JP5741581B2 - Transparent conductive film and organic electroluminescence element - Google Patents

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. Also, roll-to-roll production technology using a flexible substrate has been desired along with an increase in display screen and productivity.

  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 Documents 1 and 2). 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 3). 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 Document 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, transparent films have been increasingly used from the viewpoint of flexibility and cost for transparent substrates, and when 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, Moisture remained in the transparent conductive film, and drying of the transparent conductive film was a problem.

JP 2005-302508 A JP 2009-87843 A JP 2009-4348 A Japanese Patent No. 3716167

  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 element that has high emission uniformity using the electrode, has little deterioration in emission uniformity, and has an excellent lifetime.

  Conventionally, the transparent conductive film coating solution contains a water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) and a 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 as a transparent substrate increases, 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 film deformation. As a result, it was difficult to remove moisture from the film due to the influence of the hydrophilic binder, and the device performance using these transparent conductive films was significantly deteriorated. As a result of diligent studies to improve these phenomena, the present invention has been completed using a binder resin containing a structural unit having a hydroxy group and a structural unit not containing a hydroxy group in the repeating unit of the binder.

  That is, the object of the present invention can be achieved by including a binder resin containing a structural unit having a hydroxy group in a repeating unit and a structural unit not containing a hydroxy group in the second conductive layer, as in the configuration of the present invention. As a result, the present invention has been achieved.

  The present invention uses a conductive polymer and a binder resin in which the number of hydroxy groups is controlled for the second conductive layer to achieve both transparency and conductivity of the transparent conductive film, and excellent film strength, and in a high temperature and high humidity environment. It has been found that a highly stable transparent electrode and a long-life organic electroluminescence device using the transparent electrode, which have both high conductivity, transparency and good film strength even after an environmental test, can be obtained. .

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

(1)
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, the second conductive layer is represented by the following general formula (I) A transparent resin containing a binder resin comprising a structural unit having a hydroxy group and a structural unit having no hydroxy group and having an ester or amide bond represented by the following general formula (II): Conductive film.

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group, — (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. And is a number from 1 to 100. ]

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group,-(CH2CHRbO) x-CH2CHRb-, and Rb represents a hydrogen atom or an alkyl group. x represents the average number of repeating units and is a number from 1 to 100. y represents 0 or 1; Z represents a hydrogen atom, an alkoxy group, —O—C (═O) —Rc, —O—SO 2 —Rd, or —O—SiRe 3. Rc, Rd, and Re represent a substituted or unsubstituted alkyl group or an aryl group. However, Ra and Z may be combined to form a morpholine ring with N-A2. ]
( 2 )
The transparent conductive film according to (1) above, wherein the molar ratio of the general formula (I) in the binder resin is 10 to 50%.

( 3 )
An organic electroluminescence device using the transparent conductive film according to (1) or (2) .

  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.

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.

  FIG. 1A is a top view of the transparent conductive film, and FIG. 1B is a cross-sectional view taken along line AA ′ of FIG.

  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 characteristic in the structure of this invention contains the binder resin containing the structural unit which has a hydroxyl group in a 2nd conductive layer, and the structural unit which does not have a hydroxyl group and has an ester or amide bond.

<< Second conductive layer >>
<Binder resin>
The binder resin according to the present invention is preferably a binder resin that dissolves about 0.001 g or more in 100 g of water at 25 ° C., and specifically has the following structure and has OH in an acidic group, etc. Is not included. The degree of solubility in water can be measured with a haze meter or a turbidimeter.

  The binder resin according to the present invention is preferably transparent, and specifically has a structure containing a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). desirable.

  In the structural unit having a hydroxy group represented by formula (I) of the present invention, R represents a hydrogen atom or a methyl group. Q represents —C (═O) O— or —C (═O) NRa—, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. These alkyl groups may be substituted with a substituent. Examples of these substituents include cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyl groups, Alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, arylcarbamoyl group , Alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl group, aryl Kishisuruhoniru group, an alkylsulfonyloxy group, an an aryl sulfonyloxy group.

  The number of carbon atoms of the cycloalkyl group is preferably 3-20, more preferably 3-12, and still more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkoxy group may have a branch, 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, and 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, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably. Examples of the alkylthio group include a methylthio group and an ethylthio group. The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group. The 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 morpholino 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, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group. The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like. The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamido group include a methanesulfonamido group and the like, and the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group. The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. 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, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group. The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group. The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group. The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group. The number of carbon atoms of 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 hydroxy group represented by formula (I) of the present invention, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x —CH ₂ CHRb—. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the above-described substituents. R _b represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Further, these alkyl groups may be substituted with the above-described substituents. Furthermore, 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 hydroxy group represented by the general formula (II) of the present invention, R, Q, Ra, A, Rb, and x have the same meanings as defined in the general formula (I).

In the structural unit having no hydroxy group represented by the general formula (II) of the present invention, y represents 0 or 1. Z represents a hydrogen atom, an alkoxy group, —O—C (═O) —Rc, —O—SO ₂ —Rd, or —O—SiRe ₃ . Rc, Rd and Re represent a substituted or unsubstituted alkyl 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, still more preferably a methyl group. is there. These alkyl groups may be substituted with the substituent described above. The alkyl group is preferably a halogen-substituted alkyl group, particularly preferably a perfluoroalkyl group, for example, preferably having 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably trifluoromethyl. It is a 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 and aryl groups may be substituted with the above-described substituents.

  Typical examples of the structural units represented by general formula (I) and general formula (II) are shown below, but the present invention is not limited thereto.

  The binder resin of the present invention may contain another structural unit other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). The binder resin of the present invention may be referred to as the hydroxy group-containing nonconductive polymer of the present invention.

  In the binder resin according to the present invention, the molar ratio of the structural unit having a hydroxy group represented by the general formula (I) is preferably 5 to 90%, more preferably 10 to 50%.

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

  The molecular weight of the binder resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, and still more preferably 5,000 to 100,000.

The number average molecular weight and molecular weight distribution of the binder 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 preferably 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, A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

(Π-conjugated conductive polymer precursor monomer)
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-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(Poly anion)
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. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

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

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

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

  Among these, the compound having a sulfonic acid is 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 before irradiating the microwave. May be. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These poly anions have high compatibility with the hydroxy group-containing non-conductive polymer of the present invention, and can further increase the conductivity of the obtained conductive polymer.

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

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

  Examples of the method for producing an anionic group-containing polymerizable monomer by polymerization include a method for producing an anionic group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.

  The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

  When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

  The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion”, is preferably 1: 1 to 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; carboxylic acid having 1 to 20 aliphatic 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 also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent 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 transmitting portion excluding the light non-transmitting 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. When the line width of the thin wire is 10 μm or more, desired conductivity can be obtained, and when it is 200 μm or less, high transparency can be obtained. The height of the thin wire is preferably 0.1 to 10 μm. By setting the height of the thin wire to 0.1 μm or more, desired conductivity is obtained, and by setting the height to 10 μm or less, current leakage and poor thickness distribution of the functional layer are reduced in the formation of the organic electronic device. .

  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, 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 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. 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. 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, although a single metal may be used, in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.

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

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

  Moreover, it is preferable to heat-process a 1st conductive layer in the range which does not damage a film substrate. Thereby, fusion of metal fine particles and metal nanowires progresses and the first conductive layer becomes highly conductive, which 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 the hydroxy group-containing non-conductive polymer of the present invention. 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.

  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-described 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 further characterized by including the hydroxy group-containing nonconductive polymer of the present invention. 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 ratio of the conductive polymer of the second conductive layer to the hydroxy group-containing nonconductive polymer of the present invention is 30 to 900 parts by mass of the hydroxy group-containing nonconductive polymer when the conductive polymer is 100 parts by mass. It is preferable that the hydroxy group-containing nonconductive polymer is 100 parts by mass or more from the viewpoints of preventing current leakage, the conductivity enhancing effect of the hydroxy group-containing nonconductive polymer, and transparency.

  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, organic solvents such as water, 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, excellent flexibility, a sufficiently small dielectric loss coefficient, and a conductive material whose microwave absorption is to be heated. There is no particular limitation as long as the material is smaller than the layer. 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%) measured by a method based on 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 ml / m ² · 24 h · atm or less, and the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 × 10 A high barrier film of ⁻³ g / (m ² · 24 h) or less is preferable.

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

《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 Rubrene, distyrylbenzene derivatives, di still arylene derivatives and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material.

  The organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.

  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.

  EXAMPLES 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 water-soluble binder resin>
Synthesis Example 1 (Synthesis of P-1: within the present invention)
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. I-1: 2-hydroxyethyl acrylate (1.74 g, 15 mmol, molecular weight: 116.05), II-6: Blemmer PME-200 (9.7 g, 35 mmol, molecular weight: 276.16), AIBN (0.8 g) 5 mmol, molecular weight: 164.11) was added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK (methyl ethyl ketone) 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 water-soluble binder resin P-1 having a number average molecular weight of 33700 and a molecular weight distribution of 2.4 was obtained.

  The 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: within the present invention)
Except for using I-5: Blemmer AE-90 (7.20 g, 45 mmol, molecular weight: 160.07), II-4: methoxyethoxyethyl acrylate (0.87 g, 5 mmol, molecular weight: 174.09) as monomers. By the same method as in Synthesis Example 1, 7.10 g (yield 88%) of water-soluble binder resin P-2 having a number average molecular weight of 29200 and a molecular weight distribution of 2.6 was obtained.

Synthesis Example 3 (Synthesis of P-3: within the present invention)
Except for using I-8: Blemmer AE-200 (7.10 g, 25 mmol, molecular weight: 284.16), II-21: N-methylacrylamide (2.13 g, 25 mmol, molecular weight: 85.05) as monomers. By the same method as in Synthesis Example 1, 7.75 g (yield 84%) of water-soluble binder resin P-3 having a number average molecular weight of 31700 and a molecular weight distribution of 2.1 was obtained.

Synthesis Example 4 (Synthesis of P-4: within the present invention)
Except that I-12: Blemmer PP-500 (3.04 g, 5 mmol, molecular weight: 608.41), II-7: Blemmer PME-400 (22.3 g, 45 mmol, molecular weight: 496.59) were used as monomers. In the same manner as in Synthesis Example 1, 22.0 g (yield 87%) of water-soluble binder resin P-4 having a number average molecular weight of 33200 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 5 (Synthesis of P-5: within the present invention)
I-13: Blemmer GLM (0.22 g, 1.5 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (23.4 g, 48.5 mmol, molecular weight: 482.27) were used as monomers. Except for the above, 21.0 g (yield 89%) of water-soluble binder resin P-5 having a number average molecular weight of 27600 and a molecular weight distribution of 3.1 was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 6 (Synthesis of P-6: within the present invention)
I-13: Blemmer GLM (0.37 g, 2.5 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (22.9 g, 47.5 mmol, molecular weight: 482.27) were used as monomers. In the same manner as in Synthesis Example 1, 19.8 g (yield 85%) of water-soluble binder resin P-6 having a number average molecular weight of 31100 and a molecular weight distribution of 2.9 was obtained.

Synthesis Example 7 (Synthesis of P-7: within the present invention)
Synthesis example except that I-13: Blemmer GLM (3.56 g, 25 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (12.1 g, 25 mmol, molecular weight: 482.27) were used as monomers. 1 and the number average molecular weight 23100
Thus, 14.3 g (yield 91%) of water-soluble binder resin P-7 having a molecular weight distribution of 2.7 was obtained.

Synthesis Example 8 (Synthesis of P-8: within the present invention)
Synthesis Example except that I-13: Blemmer GLM (5.84 g, 40 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (4.82 g, 10 mmol, molecular weight: 482.27) were used as monomers. In the same manner as in Example 1, 9.38 g (yield 88%) of water-soluble binder resin P-8 having a number average molecular weight of 25400 and a molecular weight distribution of 2.6 was obtained.

Synthesis Example 9 (Synthesis of P-9: within the present invention)
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 water-soluble binder resin Z having a number average molecular weight of 35700 and a molecular weight distribution of 2.3 was obtained.

A water-soluble binder resin Z3.0 g and dehydrated tetrahydrofuran 30 ml were charged into a 100 ml flask and completely dissolved, and then the internal temperature was reduced to 10 ° C. or lower with an ice bath. A solution prepared by dissolving trifluoromethanesulfonyl chloride (0.65 g, 3.9 mmol, molecular weight: 167.93) in 10 ml of dehydrated tetrahydrofuran was separately prepared, and dropped into the water-soluble binder resin Z solution over 30 minutes. The internal temperature was maintained at 10 ° C. or lower. After stirring for 1 hour after completion of the dropwise addition, the solution was filtered with a filter paper, and the resulting solution was concentrated to 10 ml by a rotary evaporator. The reaction solution was added dropwise to 300 ml of ethyl alcohol and stirred for 1 hour, 150 ml of diisopropyl ether was added, and the mixture was further stirred for 1 hour. After decantation of the solution, the polymer was washed with 100 ml of diisopropyl ether three times, and then the polymer was dissolved in THF and transferred to a 50 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, 2.91 g (yield 87%) of water-soluble binder resin P-9 having a number average molecular weight of 30700 and a molecular weight distribution of 2.1 was obtained. The structure was confirmed by ¹ H-NMR.

Synthesis Example 10 (Synthesis of P-10: within the present invention)
A number average molecular weight of 32200 and a molecular weight distribution of 2.200 were obtained in the same manner as in Synthesis Example 9 except that 4-methylbenzoyl chloride (0.30 g, 1.9 mmol, molecular weight: 154.02) was used instead of trifluoromethanesulfonyl chloride. Thus, 2.84 g (yield 90%) of water-soluble binder resin P-10 was obtained. The structure was confirmed by ¹ H-NMR.

Synthesis Example 11 (Synthesis of P-11: within the present invention)
I-15: N-methylolacrylamide (0.25 g, 2.5 mmol, molecular weight: 101.05), II-6: Blemmer PME-200 (13.1 g, 47.5 mmol, molecular weight: 276.16) as monomers 11.7 g of water-soluble binder resin P-11 having a number average molecular weight of 35,900 and a molecular weight distribution of 2.7 was obtained in the same manner as in Synthesis Example 1 except that it was used.
(Yield 88%).

Synthesis Example 12 (Synthesis of P-12: within the present invention)
Synthesis Example 1 except that I-19: hydroxyethylacrylamide (0.58 g, 5 mmol, molecular weight: 115.06) and II-24: acryloylmorpholine (6.35 g, 45 mmol, molecular weight: 141.08) were used as monomers. By the same method, 6.03 g (yield 87%) of water-soluble binder resin P-12 having a number average molecular weight of 35900 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 13 (Synthesis of P-13: outside the present invention)
4.50 g of binder resin P-13 having a number average molecular weight of 37000 and a molecular weight distribution of 2.7 was obtained in the same manner as in Synthesis Example 1 except that 5.06 g of only I-8 was used as a monomer (yield 89%). Obtained.

Synthesis Example 14 (Synthesis of P-14: outside the present invention)
4.80 g of binder resin P-14 having a number average molecular weight of 39000 and a molecular weight distribution of 2.8 was obtained in the same manner as in Synthesis Example 1 except that 5.33 g of II-7 alone was used as a monomer (yield 90%). Obtained.

Synthesis Example 15 (Synthesis of P-B: outside the present invention)
According to the same method as in Synthesis Example 1 except that 2-hydroxyethyl acrylate (3.48 g, 30 mmol, molecular weight: 116.05) and acrylic acid (2.16 g, 30 mmol, molecular weight: 72.02) were used as monomers. 4.29 g (yield 76%) of a binder resin P-B having a number average molecular weight of 37100 and a molecular weight distribution of 2.6 was obtained using a resin having a hydroxy group.

<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 held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

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

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

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

<Formation of first conductive layer>
A first conductive layer was formed on the non-barrier surface of the transparent electrode film substrate having gas barrier properties obtained above by the following method.

(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 K303MULTICOATOR 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>
The following coating liquid A is extruded 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, using an extrusion method so as to have a dry film thickness of 300 nm. The slit gap is adjusted and applied, and heated and dried at 110 ° C. for 5 minutes to form a second conductive layer made of a conductive polymer and a water-soluble binder resin P-1, and the obtained electrode is 8 × 8 cm. Cut out. 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
(Solid content 1.89%, manufactured by HC Starck) 1.59 g
P-1 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
(Preparation of transparent electrodes TC-102 to TC-112)
In the production of the transparent electrode 1, the transparent electrodes TC-102 to TC-112 were 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-12. Was made.

(Preparation of transparent electrode TC-113)
In the production of the transparent electrode 1, PEDOT-PSS CLEVIOS PH510 (solid content 1.89%, manufactured by HC Starck) of the coating solution A was added to polyaniline M (solid content concentration 6.0%, TA Chemical). A transparent electrode TC-113 was produced in the same manner as the production of the transparent electrode TC-101 except that the thickness was changed to 0.5 g.

(Preparation of transparent electrode TC-114)
(Random network structure)
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.

  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.

  On the transparent electrode in which a random network structure was formed by silver nanowires, the second conductive layer was formed using the coating liquid A, and cut into 8 × 8 cm. Transparent electrode TC-114 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

(Preparation of comparative transparent electrode TC-115)
In the production of the transparent electrode TC-101, a transparent electrode TC-115 was produced in the same manner as the production of the transparent electrode TC-101 except that P-1 in the coating solution A was changed to P-13.

(Preparation of comparative transparent electrode TC-116)
In the production of the transparent electrode TC-101, a transparent electrode TC-116 was produced in the same manner as the production of the transparent electrode TC-101 except that P-1 in the coating solution A was changed to P-14.

(Production of comparative transparent electrodes TC-117 and TC-118)
In the production of the transparent electrode 1, the P-1 of the coating solution A was changed to PA (poly (4-vinylpyridine) (manufactured by Polyscience)), P-B. Transparent electrodes TC-117 and TC-118 were produced in the same manner as the production.

<< Evaluation of transparent electrode >>
The film shape, transparency, surface resistance (conductivity) and film strength of the obtained transparent electrode were evaluated as follows. In addition, 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 114 are superior to the transparent electrodes TC-115 to TC-118 in terms of smoothness, conductivity and light transmittance, and in a high temperature and high humidity environment. It can be seen that there is little deterioration in smoothness, conductivity, and light transmittance, 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-218 were produced using transparent electrodes TC-101 to TC-118, 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, 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, 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.

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 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-218 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. Further, the organic EL elements OEL-201 to OEL-218 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-215 to OEL-218 significantly deteriorate in light emission uniformity after heating at 80 ° C. for 30 minutes, whereas the organic EL elements OEL-201 to OEL-214 of the present invention 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 (3)

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, the second conductive layer is represented by the following general formula (I) A transparent resin containing a binder resin comprising a structural unit having a hydroxy group and a structural unit having no hydroxy group and having an ester or amide bond represented by the following general formula (II): Conductive film.

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group, — (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. And is a number from 1 to 100. ]

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) x —CH ₂ CHRb—, and Rb represents a hydrogen atom or an alkyl group. x represents the average number of repeating units and is a number from 1 to 100. y represents 0 or 1; Z represents a hydrogen atom, an alkoxy group, —O— (C═O) —Rc, —O—SO ₂ —Rd, or —O—SiRe ₃ . Rc, Rd, and Re represent a substituted or unsubstituted alkyl group or an aryl group. Moreover, Ra and Z may combine to form a morpholine ring together with NA. ] The transparent conductive film according to claim 1, wherein the molar ratio of the general formula (I) in the binder resin is 10 to 50%. An organic electroluminescence device using the transparent conductive film according to claim 1 .