WO2012039240A1

WO2012039240A1 - Method for producing transparent electrode and organic electronic device

Info

Publication number: WO2012039240A1
Application number: PCT/JP2011/069413
Authority: WO
Inventors: 孝敏末松; 昌紀後藤
Original assignee: コニカミノルタホールディングス株式会社
Priority date: 2010-09-24
Filing date: 2011-08-29
Publication date: 2012-03-29
Also published as: JPWO2012039240A1; JP5983408B2

Abstract

The purpose of the present invention is to provide a method for producing a transparent electrode having superior conductivity, transparency, resistance to washing, and surface uniformity, and having superior drive voltage when used in an organic electronic device. The purpose is also to provide an organic electronic device using the same. This method for producing a transparent electrode is a method for producing a transparent electrode that has a patterned conductive layer on a transparent substrate and a transparent conductive layer containing at least a conductive polymer and a nonconductive polymer that contains a hydroxyl group. The method is characterized by the patterned conductive layer being a metal oxide or a metal material. The method is also characterized by the nonconductive polymer that contains a hydroxyl group being a polymer (A) containing a structural unit selected from general formula (I) and general formula (II) and the transparent conductive layer being formed by heat treatment in a temperature range of 150°C - 300°C.

Description

Method for producing transparent electrode and organic electronic device

TECHNICAL FIELD The present invention relates to a method for producing a transparent electrode excellent in electrical conductivity, transparency, washing resistance, and current uniformity, and excellent in driving voltage when used in an organic electronic device, and an organic electronic device using the same. It is.

In recent years, organic electronic devices such as organic EL and organic solar cells have attracted attention. In such devices, transparent electrodes have become an indispensable constituent technology. Conventionally, a transparent electrode is an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate by a vacuum deposition method or a sputtering method. From the viewpoint of performance such as conductivity and transparency, It has been mainly used. However, the transparent electrode using the vacuum evaporation method or the sputtering method has a problem that the production cost is high because of poor productivity. Furthermore, in recent years, transparent electrodes used in organic electronic devices have been required to have a large area and a low resistance value, and the resistance value of ITO transparent electrodes has become insufficient.

A transparent conductive layer, such as a conductive polymer, is laminated on a thin metal wire formed in a pattern so that it can be used for products that require a large area and low resistance. Transparent with both current surface uniformity and high conductivity An electrode has been developed (see, for example, Patent Documents 1 and 2). In such a configuration, the transparent electrode is composed of an opening made of a thin metal wire portion and a transparent conductive layer such as a conductive polymer. From the viewpoint of current surface uniformity, the resistance of the transparent conductive layer is preferably as low as possible. As the resistance of the transparent conductive layer is lower, even if the area of the opening is increased, the surface uniformity of the current can be maintained, so that an electrode having a large opening and excellent transparency can be produced. Moreover, in such a structure, it is necessary to smooth the unevenness | corrugation of the metal fine wire which causes the leak of an organic electronic device with transparent conductive layers, such as a conductive polymer. Therefore, it is essential to increase the thickness of the transparent conductive layer such as a conductive polymer. At this time, if the transparent conductive layer is made thick by using a conductive polymer, there is a problem that the transparency of the transparent electrode is remarkably lowered due to coloring of the conductive polymer and the performance of the organic electronic device is deteriorated.

As a method for reducing the coloring of the transparent conductive layer, it is known to use a polymer obtained by mixing a conductive polymer and a hydroxyl group-containing non-conductive polymer as the transparent conductive layer. As the hydroxyl group-containing non-conductive polymer compatible with the conductive polymer, a polymer selected from the group consisting of polyvinyl alcohol (PVA), polymethacrylic acid (PMAA) and the like is disclosed (for example, Patent Document 3, 4). However, when these were used as a transparent conductive layer, there was a problem that the conductivity decreased more than the ratio of the conductive polymer due to the addition of the nonconductive polymer. Moreover, in the transparent electrode which used these together with the metal fine wire, there existed a subject that a drive voltage became high in an organic electronic device. Furthermore, when a part of the hydroxyl group-containing non-conductive polymer is heated, the non-conductive polymer is colored, and there is a problem that the transparency of the transparent electrode is lowered.

JP 2005-302508 A JP 2009-87843 A Japanese Patent Laid-Open No. 2001-115098 Japanese Patent No. 3716167

The present invention has been made in view of the above problems, and its purpose is to provide excellent conductivity, transparency, washing resistance, surface uniformity of current, and a transparent electrode excellent in driving voltage when used in an organic electronic device. And an organic electronic device using the same.

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

1. In the method for producing a transparent electrode having a patterned conductive layer and a transparent conductive layer containing at least a conductive polymer and a hydroxyl group-containing non-conductive polymer on a transparent substrate, the patterned conductive layer is a metal oxide or a metal material, and the hydroxyl group The contained nonconductive polymer is a polymer (A) containing a structural unit selected from the following general formula (I) and general formula (II), and the transparent conductive layer is heated in a temperature range of 150 ° C. or higher and 300 ° C. or lower. A method for producing a transparent electrode, characterized by being formed by processing.

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and Q ₁ and Q ₂ each independently represent —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom, an alkyl _group, A 1, _{A 2} each independently represent a substituted or unsubstituted alkylene _{_{_{group, - (CH 2 CHRbO) x}}} -, - (CH 2 CHRbO) x represents a -CH 2 CHRb-. Rb represents a hydrogen atom or an alkyl group, and x represents the average number of repeating units. y represents 0 or 1; Z represents an alkyl group, —C (═O) —Rc, —SO ₂ —Rd, —SiRe ₃ . Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, and an aryl group. When the constituent ratio of the structural unit of the general formula (I) in the polymer (A) is m and the constituent ratio of the structural unit of the general formula (II) is n, the constituent ratio (mol%) of m + n is 50 ≦ m + n ≦ 100 and m / (m + n) ≧ 0.2. ]
2. 2. The method for producing a transparent electrode according to 1 above, wherein the metal material is metal fine particles or metal nanowires.

3. An organic electronic device using the transparent electrode manufactured by the manufacturing method according to 1 or 2 above.

INDUSTRIAL APPLICABILITY According to the present invention, a method for producing a transparent electrode that can be suitably used for an organic electronic device, has excellent conductivity, transparency, washing resistance, and surface uniformity of current, and has excellent driving voltage when used in an organic electronic device. Could be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventor uses a conductive polymer and a conventional hydroxyl group-containing non-conductive polymer by using the polymer (A) as the conductive polymer and the hydroxyl group-containing non-conductive polymer. In this case, the decrease in transparency due to coloring and the decrease in conductivity due to the addition of a nonconductive polymer can be suppressed. Furthermore, when a transparent conductive layer composed of a conductive polymer and a polymer (A) is formed by heat treatment, it is found that when used in an organic electronic device, a transparent electrode excellent in driving voltage can be obtained. It is up to you.

(Transparent substrate)
The transparent substrate used in the present invention is not particularly limited as long as the substrate is not deformed even if a high temperature treatment at 150 ° C. or higher is performed, and a material having a glass transition temperature (Tg) of 150 ° C. or higher is preferably used. The material, shape, structure, thickness, hardness and the like can be appropriately selected from known materials, but preferably have high transparency. Examples thereof include a glass substrate and a polyimide film, but a glass substrate is more preferable from the viewpoints of transparency, heat resistance, ease of handling, and barrier properties.

The transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and 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. Further, when the transparent substrate is a film, a barrier coat layer may be formed in advance as necessary, or a hard coat layer may be formed in advance. As the barrier coat layer, an inorganic film, an organic film or a hybrid film of both may be formed on the front surface or the back surface, and the water vapor transmission rate (25 ± 0) measured by a method according to JIS K 7129-1992. 0.5 ° C. and relative humidity (90 ± 2)% RH) is preferably a transparent substrate having a barrier property of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and JIS K 7126- Oxygen permeability measured by a method according to 1987 is 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

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

(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-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-hexyl Offene, 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-diethoxythio , 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyl Oxythiophene, 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-anilinesulfonic acid, 3-anili Sulfonic acid and the like.

(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. It is a polymer and has at least a structural unit having an anionic group.

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

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

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned.

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

Further, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate sulfonic acid are preferable. These poly anions have high compatibility with the hydroxyl group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.

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

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

Examples of the method for producing an 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 the π-conjugated conductive polymer and the poly anion contained in the conductive polymer, “π-conjugated conductive polymer”: “poly anion” is preferably 1: 1 to 20 by 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 hemiesters having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexyl carboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic, optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms such as benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid Fe (III) salts.

Such a conductive polymer is preferably a commercially available material. 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 and 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 the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone, and the like. 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.

(Hydroxyl-containing non-conductive polymer)
The hydroxyl group-containing non-conductive polymer according to the present invention is characterized by containing a certain amount of the polymer (A). In the present invention, it is possible to improve the conductivity of the conductive polymer-containing layer by using the conductive polymer and the polymer (A) in combination with the transparent conductive layer, and the compatibility with the conductive polymer is also good. Can achieve high transparency. As a result, the thickness of the transparent conductive layer can be increased, and foreign matter adhering to the substrate surface and unevenness of the pattern conductive layer can be embedded without reducing the transparency. Can be suppressed. Further, the hydroxyl group-containing non-conductive polymer of the present invention is preferably water-soluble, and the polymer (A) is preferably dissolved in 0.001 g or more in 100 g of water at 25 ° C. The solubility can be measured with a haze meter or a turbidimeter. Further, when the polyanion has a sulfo group, the sulfo group effectively acts as a dehydration catalyst, and the conductive polymer and the polymer (A) are densely cross-linked without using an additional agent such as a cross-linking agent. A layer can be formed, and a strong transparent conductive layer can be formed. Therefore, it has high durability and is advantageous when cleaning the substrate. Crosslinking can be measured by a change in glass transition temperature and nanoindentation elastic modulus of the transparent conductive layer, and a change in functional group by FTIR measurement.

(Polymer (A))
The polymer (A) according to the present invention is a polymer containing a structural unit selected from the following general formula (I) and general formula (II).

When the constituent ratio of the structural unit of the general formula (I) in the polymer (A) is m and the constituent ratio of the structural unit of the general formula (II) is n, the constituent ratio (mol%) of m + n is 50 ≦ m + n ≦ 100 and m / (m + n) ≧ 0.2.

In the polymer (A), the total of the components of the structural unit of the general formula (I) and the general formula (II) is 50 mol% or more and 100% or less, and the component of the structural unit of the general formula (I) is 20% or more. It is a copolymer. More preferably, the sum of the components of the structural units of the general formulas (I) and (II) is 80 mol% or more and 100% or less.

The polymer (A) of the present invention may contain a structural unit other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

Moreover, when the component of the structural unit of the general formula (I) in the polymer (A) is less than 20%, the number of hydroxyl groups decreases, the number of hydroxyl groups as crosslinking points decreases, and the stability and denseness of the film decrease. Deterioration in water resistance and lifespan.

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

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As an example of the substituent, the alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and more preferably 1 to 8. Further preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.

The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, preferably an ethoxy group. The alkylthio group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6, Most preferred is 1 to 4. Examples of the alkylthio group include a methylthio group and an ethylthio group. The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms of the cycloalkoxy group is preferably 3 to 12, and more preferably 3 to 8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group. The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group. The heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the heteroaryl group include a thienyl group and a pyridyl group. The acyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group. The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like. The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonamide group include a methanesulfonamide group. The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamido group include a benzenesulfonamido group and p-toluenesulfonamido group. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group. The acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group. The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group. The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group. The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

The number of carbon atoms in the arylsulfonyloxy group is preferably 6-20, and more preferably 6-12. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

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

In the structural unit having no hydroxyl group represented by the general formula (II) of the present invention, Ra, Rb, and x have the same meaning as defined in the general formula (I).

In the structural unit having no hydroxyl group represented by formula (II) of the present invention, y represents 0 or 1. Z represents an alkyl group, —C (═O) —Rc, —SO ₂ —Rd, —SiRe ₃ , and the alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group And more preferably a methyl group. These alkyl groups may be substituted with the substituent described above. Rc, Rd and Re represent an alkyl group, a perfluoroalkyl group or an aryl group, and the alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. . These alkyl groups may be substituted with the substituent described above. The perfluoroalkyl group preferably has, for example, 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably a trifluoromethyl group. The aryl group is preferably, for example, a phenyl group or a toluyl group, and more preferably a toluyl group. Furthermore, these alkyl groups, perfluoroalkyl groups, and aryl groups may be substituted with the above-described substituents.

Polymer (A) can be obtained by copolymerization of monomers (I) and (II) whose main copolymerization components form structural units represented by general formulas (I) and (II), respectively.

The polymer (A) of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.

The number average molecular weight of the 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 in the range of 5,000 to 100,000.

The number average molecular weight and molecular weight distribution of the polymer (A) 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 polymer (A) is dissolved, and THF, DMF, and CH ₂ Cl ₂ are preferable, THF and DMF are more preferable, and DMF is more preferable. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

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

In the number average molecular weight of the polymer (A), the content of the molecular weight of 1000 or less is 0 to 5% by mass or less. For example, a redispersion method or preparative GPC is synthesized by synthesizing a monodisperse polymer by living polymerization. A method of removing the low molecular weight component or suppressing the generation of the low molecular weight component can be used. In the reprecipitation method, the polymer is dissolved in a solvent in which the polymer can be dissolved and dropped into a solvent having a lower solubility than the solvent in which the polymer is dissolved, thereby precipitating the polymer and removing low molecular weight components such as monomers, catalysts, and oligomers. It is a method to do. Further, preparative GPC can be separated by molecular weight by, for example, recycling preparative GPCLC-9100 (manufactured by Nippon Analytical Industrial Co., Ltd.), polystyrene gel column, and passing the polymer-dissolved solution through the column. It is a method that can be removed. 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 amount of monomer added, for example, if a polymer having a molecular weight of 20,000 is synthesized, the production of low molecular weight substances can be suppressed. From the viewpoint of production suitability, reprecipitation and living polymerization are preferred.

The molecular weight distribution of the polymer (A) according to the present invention is preferably 1.01 to 1.30, more preferably 1.01 to 1.25. The molecular weight distribution is represented by a ratio of (weight average molecular weight / number average molecular weight).

Content with molecular weight of 1000 or less was converted to a ratio by integrating the area of molecular weight of 1000 or less and dividing by the area of the entire distribution in the distribution obtained by GPC.

The ratio of the conductive polymer to the polymer (A) is preferably from 30 to 900 parts by mass of the polymer (A) when the conductive polymer is 100 parts by mass. From the viewpoint of properties, the polymer (A) is more preferably 100 to 900 parts by mass.

(Heat treatment)
The heat treatment in the present invention is performed at 150 ° C. or higher and 300 ° C. or lower. When the transparent conductive layer containing the conductive polymer and the polymer (A) is formed by heat treatment in a temperature range of 150 ° C. or more and 300 ° C. or less, the drive voltage is lowered when used for an organic electronic device. Although the details of the principle about lowering the driving voltage are unknown, by treating the transparent conductive layer made of the polymer (A) and the conductive polymer at a high temperature, the polymer between the polymer in the transparent conductive layer and the patterned conductive layer is removed. This is thought to be because some kind of reaction occurs, making it easier to make contacts at the molecular level and creating a conductive path. Further, by treating at a high temperature, the film structure of the transparent conductive layer is stabilized, and becomes a dense film, so that it becomes strong, has an excellent cleaning resistance, and has an electrode with little deterioration under a high temperature environment.

If the heat treatment temperature is less than 150 ° C., the drive voltage does not decrease because the reaction between the transparent conductive layer and the patterned conductive layer is insufficient. Furthermore, moisture remains in the transparent conductive layer, deteriorating the life of the organic electronic device and the storage stability at high temperatures. In addition, when heat treatment is performed at a temperature higher than 300 ° C., a part of the bond of the conductive polymer starts to break and the resistance increases, so that it cannot be suitably used for an organic electronic device.

The heat treatment method is not particularly limited as long as it can be performed at 150 ° C. or more and 300 ° C. or less, and a known treatment method can be used. For example, a heater, an IR heater, vacuum heating, etc. can be mentioned, but it is not limited to this. The heat treatment time is preferably 10 seconds or longer and 30 minutes or shorter, and more preferably 10 seconds or longer and 10 minutes or shorter. When the heat treatment time is 10 seconds or more, the moisture in the transparent conductive layer can be sufficiently reduced, and deterioration of the lifetime of the organic electronic device can be prevented. On the other hand, when the heat treatment is performed for 30 minutes or less, it is possible to prevent partial bond of the transparent conductive layer from starting to be broken and to prevent the resistance from being affected.

(Pattern conductive layer)
The patterned conductive layer according to the present invention is characterized in that a metal material or a metal oxide is formed in a pattern on a substrate. A known metal oxide such as ITO or IZO may be used for the pattern conductive layer, or a metal material may be used. When a metal oxide is used, the transparency is superior to that using a metal material, but inferior to a metal material from the viewpoint of the resistance of the transparent electrode. Therefore, a metal material is more preferable for producing a large-area transparent electrode.

When a metal material is used for the pattern conductive layer, it becomes a substrate having both a light-impermeable conductive portion made of a metal material and a light-transmitting window portion, and an electrode substrate excellent in conductivity can be manufactured. 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.

Desirable conductivity is obtained by setting the line width of the fine wire to 10 μm or more, and transparency is improved by setting the line width to 200 μm or less. The height of the fine wire is preferably 0.1 to 10 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity can be obtained, and if it is 10 μm or less, it causes current leakage and poor function layer thickness distribution in the formation of organic electronic devices. Can be prevented.

There is no particular limitation on the method for forming the stripe-shaped or mesh-shaped electrode of the conductive part, 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, plating, etc., 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, for example, referring to paragraphs 0076 to 0112 of JP2009-140750A and examples. The method for carrying out the plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, JP-A-2007-281290.

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 for 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.

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

As the metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. The average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. The basis weight of the metal nanowire is preferably 0.005 to 0.5 g / m ² , and more preferably 0.01 to 0.2 g / m ² .

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

The method for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas 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 line portion of the pattern conductive layer is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less for increasing the area. The surface specific resistance can be measured, for example, according to JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

Further, it is preferable to heat the pattern conductive layer. Thereby, fusion of metal fine particles and metal nanowires proceeds and the pattern conductive layer becomes highly conductive, which is particularly preferable. The heating temperature is preferably 150 ° C. or higher and 500 ° C. or lower, and more preferably 200 ° C. or higher and 350 ° C. or lower, if it is metal fine particles.

(Transparent conductive layer)
The transparent conductive layer may completely cover the patterned patterned conductive layer, or may partially cover or contact it. The transparent conductive layer is formed into a film by applying and drying a dispersion containing a conductive polymer and polymer (A). In addition to the above-mentioned printing methods such as gravure printing method, flexographic printing method, screen printing method, the application of the transparent conductive layer is performed by roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, Coating methods such as blade coating, bar coating, gravure coating, curtain coating, spray coating, doctor coating, and ink jet can be used. Moreover, after forming a film | membrane by apply | coating and drying a transparent conductive layer to a transfer film, a pattern conductive layer may be formed and transcribe | transferred to a transparent substrate.

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

The transparent conductive layer is further characterized by containing a polymer (A). Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength 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 dry film thickness of the transparent 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 applying the transparent conductive layer, it can be appropriately dried. It is preferable to heat at a temperature equal to or lower than the heat treatment temperature as a drying treatment condition. For example, a drying treatment at 80 to 120 ° C. for 1 minute or more and 10 minutes or less can be performed. In this invention, after completion | finish of drying, by further heat-processing, the resistance of a transparent conductive layer can be lowered | hung and the water | moisture content in a transparent conductive layer can fully be reduced. Furthermore, the film structure of the transparent conductive layer is stabilized and strengthened by processing at a high temperature. In addition, the resistance is remarkably improved by heating the electrode. With these effects, particularly in the case of an organic EL element, effects such as improvement of life and improvement of storage stability of the element under a high temperature environment can be obtained.

The dispersion containing the conductive polymer and the polymer (A) according to the present invention is a transparent non-conductive polymer, additive or cross-linking agent as long as the conductivity, transparency and smoothness of the conductive layer are simultaneously satisfied. It may contain.

As the transparent non-conductive polymer, a wide variety of natural polymer resins or synthetic polymer resins can be 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, urethane Resin, vinyl acetate resin and the like can be used.

Synthetic polymer resins include transparent thermoplastic resins (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride), A transparent curable resin (for example, a melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, or a silicone resin such as an acrylic-modified silicate) that can be cured by heat, light, electron beam, or radiation can be used.

Examples of additives 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, organic solvents such as water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.

As the crosslinking agent for the polymer (A), for example, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an aldehyde crosslinking agent, or the like is used alone or in combination. be able to.

(Organic electronic devices)
The transparent electrode of the present invention can be used for various organic electronic devices. An organic electronic device has an anode electrode and a cathode electrode on a support, and has at least one organic functional layer between the electrodes. Examples of the organic functional layer include, but are not particularly limited to, an organic light emitting layer, an organic photoelectric conversion layer, and a liquid crystal polymer layer. INDUSTRIAL APPLICABILITY The present invention is particularly effective when the functional layer is a thin film and is an organic light emitting layer or an organic photoelectric conversion layer that is a current-driven device, and can be applied to organic electronic devices such as organic EL devices and solar cells.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<< Preparation of conductive layer >>
The following coating liquids A to I are applied onto a glass substrate by adjusting the slit gap of the extrusion head so as to have a dry film thickness of 300 nm using an extrusion method, and heated at 100 ° C. for 1 minute to form a conductive layer A. ~ I.

(Coating liquid A)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%) (manufactured by HC Starck) 2.00 g
Dimethyl sulfoxide (DMSO) 0.08g
(Coating solution B)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
P-1 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
(Coating liquid C)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
P-2 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
(Coating liquid D)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
P-3 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
(Coating fluid E)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%) (manufactured by HC Starck) 1.59 g
Polyvinyl alcohol PVA-235 (manufactured by Kureha) 2% solid content aqueous solution 3.50 g
Dimethyl sulfoxide (DMSO) 0.20g
(Coating fluid F)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%) (manufactured by HC Starck) 1.59 g
Polyvinylpyrrolidone K15 (viscosity average molecular weight 10,000, Tokyo Chemical Industry Co., Ltd.) 2% solid content aqueous solution 3.50 g
Dimethyl sulfoxide (DMSO) 0.20g
(Coating liquid G)
PEDOT-PSS CLEVIOS PH750 (solid content concentration 1.03%) (manufactured by HC Starck) 3.27 g
Dimethyl sulfoxide (DMSO) 0.13g
(Coating liquid H)
PEDOT-PSS CLEVIOS PH750 (solid content concentration 1.03%) (manufactured by HC Starck) 2.92 g
P-1 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.13g
(Coating liquid I)
PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
P-4 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
Synthesis of polymer (A) <Synthesis of polymer (A)>
Synthesis Example 1 (Synthesis of P-1 as polymer (A))
After adding 200 ml of THF to a 500 ml three-necked flask and heating to reflux for 10 minutes, it was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (10.0 g, 86 mmol, molecular weight: 116.05) and AIBN (1.41 g, 8.5 mmol, molecular weight: 164.11) were added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was added dropwise into 5000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed 3 times with 200 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 9.0 g (yield 90%) of P-1 having a number average molecular weight of 35,700 and a molecular weight distribution of 2.3 was obtained.

Molecular weight was measured by GPC (Waters 2695, manufactured by Waters).

<GPC measurement conditions>
Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Synthesis Example 2 (Synthesis of P-2 as polymer (A))
P-2 was obtained in the same manner as in Synthesis Example 1 except that hydroxymethyl acrylate was used as a monomer.

Synthesis Example 3 (Synthesis of P-3 as polymer (A))
After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (4.1 g, 35 mmol, molecular weight: 116.05), Bremmer PME-900 (7.4 g, 15 mmol, molecular weight: 496.29), AIBN (0.8 g, 5 mmol, molecular weight: 164.11) ) And heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed 3 times with 100 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 10.3 g (yield 90%) of P-3 having a number average molecular weight of 33700 and a molecular weight distribution of 2.4 was obtained.

Synthesis Example 4 (Synthesis of P-4)
After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (0.6 g, 5 mmol, molecular weight: 116.05), Bremer PME-900 (21 g, 45 mmol, molecular weight: 496.29), AIBN (0.8 g, 5 mmol, molecular weight: 164.11). The mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed 3 times with 100 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 17.3 g (yield 80%) of P-4 having a number average molecular weight of 34500 and a molecular weight distribution of 2.3 was obtained.

(Production of electrodes 1 to 24)
Conductive layers A to I were heat-treated at the following temperatures to prepare electrodes 1 to 24, respectively. The heating time was 2 minutes.
The conductive layer A was heated at 150 ° C. and 200 ° C. to form electrodes 1 and 2.
Conductive layer B was heated at 130 ° C., 150 ° C., 200 ° C., 250 ° C., 300 ° C., and 330 ° C. to form electrodes 3-8.
The conductive layer C was heated at 200 ° C. and 250 ° C. to form electrodes 9 and 10.
The conductive layer D was heated at 200 ° C. and 250 ° C. to form electrodes 11 and 12.
The conductive layer E was heated at 150 ° C., 200 ° C., and 250 ° C. to form electrodes 13 to 15.
The conductive layer F was heated at 150 ° C., 200 ° C., and 250 ° C. to form electrodes 16 to 18.
The conductive layer G was heated at 200 ° C. and 250 ° C. to form electrodes 19 and 20.
The conductive layer H was heated at 200 ° C. and 250 ° C. to form electrodes 21 and 22.
The conductive layer I was heated at 200 ° C. and 250 ° C. to form electrodes 23 and 24.

<< Evaluation of electrodes 1 to 24 >>
The transparency, conductivity, and water washing resistance of the obtained electrode were evaluated as follows.

(transparency)
Total light transmittance was measured using a 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 80% or more.

○: 80% or more △: 75% to less than 80% ×: 70% to less than 75% × ×: 0% to less than 70% (conductivity)
The surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The surface resistance is preferably 1500Ω / □ or less, and more preferably 1000Ω / □ or less in order to increase the area of the organic electronic device.

◎: Less than 1000Ω / □ ○: 1000-1500Ω / □ Less than: 1500-3000Ω / □ Less than: 3000-10000Ω / □ Less than ×: 10000Ω / □ (Membrane cleaning resistance)
The cleaning liquid is ultra-pure water prepared using Milli-Q water production equipment Milli-Q Advantage (Nippon Millipore Corporation). A substrate is attached to the cleaning liquid for 10 minutes, and the surface of the transparent conductive layer is not visually disturbed. The following criteria evaluated.

○: None ×: Available Table 1 summarizes the contents of the samples such as the conductive polymer, non-conductive polymer, and heat treatment used for the electrodes 1 to 24 and the evaluation results.

From Table 1, it can be seen that the conductive polymer alone has poor transparency when it is thickened, and the layer has insufficient cleaning resistance (electrodes 1, 2, 19, 20). Moreover, when PVA and PVP other than a polymer (A) are used for a hydrophilic group containing nonelectroconductive polymer, it turns out that electroconductivity and transparency are bad. Furthermore, even when the structural unit according to the present invention is included, when the composition ratio is out of the range (m / (m + n) = 0.1), it is understood that good results cannot be obtained (electrode 23, 24). On the other hand, it can be seen that in the case of the present invention electrode obtained by using the polymer (A) as the hydrophilic group-containing non-conductive polymer and heat-treated at a high temperature, a transparent electrode excellent in transparency, conductivity and washing resistance can be obtained.

In addition, when the conductive layer 1-24 described above was formed on a glass substrate on which the same Ag thin wire with the same pattern was formed, and the transparency and washing resistance were evaluated, the transparency decreased in transmittance by the loss of the Ag thin wire. As a result, the correlation between the evaluation results was the same as in Table 1, and the cleaning resistance was the same as in Table 1.

<Production of organic EL device>
Next, pattern conductive layers of Ag fine wire lattice, ITO, and silver nanowire were formed on a glass substrate by the following method, and ITO was sputtered as a takeout electrode so as to be connected to the pattern electrode. Further, using the above-described coating liquids A to F, a transparent conductive layer was laminated on the pattern electrode layer by 300 nm by the above-described method, and excess portions were wiped off before heating. Then, the organic EL electrodes 1 to 14 were prepared by performing heat treatment at various temperatures for 2 minutes. Further, the organic EL devices 1 to 14 were formed by using the organic EL electrodes 1 to 14 by the following method so as to have a combination of the composition of the substrate and the conductive layer shown in Table 2 and the heat treatment temperature. Details of the production will be described below.

(Ag fine wire grid)
A thin wire grid was created in the center of a 3 cm square glass substrate with a size of 1.5 cm × 1.5 cm. The fine wire lattice (metal material) was produced by the inkjet method shown below.

(Inkjet method)
A silver nanoparticle ink (Harima NPS-J manufactured by Harima Kasei Co., Ltd.) is used as an ink jet recording head, and has a pressure applying means and an electric field applying means, and has a nozzle diameter of 25 μm, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi Is an ink jet printing apparatus equipped with a piezo head of 1 inch, that is, 2.54 cm), and the line width is within a range of 1.5 cm × 1.5 cm at the center of a 3 cm square glass substrate. After printing a thin wire grid having a thickness of 50 μm, a height of 0.5 μm, and an interval of 1.0 mm, a drying process was performed at 220 ° C. for 60 minutes.

(Silver nanowires)
A random network structure was prepared using silver nanowires in a 1.5 cm × 1.5 cm central portion of a 3 cm square glass substrate.

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. The excess part was wiped off.

Silver nanowire dispersions are available from Adv. Mater. , 2002, 14, 833 to 837 with reference to the method described in 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 off using a filtration membrane, washed, and then redispersed in an aqueous solution containing 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a silver nanowire dispersion. did.

(ITO substrate)
An ITO (indium tin oxide) film having a thickness of 150 nm was formed on a 3 cm square glass substrate by a sputtering method to form an ITO substrate, and was patterned by a photolithographic method so that the ITO remained in a central area of 15 mm × 15 mm.

<< Production of organic EL devices >>
After the produced organic EL electrodes 3 to 14 were washed with ultrapure water, organic EL devices were produced as anode electrodes by the following procedure. The hole transport layer and subsequent layers were formed by vapor deposition. The electrodes 1 and 2 laminated with the conductive polymer were not cleaned because a part of the conductive layer was peeled off by cleaning. After cleaning, the organic EL electrodes 1 to 14 were subjected to the same treatment to produce organic EL devices 1 to 14, respectively.

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

First, an organic EL layer composed of a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed in a range of a central portion of 17 mm × 17 mm.

<Formation of hole transport layer>
After reducing the vacuum to 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 rate 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, a hole blocking layer was formed by depositing compound 6 in a thickness of 5 nm on the same region as the formed organic light emitting layer.

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

<Formation of cathode electrode>
On the formed electron transport layer, Al was deposited as a cathode forming material of 17 mm × 17 mm under a vacuum of 5 × 10 ⁻⁴ Pa to form a cathode having a thickness of 100 nm.

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 of organic EL devices >>
For each of the obtained organic EL devices 1 to 14, the surface uniformity of the current, the driving voltage, the lifetime, and the storage stability under high temperature conditions were evaluated as follows.

(Surface uniformity of current)
The surface uniformity of the current was determined by evaluating the light emission uniformity. Using a source measure unit type 2400 manufactured by KEITHLEY, a direct current voltage was applied to each organic EL element to emit light so that the luminance became 1000 cd / m ² , and the light emission state was visually evaluated according to the following criteria.

○: Uniform light emission, no problem ×: Light emission unevenness is partially observed (drive voltage)
An organic EL device made of ITO instead of a transparent electrode for organic EL prepared as an anode electrode was prepared by the same method as described above, with the voltage when light was emitted at an initial luminance of 5000 cd / m ² as a drive voltage, and the ratio to this Was evaluated using the following indicators. It is preferably less than 95% and more preferably less than 90%.

◎: Less than 90% ○: 90 to less than 95% △: Less than 95 to 100% ×: 100% or more (Life)
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 device made of ITO instead of the transparent electrode for organic EL prepared as the anode electrode was prepared 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.

◎: 150% or more ○: 100 to less than 150% △: 80 to less than 100% ×: less than 80% (preservability)
Store in a constant temperature bath at 80 ° C. It was taken out from the thermostatic chamber every 12 hours, an initial voltage of 1000 cd / m ² light emission was applied, the luminance at that time was measured, the time when the luminance was reduced by half was evaluated, and the storage time was taken. An organic EL device made of ITO instead of the organic EL transparent electrode prepared as the anode electrode was prepared in the same manner as described above, the ratio to this was determined, and the following indicators were evaluated. 100% or more is preferable, and 120% or more is more preferable.

◎: 120% or more ○: 100 to less than 120% △: 80 to less than 100% ×: less than 80% For the organic EL devices 1 to 14, the surface uniformity of the current, the lifetime, and the luminance preservability under high temperature conditions The results of evaluation are summarized in Table 2 together with the substrate, the composition of the conductive layer, and the heat treatment temperature conditions.

From Table 2, when a conductive polymer alone (organic EL devices 1 and 2) or a non-conductive polymer not containing a hydroxyl group and a conductive polymer are used in combination (organic EL device 12) or a hydroxyl group-containing non-conductive that does not apply to the polymer (A) When the conductive polymer and the conductive polymer are used in combination (organic EL device 11), it can be seen that the drive voltage is high. Moreover, it turns out that the lifetime of an organic EL and the preservability are bad by the influence of the foreign material and the poor transparency by a conductive polymer alone (organic EL devices 1 and 2). In addition, when PVA or PVP other than the polymer (A) is used for the hydrophilic group-containing non-conductive polymer, light emission is not uniform because of poor conductivity. Furthermore, since transparency is bad, efficiency will worsen and lifetime will worsen. On the other hand, when the transparent electrode of the present invention formed by using the polymer (A) as the hydrophilic group-containing non-conductive polymer and heat-treated is used, the driving voltage is low, and the light emission uniformity, life and storage stability are excellent. It can be seen that an organic EL device can be obtained.

Claims

In the method for producing a transparent electrode having a patterned conductive layer and a transparent conductive layer containing at least a conductive polymer and a hydroxyl group-containing non-conductive polymer on a transparent substrate, the patterned conductive layer is a metal oxide or a metal material, and the hydroxyl group The contained nonconductive polymer is a polymer (A) containing a structural unit selected from the following general formula (I) and general formula (II), and the transparent conductive layer is heated in a temperature range of 150 ° C. or higher and 300 ° C. or lower. A method for producing a transparent electrode, characterized by being formed by processing.

[Wherein, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and Q 1 and Q 2 each independently represent —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, and A 1 and A 2 each independently represents a substituted or unsubstituted alkylene group, — (CH 2 CHRbO) x —, — (CH 2 CHRbO) x —CH 2 CHRb—. Rb represents a hydrogen atom or an alkyl group, and x represents the average number of repeating units. y represents 0 or 1; Z represents an alkyl group, —C (═O) —Rc, —SO 2 —Rd, —SiRe 3 . Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, and an aryl group. When the constituent ratio of the structural unit of the general formula (I) in the polymer (A) is m and the constituent ratio of the structural unit of the general formula (II) is n, the constituent ratio (mol%) of m + n is 50 ≦ m + n ≦ 100 and m / (m + n) ≧ 0.2. ]
The method for producing a transparent electrode according to claim 1, wherein the metal material is metal fine particles or metal nanowires.
An organic electronic device using the transparent electrode manufactured by the manufacturing method according to claim 1 or 2.