light, electron beam, or radiation (for example, melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, silicone resin such as acrylic-modified silicate). it can.

  Examples of the additive include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments. Furthermore, from the viewpoint of improving workability such as coating properties, solvents (for example, water, organic solvents such as alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.

<Configuration of organic electronic device>
The configuration of the organic electronic element will be described with reference to the drawings. In FIG. 2, it has the 1st electrode (11) and the 2nd electrode (12) which oppose on a board | substrate (10), and at least 1 layer of organic is between a 1st electrode (11) and a 2nd electrode (12) electrode. It has a functional layer (13). In the present invention, the first electrode (11) includes a first conductive layer (14) made of metal nanoparticles, and a second conductive layer (15) made of a conductive polymer and a hydroxyl group-containing non-conductive polymer. The second conductive layer made of a polymer and a hydroxyl group-containing non-conductive polymer is filled in the gap between the first conductive layer made of metal nanoparticles.

  Examples of the organic functional layer (13) of the present invention 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 a certain organic light emitting layer or organic photoelectric conversion layer.

<Organic functional layer configuration>
(Organic EL device)
(Organic light emitting layer)
The organic electronic device having an organic light emitting layer in the present invention is used in combination with an organic light emitting layer such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, and an electron block layer in addition to the organic light emitting layer. Thus, a layer for controlling light emission may be provided. Since the conductive polymer-containing layer of the present invention can also function 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 transporting layer / light emitting layer / hole blocking layer / electron transporting 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, or by laminating at least three of these light emitting layers. 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, carbazole, azacarbazole, oxacarbane Diazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8- Quinolinate) aluminum complex, aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyro Le 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. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.

[Second electrode part]
In the present invention, the second electrode serves as a cathode in the organic EL device. The second electrode portion of the present invention 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 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, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function 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. The metal nanowire of the first electrode part scatters or reflects part of the light backward, but by using a metal material as the conductive material of the second electrode part, this light can be reused and the extraction efficiency is improved. .

<Organic photoelectric conversion element>
The organic photoelectric conversion element has a structure in which a first electrode portion, a photoelectric conversion layer (hereinafter also referred to as a bulk heterojunction layer) having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer), and a second electrode portion are stacked. Have.

  An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the second electrode portion.

[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. 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 like 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, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes, fullerenes such as C60, C70, C76, C78 and C84, carbon nanotubes such as SWNT, dyes such as merocyanine dyes and hemicyanine dyes, σ-conjugated polymers such as polysilane and polygerman, and Organic / inorganic hybrid materials described in 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. No. 9, 2706 and the like, 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.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic 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 type), 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 a photoelectric conversion element as photoelectric conversion materials, such as a solar cell, a photoelectric conversion element may be utilized by a single layer and may be laminated | stacked (tandem type) and may be utilized.

  In addition, the photoelectric conversion material, the organic EL element, and the like are preferably sealed by a known method in order not to be deteriorated by oxygen, moisture, or the like in the environment.

  For example, after forming a photoelectric conversion element or an organic EL element using a barrier film on which the gas barrier layer or the like is formed as a sealing material, and using a substrate on which the gas barrier layer is provided as a substrate for the photoelectric conversion element or the organic EL element It can be sealed by overlapping and bonding to this.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<substrate>
As a substrate material, a 125 μm-thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was annealed and heated at 170 ° C. for 30 minutes.

Apply UV curable organic / inorganic hybrid hard coating material OPSTAR Z7501 manufactured by JSR Corporation on one side of the substrate material, apply it with a wire bar so that the (average) film thickness after drying is 4 μm, and then dry conditions: 80 ° C. After drying in 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions; 1.0 J / cm ² to form a smooth layer.

  The maximum cross-sectional height Rz at this time was 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

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

(Gas barrier layer coating solution)
Perhydropolysilazane (PHPS) 20% by weight dibutyl ether solution AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.
With a wireless bar, coating was performed so that the (average) film thickness after drying was 0.30 μm to obtain a coated sample.

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

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

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

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com
The sample fixed on the operation stage was modified under the following conditions.

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

<Underlayer>
The transparent electrode substrate was subjected to a subbing treatment as shown in the table below.

<First conductive layer>
The first conductive layer patterning shown in the table below was performed on the transparent electrode substrate with an undercoat layer obtained above.

<Second conductive layer>
On the transparent electrode substrate obtained by patterning the first conductive layer obtained above, the second conductive layer patterning shown in the table below was performed.

<< Production of organic EL element >>
In each of the produced transparent electrodes, a square tile-shaped transparent pattern having a pattern side length of 20 mm was cut into a 30 mm square so as to be arranged at the center, and used for the first electrode (anode). Produced.

  The cut out transparent pattern 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 the optimum amount for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

  Subsequently, each light emitting 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 established.

  Ir-1 and 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 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%. Formed.

  The compounds used for forming each layer are shown below.

On the formed electron transport layer, a transparent electrode is used as an anode, an anode external extraction terminal, and Al as a 15 mm × 15 mm cathode forming material is mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa, and a 100 nm thick anode Formed.

Further, a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al ₂ O ₃ is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed. After pasting the members, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

<Evaluation>
<Measurement of surface resistivity>
After the patterning of the second conductive layer, the surface specific resistance of the transparent electrode was measured.

  The surface specific resistance of each transparent electrode was measured by the four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.

<Transmissivity>
After the patterning of the second conductive layer, the transmittance of the transparent electrode was measured.

  For the transmittance, the total light transmittance of the transparent electrode was measured using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

<Measurement and evaluation of organic EL elements>
The following methods were used to measure and evaluate the light emission unevenness and bending resistance of each organic EL element produced.

<Luminance unevenness>
The luminance unevenness was evaluated by visually applying the light emission state according to the following criteria by applying a DC voltage to each organic EL element to emit light with a luminance of 1000 cd / m ² using a KEITHLEY source measure unit 2400 type.

A: Completely uniform light emission, satisfactory O: Almost uniform light emission, no problem Δ: Partial emission unevenness is partially observed, but acceptable X: Irregular emission emission is observed over the entire surface, Unacceptable XX: No light emission <Bending resistance>
The organic EL element was wound along a curved surface of a cylindrical stainless steel rod having a diameter of 50 mm and held for 3 seconds as a one-time bending test, and was bent a predetermined number of times (one time, ten times, and 100 times). When performing a plurality of folding, the folding was performed at intervals of 3 seconds. After performing a predetermined number of bending tests, the luminance unevenness was measured, and visual evaluation was performed based on the same criteria.

  It can be seen that the transparent conductive support of the present invention has high resistance to bending.

DESCRIPTION OF SYMBOLS 10 Board | substrate 11 1st electrode 12 2nd electrode 13 Organic functional layer 14 1st conductive layer 15 2nd conductive layer

Claims (8)

A first conductive layer made of fine metal wires formed in a pattern on a substrate, a second conductive layer covering the first conductive layer and containing a conductive polymer and a hydroxyl group-containing nonconductive polymer; The hydroxyl group-containing nonconductive polymer is a polymer (A) having the following structure, and has a subbing layer formed by applying a silane coupling agent to the substrate surface. A transparent conductive support characterized by comprising:

(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%), and 50 ≦ l + m + n ≦ 100.)   The transparent conductive support according to claim 1, wherein at least a part of the silane coupling agent is a compound having either a mercapto group or an amino group in the molecule. The transparent conductive material according to claim 1 or 2, wherein the hydroxyl group-containing nonconductive polymer contained in the second conductive layer is a polyhydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 5 or less carbon atoms. Sex support.   4. The transparent conductive support according to claim 3, wherein the conductive polymer contained in the second conductive layer is a polythiophene derivative doped with polysulfonic acid.   The transparent conductive support according to claim 1, wherein an undercoat layer is formed by applying a silane coupling agent after the substrate surface is subjected to excimer treatment.   The transparent conductive support according to any one of claims 1 to 5, wherein the substrate is a resin film provided with a barrier layer for blocking moisture and oxygen on the surface.   The said 1st conductive layer is a fine wire-like electrode formed by patterning the paste which consists of silver fine particles into a fine wire shape by a printing system, and baking it, The any one of Claims 1-6 characterized by the above-mentioned. The transparent conductive support described in 1.   The transparent conductive support according to claim 7, wherein the silver fine particles are silver nanoparticles having an average particle size of 30 nm or less.

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