JP2012054085A - Method of preparing dispersion, transparent conductive film, method of forming transparent conductive film, and organic electroluminescence element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparing a dispersion for the transparent electrode which uses a versatile base material, is excellent in transparency, conductivity, and film strength, and hardly deteriorates in transparency, conductivity, and film strength even under a high-temperature and high-humidity environment, and to provide the transparent conductive film, a method of forming the transparent conductive film, and an organic electroluminescence element having the transparent electrode using the transparent conductive film formed by the method of forming the transparent conductive film.SOLUTION: The method of preparing a dispersion containing at least a conductive polymer and a polymer (K) having structural units represented by general formulae (I) and (II) is characterized in that the dispersion containing at least the conductive polymer and the polymer (K) is subjected to desolvation treatment.

Description

  The present invention relates to a method for preparing a dispersion for a transparent electrode, a transparent conductive film, which 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. The present invention relates to a method for forming a transparent electrode, and an organic electroluminescence element having a transparent electrode (hereinafter also referred to as an organic EL element).

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

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

  In recent years, a transparent conductive film using a conductive polymer has been studied so as to be compatible with such a product requiring a large area and a low resistance value. For example, it has a conductive surface consisting of a transparent conductive film using a conductive polymer such as polyaniline and polypyrrole and a fine wire structure formed in a pattern of metal and / or alloy, has high transmittance, and has a surface resistivity. A low-priced and inexpensive transparent conductive sheet is known (for example, see Patent Document 1).

  On the transparent film substrate, from the side close to the transparent film substrate, a conductive pattern formed from metallic silver, and a transparent conductive film comprising a polyethylenedioxythiophene-based or polyaniline-based conductive polymer compound thereon A transparent conductive film is known which is provided adjacent to each other and has small power loss even in a large area, high transparency, strong bending, and high resistance to corrosive gases such as NOx and SOx (for example, patents) Reference 2).

However, in the case of the transparent conductive sheet described in Patent Document 1, the transparent conductive film described in Patent Document 2 was found to have the following problems.
1. Since the film strength of the transparent conductive film is weak, when each layer constituting the organic EL element is deposited by vapor deposition or spin coating, the film surface is disturbed, and leakage occurs when the organic EL element is manufactured.
2. It is necessary to smooth the irregularities of the fine metal wires that cause the 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, resulting in a significant decrease in transparency.
3. Flexibility is inferior by increasing the thickness of the transparent conductive film.
4). Since it is inferior in water resistance, when it preserve | saves on high temperature and high humidity conditions, adhesiveness will worsen.

  Polythiophenes as a transparent conductive film having high light transmittance, low surface resistivity, and excellent flexibility, on a conductive metal having a fine-line structure portion of a network metal and / or alloy. Transparent conductive film having a structure of a transparent conductive film composed of a mixture of an electronic conductive conductivity such as polypyrroles and polyanilines and an insulating polymer such as an acrylic resin, an ester resin, a urethane resin, and a polyvinyl alcohol resin Is known (for example, Patent Document 3).

  However, in the case of the transparent conductive sheet described in Patent Document 3, the addition of an insulating polymer may cause a deterioration in optical performance such as haze from the viewpoint of a decrease in conductivity and compatibility with the conductive polymer. understood.

  Conductive polymer (3,4-polyethylenedioxythiophene polystyrene sulfonate (PEDT / PSS) and polyvinylpyrrolidone (PVP) as a binder, copolymer of poly (vinylpyridine) and poly (vinyl acetate) (PVPy-VAc) , Polymethacrylic acid (PMAA), a copolymer of poly (hydroxyethyl acrylate) and poly (methacrylic acid) (PHEA-MAA), poly (2-hydroxyethyl methacrylate), polyvinyl butyral (PVB) A method of forming an organic conductive layer by using a coating solution composed of a polymer or copolymer and a suitable solvent and baking in air at least at 450 ° C. is known (for example, Patent Document 4).

However, it has been found that the method for producing an organic conductive layer described in Patent Document 4 has the following drawbacks.
1. Due to the insufficient film strength of the organic conductive layer, the film surface is disturbed when stacking by vapor deposition or spin coating, and leakage occurs when an organic electronic device is manufactured.
2. The type of substrate that is not deformed by baking at 450 ° C. is limited and is not versatile.
3. 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 remains in the transparent conductive film, which deteriorates the performance of the organic electronic device, so that drying of the transparent conductive film has been a problem.

  From such a situation, a versatile substrate is used, and the transparency, conductivity and film strength are excellent, and the transparency, conductivity and film strength are hardly deteriorated even in a high temperature and high humidity environment. Development of an organic EL device having a transparent electrode having a transparent conductive film formed by a method for preparing a dispersion, a transparent conductive film, a method for forming a transparent conductive film, and a method for forming a transparent conductive film is desired.

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 problems, and an object of the present invention is to use a general-purpose substrate, which is excellent in transparency, conductivity, and film strength, and is transparent even in a high temperature and high humidity environment. A transparent electrode having a transparent conductive film formed by a method for preparing a dispersion for a transparent electrode with little deterioration in conductivity and film strength, a transparent conductive film, a method for forming a transparent conductive film, and a method for forming a transparent conductive film An organic EL element is provided.

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

1. A method for preparing a dispersion containing at least a conductive polymer and a polymer (K) having a structural unit represented by general formulas (I) and (II),
A method for preparing a dispersion, which comprises subjecting a dispersion containing at least the conductive polymer and the polymer (K) to a solvent removal treatment.

[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, and A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) x —. 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.

  2. 2. The dispersion according to 1 above, wherein in the polymer (K), the content ratio of the structural unit represented by the general formula (I) in the polymer (K) is from 95 to 95% in terms of molar ratio. Preparation method.

  3. A transparent conductive film formed on a substrate, wherein the transparent conductive film is formed by coating and drying using a dispersion prepared by the method for preparing a dispersion described in 1 or 2 above. A transparent conductive film characterized.

  4). 4. The transparent conductive film according to 3 above, wherein the transparent conductive film is formed on a metal conductive layer made of a conductive material formed in a pattern on a substrate.

5). A method for forming a transparent conductive film using the dispersion prepared by the method for preparing a dispersion described in 1 or 2,
Formation of a transparent conductive film comprising a preparation step for preparing the dispersion, a coating step for coating the dispersion on a substrate, and a drying step for drying the coating film formed in the coating step Method.

  6). It has the transparent electrode which has the transparent conductive film formed with the formation method of the transparent conductive film of said 5 using the dispersion liquid prepared with the preparation method of the dispersion liquid of said 1 or 2. Organic electroluminescence device.

  In the present invention, a transparent conductive film is formed using a dispersion obtained by removing a solvent from a dispersion containing a conductive polymer and a polymer (K) having the structural unit represented by the general formulas (I) and (II). This ensures both transparency and conductivity of the transparent conductive film, excellent film strength, and stability that combines high conductivity, transparency and good film strength even after environmental testing under high temperature and high humidity. It has been found that an excellent transparent electrode and a long-life organic electroluminescence device having the transparent electrode can be obtained.

  The reason is not clear, but when a dispersion containing a conductive polymer and a polymer (K) having the structural unit represented by the general formulas (I) and (II) is applied and heated, it is included in the dispersion. A cross-linking reaction between the polymers occurs, and moisture is generated at that time.

  If the dispersion is not heated sufficiently, it is presumed that the crosslinking reaction of the uncrosslinked portion proceeds during storage in a high temperature environment, and the generated moisture causes the performance degradation of the organic electroluminescence device.

  Therefore, although it is not clear as a reason, it apply | coats after performing the solvent removal process for the dispersion liquid containing a conductive polymer and the polymer (K) which has a structural unit represented by the said general formula (I), (II). By performing the drying, the cross-linking reaction between the polymers contained in the dispersion proceeds and a high-density three-dimensional structure is obtained, compared with the case where the dispersion is applied and dried as it is. It has been found that high conductivity, transparency and good film strength can be obtained even after an environmental test in a humidity environment, and as soon as the present invention has been achieved.

  A method for preparing a dispersion for a transparent electrode that uses a general-purpose substrate and is excellent in transparency, conductivity, and film strength, and has little deterioration in transparency, conductivity, and film strength even under high temperature and high humidity environments. The organic electroluminescent element which has a transparent electrode with the transparent conductive film formed by the transparent conductive film, the formation method of a transparent conductive film, and the formation method of a transparent conductive film was able to be provided.

FIG. 1 is a schematic sectional view showing an example of a transparent electrode.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.

  FIG. 1 is a schematic sectional view showing an example of a transparent electrode. Fig.1 (a) is a schematic sectional drawing which shows an example of the transparent electrode which has the electroconductive metal layer formed in pattern shape on the base material, and a transparent conductive film. FIG.1 (b) is a schematic sectional drawing which shows an example of the transparent electrode which has a transparent conductive film containing the conductive metal layer formed in pattern shape. FIG.1 (c) is a schematic sectional drawing which shows an example of the transparent electrode which has the transparent conductive film formed on the base material.

  A description will be given with reference to FIG.

  In the figure, 1a indicates a transparent electrode. The transparent electrode 1a includes a base material 1a1, a conductive metal layer 1a2 formed in a pattern on the base material 1a1, and a transparent conductive film 1a3.

  The transparent electrode 1a is formed by forming a conductive metal layer 1a2 in a pattern on a substrate 1a1, then applying a transparent conductive film forming dispersion (hereinafter also referred to as a dispersion), and drying the transparent conductive film 1a3. It can be manufactured by forming.

  A description will be given with reference to FIG.

  In the figure, 1b indicates a transparent electrode. The transparent electrode 1b includes a substrate 1b1 and a transparent conductive film 1b3 having a conductive metal layer 1b2 formed in a pattern. A conductive metal layer 1b2 and a dispersion liquid are applied to form a transparent conductive film 1b3 on a release surface of a release substrate (not shown), and then these layers are transferred onto a substrate for transfer. It is possible to manufacture. Alternatively, it can be manufactured by forming the conductive metal layer 1b2 on the release surface of the release substrate (not shown) and transferring it onto the transfer substrate, and then forming the transparent conductive film 1b3. Is possible.

  This will be described with reference to FIG.

  In the figure, 1c represents a transparent electrode. The transparent electrode 1c has a base material 1c1 and a transparent conductive film 1c2. The transparent electrode 1c can be manufactured by applying a dispersion liquid on the substrate 1c1 to form the transparent conductive film 1c2. Details of the material for forming the transparent conductive film and the manufacturing method will be described later.

  In the transparent electrode shown in FIGS. 1 (a) to 1 (c), the transparent electrode shown in FIGS. 1 (a) and 1 (b) having a conductive metal layer is made of a light opaque material made of a metal material. It is preferable because it becomes a transparent electrode having both the conductive metal layer and the translucent window portion, and an electrode having excellent transparency and conductivity can be produced.

  The present invention relates to an organic EL device using a transparent conductive film prepared by a method for preparing a dispersion constituting the transparent electrode shown in FIG. 1, a transparent conductive film, a method for manufacturing a transparent conductive film, and a method for manufacturing a transparent conductive film. It is about. Next, since the manufacturing method of the transparent conductive film constituting the transparent electrode shown in FIGS. 1 (a), 1 (b), and 1 (c) is the same, FIG. 1 (a) is representatively shown. The method for producing the transparent conductive film constituting the transparent electrode shown will be described.

The manufacturing method of a transparent conductive film A transparent conductive film is manufactured through the process of mixing the aqueous solution containing a conductive polymer and a polymer (K), a solvent removal process, an application | coating process, and a drying process. By forming the transparent conductive film of the present invention by such a manufacturing method, a strong film strength that cannot be obtained simply by applying and drying the conductive film can be obtained uniformly in the electrode surface, and high conductivity. High transparency can be obtained.

(Preparation process of dispersion for forming transparent conductive film)
In the step of preparing the dispersion for forming the transparent conductive film, the conductive polymer, the polymer (K), and the solvent are mixed to prepare a dispersion for forming the transparent conductive film.

  The solvent that dissolves the polymer (K) is preferably a solvent that can dissolve about 0.001 g of the polymer (K) in 100 g of a solvent at 25 ° C., and has high compatibility when mixed with a conductive polymer, and water is particularly preferable. The degree of solubility can be measured with a haze meter or a turbidimeter.

(Desolvation process)
The dispersion containing the conductive polymer and the polymer (K) is subjected to a solvent removal treatment in a solvent removal treatment step. The solvent removal treatment includes a treatment for removing the solvent by heating at atmospheric pressure, a treatment for removing the solvent by heating under reduced pressure conditions, and a treatment for removing the solvent without heating. In addition, the solvent removal treatment can be carried out at any one of a treatment for removing the solvent by heating at atmospheric pressure, a treatment for removing the solvent by heating under reduced pressure conditions, or a treatment for removing the solvent without heating. It is possible to select a treatment. The decompression conditions are preferably set appropriately according to the solvent used.

  The time for the solvent removal treatment is more preferably 5 minutes or more. There is no particular upper limit for the time, but considering productivity, it is preferably 360 minutes or less, and more preferably 120 minutes or less.

  The viscosity of the dispersion for forming the transparent conductive film after the solvent removal treatment is preferably 30 mPa · s to 2000 mPa · s in consideration of the strength, coating stability, flatness, etc. of the transparent conductive film. More preferably, it is from 80 mPa · s to 1000 mPa · s.

  The viscosity of the dispersion can be measured with a capillary viscometer, falling ball viscometer, rotational viscometer, vibration viscometer or the like.

  In the present invention, the viscosity is a value measured at a temperature of 25 ° C. by VISCOMATE MODEL VM-1G manufactured by Yamaichi Electronics Co., Ltd.

  The value of (viscosity after heat treatment) / (viscosity before heat treatment) is preferably 1.1 to 30, more preferably 2 in consideration of dispersion stability, coating stability, and the like. To 20 is preferable.

  The ratio of the conductive polymer to the polymer (K) is preferably 30 to 900 parts by mass when the conductive polymer is 100 parts by mass, preventing current leakage and the polymer (K). From the viewpoint of the conductivity enhancement effect and transparency, the polymer (K) is more preferably 100 parts by mass or more.

  The concentration of the dispersion for forming the transparent conductive film containing the conductive polymer and the polymer (K) is 0.5% to 50% in consideration of the flatness of the transparent conductive film, the coating unevenness of the conductive metal layer, and the like. % By mass is preferable, 2% by mass to 35% by mass is more preferable, and 3% by mass to 20% by mass is still more preferable.

  In this way, the solvent containing the conductive polymer and the polymer (K) is desolvated in the desolvation treatment step, so that a cross-linked structure is formed between the polymers (K), thereby performing the desolvation treatment step. In addition, it is estimated that the film strength, durability at the time of storage in a high-humidity environment are improved over the transparent conductive film formed by applying the dispersion and drying.

  For the solvent removal treatment of the dispersion for forming the transparent conductive film containing the conductive polymer and the polymer (K), it is preferable to concentrate the dispersion for forming the transparent conductive film using a rotary evaporator during heating. . The concentration rate is preferably 5% or more and less than 80%, more preferably 10% to 70%, and still more preferably 20% to 50%. If the concentration rate is too high, the viscosity becomes too high, and there is a problem that flatness deteriorates when coating is performed. If the concentration rate is low, it is difficult to obtain the effects of the present invention.

(Coating process)
In the coating step, the dispersion liquid subjected to the solvent removal treatment is applied on the substrate or on the conductive metal layer formed in a pattern on the substrate. The thickness of the transparent conductive film after drying the transparent conductive film is preferably 30 nm to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is further preferably 200 nm or more. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.

  In addition, when there is a conductive metal layer formed in a pattern, the conductive metal layer may be completely covered, or a part thereof may be covered and can be appropriately selected as necessary. is there.

  The application of the dispersion is not particularly limited. For example, in addition to a printing method such as a gravure printing method, a flexographic printing method, and a screen printing method, a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, Coating methods such as a die coating method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.

(Drying process)
In the drying step, the transparent conductive film-forming coating film formed by applying the dispersion liquid for forming the transparent conductive film in the coating step is dried to produce a transparent conductive film. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and a transparent conductive film. For example, a drying process can be performed at 80 to 270 ° C. for 10 seconds to 10 minutes.

  In the present invention, it is also preferable to perform microwave heat treatment. The microwave heat treatment time is preferably 1 second to 120 seconds in consideration of deformation of the substrate.

  By forming the transparent conductive film of the present invention by such a manufacturing method, strong film strength, high conductivity, and high transparency that cannot be obtained simply by applying and drying the dispersion for forming the transparent conductive film. The transparent conductive film which has can be obtained.

  Next, the conductive polymer and polymer (K) relating to the dispersion for forming the transparent conductive film of the present invention will be described.

(Polymer (K))
The polymer (K) has structural units represented by the above general formula (I) and general formula (II).

  In the formula, 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, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, 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.

  The alkyl 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 8. 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 cycloalkyl group preferably has 3 to 20 carbon atoms, 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, 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, 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 cycloalkoxy group preferably has 3 to 12 carbon atoms, 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. 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, 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, 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. 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 aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 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. 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. 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 has preferably 2 to 20 carbon atoms, 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. 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. 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, more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. 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.

A is a substituted or unsubstituted alkylene _group, - represents a (CH 2 CHRbO) x-. 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.

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.

  R, Q, and A in general formulas (I) and (II) may be the same or different.

  In the polymer (K) according to the present invention, the content ratio of the structural unit represented by the general formula (I) in the polymer (K) is preferably 3% to 95%, more preferably 5% of the whole by molar ratio. To 50%.

  By setting the general formulas (I) and (II) to the above ratio, the amount of water generated by the uncrosslinked hydroxyl group can be suppressed to a range that does not affect the device performance.

  The polymer (K) used in the present invention may contain other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

  As other structural units, polymerizable monomers copolymerizable with the structural units represented by the general formulas (I) and (II) are preferable, and examples thereof include styrene derivatives (for example, styrene, α-methylstyrene, o-methyl). Styrene, m-methylstyrene, p-methylstyrene, vinylnaphthalene, etc.), acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate and the like.

  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 number average molecular weight of the polymer (K) used in 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 5000 to 100,000. .

The number average molecular weight and molecular weight distribution of the polymer (K) used in 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 (K) is dissolved, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, more preferably THF and DMF, and still more preferably DMF. is there. The measurement temperature is not particularly limited, but 40 ° C. is preferable. The polymer (K) used in the present invention is preferably transparent.

  The term “transparent” means that the total light transmittance in the visible light wavelength region is 60% or more when the polymer (K) is made into an aqueous solution having a concentration of 10%.

(Production method of polymer (K))
The polymer (K) used in 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 carried out at -10 ° C to 250 ° C, preferably 0 ° C to 200 ° C, more preferably 10 ° C to 100 ° C.

<Conductive polymer>
The conductive polymer used in the present invention is a conductive polymer having a π-conjugated conductive polymer and a polyanion. Such a conductive polymer is 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. I can do it.

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

  Among these, the compound having a sulfonic acid is formed by applying and drying a conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more before irradiation with microwaves. 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 ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable. These poly anions have high compatibility with the polymer (K), 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 π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion”, is preferably 1: 1 to 20 by mass ratio. The range of 1: 2 to 10 is more preferable from the viewpoint of conductivity and dispersibility.

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 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; aliphatic carboxylic acids having 1 to 20 carbon atoms, such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as oxalic acid And especially the aromatic Fe (III) salts of optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms, such as benzenecene sulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

  Commercially available materials can be preferably used for such a conductive polymer. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. As a Clevios series from Starck, for example, CLEVIOS P AI4083, CLEVIOS P JET, CLEVIOS P CH8000, CLEVIOS HIL1.1, CLEVIOS HIL1.3, CLEVIOS HIL1.5, CLEVIOS P HC V4, CLEVIOS PH500, and CLEVIOS PH510 are available. ing.

  It is commercially available as PEDOT-PSS 483095, 560596 from Aldrich and as the Denatron series from Nagase Chemtex. Polyaniline is commercially available from Nissan Chemical Company as the ORMECON series.

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

  Next, the conductive metal layer used for the transparent electrode shown in FIGS. 1A and 1B will be described.

(Conductive metal layer)
The transparent conductive film according to the present invention preferably contains a conductive metal obtained by forming a metal material 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 conductive metal layer formed in a pattern on the substrate is formed from a metal material. 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.

  Although there is no restriction | limiting in particular in a pattern shape, For example, a conductive metal layer may be stripe shape, mesh shape, or random mesh shape.

  The method for forming the stripe-shaped or mesh-shaped electrode of the conductive portion is not particularly limited, and a conventionally known method can be used. For example, it can be formed by forming a metal layer on the entire surface of the substrate and using a known photolithography method. Specifically, a conductive metal layer is formed on the entire surface of the substrate using a physical or chemical forming method such as printing, vapor deposition, sputtering, or plating, or a metal foil is applied to the substrate with an adhesive. After laminating, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an inkjet 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 No. 2009-140750 and Examples. About the method of carrying out the gravure printing of the catalyst ink and performing a plating process, it can implement 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 is used. I can do it.

  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.

In order to form a long conductive path with one metal nanowire, the metal nanowire preferably has an average length of 3 μm or more, more preferably 3 μm to 500 μm, and particularly preferably 3 μm 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 nm to 300 nm, and more preferably 30 nm 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 g / m ² to 0.5 g / m ^2, more preferably 0.01 g / m ² 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, a single metal may be used, but in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. 2002, 14, 833 to 837, Chem. Mater. 2002, 14, 4736 to 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.

  The conductive metal layer is preferably heat-treated within a range that does not damage the film substrate. Thereby, fusion of metal fine particles and metal nanowires proceeds and high conductivity is obtained, which is particularly preferable.

(Additives added to the dispersion for forming the transparent conductive film)
The dispersion liquid containing the conductive polymer and the polymer (K) according to the present invention is a transparent non-conductive polymer, additive, or cross-linking agent as long as the conductive layer has conductivity, transparency, and smoothness at the same time. It may contain.

  In the present invention, it is also possible to use an acid catalyst in the dispersion for forming a transparent conductive film containing a conductive polymer and a polymer (K). It is estimated that the use of an acid catalyst promotes the crosslinking reaction between the conductive polymer and the polymer (K). As the acid catalyst, hydrochloric acid, sulfuric acid, or ammonium sulfate can be used.

  Moreover, in the polyanion used as a dopant for a conductive polymer, a dopant and a catalyst can be used together by using a sulfo group-containing polyanion. In addition, the use of an acid catalyst is preferable because it leads to shortening of the microwave processing time.

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

  As the crosslinking agent, for example, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a hole mualdehyde crosslinking agent, or the like can be used alone or in combination. .

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

  In addition, as the synthetic polymer resin, transparent thermoplastic resin (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. The non-conductive polymer is preferably transparent.

(Base material)
There is no restriction | limiting in particular as a board | substrate used for the transparent electrode of this invention. Preferred examples include flexible glass, a glass substrate, a resin substrate, and a resin film in terms of excellent hardness, ease of forming a conductive layer on the surface, light transparency, and the like.

  There is no restriction | limiting in particular in the transparent resin film which can be used by this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known transparent resin films. 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. Any resin film having a transmittance of 80% or more at a visible wavelength (380 nm to 780 nm) is preferably used as the film substrate used in the present invention. Among these, 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.

  In order to ensure the wettability and adhesiveness of the dispersion liquid for forming the transparent conductive film, the substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer. 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 base material, and the water vapor transmission rate (25 ± 0.00%) measured by a method according to JIS K 7129-1992. 5 ° C., relative humidity (90 ± 2)% RH) is preferably a barrier film of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and further conforms to JIS K 7126-1987. The oxygen permeability measured by the method is 1 × 10 ⁻³ 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 It is preferably a high-barrier substrate of ⁻³ g / (m ² · 24 h) or less.

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

(Organic EL device)
The organic EL device of the present invention has an organic layer including an organic light emitting layer and the transparent electrode of the present invention. The organic EL device of 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 for organic EL devices. I can do it.

  The element configuration of the organic EL element is as follows: 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, etc. I can do it.

  In addition, as the light emitting material or doping material that can be used in the organic light emitting layer in the present invention, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex, Aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone, ru Ren, distyrylbenzene derivatives, di still arylene derivatives, and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material.

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

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

  The transparent electrode using the transparent conductive film 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, and inorganic solar cells. In addition, it can be suitably used in fields such as an electromagnetic wave shield and a touch panel. Among them, it can be particularly preferably used as a transparent electrode of an organic EL device or an organic thin film solar cell device in which the smoothness of the surface of the transparent electrode is strictly required.

Examples The present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited by the description of these examples.
<Synthesis of polymer (K)>
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)
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. I-1: 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, 3.18 g (yield 87%) of water-soluble binder resin P-2 having a number average molecular weight of 30700 and a molecular weight distribution of 2.1 was obtained.

Synthesis Example 3 (Synthesis of P-3: within the present invention)
A number average molecular weight of 32,200 and a molecular weight distribution of 2.200 were obtained in the same manner as in Synthesis Example 2 except that p-toluenesulfonyl chloride (0.30 g, 1.9 mmol, molecular weight: 154.02) was used instead of trifluoromethanesulfonyl chloride. Thus, 2.97 g (yield 90%) of water-soluble binder resin P-3 was obtained.

Synthesis Example 4 (Synthesis of P-4: within the present invention)
As monomers, I-1: 2-hydroxyethyl acrylate (0.17 g, 1.5 mmol, molecular weight: 116.05), II-19: N, N-diethylmethacrylamide (6.17 g, 48.5 mmol, molecular weight: 5.4 g (yield 85%) of water-soluble binder resin P-4 having a number average molecular weight of 32,500 and a molecular weight distribution of 2.7 was obtained in the same manner as in Synthesis Example 1, except that 127.18) was used.

Synthesis Example 5 (Synthesis of P-5: within the present invention)
As monomers, I-1: 2-hydroxyethyl acrylate (0.29 g, 2.5 mmol, molecular weight: 116.05), II-19: N, N-diethylmethacrylamide (6.04 g, 47.5 mmol, molecular weight: A water-soluble binder resin P-5 having a number average molecular weight of 31300 and a molecular weight distribution of 2.5 was obtained in the same manner as in Synthesis Example 1 except that 127.18) was used.

Synthesis Example 6 (Synthesis of P-6: within the present invention)
As monomers, I-1: 2-hydroxyethyl acrylate (2.9 g, 25 mmol, molecular weight: 116.05), II-19: N, N-diethylmethacrylamide (3.18 g, 25 mmol, molecular weight: 127.18) A water-soluble binder resin P-6 having a number average molecular weight of 34000 and a molecular weight distribution of 2.6 was obtained in the same manner as in Synthesis Example 1 except that was used.

Synthesis Example 7 (Synthesis of P-7: within the present invention)
As monomers, I-1: 2-hydroxyethyl acrylate (5.51 g, 47.5 mmol, molecular weight: 116.05), II-19: N, N-diethylmethacrylamide (0.32 g, 0.25 mmol, molecular weight: In the same manner as in Synthesis Example 1 except that 127.18) was used, 5.2 g (yield 90%) of water-soluble binder resin P-7 having a number average molecular weight of 33400 and a molecular weight distribution of 2.6 was obtained.

Synthesis Example 8 (Synthesis of P-8: within the present invention)
Except for using I-1: 2-hydroxyethyl acrylate (1.74 g, 15 mmol, molecular weight: 116.05), II-22: acryloylmorpholine (4.94 g, 35 mmol, molecular weight: 141.14) as monomers. By the same method as in Synthesis Example 1, 6.0 g (yield 90%) of water-soluble binder resin P-8 having a number average molecular weight of 31600 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 9 (Synthesis of P-9: within the present invention)
Synthesis Example except that I-13: Blemmer GLM (2.19 g, 15 mmol, molecular weight: 146.06), II-7: Blemmer AE-400 (16.89 g, 35 mmol, molecular weight: 482.59) were used as monomers. 1, 16.6 g (yield 87%) of water-soluble binder resin P-9 having a number average molecular weight of 36,500 and a molecular weight distribution of 2.8 was obtained.

Synthesis Example 10 (Synthesis of P-10: within the present invention)
Synthesis Example 1 except that I-6: (2.61 g, 15 mmol, molecular weight: 174.19) and II-6: Blemmer PME-200 (9.67 g, 35 mmol, molecular weight: 276.33) were used as monomers. By the same method, 10.8 g (yield 88%) of water-soluble binder resin P-10 having a number average molecular weight of 35200 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 11 (Synthesis of P-11: within the present invention)
Except for using I-19: hydroxyethylacrylamide (1.73 g, 15 mmol, molecular weight: 115.13), II-1: 2-methoxyethyl acrylate (4.55 g, 35 mmol, molecular weight: 130.14) as monomers. In the same manner as in Synthesis Example 1, 5.4 g (yield 86%) of water-soluble binder resin P-11 having a number average molecular weight of 30400 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 12 (Synthesis of P-12: within the present invention)
I-19: hydroxyethylacrylamide (1.73 g, 15 mmol, molecular weight: 115.13), II-19: N, N-diethylmethacrylamide (4.94 g, 35 mmol, molecular weight: 130.14) were used as monomers. 5.6 g (yield 84%) of water-soluble binder resin P-12 having a number average molecular weight of 31600 and a molecular weight distribution of 3.1 was obtained in the same manner as in Synthesis Example 1 except for the above.

Synthesis Example 13 (Synthesis of P-13: within the present invention)
Except for using I-5: Blemmer AE-90 (7.21 g, 45 mmol, molecular weight: 160.17) and II-4: methoxyethoxyethyl acrylate (0.87 g, 5 mmol, molecular weight: 174.19) 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.

<Comparison>
Synthesis Example 14 (Synthesis of P-14: outside the present invention)
4.50 g of binder resin P-14 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 15 (Synthesis of P-15: outside the present invention)
4.80 g of binder resin P-15 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.

<Production of film substrate>
Average after drying UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7501) manufactured by JSR Co., Ltd. on the surface of 100 μm thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) Apply with a wire bar to a film thickness of 4μm, dry at 80 ° C for 3 minutes, and then cure under an air atmosphere using a high-pressure mercury lamp under curing conditions of 1.0 J / cm ² to form a smooth layer did. Next, a gas barrier layer was formed on the smooth layer under the following conditions to produce a film substrate.

(Gas barrier layer coating solution)
A 20% by weight dibutyl ether solution of perhydropolysilazane ((PHPS), AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) was applied with a wireless bar so that the (average) film thickness after drying was 0.30 μm. After that, a drying process, a dehumidification process, and a modification process described below were sequentially performed to form a gas barrier layer.

(Drying process)
The treatment was performed for 1 minute in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH.

(Dehumidification treatment)
The treatment was performed for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.).

(Modification process)
The dew point temperature during the reforming treatment was -8 ° C.

Reforming apparatus: excimer irradiation apparatus MODEL manufactured by M.D. Co., Ltd .: MECL-M-1-200, wavelength 172 nm, lamp gas: Xe
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)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1%
Excimer irradiation time: 3 seconds <Formation of conductive metal layer>
A conductive metal layer having a fine wire lattice and a random network structure was formed on the surface of the film substrate having the gas barrier layer thus prepared on which the gas barrier layer was not formed by the following method.

(Thin wire grid)
The fine wire lattice (metal material) was produced by gravure printing as shown below.

(Gravure printing)
After silver nanoparticle paste 1 (M-Dot SLP manufactured by Mitsuboshi Belting Co., Ltd.) is printed on a thin wire grid having a line width of 50 μm, a height of 1.5 μm, and an interval of 1.0 mm using a gravure printing tester K303MULTICATOR manufactured by RK Print Coat Instruments Ltd. , 110 ° C. for 5 minutes.

(Random network structure)
For a random network structure, a silver nanowire dispersion liquid is used as shown below, and applied using a bar coating method so that the amount of silver nanowires is 0.06 g / m ² and dried at 110 ° C. for 5 minutes. Prepared by heating.

  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 prepared. 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>
A coating liquid containing the conductive polymer prepared by the method described below and the polymer (K) of the present invention is formed on the produced thin wire grid conductive metal layer using an extrusion head so that the dry film thickness becomes 300 nm. The film was applied by adjusting the slit gap of the extrusion head, heated and dried at 110 ° C. for 5 minutes to form a transparent conductive film, and the obtained electrode was cut into 8 × 8 cm. Transparent electrode TC-101 was produced by heating the obtained electrode using an oven at 110 ° C. for 30 minutes.

<Formation of transparent conductive film>
(Preparation of coating solution A)
The following components were mixed, and the viscosity before heating at a liquid temperature of 25 ° C. was measured using a vibration viscometer Model VM-1G manufactured by Yamaichi Electronics Co., Ltd. Next, the solvent was removed at 100 ° C. while reducing the pressure with a rotary evaporator until the viscosity became 110 cp.

  In addition, the viscosity before reduced pressure and heat treatment was 60 cp.

Polythiophene: PEDOT-PSS CLEVIOS PH510 1.59g
(Solid content 1.89%, manufactured by HC Starck)
P-1 (20% solid content aqueous solution) 0.35 g
Dimethyl sulfoxide (DMSO) 0.08g
(Preparation of transparent electrodes TC-102 to TC-117, comparative transparent electrodes TC-134 and 135)
In the production of the transparent electrode TC-101, the transparent electrodes TC-102 to TC- were prepared in the same manner as the production of the transparent electrode TC-101 except that the P-1 and the viscosity of the coating liquid A were changed as shown in Table 1. 117 and comparative transparent electrodes TC-134 and 135 were produced.

(Preparation of transparent electrode TC-118)
In the production of the transparent electrode TC-101, the polythiophene of the coating solution was changed to 0.5 g of polyaniline M (solid content concentration 6.0%, manufactured by TA Chemical Co., Ltd.), and P-1 of the coating solution A was changed to P- A transparent electrode TC-118 was produced in the same manner as the production of the transparent electrode TC-101 except that the viscosity was changed to 5 and the viscosity was as shown in Table 1.

(Preparation of transparent electrode TC-119)
In the production of the transparent electrode TC-101, the coating liquid is used on the metal conductive layer having a random network structure of the film substrate having the metal conductive layer having a random network structure instead of the film substrate having the first conductive layer in the form of a fine line lattice. A transparent electrode TC-119 was produced in the same manner as the production of the transparent electrode TC-101 except that P-1 was changed to P-5 and the viscosity was as shown in Table 1.

(Preparation of transparent electrode TC-120)
In the production of the transparent electrode 1, the first conductive layer is not formed by gravure printing on the film substrate for the transparent electrode, P-1 of the coating liquid A is changed to P-5, and the viscosity is as shown in Table 1. A transparent electrode TC-120 was produced in the same manner as in the production of the transparent electrode TC-101, except for the above.

(Production of comparative transparent electrodes TC-121 to 133, 136, 137)
In the production of the transparent electrode TC-101, the coating solution A was applied without removing the solvent, and P-1 of the coating solution was as shown in Table 1, and was the same as the transparent electrode TC-101. Thus, transparent electrodes TC-121 to 133, 136 and 137 were produced.

(Evaluation)
Table 2 shows the results of evaluating the transparency, surface resistance, and film strength of each of the produced transparent electrodes TC-101 to TC-137 by the following methods. In addition, in order to evaluate the stability of the transparent electrode, the results of evaluating the 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 85 hours by the same method are shown. 1 and Table 2 show.

(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.

Evaluation rank of transparency ◎: 80% or more ○: 75% or more, less than 80% △: 70% or more, 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 20Ω / □ 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. Using a Scotch tape manufactured by Sumitomo 3M Co., Ltd. on the conductive layer, press the film with the belly of the finger and peel it off at right angles to the coating surface with the end of the tape. Observed and evaluated according to the following criteria.

◎: No change after repeated crimping / peeling 5 times or more ○: No change until 4 times of crimping / peeling △: Peeling is observed after 2 or 3 times of crimping / peeling, 8 More than 10% of the pattern remains ×: Peeling is observed after one press-release, and the remaining pattern is less than 80%

  The present invention prepared by using a dispersion containing a conductive polymer and a polymer (K) having the structural units represented by the general formulas (I) and (II) described in the text, after removing the solvent. The transparent electrodes TC-101 to 120 are superior to the comparative transparent electrodes TC-121 to 137 in transparency, surface resistance and film strength, and are transparent, surface resistance and film strength even in high temperature and high humidity environments. It can be seen that there is little deterioration of the material and it is excellent in stability. The effectiveness of the present invention was confirmed.

Example 2
(Production of organic EL element)
Each transparent electrode No. 1 produced in Example 1 was used. The film on which TC-101 to TC-137 were formed was washed with ultrapure water, and then cut into a 30 mm square so that one square tile-shaped transparent pattern having a pattern side length of 20 mm was placed in the center to obtain a transparent electrode substrate. Each transparent electrode No. Using TC-101 to TC-137 as an anode electrode, an organic EL device having a structure of hole transport layer / organic light emitting layer / hole blocking layer / electron transport layer / cathode electrode / sealing layer in the following procedure Produced, No. From OEL-201 to OEL-237.

  The hole transport layer, organic light emitting layer, hole blocking layer, electron transport layer, and cathode electrode were formed by vapor deposition.

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

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

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

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

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

<Formation of electron transport layer>
Subsequently, in the same region as the formed hole blocking layer, CsF (cesium fluoride) 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 mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as a cathode forming material having a transparent electrode as an anode and an anode external takeout terminal of 15 mm × 15 mm, and a cathode having a thickness of 100 nm Formed.

Furthermore, a flexible seal in which an adhesive is applied to the periphery of the anode except for the end, and polyethylene terephthalate is used as a base material and Al ₂ O ₃ is deposited to 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 layer, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

(Evaluation)
Each produced organic EL element No. Table 3 shows the results of evaluating the light emission unevenness and the lifetime of OEL-201 to OEL-237 by the method shown below and evaluating according to the evaluation rank shown below.

(Emission uniformity evaluation method)
The light emission uniformity was obtained by applying a direct current voltage to the organic EL element using a source measure unit type 2400 manufactured by KEITHLEY. Light was emitted at 1000 cd / m ² , and each light emission uniformity was observed with a 50 × microscope. Further, after heating in an oven at 80 ° C. and 60% RH for 36 hours, the humidity was adjusted again for 1 hour or more in the environment of 23 ± 3 ° C. and 55 ± 3% RH, and the emission uniformity was observed in the same manner. .

Evaluation rank of light emission uniformity ◎: Completely uniform light emission, satisfactory ○: Almost uniform light emission, no problem △: Some uneven light emission is observed, but acceptable ×: Over the entire surface Unevenness due to uneven emission (life evaluation method)
The obtained organic EL device was allowed to emit light continuously 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.

  The luminance was measured with a spectral radiance meter CS-2000 manufactured by Konica Minolta Sensing Co., Ltd.

Evaluation rank of life ◎: 150% or more ○: 100 or more, less than 150% △: 80 or more, less than 100% ×: less than 80%

  From Table 3, the organic EL elements OEL-221 to 237 using the comparative transparent electrode are significantly deteriorated in light emission uniformity and life after heating at 80 ° C. and 60% RH for 36 hours, whereas the transparent electrode of the present invention is used. It can be seen that the light emission uniformity and life of the organic EL elements OEL-201 to OEL-220 are stable even after heating and have excellent durability. The effectiveness of the present invention was confirmed.

1a, 1b, 1c Transparent electrode 1a1, 1b1, 1c1 Base material 1a2, 1b2 Conductive metal layer 1a3, 1b3, 1c2 Transparent conductive film D Width E Height

Claims (6)

A method for preparing a dispersion containing at least a conductive polymer and a polymer (K) having a structural unit represented by general formulas (I) and (II),
A method for preparing a dispersion, which comprises subjecting a dispersion containing at least the conductive polymer and the polymer (K) to a solvent removal treatment.

[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, and A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) x —. 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.   2. The dispersion according to claim 1, wherein in the polymer (K), the content ratio of the structural unit represented by the general formula (I) in the polymer (K) is from 95 to 95% in terms of molar ratio. Liquid preparation method.   A transparent conductive film formed on a substrate, wherein the transparent conductive film is formed by coating and drying using a dispersion prepared by the method for preparing a dispersion according to claim 1 or 2. A transparent conductive film.   The transparent conductive film according to claim 3, wherein the transparent conductive film is formed on a metal conductive layer made of a conductive material formed in a pattern on a substrate. A method for forming a transparent conductive film using the dispersion prepared by the method for preparing a dispersion according to claim 1,
Formation of a transparent conductive film comprising a preparation step for preparing the dispersion, a coating step for coating the dispersion on a substrate, and a drying step for drying the coating film formed in the coating step Method.   It has the transparent electrode which had the transparent conductive film formed with the formation method of the transparent conductive film of Claim 5 using the dispersion liquid prepared with the preparation method of the dispersion liquid of Claim 1 or 2. An organic electroluminescence element.

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