JP2012243401A - Transparent conductive film and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode having excellent transparency, conductivity and film strength which do not deteriorate significantly even under a high temperature high humidity environment, and producing an organic EL element having excellent stability, excellent emission uniformity which does not deteriorate significantly, and an excellent emission life, and to provide an organic EL element using that electrode and having high emission uniformity which does not deteriorate significantly, and an excellent life.SOLUTION: In a transparent conductive film having a first conductive layer composed of a metallic material and patterned on a substrate, and a second conductive layer including a conductive polymer and a partially esterified polycarboxylic acid resin, the partially esterified polycarboxylic acid resin is produced by causing an acetal compound to react on the polycarboxylic acid.

Description

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

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays with different display methods, the transparent electrode is an essential constituent technology. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.

  Conventionally, an ITO transparent electrode in which a composite oxide (ITO) film of indium-tin is formed on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method has been mainly used. It was. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. In addition, with the increase in display screen and productivity, a roll-to-roll production technique using a flexible substrate is desired.

  In recent years, a transparent conductive film such as a conductive polymer is laminated on a thin metal wire formed in a pattern so that it can be used for products requiring such a large area and a low resistance value, and the surface uniformity of current is high. A transparent conductive film having both conductivity has been developed (see, for example, Patent Document 1). However, in such a configuration, it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent conductive film such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer. . However, since the conductive polymer has absorption in the visible light region, there is a problem that when the film is thickened, the transparency of the transparent electrode is significantly lowered.

  Moreover, the technique which laminates | stacks the mixture of a conductive polymer and an insulating polymer on a thin wire | line structure part is disclosed as making electroconductivity and transparency compatible (for example, patent document 2). However, the addition of an insulating polymer has a problem that it causes deterioration of optical performance such as haze from the viewpoint of a decrease in conductivity and compatibility with the conductive polymer.

  Furthermore, as a polymer compatible with the conductive polymer, polyvinylpyrrolidone (PVP), a copolymer of poly (vinyl pyridine) and poly (vinyl acetate) (PVPy-VAc), polymethacrylic acid (PMAA), poly (hydroxyethyl) A polymer or copolymer selected from the group consisting of (acrylate) and poly (methacrylic acid) copolymer (PHEA-MAA), poly (2-hydroxyethyl methacrylate), polyvinyl butyral (PVB) is disclosed (eg, Patent Documents 3 and 4). However, when these polymers are used, since the film strength is insufficient, the film surface is disturbed when lamination is performed by vapor deposition or spin coating, and leakage occurs when an organic electronic device is manufactured.

  Furthermore, when a transparent conductive film such as a conductive polymer is used, it is known that if water remains in the transparent conductive film, the performance of the organic electronic device is deteriorated. Is essential. However, in recent years, a transparent film has been increasingly used from the viewpoint of flexibility and cost for a transparent substrate, and a transparent conductive film such as a conductive polymer is heated at a low temperature below the glass transition temperature Tg at which the film does not deform. In this case, moisture remains in the transparent conductive film, and drying of the transparent conductive film has been a problem.

JP 2009-87843 A JP 2009-4348 A Japanese Patent No. 3716167 JP 2011-54297 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is excellent in transparency, conductivity, and film strength, as well as deterioration in transparency, conductivity, and film strength even in a high temperature and high humidity environment. An object of the present invention is to provide a transparent electrode that provides an organic EL device that is less in stability, excellent in light emission uniformity, and less in light emission uniformity and excellent in light emission life.

  It is another object of the present invention to provide an organic EL device that uses the electrode and has high light emission uniformity, little deterioration of light emission uniformity, and excellent life.

  Conventionally, the coating liquid for transparent conductive film contains water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) and water-soluble binder in order to achieve both conductivity and transmittance. Compositions have been developed. Here, hydrophilic binders have been studied as water-soluble polymers from the viewpoint of compatibility with water-dispersible conductive polymers. However, the demand for flexibility increases as a transparent substrate, and when a resin film such as polyethylene terephthalate is used, the drying temperature is lower than that of the glass substrate from the viewpoint of avoiding deformation in the resin film. As a result, it was difficult to remove moisture from the film due to the influence of the hydrophilic binder, and the performance of the device using these transparent conductive films was significantly deteriorated. As a result of intensive studies to improve these phenomena, a structural unit having a carboxy group in a repeating unit of a binder and a structural unit not containing a carboxy group as a binder resin together with a water-dispersible conductive polymer in a transparent conductive film It came to the structure of this invention using the resin containing this.

  That is, the present invention uses a partially esterified polycarboxylic acid resin for the second conductive layer as in the structure of the present invention, which has a structure unit having a carboxy group in a repeating unit and a structure not containing a carboxy group. It was a binder resin in which the units were appropriately controlled, and it was found that the object of the present invention can be achieved by including these partially esterified polycarboxylic acid resins as the binder resin.

  A technique for obtaining a partially esterified polycarboxylic acid is to obtain a fully esterified polymer such as polymethyl methacrylate from a fully esterified monomer raw material such as methyl methacrylate. , A method of partially saponifying with an alkali, a method of copolymerizing monomers having a carboxy group such as acrylic acid and an esterified monomer such as methyl acrylate, and the like by allowing a glycidyl compound to act on a polycarboxylic acid. For example, a method of esterifying is known. Here, in the method of partially esterifying a completely esterified polymer by saponification, impurities are removed from the polymer in order to saponify again with alkali after obtaining the polymer by polymerization reaction. When it is difficult to copolymerize, it is difficult to obtain a partially esterified polymer with a completely random distribution due to the reactivity of the monomers, and when using a glycidyl compound, it is difficult to introduce quantitatively. There was a problem.

  In the present invention, the second conductive layer is made of a conductive polymer, a binder resin in which the number of carboxy groups and the random distribution of carboxy groups are controlled, so that the transparency and conductivity of the transparent conductive film are compatible and the film strength is increased. Excellent transparent electrode having excellent conductivity, transparency and good film strength even after environmental test under high temperature and high humidity environment, and long-life organic electroluminescence device using the transparent electrode Has been found to be obtained.

  The object of the present invention is achieved by adopting the following configuration.

  1. In the transparent conductive film having a first conductive layer made of a metal material formed in a pattern on a substrate and a second conductive layer containing a conductive polymer and a partially esterified polycarboxylic acid resin, the partial esterification A transparent conductive film, wherein the polycarboxylic acid resin is a resin obtained by reacting a polycarboxylic acid with an acetal compound.

  2. 2. The transparent conductive film according to 1 above, wherein the partially esterified polycarboxylic acid resin has a carboxy group concentration of 0.5 mmol / g to 5.0 mmol / g.

  3. 1 or 2 above, wherein the polycarboxylic acid of the partially esterified polycarboxylic acid resin is selected from polyacrylic acid, polymethacrylic acid, polycarboxystyrene, and copolymers thereof. The transparent conductive film as described in 2.

  4). The organic electroluminescent element characterized by using the transparent conductive film of any one of said 1-3.

  By the above means of the present invention, the transparency, conductivity and film strength are excellent, and transparency, conductivity and film strength are hardly deteriorated even in a high temperature and high humidity environment, and stability and light emission uniformity are excellent. It is possible to provide a transparent electrode that provides an organic EL device that has little emission uniformity deterioration and excellent emission lifetime.

  Furthermore, it is possible to provide an organic EL element that has high emission uniformity using the electrode, has little deterioration in emission uniformity, and has an excellent lifetime.

It is the schematic which illustrated an example of the transparent conductive film of the structure of this invention.

  Hereinafter, modes for carrying out the present invention will be described.

  FIG. 1 is a schematic diagram illustrating an example of the transparent conductive film having the structure of the present invention.

  In FIG. 1, 1 is a first conductive layer made of a metal material formed in a pattern, 2 is a second conductive layer containing a conductive polymer, and 3 is a substrate. The feature of the configuration of the present invention includes a polycarboxylic acid resin partially esterified on the second conductive layer 2.

<< Second conductive layer >>
<Partially esterified polycarboxylic acid resin>
In the present invention, a partially esterified polycarboxylic acid used as a binder resin together with a water-dispersible conductive polymer in the second conductive layer will be described.

  The polycarboxylic acid in the present invention has a carboxy group in the polymer main chain or side chain. Such as polyacrylic acid obtained by reacting tetracarboxylic acid or its acid dianhydride and diamine, or polyacrylic acid obtained by polymerizing acrylic acid, methacrylic acid, maleic acid or carboxystyrene. List the acid, polymethacrylic acid, polymaleic acid, polycarboxystyrene, and these and other monomers such as methyl acrylate, methyl methacrylate, styrene, ethylene, propylene, and other vinyl compounds. Can do.

  Moreover, the polymer which has a carboxy group other than this can be used similarly.

  The partially esterified polycarboxylic acid resin can be obtained by reacting these polycarboxylic acids with an acetal compound and esterifying them.

  The degree of esterification of the partially esterified polycarboxylic acid in the present invention can be determined by quantifying the amount of the remaining carboxy group. The remaining carboxy group is most easily and accurately determined by a titration method. The carboxy group concentration is preferably 0.5 mmol / g to 5.0 mmol / g. Accordingly, when esterification proceeds and the carboxy group concentration becomes lower than 0.5 mmol / g, there is no difference in solubility from the completely esterified polymer obtained from the esterified monomer in advance. Further, if the remaining carboxy group exceeds 5.0 mmol / g, problems such as excessive dissolution in water appear, which is not preferable.

  In the present invention, the adjustment of the degree of esterification is preferably controlled by the amount of an acetal compound that is an esterifying agent. The esterification rate can be freely controlled according to the amount of the acetal compound added. Other esterification reagents can also be used. In the present invention, an acetal compound is a compound obtained by reacting two equivalents of an alcohol with a carbonyl group, and collectively refers to so-called acetals and ketals. Specifically, bipolar aprotic having a carbonyl group such as N, N-dimethylformamide, N-methyl-pyrrolidone, gamma butyrolactone, N, N-dimethylacetamide, N, N-diethylformamide, ethylene carbonate, propylene carbonate The solvent acetal compound is preferred. A partially esterified polycarboxylic acid can be obtained by mixing such an acetal compound with a polycarboxylic acid solution to be reacted and reacting at 0 ° C. to 100 ° C. for 10 minutes to 8 hours. These acetal compounds are described in H.C. A synthetic method is described in Meerwein, Angewante Chemie 71, 530 (1959).

  In the present invention, the acetal compound is a dialkyl acetal having 1 to 10 carbon atoms such as dimethyl acetal, diethyl acetal, dipropyl acetal, dibutyl acetal, dihexyl acetal, dioctyl acetal, didecyl acetal, etc. Acetal compounds having an unsaturated bond such as divinyl acetal, diallyl acetal, di (ethyl methacrylate) acetal, di (ethyl acrylate) acetal, and the like can also be preferably used. In particular, when an acetal compound having an unsaturated bond is used, a cross-linking reaction is caused by actinic radiation such as ultraviolet rays, so that actinic radiation curable partial ester polycarboxylic acid can be obtained.

  The molecular weight of the partially esterified polycarboxylic acid resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably 5,000 to 100,000. Is within.

The number average molecular weight and molecular weight distribution of the partially esterified polycarboxylic acid resin of the present invention can be measured by generally known gel permeation chromatography (GPC). The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, more preferably THF and DMF, and still more preferably DMF. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

<Conductive polymer>
In the present invention, the second conductive layer contains a conductive polymer.

  The conductive polymer according to the present invention is a conductive polymer having 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)
Precursor monomers used in the formation of π-conjugated conductive polymers have a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidant, a π-conjugated system is formed in the main chain. It is what is done. 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-carboxypyrrole, 3-methyl-4-carboxypyrrole, 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-hexylthiop , 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-diethoxythiophene 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 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-isobutylaniline, 2-aniline sulfonic acid, 3-aniline sulphone Examples include phonic acid.

(Poly anion)
The polyanion used in the present invention includes 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 co-polymer thereof. A polymer comprising 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. In addition, the anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  The anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Further, it may be a polyanion further having F (fluorine atom) in the compound. Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.

  Among these, the compound having a sulfonic acid may be formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable. These poly anions are highly compatible with the carboxy group-containing resin, and the conductivity of the resulting conductive polymer can be made higher.

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

  Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and an anionic group containing The method of manufacturing by superposition | polymerization of a polymerizable monomer is mentioned.

  Examples of the method for producing an 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.

  The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion”, is preferably 1: 1 to 20 in mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 10 is more preferable.

The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.

  Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate half esters of alkanols such as lauryl sulfate; alkyl sulfonic acids of 1 to 20 carbons such as Methane or dodecanesulfonic acid; aliphatic carboxylic acid having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic (optionally) alkyl-substituted sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

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

  An organic compound may be contained as the second dopant. There is no restriction | limiting in particular in the organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

<< First conductive layer >>
The first conductive layer according to the present invention is characterized in that a metal material is formed in a pattern on a film substrate. As a result, a film substrate having both a light-impermeable conductive portion made of a metal material and a light-transmissive window portion is obtained, and an electrode substrate excellent in transparency and conductivity can be produced. The metal material is not particularly limited as long as it is excellent in conductivity. For example, the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium. In particular, the shape of the metal material is preferably metal fine particles or metal nanowires from the viewpoint of ease of pattern formation as described later, and the metal material is preferably silver from the viewpoint of conductivity.

  The pattern shape is not particularly limited. For example, the conductive portion may be a stripe shape, a mesh shape, or a random network shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. The aperture ratio is the ratio of the light-impermeable conductive portion to the whole. For example, when the conductive portion has a stripe shape or a mesh shape, the aperture ratio of the stripe pattern having a line width of 100 μm and a line interval of 1 mm is about 90%. The line width of the pattern is preferably 10 to 200 μm. If the line width of the fine wire is less than 10 μm, desired conductivity cannot be obtained, and if it exceeds 200 μm, the transparency is lowered. The height (thickness) of the thin wire is preferably 0.1 to 10 μm. If the height of the thin wire is less than 0.1 μm, desired conductivity cannot be obtained, and if it exceeds 10 μm, current leakage and the thickness of the functional layer increase in the formation of an organic electronic device, which causes a distribution failure.

  There is no particular limitation on the method for forming the stripe-shaped or mesh-shaped electrode of 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 using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, and plating, or a metal foil is used as an adhesive. After being laminated on the base material, the film 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. A method using silver salt photographic technology can be carried out with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and Examples. About the method of carrying out the gravure printing of catalyst ink and plating, it can carry out with reference to Unexamined-Japanese-Patent No. 2007-281290, for example.

  As a random network structure, for example, a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 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. The average minor axis is not particularly limited, but is preferably small from the viewpoint of transparency, while it is preferably large from the viewpoint of conductivity. 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. Basis weight of the metal nanowires is preferably ^{0.005~0.5g / m 2, 0.01~0.2g / m} 2 is more preferable.

  As the metal used for the metal nanowire, copper, iron, cobalt, gold, silver or the like can be used, and silver is preferable from the viewpoint of conductivity. In addition, a single metal may be used, but 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.

  Further, the surface specific resistance of the thin wire portion of the first conductive layer is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less for increasing the area. The surface specific resistance can be measured according to, for example, JIS K6911, ASTM D257, etc., or can be easily measured using a commercially available surface resistivity meter.

  The first conductive layer is preferably heat-treated within a range that does not damage the film substrate. Thereby, since fusion of metal fine particles or metal nanowires proceeds and the first conductive layer becomes highly conductive, it is particularly preferable.

  The second conductive layer may completely cover the patterned first conductive layer, or may partially cover or contact it. The second conductive layer is formed into a film by applying and drying a dispersion composed of a conductive polymer and a partially esterified polycarboxylic acid resin. In addition to the above-described printing methods such as gravure printing, flexographic printing, and screen printing, the second conductive layer is applied by roll coating, bar coating, dip coating, spin coating, casting, and die coating. 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.

  Further, as a means for producing a transparent electrode in which a part of the first conductive layer is covered or in contact with the second conductive layer, the first conductive layer is formed on the transfer film by the above method, and the second conductive layer is further formed. There is a method of transferring a laminate of the above to the above film substrate. Moreover, the method etc. which form a 2nd conductive layer by the well-known method by the inkjet method etc. in the nonelectroconductive part of a 1st conductive layer are mentioned.

  The second conductive layer is characterized by containing a partially esterified polycarboxylic acid resin. As a result, a network of conductive polymers is efficiently formed by the action of randomly distributed carboxy groups and an ester structure, maintaining high conductivity, and at the same time providing high transparency and strong film strength that cannot be achieved with a conductive polymer alone. Can be obtained.

  By forming the conductive layer of the present invention having such a structure, high conductivity that cannot be obtained with a metal or metal oxide fine 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 partially esterified polycarboxylic acid resin is preferably 30 to 900 parts by mass of the partially esterified polycarboxylic acid resin when the conductive polymer is 100 parts by mass. From the viewpoints of preventing current leakage, enhancing the conductivity of the partially esterified polycarboxylic acid resin, and transparency, the partially esterified polycarboxylic acid resin is more preferably 100 parts by mass or more.

  The dry film thickness of the second conductive layer is preferably 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is 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, the drying process can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes. 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.

  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.

"Base material"
The base material used for the transparent electrode of the present invention is also called a film substrate, has high light transparency, and is not particularly limited as long as it is flexible. For example, although a resin substrate, a resin film, etc. are mentioned suitably, it is preferable to use a transparent resin film from a viewpoint of productivity, a viewpoint of performance, such as lightness and a softness | flexibility.

  If it is a transparent resin film, it is resistant to deformation and impact due to external force, and is difficult to break. There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, 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 Examples thereof include a film, a polyimide resin film, an acrylic resin film, and a triacetyl cellulose (TAC) resin film. A resin film having a transmittance of 80% or more at a visible wavelength (380 to 780 nm) is preferably used as a film substrate used in the present invention. Among them, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, and a polycarbonate film are preferable, and a biaxially stretched polyethylene terephthalate film. A biaxially stretched polyethylene naphthalate film is more preferred.

  The film 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 adhesiveness 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 film, an organic film, or a hybrid film of both may be formed on the front surface or the back surface of the film substrate, and the water vapor transmission rate (25 ± 0.00 mm) 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 method is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH), A high-barrier film of 1 × 10 ⁻³ g / (m ² · 24 h) or less is preferable.

  As a material for forming a barrier film formed on the front surface or the back surface of the film substrate in order to obtain a high barrier film, any material may be used as long as it has a function of suppressing infiltration 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 layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

《Organic electroluminescence device》
The organic electroluminescence device of the present invention is characterized by having an organic layer including an organic light emitting layer and the transparent electrode of the present invention.

  The organic electroluminescent device in the present invention preferably uses the transparent electrode of the present invention as an anode, and the organic light-emitting layer and the cathode are made of any material or configuration generally used in organic electroluminescent devices. Can be used.

As an element configuration of the organic electroluminescence element,
Anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / electron transport layer / cathode,
Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / cathode,
Anode / hole injection layer / organic light emitting layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / organic light emitting layer / electron injection layer / cathode,
The thing of various structures, such as these, can be mentioned.

  In addition, as the light emitting material or doping material that can be used in the organic light emitting layer in the present invention, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex, Aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone, ru Ren, 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.

  In addition, known materials are also used for the electron transport (injection) layer, the hole injection layer, the hole transport layer, and the like.

  As for the electrodes, well-known materials can be used as the cathode and the anode in addition to the transparent electrode of the present invention.

  The organic electroluminescence device of the present invention can be used for a self-luminous display, a liquid crystal backlight, illumination, and the like. Since the organic electroluminescence element of the present invention can emit light uniformly and without unevenness, it is preferably used for lighting purposes.

  The transparent electrode of the present invention has both high conductivity and transparency, and various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, electromagnetic wave shields, touch panels. It can be suitably used in such fields. Among these, it can use especially preferably as a transparent electrode of the organic electroluminescent element and organic thin-film solar cell element by which the smoothness of the transparent electrode surface is calculated | required severely.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the configuration of the present invention is not limited to these embodiments.

<< Synthesis of binder resin (synthesis of partially esterified polycarboxylic acid resin) >>
<Measurement of residual carboxy group concentration>
The polymer solution was dropped into pure water to precipitate, and dried under reduced pressure at 80 ° C. for 20 hours. 1 g of the dried polymer was dissolved in 50 ml of N-methylpyrrolidone (NMP), and released into the polymer with a methanol solution of 1/10 normal tetrabutylammonium hydroxide using an E702 automatic titrator manufactured by Shibata Kagaku Kagaku Kogyo. The carboxy group was titrated to determine the content.

<Synthesis Example 1 (Synthesis of P-1)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 8.7 g (60 mmol) of N-methyl-2-pyrrolidone dimethylacetal was added dropwise together with 10 g of N-methyl-2-pyrrolidone over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 6.9 mmol / g.

<Synthesis Example 2 (Synthesis of P-2)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was set to 50 ° C., and 11.6 g (80 mmol) of N-methyl-2-pyrrolidone dimethylacetal was added dropwise together with 10 g of N-methyl-2-pyrrolidone over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 5.1 mmol / g.

<Synthesis Example 3 (Synthesis of P-3)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was set to 50 ° C., and 14.5 g (100 mmol) of N-methyl-2-pyrrolidone dimethylacetal was added dropwise together with 10 g of N-methyl-2-pyrrolidone over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxyl group concentration of this polymer was 4.9 mmol / g.

<Synthesis Example 4 (Synthesis of P-4)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 17.9 g (150 mmol) of N, N-dimethylformamide dimethylacetal was added dropwise together with 15 g of N, N-dimethylformamide over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 2.8 mmol / g.

<Synthesis Example 5 (Synthesis of P-5)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 23.8 g (200 mmol) of N, N-dimethylformamide dimethylacetal was added dropwise together with 15 g of N, N-dimethylformamide over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 0.6 mmol / g.

<Synthesis Example 6 (Synthesis of P-6)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 26.2 g (220 mmol) of N, N-dimethylformamide dimethylacetal was added dropwise together with 15 g of N, N-dimethylformamide over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was put into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 0.4 mmol / g.

<Synthesis Example 7 (Synthesis of P-7)>
Under a dry nitrogen stream, 17 g (200 mmol) of methacrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was set to 50 ° C., and 14.5 g (100 mmol) of N-methyl-2-pyrrolidone dimethylacetal was added dropwise together with 10 g of N-methyl-2-pyrrolidone over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was poured into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxyl group concentration of this polymer was 3.5 mmol / g.

<Synthesis Example 8 (Synthesis of P-8)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid and 3.4 g (40 mmol) of methyl acrylate were added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 11.9 g (100 mmol) of N, N-dimethylformamide dimethylacetal was added dropwise together with 15 g of N, N-dimethylformamide over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was poured into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 3.4 mmol / g.

<Synthesis Example 9 (Synthesis of P-9)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid and 4.0 g (40 mmol) of ethyl acrylate were added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. Next, the temperature of the solution was adjusted to 50 ° C., and 11.9 g (100 mmol) of N, N-dimethylformamide dimethylacetal was added dropwise together with 15 g of N, N-dimethylformamide over 10 minutes. After completion of the dropwise addition, stirring was continued at 50 ° C. for 2 hours. This solution was poured into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 3.1 mmol / g.

<Synthesis Example 10 (Synthesis of P-10)>
Under a dry nitrogen stream, 2.96 g (20 mmol) of 4-carboxystyrene and 2.40 g (20 mmol) of 4-hydroxystyrene are dissolved in 30 g of N, N-dimethylformamide. To this, 0.1 g of azoisobutyronitrile was added, and the solution was heated to 60 ° C. and stirred for 4 hours. After completion of the stirring, the temperature of the solution was cooled to 50 ° C., and a solution obtained by diluting 1.33 g (10 mmol) of N, N-dimethylacetamide dimethylacetal with 5 g of methanol was added dropwise. After dropping, stirring was continued at 50 ° C. for 2 hours. This solution was poured into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration was 1.2 mol / g.

<Comparative Synthesis Example 1 (Synthesis of HP-1)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. This solution was concentrated, washed with methyl ethyl ketone, and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 13.9 mmol / g.

<Comparative Synthesis Example 2 (Synthesis of HP-2)>
Under a dry nitrogen stream, 17 g (200 mmol) of methacrylic acid was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. This solution was concentrated, washed with methyl ethyl ketone, and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 11.2 mmol / g.

<Comparative Synthesis Example 3 (Synthesis of HP-3)>
Under a dry nitrogen stream, 14 g (200 mmol) of acrylic acid and 3.4 g (40 mmol) of methyl acrylate were added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. This solution was concentrated, washed with methyl ethyl ketone, and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 10.9 mmol / g.

<Comparative Synthesis Example 4 (Synthesis of HP-4)>
Under a dry nitrogen stream, 7 g (100 mmol) of acrylic acid and 8.6 g (100 mmol) of methyl acrylate were added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. This solution was poured into 3 liters of water, and after decanting the water, the resulting precipitate was washed with water and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was 4.8 mmol / g.

<Comparative Synthesis Example 5 (Synthesis of HP-5)>
Under a dry nitrogen stream, 23.3 g (200 mmol) of 2-hydroxyethyl acrylate was added to 200 g of methanol in a 500 ml four-necked round bottom flask and heated to 60 ° C. To this was added 0.5 g of azoisobutyronitrile, the temperature was raised to 75 ° C., and stirring was continued for 2 hours. Thereafter, 0.5 g of azoisobutyronitrile was further added, and stirring was performed for 2 hours. This solution was concentrated, washed with methyl ethyl ketone, and dried in a vacuum dryer at 60 ° C. for 20 hours to obtain a resin. The residual carboxy group concentration of this polymer was not detected.

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

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

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

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

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

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

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp-filled gas Xe manufactured by M.D.Com Co., Ltd. The sample fixed on the operating stage was subjected to a modification treatment under the following conditions.

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

<Formation of first conductive layer>
The first conductive layer was formed by the following method on the surface without the gas barrier layer on the transparent electrode film substrate having gas barrier properties obtained above.

(Thin wire grid)
The fine wire lattice (metal material) was prepared by gravure printing or silver nanowire as shown below.

(Gravure printing)
Silver nanoparticle paste 1 (M-Dot SLP: manufactured by Mitsuboshi Belting Co., Ltd.) was printed on a fine wire grid having a line width of 50 μm, a height of 1.5 μm, and an interval of 1.0 mm using a gravure printing tester K303MULTICATOR manufactured by RK Print Coat Instruments Ltd. Thereafter, a drying process was performed at 110 ° C. for 5 minutes.

(Random network structure with silver nanowires)
A random network structure was prepared using silver nanowires as shown below.

The silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m ² , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced.

  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.

Example 1
[Preparation of transparent electrode]
<< Preparation of Transparent Electrode TC-101 >>
As described above, on the transparent electrode in which the first conductive layer is formed by gravure printing on the film substrate for the transparent electrode having gas barrier properties, the coating liquid A described below is then dried using the extrusion method. Apply by adjusting the slit gap of the extrusion head to 300 nm, heat drying at 110 ° C. for 5 minutes to form a second conductive layer made of a conductive polymer and a partially esterified polycarboxylic acid resin. The electrode was cut into 8 × 8 cm. Transparent electrode TC-101 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

<Formation of second conductive layer>
(Coating liquid A)
Polythiophene: PEDOT-PSS CLEVIOS PH510 1.59g
(Solid content 1.89%, manufactured by HC Starck)
P-1 solid content 20% aqueous dispersion 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
<Preparation of Transparent Electrodes TC-102 to TC-110>
In the production of the transparent electrode TC-101, the transparent electrode TC-102 to TC was produced in the same manner as the production of the transparent electrode TC-101 except that P-1 of the coating liquid A was changed to P-2 to P-10. -110 was produced.

<Preparation of transparent electrode TC-111>
In the production of the transparent electrode TC-104, PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) of the coating liquid A was added to polyaniline M (solid content concentration 6.0%, TAE Chemical). ) A transparent electrode TC-111 was produced in the same manner as the production of the transparent electrode TC-101 except that it was changed to 0.5 g.

<Preparation of transparent electrode TC-112>
(Random network structure)
On the said silver nanowire board | substrate which formed the random network structure with silver nanowire, the 2nd conductive layer was formed using the coating liquid which replaced P-1 of the coating liquid A with P-4, and it cut out to 8x8 cm. . Transparent electrode TC-112 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

<Preparation of Comparative Transparent Electrodes TC-113 to 117>
In the production of the transparent electrode TC-101, the comparative transparent electrode TC-113 was produced in the same manner as the production of the transparent electrode TC-101 except that P-1 in the coating liquid A was changed to HP-1 to HP-5. -TC-117 was produced.

<< Evaluation of transparent electrode >>
The film shape, transparency, surface resistance (conductivity) and film strength of the obtained transparent electrode were evaluated as follows. Further, in order to evaluate the stability of the transparent electrode, the film shape, transparency, surface resistance and film strength of the transparent electrode sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 3 days were evaluated.

(transparency)
Based on JIS K 7361-1: 1997, total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. Since it is used for an organic electronic device, it is preferably 75% or more.

◎: 80% or more ○: 75% to less than 80% △: 70% to less than 75% ×: less than 70% (surface resistance)
The surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.) in accordance with JIS K 7194: 1994. The surface resistance is preferably 100Ω / □ or less, and preferably 30Ω / □ or less in order to increase the area of the organic electronic device.

(Membrane strength)
The strength of the conductive layer film was evaluated by a tape peeling method.

    Crimping / peeling was repeated 10 times on the conductive layer using a Scotch tape manufactured by Sumitomo 3M Co., and the dropping of the conductive layer was visually observed and evaluated according to the following criteria.

◎: No change after 5 times of pressure bonding / peeling ○: No change after 3 times of pressure peeling / bonding △: Peeling is observed after 1 time of pressure peeling, but more than 80% pattern remains ×: 1 time of pressure peeling Peeling is observed, and the remaining pattern is less than 80%.

  From the results shown in Table 1, the transparent electrodes TC-101 to 112 are superior to the transparent electrodes TC-113 to TC-117 in terms of light transmittance, conductivity, and film strength, and in a high temperature and high humidity environment. It can be seen that there is little deterioration in light transmittance, conductivity, and film strength, and the stability is excellent.

Example 2
<< Production of organic EL devices >>
The prepared transparent electrode substrate was washed with ultrapure water, cut into a 30 mm square so that one square tile-shaped transparent pattern with a pattern side length of 20 mm was placed in the center, and used for the anode electrode, respectively. A device was fabricated. The hole transport layer and subsequent layers were formed by vapor deposition. Organic EL elements OEL-201 to OEL-217 were produced using transparent electrodes TC-101 to TC-117, respectively.

  Each crucible for vapor deposition in a commercially available vacuum vapor deposition apparatus was filled with a constituent material of each layer in a necessary amount for device production. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

  First, an organic EL layer including a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.

<Formation of hole transport layer>
After depressurizing to a vacuum of 1 × 10 ⁻⁴ Pa, the deposition crucible containing compound 1 was heated by energization, and deposited at a deposition rate of 0.1 nm / second to provide a 30 nm thick hole transport layer. It was.

<Formation of organic light emitting layer>
Next, each light emitting layer was provided in the following procedures.

  Compound 2, Compound 3 and Compound 5 are deposited on the formed hole transport layer so that Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass. Co-evaporation was performed in the same region as the hole transport layer at a speed of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.

  Next, compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass. Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.

<Formation of hole blocking layer>
Further, in the same region as the formed organic light emitting layer, the compound 6 was deposited to a thickness of 5 nm to form a hole blocking layer.

<Formation of electron transport layer>
Subsequently, in the same region as the formed hole blocking layer, CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm.

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

In addition, a flexible seal in which an adhesive is applied around the anode except for the end, 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 of organic EL elements >>
The obtained organic EL device was evaluated for light emission unevenness and lifetime as follows.

(Emission uniformity)
For light emission uniformity, a KEITHLEY source measure unit 2400 type was used to apply a DC voltage to the organic EL element to emit light. Regarding the organic EL elements OEL-201 to OEL-217 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. In addition, the organic EL elements OEL-201 to OEL-217 were heated in an oven at 60% RH and 80 ° C. for 2 hours, and then conditioned again in the environment of 23 ± 3 ° C. and 55 ± 3% RH for 1 hour or more. Thereafter, the emission uniformity was observed in the same manner.

A: Completely uniform light emission, satisfactory O: Almost uniform light emission, no problem Δ: Some light emission unevenness is observed partially, but acceptable X: Light emission unevenness is observed over the entire surface, not acceptable (lifespan)
The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL element having an anode electrode made of ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. 100% or more is preferable, and 150% or more is more preferable.

A: 150% or more B: 100 to less than 150% B: 80 to less than 100% X: less than 80% The results of evaluation are shown in Table 2.

  From Table 2, the comparative organic EL elements OEL-213 to OEL-217 are significantly deteriorated in light emission uniformity after heating at 80 ° C. for 2 hours, whereas the organic EL elements OEL-201 to OEL-212 of the present invention are significantly deteriorated. It can be seen that the light emission uniformity is stable even after heating and has excellent durability.

DESCRIPTION OF SYMBOLS 1 1st conductive layer which consists of metal material formed in pattern shape 2 2nd conductive layer containing binder resin and conductive polymer of this invention 3 Base material

Claims (4)

  In a transparent conductive film having a first conductive layer made of a metal material formed in a pattern on a substrate and a second conductive layer containing a conductive polymer and a partially esterified polycarboxylic acid resin, the partially esterified poly A transparent conductive film, wherein the carboxylic acid resin is a resin obtained by reacting an acetal compound with polycarboxylic acid.   The transparent conductive film according to claim 1, wherein the partially esterified polycarboxylic acid resin has a carboxy group concentration of 0.5 mmol / g to 5.0 mmol / g.   The polycarboxylic acid of the partially esterified polycarboxylic acid resin is selected from polyacrylic acid, polymethacrylic acid, polycarboxystyrene, and a copolymer thereof. 2. The transparent conductive film according to 2.   The organic electroluminescent element characterized by using the transparent conductive film of any one of Claims 1-3.

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