JP6024351B2 - Conductive film, organic electroluminescence element, and method of manufacturing conductive film - Google Patents

Description

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

  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 flat-screen TVs. In any of these displays with different display methods, the transparent electrode is an essential constituent technology. In addition, transparent electrodes are an indispensable technical element in touch panels other than televisions, mobile phones, electronic paper, various solar cells, various electroluminescence light control devices, and the like.

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

  In recent years, a transparent electrode such as a conductive polymer has been laminated on a thin metal wire formed in a pattern so that it can be used for products that require such a large area and low resistance. A transparent conductive film having both properties has been developed.

However, in such a configuration, it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent electrode such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer. However, since the conductive polymer has absorption in the visible light region, there is a problem that the transparency of the transparent electrode is remarkably lowered when the film is thickened.
As a method of achieving both conductivity and transparency, a technique of laminating a conductive polymer on a fine wire structure part, a technique of using a binder resin that can be uniformly dispersed in a conductive polymer and an aqueous solvent on a conductive fiber (for example, patents) Reference 1), and a technique for realizing high conductivity, transparency and smoothness in a high temperature and high humidity environment is disclosed.

  In roll-to-roll production technology using a flexible substrate, polymer films are widely used from the viewpoint of handling, but drying at a low temperature and in a short time is desired. As a method for reducing the drying load, it is required that the content of the water-soluble polymer in the material constituting the transparent electrode is small, and a conductive composition using a polyester emulsion as a conductive material having a low water-soluble polymer content ( For example, see Patent Document 2), and as a technique for reducing the drying load by using particles, a conductive composition composed of resin particles containing polyolefin resin particles (for example, see Patent Document 3) is known. ing.

JP 2010-244746 A JP 2009-230885 A JP 2011-116860 A

  However, the technique described in Patent Document 1 also has a problem that sufficient performance under a high temperature and high humidity environment cannot be obtained, and it is difficult to maintain conductivity, transparency, and smoothness. In addition, since the materials described in Patent Documents 2 and 3 are insufficiently dry, volatile components such as water diffuse between layers during an environmental test, adversely affect the electrode and the organic EL element, and desired storage performance can be obtained. There was no problem. Furthermore, due to insufficient compatibility or coarse particles in organic and inorganic particles, haze and surface roughness performance of the conductive film cannot be obtained, or desired film physical properties cannot be obtained. There existed a problem that the performance of an organic EL element might deteriorate.

The present invention has been made in view of the above problems, and has excellent transparency, conductivity, and film strength, and a conductive film that is less deteriorated in transparency, conductivity, and film strength even in a high temperature and high humidity environment. PROBLEM TO BE SOLVED: To provide a method for producing a conductive film, and an organic EL device having excellent light emission uniformity, little deterioration in light emission uniformity even in a high temperature and high humidity environment, and excellent light emission life using the conductive film. And

The above-described problems of the present invention are solved by the following configuration.
1. A first conductive layer comprising a metal material formed in a pattern on a substrate, and an organic compound layer containing at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent . comprising a second conductive layer, wherein the organic compound layer contains at least one cationic π-conjugated conductive polymer compound and a counter salt with low molecular anions, said second conductive layer, the first conductive layer And a conductive film which is electrically connected to the conductive film.
2. 2. The conductive film according to 1 above, wherein the cationic π-conjugated conductive polymer compound is a polythiophene.
3. 3. The conductive material according to 1 or 2 , wherein the low molecular anion capable of counter-salt with the cationic π-conjugated conductive polymer compound contains any one of a sulfonate anion, a chloro anion, and a perchlorate ion. film.
4). 4. The conductive film according to any one of 1 to 3, wherein the organic compound layer contains fine particles having an average particle size of 300 nm or less.
5. 5. An organic electroluminescence device comprising the conductive film according to any one of 1 to 4 as an electrode.
6). Forming on the substrate an organic compound layer containing at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent, the organic compound layer being a low molecular weight sulfonic acid compound, a second Introducing at least one kind of low molecular anion capable of salting with a cationic π-conjugated conductive polymer compound into the organic compound layer by surface treatment with an iron compound-containing lower alcohol. Manufacturing method of electrically conductive film.
7). Forming a metal material-containing conductive layer formed in a pattern on a base material; and at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent on the base material A step of forming an organic compound layer to be contained, and a surface treatment of the organic compound layer with a low-molecular sulfonic acid compound and a ferric compound-containing lower alcohol can counteract the cationic π-conjugated conductive polymer compound. Introducing at least one kind of low-molecular anion into the organic compound layer.

  According to the present invention, a conductive film that is excellent in transparency, conductivity, and film strength, and has little deterioration in transparency, conductivity, and film strength even in a high temperature and high humidity environment, and uniform light emission using the conductive film It is possible to provide an organic EL element that is excellent in lightness, has little deterioration in light emission uniformity even in a high temperature and high humidity environment, and has an excellent light emission lifetime.

It is the schematic which shows an example of the electrically conductive film which concerns on embodiment of this invention, (a) is a top view, (b) is X arrow sectional drawing of (a).

  Conventionally, as a coating liquid for forming a conductive layer on a substrate in a conductive film, water dispersion such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) is used in order to achieve both conductivity and transmittance. A composition containing a conductive conductive polymer and a binder resin has been developed.

  As binder resins, hydrophilic binder resins have been studied from the viewpoint of compatibility with water-dispersible conductive polymers. However, since the demand for flexibility is increasing for the base material, using a resin film such as polyethylene terephthalate as the base material, from the viewpoint of avoiding film deformation, compared to the case of using a glass substrate as the base material The drying temperature needs to be low. In addition, the hydroxyl group-containing binder resin known to be compatible with PEDOT / PSS causes a hydroxyl group to undergo a dehydration reaction under acidic conditions and crosslinks between polymer chains. As a result, the cross-linking reaction progresses during storage and water is generated, and the conductive film and the device performance using the conductive film may be significantly deteriorated due to the water remaining in the film. In order to solve this problem, in the conventional conductive film, it was necessary to reduce the amount of moisture remaining in the film after drying.

  As a binder resin having a small interaction with a solvent such as water, a polymer emulsion is known. Among polymer emulsions, polyester emulsions, acrylic emulsions, polyethylene emulsions, polyurethane emulsions, etc. not only have many ester groups and urethane groups introduced into the polymer main chain and side chains, which are hydrophilic sites. In order to improve the dispersibility in a solvent, hydrophilic groups such as sulfonic acid, carboxylic acid, hydroxyl group and ammonium are present. If there are many hydrophilic sites in the polymer, there is a problem that it is difficult to release water by drying at a low temperature for a short time, and the performance of the conductive film and the organic EL device using the conductive film may be deteriorated. That is, in order to improve the drying property of the conductive film, it is indispensable to reduce the amount of the conductive polymer and the main binder resin constituting the conductive film.

  As a result of intensive studies to improve these phenomena, the present inventors have improved the conductivity of the conductive polymer compound by adding a low molecular dopant to the conductive polymer compound, resulting in a reduction in film thickness. As a result, the amount of the conductive polymer and main binder resin used was reduced, or the amount of the conductive polymer and main binder resin used was reduced by further adding fine particles. .

  That is, it has been found that the problem of the present invention can be solved by improving the conductivity accompanying the addition of a low molecular anion having a dopant function to the conductive polymer compound, or further adding fine particles. I came to get.

  The conductive polymer compound consisting of a cationic π-conjugated conductive polymer compound and a polyanion has a unit that is covalently bonded to the polyanion that functions as a dopant, and the dopant functional sites such as sulfonic acid and carboxylic acid are cationic π-conjugated conductive It is not necessarily an effective conformation for the conductive polymer compound. Introduction of a low molecular anion capable of counter-salt with a cationic π-conjugated conductive polymer compound has a function of improving the electrical conductivity of the cationic π-conjugated conductive polymer compound. In addition, polymers that can be dispersed in aqueous solvents have hydrophilic groups such as sulfonic acid, carboxylic acid, ammonium, and hydroxyl group, and have good compatibility with cationic π-conjugated conductive polymer compounds, polyanions and low-molecular anions. It plays a role in unwinding cationic π-conjugated conductive polymer compounds and polyanions composed of cationic π-conjugated conductive polymer compounds that exist in the form of particles in aqueous solution, and increases conductivity by increasing the number of contacts between conductive polymer compounds. Plays.

  The present invention uses a low molecular anion having a dopant function such as a low molecular sulfonate anion, chloride, perchlorate ion, or the addition of fine particles as the low molecular anion, By having both conductivity and excellent film strength, and also having high conductivity and transparency and good film strength even after environmental tests under high temperature and high humidity environment, it suppresses the generation of water derived from binder resin. The present inventors have found that a conductive film having excellent stability and a long-life organic EL element using the conductive film can be obtained.

  Hereinafter, embodiments of the present invention will be described. 1A and 1B are schematic views showing an example of a conductive film according to an embodiment of the present invention, in which FIG. 1A is a top view and FIG. 1B is a cross-sectional view taken along arrow X in FIG.

  As shown in FIG. 1, the conductive film 1 according to the embodiment of the present invention includes a base material 11, a first conductive layer 12, and a second conductive layer 13. The first conductive layer 12 is made of a metal material formed in a pattern, and the second conductive layer 13 is an organic compound layer containing a conductive polymer compound and a polyolefin-based copolymer. 1 is electrically connected to the conductive layer 12. A feature of the present invention is that the second conductive layer 13 contains a polyolefin copolymer. The first conductive layer 12 can be omitted.

[Low molecular anion capable of counter-salt with cationic π-conjugated conductive polymer compound]
In the present invention, the low molecular anion capable of counter-salt with the cationic π-conjugated conductive polymer compound functions as a dopant for the cationic π-conjugated conductive polymer compound, and conducts to the cationic π-conjugated conductive polymer compound. It is a compound that imparts properties. The type of anion is not particularly limited as long as it has the above function, but halogen anions such as I- (I _3- ), Br-, Cl-, PF _6- , AsF _6- , SbF _6- , SbCl ₆ - halide anions of Va group elements, such as, BF ₄ - halide anions of III a group element such as, ClO ₄ - perchloric acid anion, methanesulfonic acid, etc., ethanesulfonic acid, propanesulfonic acid, butane Sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, xylenesulfonic acid, propylbenzenesulfonic acid, isopropylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, naphthalenesulfonic acid, methyl Naphthalene sulfonic acid, ethyl naphthalene sulfo Acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, sulfonic acid anion such as dinonyl naphthalene sulfonic acid. Examples of the compound that introduces these anions into the cationic π-conjugated conductive polymer compound include halogens such as chlorine, iodine, bromine, arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, pentachloride, and the like. Metal halides such as phosphorus fluoride, aluminum chloride, aluminum bromide and aluminum fluoride, proton acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid, sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide, Silver perchlorate, tetracyanoethylene, tetracyanoquinodimethane, chloranil, 2,3-dichloro-5,6-dicyanobenzoquinone, 2,3-dibromo-5,6-dicyanobenzoquinone, FeCl3, Fe (ClO4) Ferric salts such as 3 and the like, the sulfonic acid, and the ferric salt of the sulfonic acid can be used. These may be used alone or in combination. Moreover, a commercially available reagent can be used for these compounds. The ferric salt of sulfonic acid can also be synthesized according to JP-A No. 2002-138136. As a method for introducing a low molecular anion capable of imparting conductivity to a conductive polymer compound, (i) a halide or a metal halide when polymerizing a cationic π-conjugated conductive polymer compound precursor in the presence of a polyanion , Protonic acid, ferric salt, sulfonic acid, ferric salt of sulfonic acid added, or combinations thereof, or (b) halogenated compounds, metal halides, protonic acid, ferric acid to conductive compounds Examples thereof include a method in which a salt, sulfonic acid, a ferric salt of sulfonic acid, or a combination thereof is added. In addition, after forming a conductive film on the substrate, a lower alcohol solution such as addition of halides, metal halides, protonic acid, ferric salt, sulfonic acid, or ferric salt of sulfonic acid is applied, It can also be introduced from the membrane surface. The addition amount is preferably from 0.1 to 1000 mol%, preferably from 1 to 100 mol%, more preferably from 5 to 50, based on the number of unit moles of the cationic π-conjugated conductive polymer compound in the conductive compound. Mol%. In addition, the temperature at which the low molecular anion is imparted to the cationic π-conjugated conductive polymer compound in the conductive polymer compound is preferably 0 to 100 ° C, more preferably 10 to 50 ° C.

[Polymer dispersible in aqueous solvent]
In the present invention, the polymer dispersible in an aqueous solvent does not contain a surfactant, an emulsifier, or the like that assists micelle formation, and can be dispersed in an aqueous solvent as a single polymer. In the present invention, “dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration. The size (average particle diameter) of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 μm). The size (average particle diameter) of the colloidal particles of the polymer that can be dispersed in the aqueous solvent is preferably 1 to 500 nm, more preferably 5 to 300 nm, and still more preferably the same as the colloidal particles of the conductive polymer compound. Is 5 to 100 nm. When the colloidal particles of the polymer dispersible in the aqueous solvent are large (when larger than 500 nm), the second conductive layer (transparent conductive layer) 13 generated by applying the dispersion to the substrate 11 is used. Haze and smoothness (surface roughness (Ra)) deteriorate. Further, when the colloidal particles of the polymer dispersible in the aqueous solvent are extremely small (smaller than 1 nm), the particles are aggregated to reduce the dispersibility of the dispersion liquid. As a result, the second conductive The haze and smoothness (surface roughness (Ra)) of the layer (transparent conductive layer) 13 deteriorate. In order to improve the smoothness at the time of film formation, the size of the colloidal particles is more preferably 3 to 300 nm, and further preferably 5 to 100 nm. The size of the colloidal particles can be measured with a light scattering photometer.

  The aqueous solvent is not only pure water (including distilled water and deionized water) but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  The polymer dispersible in the aqueous solvent according to the present invention is preferably transparent. The polymer dispersible in the aqueous solvent is not particularly limited as long as it is a medium for forming a film. In addition, there is no particular limitation as long as there is no problem in the bleed out to the surface of the transparent conductive film 1 and the element performance when the organic EL element is laminated, but the polymer dispersion controls the surfactant (emulsifier) and the film forming temperature. It is preferable not to contain a plasticizer or the like.

  The average particle size of the polymer dispersible in the aqueous solvent according to the present invention is desirably 5 to 100 nm. If the average particle diameter is 5 nm or more, aggregation of particles can be suppressed, dispersion stability can be improved, and smoothness of the coated surface can be improved. Moreover, if an average particle diameter is 100 nm or less, while being able to improve compatibility with a conductive polymer compound, the haze of a coating film can be suppressed and the suitable performance as an optical film can be obtained.

  The glass transition temperature (Tg) of the polymer dispersible in the aqueous solvent according to the present invention is preferably 25 to 150 ° C, more preferably 50 to 80 ° C. If Tg is 25 degreeC or more, the deterioration tendency of the surface smoothness of the transparent conductive film 1 can be suppressed, and the deterioration of the performance after the environmental test of the organic EL element provided with the conductive film 1 and the conductive film 1 can be prevented. When Tg is 50 to 80 ° C., the melting of the polymer particles that can be dispersed in the aqueous solvent sufficiently proceeds at the drying temperature when the transparent conductive film 1 is produced. When Tg exceeds 80 ° C., the polymer particles dispersible in the aqueous solvent may not sufficiently melt at the drying temperature during the production of the transparent conductive film 1, but the surface after drying is not rough and organic. If a desired performance can be obtained without causing leakage when the electroluminescent element or the like is laminated, the polymer particle shape dispersible in an aqueous solvent may be maintained. Further, in order to increase the Tg of the polymer dispersible in the aqueous solvent to higher than 150 ° C., it is necessary to make the skeleton rigid, increase the molecular weight, etc., and disperse these polymers in the dispersion by making the polymer less than 100 nm. It is difficult. The glass transition temperature Tg can be measured according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a temperature rising rate of 20 ° C./min.

  The pH of the polymer dispersion that can be dispersed in the aqueous solvent used in the production of the transparent conductive film 1 is compatible with the conductive polymer compound solution that is separately compatible, and the polymer and conductive polymer compound that can be dispersed in the aqueous solvent. From the viewpoint of the conductivity of the mixed solution, it is preferably 0.1 to 11.0, more preferably 3.0 to 9.0, and still more preferably 4.0 to 7.0.

  Examples of dissociable groups used in polymers dispersible in aqueous solvents include anionic groups (sulfonic acid and its salts, carboxylic acid and its salts, phosphoric acid and its salts, etc.), cationic groups (ammonium salts, etc.), etc. Is mentioned. The dissociable group is not particularly limited, but an anionic group is preferable from the viewpoint of compatibility with the conductive polymer solution. The amount of the dissociable group is not particularly limited as long as the polymer dispersible in the aqueous solvent is dispersible in the aqueous solvent, and is preferably as small as possible because the drying load is reduced appropriately in the process. In addition, the counter species used for the anionic group and the cationic group are not particularly limited, but from the viewpoint of performance when the organic EL element including the transparent conductive film 1 and the transparent conductive film 1 is laminated, it is hydrophobic and has a small amount. It is preferable that

  The main skeleton of the polymer that can be dispersed in the aqueous solvent includes polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyolefin copolymer, polyamide (nylon), poly Vinylidene chloride, polyester, polyacrylate, polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone-polyacrylate , Polyvinylidene fluoride-polyacrylate, polyfluoroolefin-polyvinyl ether, etc. It is. Further, based on these skeletons, copolymerization using another monomer may be the main skeleton. Among these, a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, and a polyethylene resin emulsion having an ethylene skeleton are preferable.

  As commercial products, Polysol FP3000 (polyester resin, anion, core: acrylic, shell: polyester, manufactured by Showa Denko KK), Vironal MD1480 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Vironal MD1245 (polyester resin, anion, Toyobo Co., Ltd.) ), Bironal MD1500 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD2000 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Bironal MD1930 (polyester resin, anion, manufactured by Toyobo Co., Ltd.), Plus Coat RZ105 (polyester resin, anion) , Manufactured by Mutual Chemical Co., Ltd.), Plus Coat RZ570 (polyester resin, anion, manufactured by Interactive Chemical Co., Ltd.) Itec S-9242 (polyethylene resin, anion, manufactured by Toho Chemical Co., Ltd.), Movinyl 7720 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.), Movinyl 7820 (acrylic resin, nonion, manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used. . In addition, the polymer dispersible in the aqueous solvent may contain one kind of those described above, or may contain a plurality of kinds.

[Fine particles]
The fine particles in the present invention are fine particles made of an inorganic material or an organic material. The average particle diameter of the fine particles is preferably in the range of 2 to 500 nm, more preferably in the range of 5 to 100 nm. If the average particle diameter of the fine particles is 500 nm or less, the surface roughness of the conductive film 1 is suppressed and good performance is obtained. If the average particle diameter is 2 nm or more, the occurrence of aggregation between the particles is suppressed and the dispersion liquid Dispersibility is improved, and as a result, haze and smoothness (surface roughness (Ra)) of the conductive film 1 are improved. The fine particle composition is not particularly limited. For example, the fine particle composition includes inorganic fine particles made of a single inorganic material, inorganic fine particles made of a composite inorganic material, organic fine particles made of a single organic material, organic fine particles made of a composite organic material, and an inorganic material. Examples thereof include fine particles obtained by coating the surface of the particles with an organic resin, and fine particles (including a core-shell structure) obtained by coating the surface of the organic particles with an inorganic material. In the case of inorganic and / or organic composite particles, for example, inorganic fine particles may be coated with inorganic fine particles, organic fine particles may be coated with organic fine particles, inorganic fine particles may be coated with organic fine particles, and organic fine particles may be coated with inorganic fine particles. The bonding mode of the material may be a mode physically fixed to the central core material or a mode fixed chemically. The particle shape of the fine particles is not particularly limited, but may be any particle shape such as a spherical shape, a needle shape, a plate shape, a scale shape, and a crushed shape, and is not particularly limited, but a spherical shape or a shape close to a spherical shape is preferable.

  The bonding mode between the fine particles according to the present invention and the conductive polymer compound and the polyolefin copolymer constituting the organic compound layer may be a physically fixed mode or a chemically fixed mode. There may be. The term “physically fixed” refers to, for example, a state in which a part of a conductive polymer compound or a polyolefin copolymer is fixed in fine particles having a pore structure. The term “chemically fixed” means, for example, a state in which the conductive polymer compound or the polyolefin copolymer and the fine particles are fixed by a chemical bond.

  The advantages of using the fine particles according to the present invention are considered as follows. That is, by using the fine particles, the pores exist uniformly throughout the organic compound layer, and a network structure of the pores can be formed. A conductive path is formed by the mixture of the conductive polymer compound and the polyolefin copolymer expanding the gap in the pore network structure, and the total amount of the conductive polymer compound and the polyolefin copolymer is reduced. The drying load is reduced. In addition, this pore network structure secures a route for water volatilization from the inside of the film formation to the film surface, and the water volatility during dry film formation can be further improved. As a result, the present inventors presume that an efficient conductive path can be formed with a minimum amount of the conductive polymer compound, and both improved conductivity and transparency are compatible.

  As the inorganic material of the inorganic fine particles in the present invention, for example, silicon oxide, calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, sodium silicate, aluminum oxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, Tin oxide, antimony trioxide, carbon black, molybdenum disulfide, and mixed particles thereof can be used. Of these, silicon oxide is particularly preferable as the inorganic material of the inorganic fine particles.

  The inorganic fine particles are preferably in the form of particles, and preferred inorganic particles are preferably inorganic particles having a primary particle diameter of 100 nm or less and a secondary particle diameter of 500 nm or less. Examples of such inorganic fine particles include, for example, JP-A-1-97678, JP-A-2-275510, JP-A-3-281383, JP-A-3-285814, JP-A-3-285815, JP-A-3-285815. Pseudoboehmite sols, which are hydrated aluminas disclosed in JP-A-4-92183, JP-A-4-267180, JP-A-4-275717, etc., JP-A-60-219083, JP-A-61. No. 19389, JP-A-61-188183, JP-A-63-178074, JP-A-5-51470, etc., Japanese Patent Publication No. 4-19037, Silica / alumina hybrid sol as described in JP-A-62-286787, JP-A-10-119423, Silica sol in which gas phase method silica is dispersed with a high-speed homogenizer as described in Kaihei 10-217601 and the like, smectite clay such as hectite and montmorillonite (see JP-A-7-81210), zirconia sol Typical examples include chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, and antimony oxide sol. Among these inorganic fine particles, colloidal silica can be suitably used as the inorganic fine particles.

  As colloidal silica preferably used in the present invention, in addition to conventional general-purpose unmodified colloidal silica, modified colloidal silica whose surface is coated with ions and compounds such as calcium and alumina to change the behavior with respect to ionicity and pH fluctuation. Is mentioned.

  As the colloidal silica that can be suitably used in the present invention, commercially available products can be used. Examples of commercially available colloidal silica include Snowtex 20, Snowtex 40, Snowtex N, and Snowtex manufactured by Nissan Chemical Industries. O, Snowtex S, Snowtex 20L, Snowtex AK, Snowtex UP, etc., Nippon Chemical Industry's silica doll 20, silica doll 20A, silica doll 20G, silica doll 20P, etc., Adelite AT-20 made by Asahi Denka Kogyo , Adelite AT-20N, Adelite AT-30A, Adelite AT-20Q, etc., DuPont Ludox HS-30, Ludox LS, Ludox SM-30, Ludox AS, Ludox AM and the like.

  As the organic material of fine particles in the present invention, acrylic resin, styrene resin, styrene-acrylic copolymer, divinylbenzene resin, acrylonitrile resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin, fluorine resin, Examples include benzoguanamine resin, phenol resin, nylon resin, polyethylene wax, and other reactive microgels. Among these, acrylic resins and styrene resins are preferably used as the fine organic material.

  Commercially available products can be used as the organic fine particles that can be suitably used in the present invention. Examples of commercially available organic fine particles include Tufic F167 (polymethyl methacrylate, 300 nm) and Tufic F120 (polymethyl methacrylate) manufactured by Toyobo Co., Ltd. Acrylonitrile, 200 nm), Moritex 3020A (polystyrene, 21 nm), 3030A (polystyrene, 33 nm), 3040A (polystyrene, 40 nm), 3050A (polystyrene, 46 nm), 3060A (polystyrene, 60 nm), 3070A (polystyrene, 73 nm) 3080A (polystyrene, 81 nm), 3090A (polystyrene, 92 nm), 3100A (polystyrene, 97 nm), 5003A (polystyrene, 30 nm), 5006A (polystyrene, 60 m), 5009A (polystyrene, 90nm), 5020A (polystyrene, 200 nm), and the like.

  As the fine particles according to the present invention, various combinations of fine particles such as only inorganic fine particles, a mixture of plural kinds of inorganic fine particles, only organic fine particles, a mixture of plural kinds of inorganic fine particles, a mixture of inorganic fine particles and organic fine particles can be used. It is.

<Conductive polymer compound>
In the present invention, “conductive” refers to a state in which electricity flows, and the sheet resistance measured by a method in accordance with JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is 1 ×. It means lower than 10 ⁸ Ω / □.

  In the present invention, the conductive polymer compound is a conductive polymer compound having a cationic π-conjugated conductive polymer and a polyanion. Such a conductive polymer compound can be easily obtained by chemical oxidative polymerization of a precursor monomer that forms a cationic π-conjugated conductive polymer, which will be described later, in the presence of an appropriate oxidizing agent and an oxidation catalyst, and a polyanion, which will be described later. Can be manufactured.

(Cationic π-conjugated conductive polymer)
In the present invention, the cationic π-conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, and polyacetylenes. A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, or polythiazyl compounds can be used. As the cationic π-conjugated conductive polymer, polythiophenes or polyanilines are preferable, and polyethylenedioxythiophene is more preferable from the viewpoints of conductivity, transparency, stability, and the like.

(Cationic π-conjugated conductive polymer precursor monomer)
In the present invention, a precursor monomer used for forming a cationic π-conjugated conductive polymer has a π-conjugated system in the molecule, and the main monomer even when polymerized by the action of an appropriate oxidizing agent. A π-conjugated system is formed in the chain. Examples of such precursor monomers include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.

  Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(Polyanion)
In the present invention, the polyanion used in the conductive polymer compound is substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted. Polyester and any of these copolymers, which are composed of a structural unit having an anionic group and a structural unit having no anionic group.

  This polyanion is a solubilized polymer that solubilizes a cationic π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the cationic π-conjugated conductive polymer, and improves the conductivity and heat resistance of the cationic π-conjugated conductive polymer. In addition, the polyanion is used in an excess amount with respect to the cationic π-conjugated polymer compound, thereby reducing the dispersibility and film-forming property of the conductive polymer compound particles composed of the cationic π-conjugated polymer compound and the polyanion. It also has a function to improve.

  The anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the π-conjugated conductive polymer. As such an anion group, a mono-substituted sulfate group, a mono-substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable from the viewpoint of ease of production and stability. Further, the anionic group is more preferably a sulfo group, a monosubstituted sulfate group, or a carboxy group from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer.

  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, polyisoprene sulfone. Examples include 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 and the like. . Moreover, these homopolymers may be sufficient as a polyanion, and 2 or more types of copolymers may be sufficient as it.

  Further, the polyanion may further have F (fluorine atom) in the compound. Specific examples of such a polyanion include Nafion (manufactured by Dupont) containing a perfluorosulfonic acid group, and Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group.

  Among these, when a compound having a sulfonic acid is used as a polyanion, after forming a conductive polymer-containing layer by coating and drying, it is further subjected to a heating and drying treatment at 100 to 120 ° C. for 5 minutes or more, and then the microanion. You may irradiate a wave, near infrared light, etc. In some cases, heat drying may be omitted, and only irradiation with microwaves, near infrared light, or the like may be performed.

  Furthermore, among the compounds having sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyethyl acrylate sulfonic acid, or polybutyl acrylate sulfonate is preferable.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units from the viewpoint of dispersibility of the conductive polymer compound, and from the viewpoint of solvent solubility and conductivity, it is preferably 50 to 10,000. A range is more preferred.

  Examples of the polyanion production method 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 polymerizable monomer. And the like.

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

  In addition, when the obtained polymer is a salt of a polyanion, it is preferable to change the acid to a polyanion acid. Examples of methods for transforming polyanion salts into polyanionic acids include ion exchange methods using ion exchange resins, dialysis methods, ultrafiltration methods, etc. Among these, ultrafiltration is used because it is easy to work with. The method is preferred.

  The ratio between the cationic π-conjugated conductive polymer contained in the conductive polymer compound and the polyanion constituting the conductive polymer compound, that is, the weight ratio of the polyanion to the cationic π-conjugated conductive polymer From the viewpoints of properties and dispersibility, 0.5 or more and less than 25 are preferable.

  If the weight ratio of the polyanion to the cationic π-conjugated conductive polymer is less than 25, in addition to improving the conductivity, the amount of water retained by the hydrophilic polyanion or the conductive polymer compound is Thus, the storability of the conductive film and the organic EL element using the conductive film is improved. If the weight ratio is 0.5 or more, the resistance of the conductive polymer compound decreases as the dopant increases, and the effect of the polyanion acting as a protective colloid increases, and the stability of the particles Is improved and the particle size is suppressed. Thus, from the viewpoint of the storage stability of the electroconductivity, particle stability, the conductive film and the organic electroluminescence device using the conductive film, the weight ratio of the polyanion to the cationic π-conjugated conductive polymer is 0.5. More than 25 is preferable.

  Examples of a method for setting the weight ratio of the polyanion to the cationic π-conjugated conductive polymer to a desired value include a method of adjusting the amount of polyanion used during the synthesis of the conductive polymer compound. In this method, if the weight ratio of polyanion is 1.0 or less with respect to the cationic π-conjugated conductive polymer, the conductive polymer compound particles tend to be large. Sometimes other polymer compounds can be used in combination. The polymer compound that can be used in combination is not particularly limited as long as the conductive compound particles are stabilized and the transmittance and conductivity are not deteriorated, but polyacryl such as 2-hydroxyethyl acrylate, or a dissociative group An aqueous dispersion polymer such as a contained self-dispersing polymer is preferred. Also, water in commercially available PEDOT / PSS is removed by drying, azeotropic removal with toluene, or pulverized by a known method such as freeze-drying, then washed with water, PSS is removed, and PSS is removed by ultrafiltration. A method of replacing with water can be used.

As an oxidant used when obtaining a conductive polymer according to the present invention by chemical oxidative polymerization of a precursor monomer that forms a cationic π-conjugated conductive polymer in the presence of a polyanion, for example, J. et al. Am. Soc. 85, 454 (1963), and any oxidizing agent suitable for oxidative polymerization of pyrrole. Such oxidants include, for practical reasons, cheap and easy to handle oxidants such as iron (III) salts (eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and inorganic acids containing organic residues). Iron (III) salt), hydrogen peroxide, potassium dichromate, alkali persulfate (eg, potassium persulfate, sodium persulfate), ammonium, alkali perborate, potassium permanganate, or copper salts (eg, tetrafluoride). It is preferable to use copper borate). In addition, air or oxygen in the presence of catalytic amounts of metal ions (for example, iron ions, cobalt ions, nickel ions, molybdenum ions, vanadium ions) can be used as an oxidizing agent. Among these, the use of persulfate, iron (III) salts of inorganic acids including organic acids, or iron (III) salts of inorganic acids including organic residues has great application advantages.

  Examples of the iron (III) salt of an inorganic acid containing an organic residue include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms (for example, lauryl sulfate), alkyl sulfonic acids having 1 to 20 carbon atoms. (For example, methane, dodecanesulfonic acid), carboxylic acid having 1 to 20 aliphatic carbon atoms (for example, 2-ethylhexylcarboxylic acid), aliphatic perfluorocarboxylic acid (for example, trifluoroacetic acid, perfluorooctanoic acid), aliphatic dicarboxylic acid Acids (eg oxalic acid), in particular aromatic, optionally alkyl substituted sulfonic acids having 1 to 20 carbon atoms (eg Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid) Is mentioned.

  A commercially available material can also be preferably used as such a conductive polymer compound. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is a Clevios series from Helios, and PEDOT-PSS 483095 and 560596 from Aldrich. , Commercially available from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used as the conductive polymer compound.

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

[Dispersion made of conductive polymer compound and polymer dispersible in aqueous solvent]
The dispersion containing the conductive polymer compound and the polymer dispersible in the aqueous solvent according to the present invention is a liquid in which the conductive polymer compound and the polymer dispersible in the aqueous solvent are dispersed in the aqueous solvent. . The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  The dispersion according to the present invention is preferably transparent and is not particularly limited as long as it is a medium for forming a film. In addition, there is no particular limitation as long as there is no problem in the bleed out to the surface of the conductive film 1 and the element performance when the organic EL element is laminated, but the dispersion is a surfactant (emulsifier) or a film forming agent that assists micelle formation. It is preferable not to include a plasticizer for controlling the temperature.

  The pH of the dispersion according to the present invention is not particularly problematic as long as desired conductivity is obtained, but is preferably 0.1 to 7.0, and more preferably 0.3 to 5.0.

  In order to control the surface tension of the dispersion according to the present invention, an organic solvent may be added to the dispersion. The organic solvent is not particularly limited as long as a desired surface tension can be obtained, but a monovalent, divalent or polyvalent alcohol solvent is preferable. The boiling point of the organic solvent is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

  The size (average particle size) after dispersion treatment of the conductive polymer compound after dispersion treatment and the polymer dispersible in an aqueous solvent contained in the dispersion according to the present invention is preferably 1 to 100 nm, and more Preferably it is 3-80 nm, More preferably, it is 5-50 nm. If the size of the particles in the dispersion is 100 nm or less, the haze and smoothness (surface roughness (Ra)) of the second conductive layer (conductive layer) 13 generated by applying the dispersion to the substrate 11. ) And the performance of the organic electroluminescence device is improved. Further, if the size of the particles in the dispersion is 1 nm or more, the occurrence of aggregation between the particles is suppressed and the dispersibility of the dispersion is improved. As a result, the haze of the second conductive layer (conductive layer) 13 and Smoothness (surface roughness (Ra)) is improved. In order to improve the smoothness during film formation, the size of the particles in the dispersion is more preferably 3 to 80 nm, and further preferably 5 to 50 nm. In addition, even if the average particle size is controlled, if the film forming temperature of the polymer that can be dispersed in the aqueous solvent used is too high, the film shape does not form within the drying temperature, and the particle shape remains and the average roughness of the film surface is reduced. Since the film may deteriorate, it is desirable to control the film forming temperature.

  Examples of a method for setting the average particle size of the dispersion to a desired range include a homogenizer, an ultrasonic disperser (US disperser), a dispersion technique using a ball mill, a reverse osmosis membrane, an ultrafiltration membrane, and a microfiltration membrane. The classification of the used particles can be used. Dispersion techniques using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, etc. all tend to increase particles at high temperatures. Therefore, the temperature during the dispersion operation is preferably -10 ° C to 50 ° C. It is below, More preferably, it is higher than 0 degreeC and less than 30 degreeC. In the case of a dispersion operation by a large shearing force that cuts the polymer, the temperature of the dispersion liquid tends to be high, and the conjugated system of the conductive polymer is broken by heat, which may cause performance deterioration. As a result, when the temperature exceeds 50 ° C., the particle size tends to be small, but the sheet resistance of the second conductive layer (conductive layer) 13 generated by the dispersion may increase. In addition, when an organic solvent is contained in the aqueous solvent, even when the temperature is 0 ° C. or lower (for example, −10 ° C. or higher and 0 ° C. or lower), the dispersion operation can be suitably performed as long as the solvent does not solidify. It is. Further, since the dispersion is water-rich, the viscosity increases at 0 ° C. or lower, and a load is applied to the stirring. Further, if the temperature is 30 degrees or more, the solvent is evaporated and the dispersion concentration is likely to fluctuate. As a result, the performance of the conductive film 13 may be affected. Classification is not particularly limited as long as a membrane to be used is selected as necessary.

  The polymer particles and conductive polymer particles dispersible in the aqueous solvent in the dispersion according to the present invention are in a state where each particle is dispersed independently, and the particle size is the sum of the particle sizes. Alternatively, particles having different compositions may be aggregated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.

  The amount (solid content) of the polymer dispersible in the aqueous solvent according to the present invention is preferably 50 to 5000 mass%, more preferably 100 to 3500 mass%, based on the solid content of the conductive polymer compound. Yes, more preferably 200 to 2000% by weight. Here, it is more preferable that the amount of the polymer dispersible in the aqueous solvent is 50 to 5000% by mass with respect to the conductive polymer compound. (The conductive polymer compound absorbs light in the visible light region, so in order to improve the transmittance, it is desirable to reduce the conductive polymer compound as much as possible without reducing the conductivity.) If it exists, it is because the suitable electroconductivity is obtained, without the ratio of a conductive polymer becoming small too much. Thus, in order to obtain the effect of improving the transmittance and prevent the decrease in conductivity, the amount of the polyolefin-based copolymer used is more preferably 100 to 3500% by mass with respect to the conductive polymer. More preferably, it is 200-2000 mass% with respect to a conductive polymer compound.

The particle size measurement method of the dispersion according to the present invention is not particularly limited, but is preferably a dynamic light scattering method, a laser diffraction method or an image imaging method, and more preferably a dynamic light scattering method. Since the particle size of the polymer particles and conductive polymer particles dispersible in an aqueous solvent becomes unstable due to dilution, a concentrated particle size measuring machine that can measure as it is without diluting the solvent is preferable. Examples of the diameter measuring device include a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), a zeta sizer nano series (manufactured by Malvern), and the like.
The fine particles of the present invention may be added to the dispersion according to the present invention, and such fine particles can be dispersed in the aqueous solvent constituting the organic compound layer from the viewpoint of reducing the drying load and suppressing the film thickness of the organic compound layer. It is preferably used in the replacement of new polymers. The amount of the fine particles used is preferably 25 to 75% by mass in terms of solid content based on the polymer dispersible in the aqueous solvent, and more preferably 30 to 60% by mass based on the conductive polymer compound. Here, the reason why the amount of the polymer dispersible in the aqueous solvent is preferably 25 to 75% by mass with respect to the conductive polymer is that if it is 25% by mass or more, the drying load reduction effect is sufficient, If it is 75% by mass or less, the film physical properties of the organic compound layer are improved. As described above, in order to obtain a drying load reduction effect and prevent a decrease in film physical properties of the organic compound layer, the amount of the polymer dispersible in the aqueous solvent can be reduced to a solid weight of 25 with respect to the polymer dispersible in the aqueous solvent. More preferably, it is -75 mass%.

(Metal material)
As shown in FIG. 1, the conductive film 1 according to the embodiment of the present invention includes a conductive layer (second conductive layer 13 in FIG. 1) containing a conductive polymer compound and a polyolefin-based copolymer. And a metal material-containing conductive layer (first conductive layer 12 in FIG. 1) formed in a pattern on the substrate 11.

  The metal material is not particularly limited as long as it has conductivity, and may be an alloy in addition to a metal such as gold, silver, copper, iron, nickel, or chromium. In particular, from the viewpoint of ease of pattern formation as described later, the shape of the metal material is preferably metal fine particles or metal nanowires, and the metal material is preferably silver from the viewpoint of conductivity.

  In order to form the transparent conductive film 1, the first conductive layer 12 according to the present invention is formed on the substrate 11 so as to have a pattern shape having the opening 12a. The opening part 12a is a part which does not have a metal material on the base material 11, and is a translucent window part. Although there is no restriction | limiting in particular in a pattern shape, For example, it is preferable that they are stripe shape, mesh shape, or random mesh shape. The ratio of the opening 12a to the entire surface of the conductive film 1, that is, the opening ratio is preferably 80% or more from the viewpoint of transparency. The aperture ratio is the ratio of the light-impermeable conductive portion to the whole. For example, when the light-impermeable conductive portion is striped or meshed, the aperture ratio of the striped pattern having a line width of 100 μm and a line interval of 1 mm is about 90%.

  The line width of the pattern is preferably 10 to 200 μm from the viewpoint of transparency and conductivity. If the line width of the fine line is 10 μm or more, desired conductivity can be obtained, and if the line width of the fine line is 200 μm or less, desired transparency can be obtained. The height of the thin wire is preferably 0.1 to 10 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and if the height of the fine wire is 10 μm or less, current leakage and functional layer thickness distribution in the formation of an organic electronic device Defects are prevented.

  There is no restriction | limiting in particular as a method of forming the stripe-shaped or mesh-shaped 1st conductive layer 12, A conventionally well-known method can be utilized. For example, it can be formed by forming a metal layer on the entire surface of the substrate 11 and subjecting the metal layer to a known photolithography method. Specifically, a metal layer is formed on the entire surface of the substrate 11 using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, or the like, or a metal foil is used as an adhesive. The first conductive layer 12 processed into a desired stripe shape or mesh shape can be obtained by laminating the substrate 11 on the substrate 11 and then etching using a known photolithography method. The metal species is not particularly limited as long as it can be energized, and copper, iron, cobalt, gold, silver, and the like can be used. From the viewpoint of conductivity, silver or copper is preferable, and silver is more preferable. It is.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, a method of applying a plating catalyst ink in a desired shape by gravure printing or an inkjet method, or a plating process, or A method using silver salt photography technology is mentioned.

  A technique using silver salt photography technology can be implemented with reference to, for example, [0076]-[0112] of Japanese Patent Application Laid-Open No. 2009-140750 and Examples. Further, a method for carrying out a plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, Japanese Patent Application Laid-Open No. 2007-281290.

  In addition, as a random network structure, for example, as described in JP 2005-530005 A, a random network structure of conductive fine particles is spontaneously formed by coating and drying a liquid containing metal fine particles. Techniques for forming can be used. As another method, for example, as described in JP-T-2009-505358, a coating solution (dispersion) containing metal nanowires is applied and dried to form a random network structure of metal nanowires. Techniques to form are available.

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

As a metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, and more preferably 3 to 500 μm. If the length of the metal nanowire is 500 μm or less, one wire spreads well and is arranged without overlapping with other wires, and as a result, the film thickness of the first conductive layer 12 is suppressed, and thinning is achieved. As a result, the transmittance is improved. Moreover, if the length of metal nanowire is 3 micrometers or more, the contact of metal nanowire will increase and desired sheet resistance and transmittance | permeability will be obtained, suppressing the addition amount of metal nanowire. In addition, the relative standard deviation of the length is preferably 40% or less. This is because when the relative standard deviation of the length is 40% or less, the film thickness unevenness of the first conductive layer 12 and the uniformity of the sheet resistance are prevented from being reduced. 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. Therefore, the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. This is because when the relative standard deviation of the minor axis is 20% or less, the occurrence of unevenness in the thickness of the first conductive layer 12 is suppressed, and the occurrence of unevenness in luminance of the organic EL element is suppressed. The basis weight of the metal nanowire is preferably 0.02 to 0.5 g / m ² . If the basis weight of the metal nanowire is 0.02 g / m ² or more, a desired sheet resistance is obtained, and if the basis weight is 0.5 g / m ² or less, desired sheet resistance and transmittance are obtained. The weight of the metal nanowire is more preferably 0.03 to 0.2 g / m ² from the viewpoint of sheet resistance and transmittance.

  Examples of the metal used for the metal nanowire include copper, iron, cobalt, gold, silver and the like, and silver is preferable from the viewpoint of conductivity. In addition, although a single metal may be used, in order to achieve both conductivity and stability (sulfurization resistance, oxidation resistance, and migration resistance of metal nanowires), the metal as the main component and one or more other types are used. These 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 methods, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745, a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871. In particular, the method for producing silver nanowires disclosed in the above-mentioned literature can easily produce silver nanowires in an aqueous solution, and the electrical conductivity of silver is the highest among metals, so it is preferably applied to the present invention. can do.

In addition, the surface specific resistance of the thin wire portion (first conductive layer 12) made of a metal material is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less, from the viewpoint of increasing the area. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
Moreover, it is preferable that the thin wire | line part (1st conductive layer 12) which consists of metal materials is heat-processed in the range which does not damage the base material 11. FIG. As a result, fusion between the metal fine particles and the metal nanowires proceeds, and the thin wire portion made of the metal material becomes highly conductive.

(Base material)
The base material 11 is a plate-like body that can carry the conductive layers 12 and 13, and in order to obtain the transparent conductive film 1, JIS K 7361-1: 1997 (Plastic-Transparent Material Total Light Transmittance Test Preferably, those having a total light transmittance of 80% or more in the visible light wavelength region measured by a method based on (Method) are preferably used.

  As the substrate 11, a material that is excellent in flexibility, has a sufficiently low dielectric loss coefficient, and is a material that absorbs microwaves smaller than the conductive layers 12 and 13 is preferably used.

  As the base material 11, for example, a resin substrate, a resin film, and the like are preferably exemplified. However, it is preferable to use a transparent resin film from the viewpoints of productivity and performance such as lightness and flexibility. The transparent resin film is a film having a total light transmittance of 50% or more measured in a visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (a test method for total light transmittance of plastic-transparent material). Say.

  There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. Examples of such transparent resin films include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, and cyclic olefin resins. Polyolefin resin films such as polyvinyl chloride, polyvinyl resin such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate ( PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. .

  If it is a resin film whose above-mentioned total light transmittance is 80% or more, it is preferably used as a film board | substrate used as the base material 11 of this invention. The film substrate is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film from the viewpoint of transparency, heat resistance, ease of handling, strength and cost. An axially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.

  The base material 11 used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure wettability and adhesion of the coating liquid (dispersion). Surface treatment and easy adhesion 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 of these may be formed on the front or back surface of the film substrate, and the film substrate on which such a film is formed conforms to JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the above method is 1 × 10 ⁻³ g / (m ² · 24 h) or less barrier film. More preferably, the oxygen transmission rate measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, water vapor transmission rate (25 ± 0.5 ° C., relative humidity) (90 ± 2)% RH) is preferably a high barrier film of 1 × 10 ⁻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 a film substrate in order to obtain a high barrier film, any material may be used as long as it has a function of suppressing invasion of elements such as moisture, oxygen, etc. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier 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 order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

(Coating, heating, drying)
The second conductive layer 13 of the present invention is obtained by applying a coating liquid (dispersion liquid) containing the above-described conductive polymer compound and a polyolefin-based copolymer on the substrate 11, heating and drying. It is formed. When the transparent conductive film 1 has a fine wire portion made of a metal material as the first conductive layer 11, the above-described coating solution is applied onto the substrate 11 on which the thin wire portion made of the metal material is formed, and is heated and dried. Thus, the second conductive layer 13 is formed. Here, the second conductive layer 13 only needs to be electrically connected to the thin metal wire portion that is the first conductive layer 12, and may completely cover the patterned thin metal wire portion. A part of the part may be covered, or may be in contact with the fine metal wire part.

  In addition to printing methods such as gravure printing method, flexographic printing method, screen printing method, etc., coating of coating liquid consisting of conductive polymer compound and polyolefin-based copolymer can be performed by roll coating method, bar coating method, dip coating. Any of coating methods such as coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and ink jet method can be used. .

  In addition, a conductive film 1 is manufactured in which a part of the thin metal wire portion (first conductive layer 12) is covered or in contact with a second conductive layer 13 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent. As a method for forming, the first conductive layer 12 was formed on the transfer film by the method described above, and the second conductive layer 13 containing a conductive polymer and a polymer dispersible in an aqueous solvent was laminated by the method described later. A method of transferring the material to the above-described base material 11 is exemplified.

  In addition, as a method for producing the conductive film 1, a second method containing a conductive polymer and a polymer dispersible in an aqueous solvent in a non-conductive portion (opening portion 12 a) of the thin metal wire portion by a known method such as an inkjet method. Examples thereof include a method of forming the conductive layer 13.

  The second conductive layer 13 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent is a conductive polymer in which the weight ratio of the polyanion to the cationic π-conjugated polymer is less than 0.5 to 2.5. It is preferable to include a compound. Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength can be obtained.

  By forming the conductive layers 12 and 13 of the present invention having such a structure, high conductivity that cannot be obtained by a metal or metal oxide fine wire or a conductive polymer layer alone is obtained. Can be obtained uniformly.

  The dry film thickness of the second conductive layer 13 is preferably 30 to 2000 nm from the viewpoint of surface smoothness and transparency, more preferably 100 nm or more from the viewpoint of conductivity, and the surface of the conductive film 1. From the viewpoint of smoothness, it is more preferably 200 nm or more. The dry film thickness of the second conductive layer 13 is more preferably 1000 nm or less from the viewpoint of transparency.

  The second conductive layer 12 is formed by applying a coating liquid (dispersion liquid) containing a conductive polymer compound and a polymer dispersible in an aqueous solvent and then performing a drying treatment. 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 in which the base material 11 and the conductive layers 12 and 13 are not damaged. For example, the drying process can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes. As a result, the cleaning resistance and solvent resistance of the conductive film 1 are remarkably improved, and the device performance is further improved. In particular, in an organic EL element including the conductive film 1, effects such as a reduction in driving voltage and an improvement in life are obtained.

  The coating liquid described above contains, as additives, plasticizers, stabilizers (antioxidants, antioxidants, etc.), surfactants, dissolution accelerators, polymerization inhibitors, colorants (dyes, pigments, etc.) and the like. May be. Furthermore, from the viewpoint of improving workability such as coating properties, the coating liquid described above is a solvent (for example, water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons). Or other organic solvents).

  In the present invention, Ry and Ra representing the smoothness of the surface of the second conductive layer 13 which is a conductive layer are Ry = maximum height (the difference in height between the top and bottom of the surface) and Ra = arithmetic mean roughness. This is a value according to the surface roughness defined in JIS B601 (1994). In the conductive film 1 according to the present invention, the surface smoothness of the second conductive layer 13 that is a conductive layer is Ry ≦ 50 nm and the second conductive layer 13 that is a conductive layer has a smoothness from the viewpoint of improving conductivity. The surface smoothness is preferably Ra ≦ 10 nm. In the present invention, a commercially available atomic force microscope (AFM) can be used for the measurement of Ry and Ra. For example, it can be measured by the following method.

  Using an SPI 3800N probe station manufactured by Seiko Instruments Inc. and a SPA400 multifunctional unit as the AFM, set a sample cut to a size of about 1 cm square on a horizontal sample table on a piezo scanner, and place the cantilever on the sample surface. When approaching and reaching the region where the atomic force works, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 1 Hz.

  In the present invention, the value of Ry is more preferably 50 nm or less, and further preferably 40 nm or less, from the viewpoint of improving conductivity. Similarly, the value of Ra is more preferably 10 nm or less, and further preferably 5 nm or less, from the viewpoint of improving conductivity.

In the present invention, the conductive film 1 preferably has a total light transmittance of 60% or more, more preferably 70% or more, and further preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. In addition, the electrical resistance value of the second conductive layer 13 which is a conductive layer in the conductive film 1 of the present invention is preferably 1000Ω / □ or less as the surface resistivity from the viewpoint of performance improvement, and is 100Ω / □ or less. More preferably. Furthermore, in order to apply the conductive film 1 to a current-driven optoelectronic device, the surface resistivity is preferably 50Ω / □ or less from the viewpoint of improving the performance when applied to a current-driven optoelectronic device. More preferably, it is 10Ω / □ or less. That is, when the surface resistivity is 10 ³ Ω / □ or less, the conductive film 1 can preferably function as an electrode in various optoelectronic devices. The above-mentioned surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method by conductive probe four-probe method) or the like, or using a commercially available surface resistivity meter. It can be easily measured.

  There is no restriction | limiting in particular in the thickness of the electrically conductive film 1 which concerns on this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and a softness | flexibility improve, so that thickness becomes thin. Therefore, it is more preferable.

<Organic EL device>
An organic EL device according to an embodiment of the present invention includes the conductive film 1 as an electrode, and includes an organic layer including an organic light emitting layer and the conductive film 1. The organic EL element according to the embodiment of the present invention preferably includes the conductive film 1 as an anode, and the organic light-emitting layer and the cathode are arbitrarily selected from materials and configurations generally used for organic EL elements. Can be used.

  The element structure of the organic EL element includes 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. it can.

  In the present invention, the light emitting material or doping material that can be used in the organic light emitting layer includes anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bis. Benzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex , Aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone Rubrene, distyrylbenzene derivatives, di still arylene derivatives, various fluorescent dyes, rare earth metal complex, but phosphorescent material and the like, but is not limited thereto. Moreover, it is preferable to contain 90-99.5 mass parts of luminescent materials selected from these compounds, and 0.5-10 mass parts of doping materials. An organic light emitting layer is manufactured by well-known methods, such as vapor deposition, application | coating, transcription | transfer, using the above-mentioned material. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm and more preferably 0.5 to 200 nm from the viewpoint of light emission efficiency.

  The conductive film 1 according to an embodiment of the present invention has both high conductivity and transparency, and various optoelectronics such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, electronic paper, an organic solar cell, and an inorganic solar cell. It can be suitably used in the fields of devices, electromagnetic wave shields, touch panels and the like. Among these, it can use especially preferably as an electrically conductive film of the organic EL element and organic thin-film solar cell element by which the smoothness of the electrically conductive film surface is calculated | required severely.

  Moreover, since the organic EL element according to the present invention can emit light uniformly and without unevenness, it is preferably used for lighting applications, and can be used for self-luminous displays, liquid crystal backlights, lighting, and the like. .

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" and "%" is used in an Example, unless there is particular notice, "mass part" and "mass%" are represented.

<Synthesis of the polyolefin copolymer of the present invention>
The synthesis examples of the polyolefin copolymer dispersion and the comparative copolymer dispersion according to the present invention are shown below.

Synthesis example 1
Synthesis of conductive polymer compound CP-1 (PEDOT (polyethylenedioxythiophene) / PSS, PEDOT / PSS = 1.0 / 2.4 (mass ratio)) Polystyrene sulfonic acid (PSS) (2.7 g, 2. 6 mmol; monomer conversion, monomer molecular weight 184.02) added to 18% aqueous solution, and further potassium persulfate (0.46 g, 1.7 mmol, molecular weight 270.32, manufactured by Kanto Chemical Co., Inc.) and iron (III) sulfate n water A Japanese product (2.6 mg, 4.5 × 10 ⁻³ mmol (purity 70% conversion), molecular weight 399.88, manufactured by Kanto Chemical Co., Inc.) and 68 ml of pure water were added and dissolved. A homogenizer (main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was installed and operated under the surface of the solution, and then 3.4-ethylenedioxythiophene ( 0.2 g, 1.4 mmol, molecular weight 142.18, manufactured by Aldrich) was added and polymerized at room temperature for 24 hours. Subsequently, 5.0 g of an anion exchanger (Bayer AG Lewatit MP62) and 5.0 g of a cation exchanger (Bayer AG Lewatit S100) were added to the solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive polymer compound CP-A. (Solid content concentration: 1.0%).

Synthesis example 2
Synthesis of conductive polymer compound CP-2 (PEDOT (polyethylenedioxythiophene) / PSS, ethanol dispersion of PEDOT / PSS = 1.0 / 2.5 (mass ratio)) PEDOT-PSS CLEVIOS PH510 (solid content concentration) An aqueous dispersion of 1.89% (manufactured by HC Starck) was lyophilized with a freeze dryer FDU-2200 (manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a solid of PEDOT-PSS. Ethanol was added to this solid, and this ethanol dispersion liquid was almost contacted with a grinder ("Kurita Kikai Seisakusho" KM1-10 ") between the disks rotating at 1200 rpm from the center to the outside. The operation to pass through was performed 12 times (12 passes) to produce a conductive polymer compound CP-B having a solid content of 1%.

Synthesis example 3
Synthesis of conductive polymer compound CP-3 (PANI (polyaniline) / PSS, PANI / PSS = 1.0 / 2.0 (mass ratio)) 20% polystyrene sodium sulfonate aqueous solution (PS5 manufactured by Tosoh Corporation, molecular weight 5) −100,000) 50 ml was diluted with 1 L of distilled water and treated with an H-type cation exchange resin (Dowex 50W X12) packed in a column to obtain a solution containing polystyrene sulfonic acid. This solution was concentrated with a rotary evaporator to obtain a 20% aqueous polystyrene sulfonic acid solution.

  0.366 g (1.5 mmol) of ammonium dichromate was dissolved in 20 ml of distilled water. Separately, 80 g of distilled water and 3.73 g (4 mmol) of the above 20% polystyrene sulfonic acid solution are added to a 300 ml beaker, and a homogenizer (main body: UltraTex T-25, shaft generator: S25N-10G (manufactured by IKA) )) Was placed and operated under the surface of the solution, and 0.373 g (4 mmol) of aniline was added to the solution. While maintaining the internal temperature at 5 ° C., the aqueous ammonium dichromate solution was added dropwise over 30 minutes. After a few minutes, the reaction solution turned green. After dropwise addition of the aqueous ammonium dichromate solution, the reaction solution was stirred for 1 hour. Subsequently, 5.0 g of an anion exchanger (Bayer AG Lewatit MP62) and 5.0 g of a cation exchanger (Bayer AG Lewatit S100) were added to the black-green solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive polymer compound CP-C. (Solid content concentration: 1.3%).

Synthesis example 4
Synthesis of polyester polymer dispersion PO-1 (polyester copolymer dispersion) <Polyester Production Example>
In a reaction kettle equipped with a stirrer, thermometer and reflux condenser, 75 g of terephthalic acid, 75 g of isophthalic acid, 10 g of dimethyl 5-Nasulfoisophthalate, 100 g of ethylene glycol, 100 g of neopentyl glycol, n-tetrabutyl titanate as a catalyst 0.1 g, 0.3 g of sodium acetate as a polymerization stabilizer and 2 g of Irganox 1330 as an antioxidant were charged, and a transesterification reaction was performed at 170 to 230 ° C. for 2 hours. After completion of the transesterification reaction, the temperature of the reaction system was raised from 230 ° C. to 270 ° C., while the pressure in the system was slowly reduced to 5 Torr at 270 ° C. over 60 minutes. Further, a polycondensation reaction was carried out at 1 Torr or less for 30 minutes. After completion of the polycondensation reaction, the system was returned from vacuum to normal pressure using nitrogen to obtain molten polyester (A). As for the polyester (D), as a result of NMR analysis, the dicarboxylic acid component was 49 mol% terephthalic acid, 48.5 mol% isophthalic acid, 2.5 mol% 5-Na sulfoisophthalic acid, the diol component was 50 mol% ethylene glycol, Neopentyl glycol was 50 mol%, the glass transition temperature was 67 ° C., and the reduced viscosity was 0.53 dl / g.

<Example of water dispersion production>
After completion of the polycondensation reaction, a reaction vessel equipped with a stirrer containing 25 g of polyester (D), a thermometer and a reflux condenser was cooled with stirring in a nitrogen atmosphere until the temperature inside the system reached 200 ° C. After reaching a predetermined temperature, 15 g of butyrocelsolve was added while continuing stirring, and the resin was dissolved while adjusting the temperature in the system to 80 ° C. After confirming the dissolution of the resin, water was dispersed by adding 55 g of water little by little while stirring. Thereafter, an aqueous dispersion (D) was obtained by cooling. Ion exchange water was added to the obtained dispersion to prepare a solid content concentration of 25%, and a polyester copolymer dispersion PO-1 was obtained.

Synthesis example 5
Synthesis of polyolefin polymer PO-2 (ethylene-methacrylic acid copolymer dispersion) In a 300 ml autoclave, 62.5 g of ethylene-methacrylic acid copolymer (20% methacrylic acid), 4.74 g of KOH, ZnO 3.55 g and 187.5 g of ion-exchanged water were charged, sealed, and stirred at 150 ° C. for 2 hours to carry out a dispersion reaction. After completion of the reaction, the mixture was quenched in an ice bath to obtain a slightly cloudy dispersion. Ion exchange water was added to this dispersion to prepare a solid content concentration of 25% to obtain a polyolefin polymer PO-2.

Synthesis Example 6
Synthesis of Comparative Binder Resin PO-A (Polyacrylic Aqueous Solution): Comparative Compound [Synthesis of Poly-2-hydroxyethyl Acrylate (PO-A)]
In a 300 ml eggplant flask, 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g (43.1 mmol, Fw 116.12), 2,2′-azobis (2-methylisopropionitrile) 0.7 g (4.3 mmol, Fw164.21) and 100 ml of tetrahydrofuran were added, and the mixture was heated to reflux for 8 hours. The solution was then cooled to room temperature and added dropwise into 2.0 L of vigorously stirred methyl ethyl ketone. After stirring the reaction solution for 1 hour, methyl ethyl ketone was decanted and the polymer adhering to the wall surface was washed three times with 100 ml of methyl ethyl ketone. The polymer was dissolved in 100 ml of tetrahydrofuran, transferred to a 200 ml flask, and tetrahydrofuran was distilled off under reduced pressure using a rotary evaporator. Then, the remaining THF was distilled off by reducing the pressure at 80 ° C. for 3 hours, and 4.1 g (yield 82%) of P-1 having a number average molecular weight of 57,800 and a molecular weight distribution of 1.24 was obtained.

The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively. Further, P-14.0 g obtained was dissolved in 16.0 g of pure water to prepare a 20% aqueous solution of PO-A.

<GPC measurement conditions>
Device: Waters 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (containing 20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C

Synthesis example 7
Synthesis of oxidizing agent / dopant compound OX-1 (butanol solution of ferric p-toluenesulfonate) 108.6 g (0.2 mol) of Fe ₂ (SO ₄ ) ₃ · 8H ₂ O in 1000 ml of distilled water at room temperature ) While stirring this solution vigorously while stirring the solution, slowly add a 5 mol / l sodium hydroxide aqueous solution to adjust the pH to 7, then remove the supernatant by centrifugation and remove ferric hydroxide. A precipitate was obtained. Then, in order to remove excess water-soluble salt, the operation of dispersing the ferric hydroxide precipitate in 4000 ml of distilled water and then removing the supernatant by centrifugation was repeated twice. The obtained ferric hydroxide precipitate was dispersed in 500 g of normal butanol. Separately from the above, 206 g of p-toluenesulfonic acid was previously dissolved in 500 g of normal butanol, the above-mentioned ferric hydroxide dispersion was added to the solution, and the mixture was stirred at room temperature for 12 hours to be reacted. After distillation, a normal butanol solution OX-1 of p-toluenesulfonic acid ferric salt having a concentration of 40% by weight was obtained.

Synthesis Examples 8 and 9
Synthesis of oxidizing agent / dopant compound OX-2, OX-3 (butanol solution of ferric p-methoxysulfonate and ferric dodecylbenzenesulfonate) In the synthesis of oxidizing agent / dopant compound OX-1, p-toluene Similarly, except that 206 g of sulfonic acid was changed to 225 g of ferric p-methoxysulfonate and 357 g of dodecylbenzenesulfonic acid, a normal butanol solution of oxidizer and dopant compounds OX-2 and OX-3 having a concentration of 40% by weight was prepared. Synthesized.

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

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

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

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

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

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

(Reforming treatment conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds As described above, a film substrate (base material 11) for a conductive film (conductive film 1) having gas barrier properties was produced.

<Example 1>
<Preparation of conductive film>
<Preparation of Conductive Film TC-101>
Adjust the slit gap of the extrusion head to a dry film thickness of 200 nm on the non-barrier surface of the film substrate for a conductive film having gas barrier properties by using the extrusion method to achieve a dry film thickness of 200 nm. Then, it was heated and dried at 110 ° C. for 3 minutes to form a conductive layer, and the obtained electrode was cut into 8 × 8 cm. The obtained electrode was heated in an oven at 110 ° C. for 7 minutes to produce a conductive film TC-101.

(Synthesis of conductive polymer compound CP-A1)
Conductive polymer compound CP-A (solid content concentration: 1.0%) to methanesulfonic anhydride (40.4 mg, 0.42 mmol, molecular weight 96.11, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium persulfate (0.11 g) , 0.42 mmol, molecular weight 270.32, manufactured by Kanto Chemical Co., Ltd.) and iron (III) sulfate n hydrate (0.78 mg, 4.5 × 10 ⁻⁴ mmol (purity 70% conversion), molecular weight 399.88 A homogenizer (main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was placed and operated under the liquid level of the solution, and then at room temperature. Subsequently, 0.5 g of an anion exchanger (Bayer AG Lewatit MP62) and 0.5 g of a cation exchanger (Bayer AG Lewatit S100) were added as a solution. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. A polymer compound CP-A1 was obtained (solid content concentration: 1.0%).

(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a coating solution A.
Conductive polymer dispersion: conductive polymer compound CP-A1 (solid content concentration 1.0%) 37.5 g
Polyester copolymer dispersion: PO-1 (solid content concentration 25%, solid content 875 mg) 3.5 g
1.0 g of dimethyl sulfoxide (DMSO, 1/5 of the conductive polymer solution mass)

(Production of conductive films TC-102 to TC-104)
In the production of the conductive film TC-101, methanesulfonic acid used for the synthesis of the conductive polymer compound CP-A1 was changed to benzenesulfonic anhydride (66.4 mg, 0.42 mmol, molecular weight 158.18, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-Naltalenesulfonic acid (87.5 mg, 0.42 mmol, molecular weight 208.23, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (79.9 mg, 0.42 mmol, molecular weight 190.22, Tokyo) Manufactured by Kasei Co., Ltd., and produced conductive polymer compounds CP-A2 to CP-A4, and the conductive polymer compounds CP-A2 to CP-A4 in the coating liquid A were prepared. Conductive films TC-102 to TC-104 were prepared in the same manner as the conductive film TC-101 except that was used.

(Production of conductive films TC-105 to TC-107)
In the production of the conductive film TC-104, the polyester-based copolymer dispersion of the coating liquid A was added to plus coat Z561 (manufactured by Kyoyo Chemical Co., Ltd., solid content concentration 25%), iodosol AD166 (manufactured by Henkel Co., Ltd., solid content concentration 49%). The conductive films C-105 to TC-107 were prepared by changing to PO-2 (solid content concentration 25%) and adding the solid content to 875 mg.
<Preparation of Conductive Film TC-108>
Adjust the slit gap of the extrusion head to a dry film thickness of 300 nm on the non-barrier surface of the film substrate for a conductive film having gas barrier properties by using the extrusion method to a dry film thickness of 300 nm. Then, it was heated and dried at 110 ° C. for 5 minutes to form a conductive layer made of a conductive polymer and an olefin copolymer, and the obtained electrode was cut into 8 × 8 cm. The obtained electrode was heated in an oven at 110 ° C. for 15 minutes to produce a conductive film TC-108.

(Synthesis of conductive polymer compound CP-B1)
0.14 g of a normal butanol solution (solid content concentration: 40%) of an oxidizing agent / dopant compound OX-1 is added to 5.0 g of the conductive polymer compound CP-B (solid content concentration: 1.0%), and a homogenizer. (Main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was placed and operated under the liquid level of the solution, and then stirred at room temperature for 12 hours. Subsequently, 0.5 g of an anion exchanger (Bayer AG Lewatit MP62) and 0.5 g of a cation exchanger (Bayer AG Lewatit S100) were added to the solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive polymer compound CP-B1. (Solid content concentration: 1.0%).

(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a coating solution A.
Conductive polymer dispersion: conductive polymer compound CP-B1 (solid content concentration 1.0%) 37.5 g
Polyester copolymer dispersion: PO-1 (solid content concentration 25%, solid content 875 mg) 3.5 g
1.0 g of dimethyl sulfoxide (DMSO, 1/5 of the conductive polymer solution mass)

(Preparation of conductive films TC-109 to TC-112)
In the production of the conductive film TC-108, instead of adding 0.14 g of the normal butanol solution (solid content concentration: 40%) of the oxidizer and dopant compound OX-1, the normal butanol solution of the oxidizer and dopant compound OX-2 (Solid content concentration: 40%) 0.15 g, normal butanol solution of oxidizer and dopant compound OX-3 (solid content concentration: 40%) 0.24 g, anhydrous ferric chloride 16.2 mg (manufactured by Kanto Chemical Co., Inc.) The ferric perchlorate was changed to 35.4 mg (manufactured by Kanto Chemical Co., Inc.), and conductive polymer compounds CP-B2 to CP-B5 were prepared, and the conductive polymer compound CP-B1 in the coating liquid A was prepared. Conductive films TC-109 to TC-112 were prepared in the same manner as the conductive film TC-104 except that the conductive polymer compounds CP-B2 to CP-B5 were used.

(Preparation of conductive film TC-113)
In the production of the conductive film TC-101, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ) To prepare a conductive film TC-W. The conductive film TC-W was immersed in a separately prepared 10% ethanol solution of p-toluenesulfonic acid for 1 hour. Thereafter, the conductive film was taken out of the solution, washed with ethanol, and dried by heating at 110 ° C. for 5 minutes, whereby a conductive film TC-113 was produced.

(Production of conductive films TC-114 and TC-115)
In the production of the conductive film TC-113, p-toluenesulfonic acid was replaced with anhydrous ferric chloride (manufactured by Kanto Chemical Co., Ltd.) and ferric perchlorate (manufactured by Kanto Chemical Co., Ltd.). Conductive films C-114 and TC-115 were produced in the same manner as the production.

(Production of conductive films TC-116 to TC-118)
In the production of the conductive film TC-104, half of the solid content weight (438 mg) of the polyester copolymer dispersion of the coating liquid A was cross-linked PMMA-based fine particles (Toughtic FH-S010, average particle size 300 nm, solid content concentration 27%. Manufactured by Toyobo Co., Ltd.), polystyrene fine particles (5003A, average particle size 30 nm, solid content concentration 10%, manufactured by Moritex Corporation), colloidal silica (Snowtex O, average particle size 18 nm, solid content concentration 20.6%, Nissan Chemical Co., Ltd.) The conductive films C-116 to TC-118 were manufactured in the same manner as the conductive film TC-104 except that the conductive films TC-104 were replaced.

(Preparation of conductive film TC-119)
In the production of the conductive film TC-104, the conductive polymer compound CP-A used in the synthesis of the conductive polymer compound CP-A1 was changed to the conductive polymer compound CP-C. -C was prepared, and 137.5 g of the conductive polymer compound CP-A (solid content concentration 1.0%) of the coating liquid A was replaced with 128.8 g of the conductive polymer compound CP-C (solid content concentration 1.3%). A conductive film TC-119 was manufactured in the same manner as the conductive film TC-104 except that the conductive film TC-104 was changed.

(Preparation of comparative conductive film TC-120)
In the production of the conductive film TC-101, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ) To produce a conductive film TC-Z. This conductive film TC-Z was used as a comparative conductive film TC-120.
(Preparation of comparative conductive film TC-121)
In the production of the conductive film TC-104, the polyester-based copolymer dispersion PO-13.5 g (solid content concentration 25%) of the coating liquid A was changed to 4.38 g of a comparative binder resin PO-A (solid content concentration 20%). A conductive film TC-121 was produced in the same manner as in the production of the conductive film TC-104 except for the change.

(Preparation of comparative conductive film TC-122)
In the production of the conductive film TC-116, half of the solid content weight of the polyolefin copolymer dispersion of the coating liquid A (438 mg) was converted to a silica sol dispersion (product name IPA-ST, particulate, average particle size 10 nm, solid content). Concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.) 243 mg, polyethylene particles (Ceracol 39, average particle size 13000 nm, solid content concentration 40%, manufactured by BYK-Chemie) 913 mg, except for changing to 913 mg Thus, a comparative conductive film TC-122 was produced.

(Preparation of comparative conductive film TC-123)
In the production of the conductive film TC-101, the polyester-based copolymer dispersion of coating solution A: PO-1 was not added, and methanesulfonic anhydride (40.4 mg, 0.42 mmol, molecular weight 96.11, Tokyo Chemical Industry Co., Ltd.) Comparison with p-toluenesulfonic acid monohydrate (79.9 mg, 0.42 mmol, molecular weight 190.22, manufactured by Tokyo Chemical Industry Co., Ltd.) Example Conductive film TC-123 was produced.

<Evaluation of conductive film>
The shape, transparency, surface resistance (conductivity), surface roughness and film strength of the obtained conductive film were evaluated as follows. In addition, in order to evaluate the stability of the conductive film, the film shape, transparency, surface resistance, surface roughness and film strength of the conductive film sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 14 days are evaluated. Went.

(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.
A: 80% or more B: 75% to less than 80% B: 70% to less than 75% X: Less than 70% Evaluation criteria: Samples evaluated as A and B pass as the present invention.

(Surface resistance)
The surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.) in accordance with JIS K 7194: 1994. The surface resistance is preferably 100Ω / □ or less, and preferably 30Ω / □ or less in order to increase the area of the organic electronic device.
Evaluation criteria: Samples evaluated as 30 Ω / □ or less after forced deterioration pass the present invention (surface roughness (Ra, Ry))
Using an AFM (Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit) and using a sample cut to a size of about 1 cm square, the surface roughness specified in the above method (JIS B601 (1994)). ).
Evaluation criteria: Samples evaluated as Ry ≦ 50 nm and Ra ≦ 10 nm passed the present invention.

(Membrane strength)
The strength of the conductive layer film was evaluated by a tape peeling method.
Crimping / peeling was repeated 10 times on the conductive layer using a Scotch tape manufactured by Sumitomo 3M Co., and the dropping of the conductive layer was visually observed and evaluated according to the following criteria.
◎: No change after 5 times of pressure bonding / peeling ○: No change after 3 times of pressure peeling / bonding △: Peeling is observed after 1 time of pressure peeling, but more than 80% pattern remains ×: 1 time of pressure peeling Table 1 shows the results of the pass evaluation of the present invention, in which peeling is observed and the remaining pattern is evaluated as less than 80% of the evaluation criteria: ◎, ○.

  From Table 1, with respect to the conductive films TC-120 to TC-123 of the comparative examples, the conductive films TC-101 to 119 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, and at a high temperature. It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.

<Example 2>
<Preparation of conductive film>
<Formation of first conductive layer>
A first conductive layer was formed on the barrier surface on the film substrate (base material 11) for the conductive film (conductive film 1) having gas barrier properties obtained above by the following method.

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

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

<Preparation of Conductive Film TC-101>
Adjust the slit gap of the extrusion head to a dry film thickness of 200 nm on the non-barrier surface of the film substrate for a conductive film having gas barrier properties by using the extrusion method to achieve a dry film thickness of 200 nm. Then, it was heated and dried at 110 ° C. for 3 minutes to form a conductive layer, and the obtained electrode was cut into 8 × 8 cm. The obtained electrode was heated in an oven at 110 ° C. for 7 minutes to produce a conductive film TC-201.

(Synthesis of conductive polymer compound CP-A1)
Conductive polymer compound CP-A (solid content concentration: 1.0%) to methanesulfonic anhydride (40.4 mg, 0.42 mmol, molecular weight 96.11, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium persulfate (0.11 g) , 0.42 mmol, molecular weight 270.32, manufactured by Kanto Chemical Co., Ltd.) and iron (III) sulfate n hydrate (0.78 mg, 4.5 × 10 ⁻⁴ mmol (purity 70% conversion), molecular weight 399.88 A homogenizer (main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was placed and operated under the liquid level of the solution, and then at room temperature. Subsequently, 0.5 g of an anion exchanger (Bayer AG Lewatit MP62) and 0.5 g of a cation exchanger (Bayer AG Lewatit S100) were added as a solution. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. A polymer compound CP-A1 was obtained (solid content concentration: 1.0%).

(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a coating solution A.
Conductive polymer dispersion: conductive polymer compound CP-A1 (solid content concentration 1.0%) 37.5 g
Polyester copolymer dispersion: PO-1 (solid content concentration 25%, solid content 875 mg) 3.5 g
1.0 g of dimethyl sulfoxide (DMSO, 1/5 of the conductive polymer solution mass)

(Production of conductive films TC-202 to TC-204)
In the production of the conductive film TC-201, methanesulfonic acid used for the synthesis of the conductive polymer compound CP-A1 was changed to benzenesulfonic anhydride (66.4 mg, 0.42 mmol, molecular weight 158.18, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-Naltalenesulfonic acid (87.5 mg, 0.42 mmol, molecular weight 208.23, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (79.9 mg, 0.42 mmol, molecular weight 190.22, Tokyo) Manufactured by Kasei Co., Ltd., and produced conductive polymer compounds CP-A2 to CP-A4, and the conductive polymer compounds CP-A2 to CP-A4 in the coating liquid A were prepared. The conductive films TC-202 to TC-204 were prepared in the same manner as the conductive film TC-101 except that the conductive film TC-101 was used.

(Production of conductive films TC-205 to TC-207)
In the production of the conductive film TC-204, the polyester-based copolymer dispersion of the coating liquid A was added to PLUS COAT Z561 (manufactured by Kyoyo Chemical Co., Ltd., solid content concentration 25%), Yodosol AD166 (manufactured by Henkel Co., Ltd., solid content concentration 49%). The conductive films C-205 to TC207 were prepared by changing to PO-2 (solid concentration 25%) and adding so that the solid content was 875 mg.

<Preparation of Conductive Film TC-208>
Adjust the slit gap of the extrusion head to a dry film thickness of 300 nm on the non-barrier surface of the film substrate for a conductive film having gas barrier properties by using the extrusion method to a dry film thickness of 300 nm. Then, it was heated and dried at 110 ° C. for 5 minutes to form a conductive layer made of a conductive polymer and an olefin copolymer, and the obtained electrode was cut into 8 × 8 cm. The obtained electrode was heated in an oven at 110 ° C. for 15 minutes to produce a conductive film TC-208.

(Synthesis of conductive polymer compound CP-B1)
0.14 g of a normal butanol solution (solid content concentration: 40%) of an oxidizing agent / dopant compound OX-1 is added to 5.0 g of the conductive polymer compound CP-B (solid content concentration: 1.0%), and a homogenizer. (Main body: Ultratatex T-25, shaft generator: S25N-10G (manufactured by IKA)) was placed and operated under the liquid level of the solution, and then stirred at room temperature for 12 hours. Subsequently, 0.5 g of an anion exchanger (Bayer AG Lewatit MP62) and 0.5 g of a cation exchanger (Bayer AG Lewatit S100) were added to the solution and stirred for 8 hours. The ion exchanger was removed by filtration, and the resulting solution was homogenized twice using a high pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a conductive polymer compound CP-B1. (Solid content concentration: 1.0%).

(Coating liquid A)
The solution having the following composition was homogenized twice using a high-pressure homogenizer under conditions of 71 kPa, nozzle diameter 0.1 mm, and 5 to 10 ° C. to obtain a coating solution A.
Conductive polymer dispersion: conductive polymer compound CP-B1 (solid content concentration 1.0%) 37.5 g
Polyester copolymer dispersion: PO-1 (solid content concentration 25%, solid content 875 mg) 3.5 g
1.0 g of dimethyl sulfoxide (DMSO, 1/5 of the conductive polymer solution mass)

(Production of conductive films TC-209 to TC-212)
In the production of the conductive film TC-208, instead of adding 0.14 g of the normal butanol solution (solid content concentration: 40%) of the oxidizer and dopant compound OX-1, the normal butanol solution of the oxidizer and dopant compound OX-2 (Solid content concentration: 40%) 0.15 g, normal butanol solution of oxidizer and dopant compound OX-3 (solid content concentration: 40%) 0.24 g, anhydrous ferric chloride 16.2 mg (manufactured by Kanto Chemical Co., Inc.) The ferric perchlorate was changed to 35.4 mg (manufactured by Kanto Chemical Co., Inc.), and conductive polymer compounds CP-B2 to CP-B5 were prepared, and the conductive polymer compound CP-B1 in the coating liquid A was prepared. Conductive films TC-209 to TC-212 were prepared in the same manner as the conductive film TC-204 except that the conductive polymer compounds CP-B2 to CP-B5 were used.

(Preparation of conductive film TC-213)
In the production of the conductive film TC-201, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ) To prepare a conductive film TC-X. The conductive film TC-X was immersed in a 10% ethanol solution of p-toluenesulfonic acid prepared separately for 1 hour. Thereafter, the conductive film was taken out of the solution, washed with ethanol, and dried by heating at 110 ° C. for 5 minutes, whereby a conductive film TC-213 was produced.

(Production of conductive films TC-214 and TC-215)
In the production of the conductive film TC-213, p-toluenesulfonic acid was replaced with anhydrous ferric chloride (manufactured by Kanto Chemical Co., Inc.) and ferric perchlorate (manufactured by Kanto Chemical Co., Ltd.). Conductive films TC-214 and TC-215 were produced in the same manner as the production.

(Production of conductive films TC-216 to TC-218)
In the production of the conductive film TC-204, half of the solid content weight (438 mg) of the polyester copolymer dispersion of the coating liquid A was used as crosslinked PMMA-based fine particles (Toughtic FH-S010, average particle size 300 nm, solid content concentration 27%. Manufactured by Toyobo Co., Ltd.), polystyrene fine particles (5003A, average particle size 30 nm, solid content concentration 10%, manufactured by Moritex Corporation), colloidal silica (Snowtex O, average particle size 18 nm, solid content concentration 20.6%, Nissan Chemical Co., Ltd.) The conductive films TC-216 to TC218 were manufactured in the same manner as the conductive film TC-204 except that the conductive films TC-204 were replaced.

(Preparation of conductive film TC-219)
In the production of the conductive film TC-204, the conductive polymer compound CP-A used in the synthesis of the conductive polymer compound CP-A1 was changed to the conductive polymer compound CP-C. -C was prepared, and 137.5 g of the conductive polymer compound CP-A (solid content concentration 1.0%) of the coating liquid A was replaced with 128.8 g of the conductive polymer compound CP-C (solid content concentration 1.3%). A conductive film TC-219 was manufactured in the same manner as the conductive film TC-204 except that the conductive film TC-204 was changed.

(Preparation of conductive film TC-220)
(Random network structure)
Silver nanowire dispersions are described in Adv. Mater. , 2002, 14, 833 to 837, by using PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were produced. Silver nanowires are filtered and washed using a filtration membrane, and then redispersed in an aqueous solution in which 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to silver to prepare a silver nanowire dispersion. did.

The random network structure was prepared using silver nanowires as shown below. The silver nanowire dispersion liquid is applied by using a bar coating method so that the amount of silver nanowires is 0.06 g / m ^2, and dried and heated at 110 ° C. for 5 minutes to form a silver nanowire substrate ( Substrate). A second conductive layer is formed on the first conductive layer having a random network structure formed of silver nanowires by using the same coating solution A as that for TC-204 and by the same method as that for forming the conductive film TC-204. Cut out to 8 cm. The obtained electrode was heated using an oven at 110 ° C. for 15 minutes to produce a conductive film TC-220.

(Production of conductive films TC-221 and TC-222)
Conductive films TC-221 and TC-222 were prepared in the same manner as the conductive films TC-217 and TC-218 except that the coating solution A used in the preparation of the conductive films TC-217 and TC-218 was used. .

(Preparation of conductive film TC-223)
In the production of the conductive film TC-201, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ), Colloidal silica (Snowtex O, average particle size 18 nm, solid content concentration 20.6%, manufactured by Nissan Chemical Co., Ltd.) is used as a solid weight (438 mg) of the polyester copolymer dispersion of coating liquid A. The conductive film TC-Y was manufactured by substituting The conductive film TC-Y was immersed in a separately prepared 10% ethanol solution of p-toluenesulfonic acid for 1 hour. Thereafter, the conductive film was taken out of the solution, washed with ethanol, and dried by heating at 110 ° C. for 5 minutes, whereby a conductive film TC-213 was produced.

(Preparation of conductive film TC-224)
(Copper mesh substrate)
On the substrate (base material), a copper mesh was prepared as an auxiliary electrode by the following method, followed by patterning with the metal fine particle removing liquid BF, to prepare a copper mesh substrate.

  The catalyst ink GIPD-7 manufactured by Morimura Chemical Co. containing palladium nanoparticles is used, and the CAB-O-JET300, a self-dispersing carbon black solution manufactured by Cabot, has a carbon black ratio of 10.0% by mass with respect to the catalyst ink. In addition, Surfinol 465 (Nisshin Chemical Industry Co., Ltd.) was added to prepare a conductive ink having a surface tension at 25 ° C. of 48 mN / m.

  Conductive ink as an ink jet recording head has a pressure applying means and an electric field applying means, and has a nozzle diameter of 25 μm, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi (dpi is 1 inch, that is, 2.54 cm per 2.54 cm). A grid-like conductive thin wire having a line width of 10 μm, a film thickness after drying of 0.5 μm, and a line spacing of 300 μm is loaded on the base material. After forming into parts, it was dried.

  Subsequently, using a high-speed electroless copper plating solution CU-5100 manufactured by Meltex, the substrate was immersed for 10 minutes at a temperature of 55 ° C., washed, and subjected to electroless plating treatment to produce an auxiliary electrode having a plating thickness of 3 μm. .

  On the conductive film in which the copper mesh is formed as the first conductive layer, the second conductive layer is formed by the same method as the production of the conductive film TC-204 using the same coating liquid A as TC-204, and 8 × 8 cm. Cut out. The obtained electrode was heated using an oven at 110 ° C. for 15 minutes to produce a conductive film TC-224.

(Production of conductive films TC-225 and TC-226)
Conductive films TC-225 and TC-226 were prepared in the same manner as the conductive films TC-217 and TC-218 except that the coating solution A used in the preparation of the conductive films TC-217 and TC-218 was used. .

(Preparation of conductive film TC-227)
In the production of the conductive film TC-201, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ), Colloidal silica (Snowtex O, average particle size 18 nm, solid content concentration 20.6%, manufactured by Nissan Chemical Co., Ltd.) is used as a solid weight (438 mg) of the polyester copolymer dispersion of coating liquid A. The conductive film TC-Z was produced by replacing with. The conductive film TC-Y was immersed in a separately prepared 10% ethanol solution of p-toluenesulfonic acid for 1 hour. Thereafter, the conductive film was taken out of the solution, washed with ethanol, and dried by heating at 110 ° C. for 5 minutes, whereby a conductive film TC-227 was produced.

(Preparation of comparative conductive film TC-228)
In the production of the conductive film TC-201, instead of the conductive polymer compound CP-A1 (solid content concentration 1.0%) of the coating liquid A, the conductive polymer compound CP-A (solid content concentration 1.0%). ) To prepare a conductive film TC- *. This conductive film TC- * was used as a comparative conductive film TC-228.

(Preparation of comparative conductive film TC-229)
In the production of the conductive film TC-204, the polyester-based copolymer dispersion PO-13.5 g (solid content concentration 25%) of the coating liquid A was changed to 4.38 g of a comparative binder resin PO-A (solid content concentration 20%). A conductive film TC-229 was produced in the same manner as in the production of the conductive film TC-204 except that it was changed.

(Preparation of comparative conductive film TC-230)
In the production of the conductive film TC-216, half the solid weight (438 mg) of the polyolefin copolymer dispersion of the coating liquid A was used as a silica sol dispersion (product name IPA-ST, particulate, average particle size 10 nm, solid content). Concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.) 243 mg, polyethylene particles (Ceracol 39, average particle size 13000 nm, solid content concentration 40%, manufactured by BYK-Chemie) 913 mg, except for changing to 913 mg Thus, a comparative conductive film TC-230 was produced.

(Preparation of comparative conductive film TC-231)
In the production of the conductive film TC-201, the polyester copolymer dispersion of coating liquid A: PO-1 was not added, and methanesulfonic anhydride (40.4 mg, 0.42 mmol, molecular weight 96.11, Tokyo Chemical Industry Co., Ltd.) Comparison with p-toluenesulfonic acid monohydrate (79.9 mg, 0.42 mmol, molecular weight 190.22, manufactured by Tokyo Chemical Industry Co., Ltd.) Example A conductive film TC-231 was produced.

<Evaluation of conductive film>
The obtained conductive film was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  From Table 2, with respect to the conductive films TC-228 to TC-231 of the comparative examples, the conductive films TC-201 to 227 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, and at a high temperature. It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.

<Example 3>
<Production of organic EL device>
The conductive film produced in Example 2 was washed with ultrapure water, then cut into 30 mm squares so that one square tile-shaped pattern with a pattern side length of 20 mm was placed in the center, and used for the anode electrode according to the following procedure. An organic EL device was produced. The hole transport layer and subsequent layers were formed by vapor deposition. Using the conductive films TC-201 to TC-231, organic EL elements OEL-301 to OEL-331 were produced, respectively.

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

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

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

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

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

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

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

<Formation of cathode electrode>
On the formed electron transport layer, Al was mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as a cathode forming material having a conductive film as an anode and an anode external takeout terminal of 15 mm × 15 mm, and an anode having a thickness of 100 nm Formed.
Further, a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al ₂ O ₃ is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed. After pasting the members, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm × 15 mm was produced.

<Evaluation of organic EL element>
About the obtained organic EL element, the light emission nonuniformity and lifetime were evaluated as follows.
(Emission uniformity)
For light emission uniformity, a KEITHLEY source measure unit 2400 type was used to apply a DC voltage to the organic EL element to emit light. Regarding the organic EL elements OEL-201 to OEL-230 that emitted light at 1000 cd / m ² , each light emission luminance unevenness was observed with a 50 × microscope. In addition, after heating the organic EL elements OEL-201 to OEL-230 in an oven at 60% RH and 80 ° C. for 2 hours, the humidity was adjusted again in the environment of 23 ± 3 ° C. and 55 ± 3% RH for 1 hour or more. Thereafter, the emission uniformity was observed in the same manner.
A: Completely uniform light emission, satisfactory O: Almost uniform light emission, no problem Δ: Some light emission unevenness is observed partially, but acceptable X: Light emission unevenness is observed over the entire surface, not acceptable Evaluation criteria: Samples evaluated as ◎ and ○ after forced deterioration pass the present invention.

(lifespan)
The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL element having an anode electrode made of ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. 100% or more is preferable, and 150% or more is more preferable.
◎: 150% or more ○: 100 to less than 150% △: less than 80 to 100% ×: less than 80% Evaluation criteria: After forced deterioration ◎, samples evaluated as ○ pass as the present invention.

Table 3 shows the evaluation results. In Table 3, “Invention” in the remarks indicates that it corresponds to an example of the present invention, and “Comparison” indicates that it is a comparative example.

  From Table 3, the organic EL elements OEL-328 to OEL-331 of the comparative examples are significantly deteriorated in light emission uniformity after heating at 60% RH and 80 ° C. for 2 hours, whereas the organic EL elements OEL- of the present invention. It can be seen that 301 to OEL-327 have stable emission even after heating and excellent durability.

DESCRIPTION OF SYMBOLS 1 Conductive film 11 Base material 12 1st conductive layer 13 2nd conductive layer

Claims (7)

On a substrate,
A first conductive layer including a metal material formed in a pattern;
A second conductive layer comprising an organic compound layer containing at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent;
With
The organic compound layer contains at least one kind of a low molecular anion capable of salting with a cationic π-conjugated conductive polymer compound ,
The conductive film, wherein the second conductive layer is electrically connected to the first conductive layer . The cationic π-conjugated conductive polymer compound is a polythiophene
The conductive film according to claim 1. The cationic π-conjugated conductive polymer compound and a counter salt with Low molecular anions, sulfonate anions, chlorine anion, claim characterized by containing one kind of perchlorate ions 1 or claim 2 The electrically conductive film of description. The conductive film according to any one of claims 1 to 3, wherein the organic compound layer contains fine particles having an average particle size of 300 nm or less. An organic electroluminescence element comprising the conductive film according to any one of claims 1 to 4 as an electrode. On the substrate, forming an organic compound layer containing at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent;
By subjecting the organic compound layer to a surface treatment with a low molecular sulfonic acid compound and a ferric compound-containing lower alcohol, at least one kind of low molecular anion capable of salting with a cationic π-conjugated conductive polymer compound is converted into the organic compound layer. The steps to introduce into,
The manufacturing method of the electrically conductive film characterized by including. Forming a metal material-containing conductive layer formed in a pattern on a substrate;
Forming an organic compound layer containing at least a cationic π-conjugated conductive polymer compound, a polyanion and a polymer dispersible in an aqueous solvent on the substrate;
By subjecting the organic compound layer to a surface treatment with a low molecular sulfonic acid compound and a ferric compound-containing lower alcohol, at least one kind of low molecular anion capable of salting with a cationic π-conjugated conductive polymer compound is converted into the organic compound layer. The steps to introduce into,
The manufacturing method of the electrically conductive film characterized by including.

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