WO2011105148A1 - Film conducteur transparent et élément électroluminescent organique - Google Patents

Film conducteur transparent et élément électroluminescent organique Download PDF

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Publication number
WO2011105148A1
WO2011105148A1 PCT/JP2011/051179 JP2011051179W WO2011105148A1 WO 2011105148 A1 WO2011105148 A1 WO 2011105148A1 JP 2011051179 W JP2011051179 W JP 2011051179W WO 2011105148 A1 WO2011105148 A1 WO 2011105148A1
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transparent conductive
group
conductive film
transparent
polymer compound
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PCT/JP2011/051179
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English (en)
Japanese (ja)
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中村　和明
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コニカミノルタホールディングス株式会社
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Priority to JP2012501709A priority Critical patent/JP5660121B2/ja
Publication of WO2011105148A1 publication Critical patent/WO2011105148A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes

Definitions

  • the present invention provides a transparent 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 material using the transparent conductive film.
  • the present invention relates to an electroluminescence element (hereinafter also referred to as an organic EL element).
  • the transparent electrode transparent conductive film
  • transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.
  • 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 has been mainly used. It was. However, since indium used for ITO is a rare metal and is relatively expensive, indium removal is desired. Also, roll-to-roll production technology using a flexible substrate has been desired along with an increase in display size and productivity.
  • ITO indium-tin composite oxide
  • a composition in which a water-soluble compound or sulfoxide compound having an amide bond or a hydroxyl group is added to a dispersion of a poly 3,4-dialkoxythiophene and a polyanion complex for example, a patent Reference 2
  • aqueous dispersions to which organic compounds containing polyhydroxy, carboxy group, amide group, and lactam group are added for example, see Patent Document 3
  • a transparent surface electrode has been proposed in which polyurethane is overcoated on silver nanowires coated on a transparent substrate and the electrode surface is smooth (see, for example, Patent Document 5).
  • an organic EL element is laminated on the transparent electrode, there is a problem that the surface light emission property and the light emission lifetime are poor.
  • an electrode used for an organic EL element As an electrode used for an organic EL element, a smooth electrode having an average surface roughness (Ra) of 10 nm or less is usually used.
  • Ra average surface roughness
  • an organic EL element is produced using an electrode having protrusions on the surface of the transparent electrode as in Patent Document 4, there is a problem that the protrusions are shorted, such as a short circuit between the anode and the cathode. Below, there was a problem that this phenomenon becomes more prominent. Further, there is a problem that a transparent resin exists between the protrusions and a function as a surface electrode cannot be obtained.
  • Patent Document 6 a transparent electrode in which a silver nanowire that is a metal nanowire is used as a conductive fiber and a conductive polymer material is laminated on the silver nanowire has been proposed (see, for example, Patent Document 6).
  • the conductivity is lowered under high temperature and high humidity environment, and when the organic EL element is laminated on the transparent electrode, there is a problem that the surface light emission and the light emission life are remarkably deteriorated.
  • Patent Document 2 cannot achieve both low resistivity and high transmittance, it is said that when used in an organic EL device, the surface light emission and the light emission life are deteriorated when used in an organic EL element at a high temperature and high humidity. Had problems.
  • a transparent conductive film such as a conductive polymer compound is laminated on a thin metal wire formed in a pattern, and the current surface is highly uniform.
  • a transparent conductive film having both conductivity has been developed (see, for example, Patent Documents 7 and 8).
  • the conductive polymer compound has absorption in the visible light region, there is a problem that when the film is thickened, the transparency of the transparent electrode is significantly lowered.
  • the present invention has been made in view of the above problems.
  • the object of the present invention is excellent in smoothness, conductivity, and light transmittance, and also has smoothness, conductivity, and light transmittance even in a high temperature and high humidity environment.
  • An object of the present invention is to provide a transparent conductive film which gives an organic EL device which is less deteriorated, excellent in stability and light emission uniformity, and less deteriorated in light emission uniformity and excellent in durability.
  • Another object of the present invention is to provide an organic EL device having high emission uniformity using the transparent conductive film, less deterioration of emission uniformity, and excellent durability.
  • the particle size of the conductive polymer and water-soluble polymer dispersion used in the present invention is 100 nm or less, and the smoothness of the transparent conductive film is excellent by using it together with the conductive fiber.
  • a transparent electrode with excellent stability, having both conductivity and transparency, having both high conductivity, transparency and good smoothness even after an environmental test in a high-temperature and high-humidity environment, and an organic material using the transparent electrode It has been found that an electroluminescence element can be obtained.
  • a transparent conductive film comprising a conductive fiber and an organic compound layer on a transparent substrate
  • the organic compound layer is a conductive material comprising a polymer compound having a repeating structural unit represented by the following general formula (I) and a polyanion
  • a water-soluble binder resin having a polymer compound and a repeating structural unit represented by the following general formula (1) is contained, and the organic compound layer is a dispersion of the conductive polymer compound and the water-soluble binder resin.
  • a transparent conductive film which is an organic compound layer formed by applying and drying a liquid, and the average particle size of the particles in the dispersion is 5 to 100 nm.
  • A represents an optionally substituted alkylene group having 1 to 4 carbon atoms
  • Q represents an oxygen atom or a sulfur atom.
  • R 1 represents at least one selected from an alkyl group, a cycloalkyl group, an aryl group, a heterocycloalkyl group, and a heteroaryl group containing at least one hydroxyl group
  • R 2 represents a hydrogen atom or a methyl group.
  • a transparent conductive film having a first conductive layer made of a metal material formed in a pattern on a substrate and a second conductive layer containing a conductive polymer compound, the repetition represented by the general formula (I)
  • a transparent conductive film comprising a polymer compound having a structural unit.
  • An organic electroluminescence device comprising the transparent conductive film according to any one of 1 to 5 above.
  • the smoothness, conductivity and light transmittance are excellent, and the smoothness, conductivity and light transmittance are hardly deteriorated even in a high temperature and high humidity environment, and the stability and light emission uniformity are excellent.
  • the transparent conductive film which gives the organic EL element which is excellent in durability with little deterioration of light emission uniformity can be provided.
  • the present invention relates to a conductive fiber on a transparent substrate, a polymer compound having a repeating structural unit represented by the general formula (I), a polyanion, and a water solution having a repeating structural unit represented by the general formula (1).
  • a transparent conductive film having a transparent conductive layer containing a conductive binder resin, a polymer compound having a repeating structural unit represented by the general formula (I), a polyanion, and a repeating represented by the general formula (1) is characterized in that the dispersion having an average particle size of 50 nm or less in the dispersion comprising the water-soluble binder resin having a structural unit is used.
  • the electrode has a conductive fiber and a polymer compound having a repeating structural unit represented by the general formula (I), a polyanion, and a water-soluble compound having a repeating structural unit represented by the general formula (1).
  • a transparent conductive layer using a dispersion composed of a binder resin, it is excellent in smoothness, conductivity and light transmittance, and smoothness, conductivity and light transmittance are deteriorated even in a high temperature and high humidity environment.
  • a transparent conductive film that provides an organic EL device that is small and excellent in durability, has high emission uniformity, and has a long emission lifetime can be obtained.
  • 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 for Conductive Plastics by Four-Probe Method” is 10 ⁇ 8 ⁇ . / It means lower than ⁇ .
  • the transparent electrode contains a polymer compound having a repeating structural unit represented by the above general formula (I) in the first transparent conductive layer, or on the first transparent conductive layer. It has the 2nd transparent conductive layer containing the high molecular compound which has a repeating structural unit represented by (I).
  • A represents an optionally substituted alkylene group having 1 to 4 carbon atoms,
  • 1,2-alkylene, 1,2-cyclohexylene, 2,3-butylene, 2,3-dimethylene, 2,3-butylene, 2,3-pentylene and the like can be mentioned.
  • Preferred are a methylene group, 1,2-ethylene and 1,2-propylene. More preferred is 1,2-ethylene.
  • Q represents a divalent atom, for example, an oxygen atom or a sulfur atom, Preferably it is an oxygen atom.
  • Q may be the same or different.
  • the repeating structural unit represented by the general formula (I) of the present invention may contain two or more types of molecular structures that are the same or different.
  • Examples of the polyanion used in the present invention include compounds selected from the group consisting of polymer carboxylic acids, polymer sulfonic acids, and derivatives of these salts, preferably polymer sulfonic acids and salts thereof. .
  • the polyanions may be contained alone or in combination of two or more.
  • the polyanion may form a copolymer with a structural unit having carboxylic acid or sulfonic acid and a monomer having no acid residue, such as acrylate, methacrylate, styrene, or the like.
  • polymer carboxylic acid, polymer sulfonic acid and salts thereof include, for example, polyacrylic acid, polymethacrylic acid or polymaleic acid, polymer sulfonic acid, polystyrene sulfonic acid and polyvinyl sulfonic acid and salts thereof.
  • Polystyrene sulfonic acid and its salt are preferable.
  • M represents H + , an alkali metal ion, or an ammonium ion, preferably proton, lithium ion, sodium Ions and potassium ions, more preferably protons and sodium ions.
  • the synthesis of the polyanion having the repeating structural unit represented by the general formula (II) can be carried out by bulk, solution, precipitation, suspension or (inverse) emulsion polymerization.
  • a solution polymerization method is preferred for obtaining an appropriate molecular weight.
  • a peroxide, a hydroperoxide, a persulfate, an azo compound, a redox catalyst, or the like can be used as the initiator used for the synthesis of the polyanion having the repeating structural unit represented by the general formula (II).
  • a persulfate such as potassium persulfate, sodium persulfate and ammonium persulfate, and an azo compound such as 2,2′-azobisbutyronitrile are preferably used.
  • the polymerization solvent used for the synthesis of the polyanion having the repeating structural unit represented by the general formula (II) is inactive under the reaction conditions, and is not particularly limited as long as the monomer and the polymer to be formed can be dissolved, but water is preferable. .
  • the solution polymerization can be carried out at a total monomer concentration of 1 to 80% by weight, preferably 10 to 60% by weight.
  • the polymerization temperature for carrying out the synthesis of the polyanion having the repeating structural unit represented by the general formula (II) varies depending on the initiator used, but is generally ⁇ 10 to 250 ° C., preferably 0 to 200 ° C., more preferably 10 Performed at ⁇ 100 ° C.
  • the starting materials may be introduced first into the solvent, introduced separately into the solvent or together.
  • the addition of the free radical initiator dissolved in a suitable solvent can be carried out before, simultaneously with or after the addition of the starting material.
  • the reaction is preferably carried out under reflux or in a protective gas atmosphere, preferably nitrogen gas or argon.
  • Monomers used for the synthesis of polyanions include acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid and alkali metal salts and ammonium salts thereof. These may be used alone or in combination. May be synthesized.
  • the molecular weight of the polyanion having the repeating structural unit represented by the general formula (II) is preferably in the range of 1,000 to 2,000,000, more preferably 2,000 to 500,000, and still more preferably 3,000 to 100,000. Within range.
  • the molecular weight of the polyanion can be measured by a conventional method such as gel permeation chromatography or osmotic pressure measurement.
  • the conductive polymer compound of the present invention has a cationic polymer compound in which the main chain is a ⁇ -conjugated system, and has a composite structure having the polyanion as a counter anion.
  • the cationic polymer compound of the present invention is not particularly limited as long as the main chain is an organic polymer composed of a ⁇ -conjugated system.
  • polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes examples thereof include polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof.
  • polypyrroles, polythiophenes and polyanilines are preferably used.
  • the cationic polymer compound is not substituted, sufficient conductivity and compatibility with the binder resin can be obtained.
  • an alkyl group, a carboxy group, a sulfo group can be obtained. It is preferable to introduce a functional group such as a group, an alkoxy group or a hydroxy group into the polymer compound.
  • cationic polymer compound examples include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly ( 3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), Poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3- Hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3 Methyl-4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene),
  • the polymer compound having the repeating structural unit represented by the general formula (I) is contained, and the conductive polymer compound according to the present invention is further represented by the general formula (II).
  • the aspect which has the polyanion which has is a preferable aspect.
  • A represents an optionally substituted alkylene group having 1 to 4 carbon atoms
  • Q represents an oxygen atom or a sulfur atom.
  • the polymer compound containing the repeating structural unit represented by the general formula (I) may contain the same structural unit repeatedly or may contain two or more different structural units repeatedly.
  • the polymer compound containing the repeating structural unit represented by the general formula (I) can be obtained by oxidative polymerization of a compound represented by the following general formula (Ia).
  • a and Q have the same meanings as A and Q in general formula (I).
  • the 3,4-di-substituted thiophene in which Q is an oxygen atom in the general formula (Ia) is obtained by combining an alkali metal salt of 3,4-dihydroxythiophene-2,5-dicarboxylic acid ester with an appropriate alkylene dihalide.
  • the free 3,4- (alkylenedioxy-) thiophene-2,5-dicarboxylic acid can then be obtained by decarboxylation (see, for example, Tetrahedron, 1967, 23, 2437-2441 and J. Am. Chem. Soc., 1945, 67, 2217-2218).
  • Polythiophene is positively charged by oxidative polymerization, but it is difficult to determine its number and position clearly.
  • the conductive polymer compound according to the present invention may have a structural unit having an anionic group in addition to the repeating structural unit represented by the general formula (II), but 50% (mol) of the total anionic group.
  • the above is preferably a repeating structural unit represented by the general formula (II), and particularly preferably 90% or more is a repeating structural unit represented by the general formula (II).
  • the synthesis of the polymer compound having the repeating structural unit represented by the general formula (I) according to the present invention forms a cationic polymer compound with the polyanion having the repeating structural unit represented by the general formula (II). It is carried out by stirring at a predetermined polymerization temperature in a solvent containing a compound having a repeating structural unit until the polymerization reaction is completed.
  • the mass ratio of the cationic polymer compound to the polyanion having the repeating structural unit represented by the general formula (II) is not particularly limited as long as the polyanion is rich, but the cationic polymer compound is 50 or less relative to 1. Is preferable, more preferably 25 or less, and still more preferably 10 or less.
  • Polymerization time can be between a few minutes and 30 hours depending on batch size, polymerization temperature and oxidant. Preferred polymerization times are generally between 30 minutes and 24 hours.
  • Suitable oxidizing agents are for example described in J. Am. Soc. 85, 454 (1963). Any oxidant suitable for oxidative polymerization of pyrrole.
  • oxidants such as iron (III) salts such as FeCl 3 , Fe (ClO 4 ) 3 , organic acids and iron (III) salts of inorganic acids containing organic residues (eg Fe 2 (SO 4 ) 3 ), or H 2 O 2 , K 2 Cr 2 O 7 , alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper It is preferred to use a salt such as copper tetrafluoroborate.
  • iron (III) salts such as FeCl 3 , Fe (ClO 4 ) 3
  • organic acids and iron (III) salts of inorganic acids containing organic residues eg Fe 2 (SO 4 ) 3
  • iron (III) salts of inorganic acids containing organic acids and organic residues have great application advantages because they are not corrosive.
  • iron (III) salt of an inorganic acid containing an organic residue include an iron (III) salt of an alkanol sulfate ester having 1 to 20 carbon atoms, such as an Fe (III) salt of lauryl sulfate.
  • iron (III) salts of organic acids include: alkyl sulfonic acids having 1 to 20 carbon atoms such as methane or dodecane sulfonic acid; aliphatic carboxylic acids having 1 to 20 carbon atoms such as 2-ethylhexyl.
  • Carboxylic acids aliphatic perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as oxalic acid and especially aromatic, optionally alkyl substituted sulfonic acids having 1 to 20 carbon atoms, such as It is also possible to use iron (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid, and also mixtures of iron (III) salts of the above mentioned organic acids.
  • the repeating structural unit represented by the general formula (II) is present in an amount of 0.25 to 10, preferably 0.8 to 8, anionic groups for each mole of the corresponding thiophene. It is preferable to add in.
  • Organic solvents used for the polymerization are inert under reaction conditions, such as aliphatic alcohols such as methanol, ethanol and propanol; aliphatic ketones such as acetone, methyl ethyl ketone; aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate.
  • aliphatic alcohols such as methanol, ethanol and propanol
  • aliphatic ketones such as acetone, methyl ethyl ketone
  • aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate.
  • Aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; chlorinated hydrocarbons such as dichloromethane and dichloroethane; aliphatic nitriles such as acetonitrile; aliphatic sulfoxides and sulfones such as dimethyl sulfoxide and Sulfolane; aliphatic carboxamides such as methylacetamide and dimethylformamide; aliphatic and aromatic ethers such as diethyl ether and anisole It is. Furthermore, water or a mixture of water and the above organic solvent can also be used as the solvent. Preferably it is water.
  • the amount of the solvent used for the oxidative polymerization is 0.1 to 80% by mass, preferably 0.5 to 50% by mass of the polymer compound according to the present invention from the viewpoint of dispersibility of the synthesized polymer compound.
  • the oxidative polymerization is generally carried out at ⁇ 10 to 250 ° C., preferably 0 to 200 ° C., more preferably 10 to 100 ° C., depending on the oxidizing agent used and the required reaction time.
  • the starting material may be introduced first into the solvent, separately into the solvent or introduced together.
  • the addition of the oxidizing agent dissolved in a suitable solvent can be carried out before, simultaneously with or after the addition of the starting materials.
  • the reaction is preferably carried out under reflux or in a protective gas atmosphere, preferably nitrogen gas or argon.
  • the synthesis of the polymer compound having the repeating structural unit represented by the general formula (I) according to the present invention forms a cationic polymer compound with the polyanion having the repeating structural unit represented by the general formula (II).
  • Polymerization is carried out in a solvent containing a compound as a structural unit while shearing with an ultrasonic wave, a high-pressure homogenizer or the like until the polymerization reaction is completed.
  • the dispersed particles can be reduced in size by an appropriate pulverization method.
  • Examples of the pulverization method include a ball mill, a stirring mill, high-speed stirring, ultrasonic treatment, and high-pressure homogenizer treatment. Of these, ultrasonic treatment and high-pressure homogenizer treatment are preferable. More preferred is a high-pressure homogenizer treatment.
  • the dispersion can be passed through a metal or ceramic nozzle one or more times under high pressure.
  • the nozzle diameter is 1 to 0.1 mm, or in the case of a slot nozzle, the width is 0.1 to 1 mm.
  • the homogenizer treatment is carried out at a pressure of 1 to 2000 bar, preferably 100 to 1000 bar (1 bar is 1 ⁇ 10 5 Pa).
  • the water-soluble binder resin according to the present invention is a water-soluble binder resin, and means a binder resin in which 0.001 g or more is dissolved in 100 g of water at 25 ° C.
  • the dissolution can be measured with a haze meter or a turbidimeter.
  • the water-soluble binder resin of the present invention is a water-soluble binder resin having a repeating structural unit represented by the general formula (1), and may be a homopolymer or a copolymer, and the water-soluble binder according to the present invention.
  • a transparent water-soluble binder resin can be used in combination.
  • the water-soluble binder resin that can be used in combination is not particularly limited as long as it is a natural polymer, synthetic resin (homopolymer, copolymer), or other medium for forming a film.
  • water-soluble binders include: gelatin, casein, starch, gum arabic, poly (vinyl alcohol), poly (vinyl pyrrolidone), carboxymethyl ether cellulose, hydroxyethyl cellulose, methyl hydroxyethyl ether cellulose and other celluloses, chitosan, dextran , Guar gum, poly (acrylamide), poly (acrylamide-acrylic acid), poly (acrylic acid), poly (methacrylic acid), poly (allylamine), poly (butadiene-maleic anhydride), poly (n-butyl acrylate-2) -Methacryloyltrimethylammonium bromide), poly (3-chloro-2-hydroxypropyl-2-methacryloxytrimethylammonium bromide), poly (2-dimethyla
  • the polymer having carboxylic acid, sulfonic acid, phosphoric acid or the like may have a salt such as lithium, sodium or potassium, and the polymer having a nitrogen atom has a structure such as hydrochloride. Also good.
  • the binder resin can be used alone or in combination.
  • water-soluble binder resin examples include gelatin, poly (vinyl alcohol), poly (vinyl alcohol) copolymer, poly (vinyl pyrrolidone), and poly (vinyl pyrrolidone) copolymer.
  • Polymers, celluloses, poly (acrylic acid), poly (acrylic acid) copolymers, poly (ethylene glycol), poly (ethylene glycol) copolymers, poly (2-hydroxyethylacrylamide), poly (2-hydroxyethyl) Acrylamide) copolymer, poly (vinyl sulfonic acid), poly (vinyl sulfonic acid) copolymer and the like are preferable.
  • a water-soluble binder resin having a structure having a hydroxyl group in the repeating unit is more preferable.
  • poly (vinyl pyrrolidone) Poly (vinyl pyrrolidone) copolymer, poly (vinyl alcohol), poly (vinyl alcohol) copolymer, celluloses and the like.
  • the water-soluble binder resin having a repeating structural unit represented by the general formula (1) of the present invention will be described.
  • R 1 is at least one selected from an alkyl group, a cycloalkyl group, an aryl group, a heterocycloalkyl group, and a heteroaryl group containing at least one hydroxyl group. .
  • they are an alkyl group, a cycloalkyl group, and an aryl group, More preferably, it is an alkyl group.
  • substituents are further alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxyl groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyl groups.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12, and still more preferably 3 to 8.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, preferably an ethoxy group.
  • the alkylthio group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6, Most preferred is 1 to 4.
  • Examples of the alkylthio group include a methylthio group and an ethylthio group.
  • the arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylthio group include a phenylthio group and a naphthylthio group.
  • the number of carbon atoms of the cycloalkoxy group is preferably 3 to 12, and more preferably 3 to 8.
  • Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • the aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
  • the heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms.
  • heterocycloalkyl group examples include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.
  • the heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.
  • examples of the heteroaryl group include a thienyl group and a pyridyl group.
  • the acyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
  • the alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the alkylcarbonamide group include an acetamide group.
  • the arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the arylcarbonamide group include a benzamide group and the like.
  • the alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the sulfonamido group include a methanesulfonamido group and the like, and the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the arylsulfonamido group include a benzenesulfonamido group and p-toluenesulfonamido group.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
  • the aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms.
  • Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
  • the aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms.
  • Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
  • the acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
  • the alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms.
  • Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.
  • the alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms.
  • Examples of the alkynyl group include an ethynyl group.
  • the alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.
  • the arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
  • the alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.
  • the aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.
  • the alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
  • the arylsulfonyloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • arylsulfonyloxy group examples include a phenylsulfonyloxy group and a naphthylsulfonyloxy group.
  • the substituents may be the same or different, and these substituents may be further substituted.
  • examples of R 1 include 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl, and the like. Preferably, it is a 2-hydroxyethyl group, and R 2 represents hydrogen or a methyl group.
  • the water-soluble binder resin having a repeating structural unit represented by the general formula (1) of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst.
  • the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization.
  • the polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.
  • the molecular weight of the water-soluble binder resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, and still more preferably in the range of 5,000 to 100,000.
  • the number average molecular weight and molecular weight distribution of the water-soluble binder resin of the present invention can be measured by generally known gel permeation chromatography (GPC).
  • the solvent to be used is not particularly limited as long as the water-soluble binder resin dissolves, and THF, DMF, and CH2Cl2 are preferable, THF and DMF are more preferable, and DMF is more preferable.
  • the measurement temperature is not particularly limited, but 40 ° C. is preferable.
  • the average particle size is preferably 50 nm or less, more preferably 30 nm or less.
  • the smoothness of the surface after drying increases.
  • a functional layer is laminated on the transparent conductive film such as an organic EL element, if the smoothness is poor, it causes a leak between the anode and the cathode, and the element performance is remarkably deteriorated.
  • the average particle size is 50 nm or less, if the large particle size is too much mixed, the filterability of the dispersion is deteriorated and the productivity is remarkably lowered. For this reason, it is preferable that 90 mass% of the particles in the dispersion is 50 nm or less.
  • Conductive fibers may be included in the conductive dispersion, and other additives may be added as long as the particle size is maintained.
  • the mixing ratio of the polymer compound having the repeating structural unit represented by the general formula (I) according to the present invention, the polyanion and the water-soluble binder resin having the repeating structural unit represented by the general formula (1) is as follows.
  • the mass of the water-soluble binder resin is preferably from 100 to 1000% by mass, more preferably from 200 to 800% by mass, based on the mass of the polymer compound and polyanion.
  • the mass of the water-soluble binder resin relative to the mass of the polymer compound or polyanion is 100% by mass or less, the transmittance is not improved, and it is impossible to achieve both conductivity and transmittance.
  • electroconductivity will not satisfy performance requirements.
  • a polymer compound having a repeating structural unit represented by the formula (I), a polyanion and a water-soluble binder resin having a repeating structural unit represented by the general formula (1) are mixed, and then a ball mill, a stirring mill, and a high-speed stirring are mixed.
  • Ultrasonic treatment and high-pressure homogenizer treatment can be performed. Of these, ultrasonic treatment and high-pressure homogenizer treatment are preferable. More preferred is a high-pressure homogenizer treatment.
  • the temperature for the homogenization treatment is not particularly limited, but is ⁇ 10 to 100 ° C., more preferably 0 to 80 ° C., and still more preferably 10 to 50 ° C.
  • the organic compound layer according to the present invention has a polymer compound composed of a polymer compound having a repeating structural unit represented by the general formula (I) and a polyanion, and a repeating structural unit represented by the following general formula (1). Contains a water-soluble binder resin.
  • the organic compound layer according to the present invention is formed by applying and drying the conductive dispersion on a transparent material.
  • Application method is not particularly limited, roll coating method, bar coating method, dip 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, A doctor coat method etc. can be used.
  • As the printing method a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.
  • the drying temperature may be 0 to 250 ° C., more preferably 5 to 200 ° C., and still more preferably 10 to 150 ° C., as long as the solvent used for the conductive polymer compound and the water-soluble binder resin is removed from the organic compound layer.
  • the thickness of the organic compound layer according to the present invention is preferably 1 nm to 1 ⁇ m or less, more preferably 3 nm to 500 nm, as long as the smoothness of the surface of the transparent conductive film is maintained by covering the conductive fibers.
  • the transparent conductive film according to the present invention may contain other conductive polymer compounds and additives in addition to the conductive polymer compound according to the present invention as long as the effects of the present invention are not impaired.
  • the thickness of the transparent conductive film according to the present invention varies depending on the shape and content of the conductive fiber to be used, but as a rough guide, the average diameter of the conductive fiber is preferably 500 nm or less. It is preferable to reduce the thickness of the first transparent conductive film according to the present invention by a pressurizing method described later, because the network formation of conductive fibers in the thickness direction can be made dense.
  • the thickness of the second transparent conductive film is preferably 1 nm to 1 ⁇ m, particularly preferably 3 nm to 500 nm.
  • the transparent conductive film preferably has a total light transmittance of 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the total light transmittance can be measured according to a known method using a spectrophotometer or the like.
  • an electrical resistance value in the transparent conductive film of this invention it is preferable that it is 1000 ohms / square or less as surface resistivity, and it is more preferable that it is 100 ohms / square or less.
  • it is preferably 50 ⁇ / ⁇ or less, particularly preferably 10 ⁇ / ⁇ or less. 10 3 ⁇ / ⁇ or less is preferable because it can function as a transparent conductive film in various optoelectronic devices.
  • the surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity testing method using a conductive plastic four-probe method), and can be easily performed using a commercially available surface resistivity meter. Can be measured.
  • the thickness of the transparent conductive film of this invention there is no restriction
  • the amount of sulfur oxide generated by heating a dispersion containing a polymer compound having a repeating structural unit represented by the general formula (I) of the present invention and a polyanion at 200 ° C. for 60 minutes is oxidized with hydrogen peroxide.
  • the amount can be determined by ion chromatography. If sulfur oxides are generated due to the use of transparent conductive films, organic electroluminescence elements over time, energization, light emission, etc., it is necessary to use materials that do not generate sulfur oxides significantly because the stability of electrodes and elements deteriorates significantly. There is.
  • the range in which there is no problem in storage and use of the transparent conductive film and the organic electroluminescence device is preferably 0 to 300 ppm, more preferably 0 to 100 ppm, and still more preferably 0 to 50 ppm with respect to the total amount of the dispersion in terms of sulfate ions. It is.
  • the method for reducing the amount of sulfur oxide is not particularly limited, but degassing the dispersion by bubbling an inert gas into the dispersion to remove gaseous components, and extracting the solid content obtained by removing the solvent from the dispersion is a Soxhlet extraction
  • Examples of the method include washing with a vessel, washing the dispersion by ultrafiltration, further using a high-purity solvent, re-dispersing after purification by reprecipitation, and using a plurality of these.
  • Examples of the gas for bubbling the inert gas in the dispersion of the present invention include rare gases such as carbon dioxide, nitrogen, helium, neon, argon, and xenon.
  • rare gases such as carbon dioxide, nitrogen, helium, neon, argon, and xenon.
  • carbon dioxide, nitrogen, and argon are preferable, nitrogen and argon are more preferable, and nitrogen is more preferable.
  • the amount and time for bubbling the inert gas in the dispersion of the present invention vary depending on the total amount, the presence or absence of stirring and the speed, but the total amount of inert gas used is 0.1 to 100 times the volume of the dispersion. Preferably, it is 0.5 to 50 times, and more preferably 1 to 30 times.
  • the bubbling time is not particularly limited, but is preferably within 10 hours, more preferably within 3 hours, and even more preferably within 1 hour.
  • the method for washing the dispersion of the present invention by ultrafiltration is not particularly limited, and can be carried out by a known method such as an apparatus or a filter type. It is desirable to perform ultrafiltration to replace with pure water or ultrapure water while removing impurities. In addition, when synthesizing a conductive polymer, it is preferable to use ultrapure water instead of pure water, and it is further preferable to combine with cleaning such as degassing, a Soxhlet extractor or ultrafiltration. In addition, the dispersion of the present invention is dropped in a large amount of solvent having low solubility in the polyanion with a polymer compound having a repeating structural unit represented by the general formula (I), re-precipitated, and washed with the solvent used. After drying, it may be redispersed in ultrapure water or the like.
  • transparent means in the visible light wavelength range measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1 (corresponding to ISO 13468-1). It means that the total light transmittance is 60% or more.
  • the transparent substrate used for the transparent conductive film of the present invention is not particularly limited as long as it has high light transmittance.
  • a transparent glass substrate, a transparent resin substrate, a transparent resin film, etc. are preferably mentioned in terms of excellent hardness as a base material and ease of forming a transparent conductive layer on the surface. From the viewpoint of flexibility, it is preferable to use a transparent resin film.
  • the transparent resin film that can be preferably used as the transparent substrate is not particularly limited, and the material, shape, structure, thickness, and the like can be appropriately selected from known ones.
  • polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester
  • polyolefins such as polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, and cyclic olefin resin Resin films
  • vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resins Film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc.
  • Resin film preferably (380 ⁇ 780 nm) transmittance of 80% or more in.
  • biaxially stretched polyethylene terephthalate film preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • 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, epoxy copolymer and the like.
  • the transparent resin film is a biaxially stretched polyethylene terephthalate film
  • the refractive index of the easy-adhesion layer adjacent to the film is set to 1.57 to 1.63, so that the interface reflection between the film substrate and the easy-adhesion layer can be reduced. Since it can reduce and can improve the transmittance
  • a ratio of an oxide sol having a relatively high refractive index such as a tin oxide sol or a cerium oxide sol and a binder resin can be appropriately prepared and coated.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer may be formed in advance on the opposite side of the transparent conductive layer.
  • the transparent substrate can be subjected to surface treatment as described above, and various functional layers can be provided depending on the purpose.
  • the first transparent conductive layer contains conductive fibers, and when a metal material formed in a pattern is used, the first transparent conductive layer is made of metal. The material is formed in a pattern.
  • the conductive fiber according to the present invention has conductivity and a length that is sufficiently longer than the diameter (thickness).
  • the conductive fiber according to the present invention is considered to function as an auxiliary electrode by forming a three-dimensional conductive network when the conductive fibers contact each other in the transparent conductive layer. Accordingly, a longer conductive fiber is preferable because it is advantageous for forming a conductive network.
  • the conductive fibers are long, the conductive fibers are entangled to form aggregates, which may deteriorate the optical characteristics.
  • the one with the optimal average aspect ratio should be used according to the conductive fibers used. Is preferred. As a rough guide, an average aspect ratio of 10 to 10,000 is preferable.
  • the shape examples include a hollow tube shape, a wire shape, and a fiber shape, such as organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, and carbon nanotubes.
  • a conductive fiber having a thickness of 300 nm or less is preferable from the viewpoint of transparency.
  • the conductive fiber is at least selected from the group of metal nanowires and carbon nanotubes. One type is preferable.
  • silver nanowires can be most preferably used from the viewpoint of cost (raw material costs, manufacturing costs) and performance (conductivity, transparency, flexibility).
  • the average value of the length, diameter, and aspect ratio of the conductive fiber can be obtained from an arithmetic average of measured values of individual conductive fiber images by taking an electron micrograph of a sufficient number of conductive fibers. it can.
  • the relative standard deviation of length and diameter is expressed by a value obtained by multiplying 100 by the value obtained by dividing the standard deviation of the measured value by the average value.
  • the number of conductive fiber samples to be measured is preferably at least 100 or more, more preferably 300 or more.
  • the metal nanowire refers to a linear structure having a metal element as a main component.
  • the metal nanowire in the present invention means a linear structure having a diameter from the atomic scale to the nm size.
  • the average length is preferably 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, In particular, the thickness is preferably 3 to 300 ⁇ m.
  • the relative standard deviation of the length is preferably 40% or less.
  • an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint.
  • the average diameter of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm.
  • the relative standard deviation of the diameter is preferably 20% or less.
  • a metal composition of the metal nanowire which concerns on this invention, although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. Further, in order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and resistance to magnesium), it is also preferable that silver and at least one metal belonging to a noble metal other than silver are included.
  • the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.
  • the means for producing the metal nanowire there are no particular limitations on the means for producing the metal nanowire, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction
  • a carbon nanotube is a carbon-based fiber material having a shape in which a graphite-like carbon atomic plane (graphene sheet) having a thickness of several atomic layers is wound into a cylindrical shape, and single-walled nanotubes (SWNT) and multilayers are formed from the number of peripheral walls. It is roughly divided into nanotubes (MWNT), and it is divided into a chiral type, a zigzag type, and an armchair type depending on the structure of the graphene sheet, and various types are known.
  • MWNT nanotubes
  • any type of carbon nanotube can be used, and a mixture of these various carbon nanotubes may be used.
  • An excellent single-walled carbon nanotube is preferable, and a metallic armchair-type single-walled carbon nanotube is more preferable.
  • carbon nanotubes having an aspect ratio of 102 or more, preferably 103 or more can be mentioned.
  • the average length of the carbon nanotube is preferably 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, and particularly preferably 3 to 300 ⁇ m.
  • the relative standard deviation of the length is preferably 40% or less.
  • the average diameter is preferably smaller than 100 nm, preferably 1 to 50 nm, and more preferably 1 to 30 nm.
  • the relative standard deviation of the diameter is preferably 20% or less.
  • the method for producing carbon nanotubes is not particularly limited, and catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, carbon monoxide is reacted with iron catalyst at high temperature and high pressure.
  • Well-known means such as HiPco method for growing in a gas phase can be used.
  • carbon nanotubes that have been further purified by various purification methods such as washing methods, centrifugal separation methods, filtration methods, oxidation methods, chromatographic methods, etc. Is more preferable because various functions can be sufficiently expressed.
  • a metal material When a metal material is formed in a pattern on the first conductive layer, it becomes a film substrate having both a light-impermeable conductive portion made of a metal material and a light-transmissive window portion, and an electrode substrate excellent in transparency and conductivity can be produced.
  • the metal material is not particularly limited as long as it is excellent in conductivity.
  • the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium.
  • the shape of the metal material is preferably metal fine particles or metal nanowires from the viewpoint of ease of pattern formation as described later, and the metal material is preferably silver from the viewpoint of conductivity.
  • the pattern shape is not particularly limited.
  • the conductive portion may be a stripe shape, a mesh shape, or a random network shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency.
  • the aperture ratio is the ratio of the light-impermeable conductive portion to the whole.
  • the aperture ratio of the stripe pattern having a line width of 100 ⁇ m and a line interval of 1 mm is about 90%.
  • the line width of the pattern is preferably 10 to 200 ⁇ m.
  • the height of the fine wire is preferably 0.1 to 10 ⁇ m. If the height of the thin wire is less than 0.1 ⁇ m, desired conductivity cannot be obtained.
  • a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method.
  • a conductor layer is formed on the entire surface using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, etc., or a metal foil is used as an adhesive.
  • the film After being laminated on the base material, the film can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.
  • a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used.
  • a method using silver salt photographic technology can be carried out with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and Examples.
  • the method for carrying out the plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, JP-A-2007-281290.
  • a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 can be used.
  • FIG. 1 is a structural schematic diagram showing an example of a representative transparent conductive film of the present invention.
  • the transparent conductive film has a first transparent conductive layer 31 on a transparent substrate 41, and the first transparent conductive layer 31 is composed of conductive fibers 11, the conductive polymer compound according to the present invention, and a water-soluble binder resin. 21 is contained.
  • FIG. 2 is a structural schematic diagram showing another example of a representative transparent conductive film of the present invention, which has a first transparent conductive layer 31 containing conductive fibers 11 on a transparent substrate 41, and On the first transparent conductive layer 31, a second transparent conductive layer containing the conductive polymer compound according to the present invention and the water-soluble binder resin 21 is formed.
  • FIG. 3 is a structural schematic diagram showing still another example of a representative transparent conductive film of the present invention, which has a first transparent conductive layer 31 containing conductive fibers 11 on a transparent substrate 41, On the first transparent conductive layer 31, a second transparent conductive layer 32 containing the conductive polymer compound according to the present invention and the water-soluble binder resin 21 is formed. Some include conductive fibers 11. That is, the conductive fiber 11 is shared by both the first transparent conductive layer 31 and the second transparent conductive layer 32.
  • 1 is a first conductive layer made of a metal material formed in a pattern
  • 2 is a second conductive layer containing a conductive polymer compound according to the present invention
  • 3 is a substrate.
  • the transparent conductive film of the present invention can be produced by the following methods (1) to (3).
  • a production method comprising a step of forming a layer containing a polymer compound having a repeating structural unit.
  • the mixture is an aqueous dispersion as described below.
  • the method used in the step of forming the first or second transparent conductive layer is not particularly limited, but from the viewpoint of improving productivity, improving electrode quality such as smoothness and uniformity, and reducing environmental impact. It is preferable to use a liquid phase film forming method such as a coating method or a printing method.
  • Application methods include roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, gravure coating, curtain coating, spray coating, and doctor coating.
  • a letterpress (letter) printing method a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.
  • a method of forming by applying a mixture containing conductive fibers and a polymer compound having a repeating structural unit represented by the general formula (I) on a transparent substrate As a method used in the step (1), a method of forming by applying a mixture containing conductive fibers and a polymer compound having a repeating structural unit represented by the general formula (I) on a transparent substrate.
  • the conductive layer formed by applying a mixture containing conductive fibers and a polymer compound having a repeating structural unit represented by the general formula (I) on the release surface of the release substrate is transparent.
  • There is a method of transferring and forming on a substrate There is a method of transferring and forming on a substrate.
  • the second transparent conductive layer of the above (2) and (3) As a method used in the step of forming the second transparent conductive layer of the above (2) and (3), it has a repeating structural unit represented by the general formula (I) on the first transparent conductive layer. There is a method of applying and forming a coating liquid containing a polymer compound.
  • the coating liquid for forming the mixture or the second transparent conductive layer containing the conductive fiber and the polymer compound having the repeating structural unit represented by the general formula (I) is water-soluble. It is a preferable embodiment to use an aqueous dispersion containing a binder resin.
  • the following means are particularly preferably used.
  • a first transparent conductive layer by applying an aqueous dispersion containing conductive fibers, a polymer compound having a repeating structural unit represented by the general formula (I), and a water-soluble binder resin on a transparent substrate. Manufacturing method.
  • the aqueous dispersion contains a water-soluble binder resin and contains conductive fibers in a dispersed manner.
  • the water-soluble binder resin the water-soluble binder described above can be used.
  • a step of forming a second transparent conductive layer by applying a coating liquid containing a polymer compound having a repeating structural unit represented by formula (I) and a water-soluble binder resin on the conductive layer A manufacturing method for forming a transparent conductive layer.
  • the first transparent conductive layer After forming the first transparent conductive layer containing the conductive fibers on the release surface of the releasable base material, the first transparent conductive layer is transferred onto the transparent base material to transfer the first transparent conductive layer.
  • a step of forming a conductive layer and applying a coating solution containing a polymer compound having a repeating structural unit represented by the general formula (I) and a water-soluble binder resin on the first transparent conductive layer The manufacturing method which forms a transparent conductive layer by the method which has the process of forming the transparent conductive layer of.
  • the conductive fiber is preferably 0.50 g / m 2 from the relationship between conductivity and transmittance. More preferably, it is 0.10 g / m 2 or less.
  • the conductive polymer compound has a solid content of preferably 50 times or less, more preferably 10 times or less, and further preferably 5 times or less of the mass of the conductive fiber.
  • the water-soluble binder resin is preferably 5 times or less, more preferably 3 times or less, of the conductive binder solid content.
  • the amount of conductive fiber or patterned metal material, conductive polymer compound, and water-soluble binder resin added is the same as that for the above transparent conductive film production method a) and Similar addition amounts are preferred.
  • examples of the releasable substrate that can be used include a resin substrate and a resin film.
  • limiting in particular in this resin It can select suitably from well-known things, For example, synthesis
  • a substrate or film composed of a single layer or multiple layers of resin is preferably used.
  • a glass substrate or a metal substrate can also be used.
  • a surface treatment may be applied to the surface (release surface) of the releasable substrate by applying a release agent such as silicon resin, fluororesin, or wax as necessary.
  • the surface of the releasable substrate affects the smoothness of the surface after the transparent conductive layer is transferred, it is desirable that the surface of the releasable substrate be highly smooth.
  • Ry ⁇ 50 nm is preferable, and Ry ⁇ 40 nm. More preferably, it is more preferable that Ry ⁇ 30 nm.
  • Ra ⁇ 10 nm is preferable, Ra ⁇ 5 nm is more preferable, and Ra ⁇ 1 nm is further more preferable.
  • the release surface of the releasable substrate may be previously hydrophilized by corona discharge (plasma) or the like.
  • the transfer may be performed via an adhesive layer.
  • the transfer layer may be provided on the releasable substrate side or may be provided on the transparent substrate side.
  • the adhesive used for the adhesive layer is not particularly limited as long as it is a material that is transparent in the visible region and has transfer ability. As long as it is transparent, a curable resin or a thermoplastic resin may be used.
  • curable resins examples include thermosetting resins, ultraviolet curable resins, and electron beam curable resins.
  • the equipment for resin curing is simple and excellent in workability. It is preferable to use an ultraviolet curable resin.
  • the ultraviolet curable resin is a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation, and a component containing a monomer having an ethylenically unsaturated double bond is preferably used.
  • acrylic urethane type resin, polyester acrylate type resin, epoxy acrylate type resin, polyol acrylate type resin and the like can be mentioned.
  • an acrylic or acrylic urethane-based ultraviolet curable resin is a main component as a binder.
  • Acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Corporation) is preferably used.
  • UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, generally as disclosed in JP-A-59-151112. Can be used.
  • ultraviolet curable epoxy acrylate resin examples include those produced by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto, and reacting them. Those described in Japanese Patent No. 105738 can be used.
  • UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Polymerized products can be mentioned.
  • Examples of the monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond.
  • Monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
  • 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate are the main components of the binder.
  • photoinitiators of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.
  • the photoinitiator can also be used as a photosensitizer.
  • a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • the photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.
  • the transparent conductive layer is made transparent by bonding (bonding) the release substrate formed with the transparent conductive layer and the transparent base material, curing the adhesive by irradiating ultraviolet rays and the like, and then peeling the release substrate. It can be transferred to the substrate side.
  • the bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine.
  • the roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated.
  • the roll press is uniformly applied with pressure, and has a higher productivity than the sheet press and can be used preferably.
  • the first transparent conductive layer or the transparent conductive layer comprising the first transparent conductive layer and the second transparent conductive layer according to the present invention can be patterned.
  • a known method can be applied as appropriate.
  • a method of forming a patterned transparent conductive film by transferring onto a transparent substrate can be used. Such a method can be preferably used.
  • i) A method of directly forming a transparent conductive layer in a pattern-like manner on a releasable substrate using a printing method.
  • ii) After a uniform formation of a transparent conductive layer on a releasable substrate, a general photolithographic process is used.
  • Iii) A method in which a transparent conductive layer is uniformly formed using a conductive material containing, for example, an ultraviolet curable resin, and then patterned in a photolithography process.
  • Iv) A photoresist is previously formed on a releasable substrate.
  • the smoothness of the surface of the transparent conductive layer (the smoothness of the surface of the first transparent conductive layer or the second transparent conductive layer) is Ry ⁇ 50 nm. Is preferably Ra ⁇ 10 nm.
  • a commercially available atomic force microscope (AFM) can be used. For example, it can be measured by the following method.
  • an SPI 3800N probe station manufactured by Seiko Instruments Inc. and an SPA400 multifunctional unit as the AFM set the sample cut to a size of about 1 cm square on a horizontal sample stage on the piezo scanner, and place the cantilever on the sample surface.
  • 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 20 ⁇ m in the XY direction and 2 ⁇ m in the Z direction 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 ⁇ m is measured at a scanning frequency of 1 Hz.
  • the value of Ry is more preferably 50 nm or less, and further preferably 40 nm or less.
  • the value of Ra is more preferably 10 nm or less, and further preferably 5 nm or less.
  • the transparent conductive film of the present invention further has an auxiliary electrode composed of a light-impermeable conductive portion and a light-transmissive window portion.
  • the light-opaque conductive portion of the auxiliary electrode is preferably a metal from the viewpoint of good conductivity, and examples of the metal material include gold, silver, copper, iron, nickel, and chromium.
  • the metal of the conductive part may be an alloy, and the metal layer may be a single layer or a multilayer.
  • the shape of the auxiliary electrode is not particularly limited, but, for example, the conductive portion has a stripe shape, a mesh shape, or a random mesh shape.
  • a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method.
  • a conductor layer is formed on the entire surface of the substrate using one or more physical or chemical forming methods such as vapor deposition, sputtering, and plating, or a metal foil is formed with an adhesive. After being laminated on the material, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.
  • a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used.
  • a method using silver salt photographic technology can be carried out with reference to, for example, 0076-0112 of JP-A-2009-140750 and Examples.
  • the method for carrying out the plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, JP-A-2007-281290.
  • a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 can be used.
  • a method for forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.
  • Organic electroluminescence element of the present invention has the transparent conductive film of the present invention.
  • the organic electroluminescence element of the present invention has an organic layer including an organic light emitting layer and the transparent conductive film of the present invention.
  • the organic electroluminescent device of the present invention preferably uses the transparent conductive film of the present invention as an anode, and the organic light-emitting layer and the cathode are arbitrarily selected from materials and structures generally used for organic electroluminescent devices. Can be used.
  • the element configuration of the organic electroluminescence element is 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.
  • Examples of various configurations such as 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. Can do.
  • the organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.
  • the thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.
  • the organic electroluminescence element of the present invention can be used for a self-luminous display, a liquid crystal backlight, illumination, and the like. Since the organic electroluminescent element of the present invention can emit light uniformly and without unevenness, it is preferably used for lighting purposes.
  • the transparent conductive film of the present invention has both high conductivity and transparency, various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, electromagnetic wave shields, It can be suitably used in the field of touch panels and the like. Among these, it can use especially preferably as a transparent conductive film of the organic electroluminescent element and organic thin-film solar cell element by which the smoothness of the surface of a transparent conductive film is calculated
  • 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.
  • ⁇ Synthesis 4 of PEDOT / PSS (Comparative Synthesis Example)> A conductive polymer compound P-4 was obtained in the same manner as in ⁇ PEDOT / PSS synthesis 1> except that the polymerization was carried out at 5 to 10 ° C. for 8 hours (solid content concentration 1.3%).
  • the d90 values indicating the average particle diameter of P-4 and the particle diameter of 90% by mass of the particles were 123 nm and 4.1 nm, respectively.
  • ⁇ Synthesis 5 of PEDOT / PSS (Comparative Synthesis Example)>
  • the P-2 obtained in ⁇ PEDOT / PSS synthesis 2> was filtered twice with a filter (Millipore, VSWP04700, pore size 0.025 ⁇ m) to obtain a conductive polymer compound P-5 (solid) Minor concentration 1.3%).
  • the d90 values indicating the average particle size of P-5 and the particle size of 90% by mass of the particles were 5.3 nm and 3.3 nm, respectively.
  • ⁇ Synthesis 6 of PEDOT / PSS (Comparative Synthesis Example)>
  • polymerization was performed for 6 hours without using a homogenizer (main body: Ultra Turrax T-25, shaft generator: S25N-10G (manufactured by IKA)) during polymerization.
  • a conductive polymer compound P-6 was obtained (solid content concentration 1.3%).
  • the d90 values indicating the average particle size of P-6 and the particle size of 90% by mass of the particles were 127 nm and 132 nm, respectively.
  • Synthesis Example 2 (present invention) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 400% by mass with respect to the solid content of the conductive polymer compound P-2, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-12 was obtained.
  • D90 indicating an average particle diameter of D-12 and a particle diameter of 90% by mass of the particles was 26 nm and 37 nm, respectively.
  • Synthesis Example 3 (present invention) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 150 mass% with respect to the solid content of the conductive polymer compound P-2, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-13 was obtained.
  • D90 indicating the average particle diameter of D-13 and the particle diameter of 90% by mass of the particles were 27 nm and 38 nm, respectively.
  • Synthesis Example 4 (present invention) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 900% by mass with respect to the solid content of the conductive polymer compound P-2, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-14 was obtained.
  • D90 indicating the average particle diameter of D-14 and the particle diameter of 90% by mass of the particles were 13 nm and 19 nm, respectively.
  • Synthesis Example 5 (present invention) The water-soluble binder resin PHEA-1 was added to a solid content concentration of 400% by mass with respect to the solid content of the conductive polymer P-3, and then dispersed by performing the same homogenization treatment as in Synthesis Example 1. A liquid D-15 was obtained. The d90 values indicating the average particle diameter of D-15 and the particle diameter of 90% by mass of the particles were 61 nm and 78 nm, respectively.
  • Synthesis Example 6 (Comparative Example) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 400% by mass with respect to the solid content of the conductive polymer compound P-4, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-16 was obtained.
  • D90 indicating an average particle diameter of D-16 and a particle diameter of 90% by mass of the particles was 115 nm and 3.7 nm, respectively.
  • Synthesis example 7 (comparative example) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 400% by mass with respect to the solid content of the conductive polymer compound P-5, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-17 was obtained.
  • D90 indicating the average particle diameter of D-17 and the particle diameter of 90% by mass of the particles were 4.8 nm and 3.1 nm, respectively.
  • Synthesis Example 8 (Comparative Example) By adding the water-soluble binder resin PHEA-1 to a solid content concentration of 400% by mass with respect to the solid content of the conductive polymer compound P-6, the same homogenization treatment as in Synthesis Example 1 is performed. Dispersion D-18 was obtained.
  • D90 indicating the average particle diameter of D-18 and 90% by mass of the particles was 112 nm and 119 nm, respectively.
  • Example 1 Preparation of Transparent Conductive Film TC-101; Present Invention
  • the dispersion of silver nanowires was applied to a polyethylene terephthalate film support having a thickness of 100 ⁇ m that had been subjected to easy adhesion processing of the aqueous dispersion of silver nanowires so that the basis weight of the silver nanowires was 0.05 g / m 2. It was applied and dried using a spin coater. Subsequently, the silver nanowire coating layer was calendered, and then a striped transparent pattern electrode TCF-1 having an electrode pattern width of 10 mm was produced by a known photolithography method.
  • D-1 was applied by a spin coater so that the dry film thickness was 300 nm, and dried at 120 ° C. for 30 minutes to produce a transparent conductive film TC-101.
  • the total light transmittance, surface resistivity, and surface smoothness are obtained by the following methods to obtain light transmittance, conductivity. It was used as an index of property and smoothness.
  • the total light transmittance, surface resistivity, and surface roughness (Ra, Ra) of the transparent conductive film sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 14 days Ry) was evaluated and used as an index of stability.
  • the evaluation results are shown in Table 1.
  • Total light transmittance Based on JIS K 7361-1: 1997, measurement was performed using a haze meter HGM-2B manufactured by Suga Test Instruments Co., Ltd.
  • the transparent conductive films TC-101 to TC-105 are superior in smoothness, conductivity and light transmittance to the transparent conductive films TC-106 to TC-109, as well as high temperature, high It can be seen that even in a humidity environment, there is little deterioration in smoothness, conductivity, and light transmittance, and the stability is excellent.
  • Example 2 [Preparation of Transparent Conductive Film TC-201; Present Invention]
  • the conductive polymer compound P-1 (solid content concentration 1.3%) of the present invention is concentrated with a rotary evaporator until the solid content concentration becomes 13%.
  • the dispersion D-21 was obtained by performing the crystallization treatment.
  • the d90 indicating the average particle diameter of D-21 and the particle diameter of 90% by mass of the particles were 42 nm and 48 nm, respectively.
  • a gravure coating machine K printing proofer manufactured by Matsuo Sangyo Co., Ltd.
  • a gravure coating machine K printing proofer manufactured by Matsuo Sangyo Co., Ltd.
  • the viscosity of the metal nanowire remover BF-1 produced above was appropriately adjusted with CMC, and the number of times of printing was adjusted so that the coating film thickness was 30 ⁇ m on the silver nanowire coating layer, and gravure printing was performed. After printing, it was left for 1 minute, and then washed with running water to produce a transparent conductive film TC-201.
  • the total light transmittance, surface resistivity, and surface smoothness (Ra, Ry) were determined by the method described in Example 1. Further, in order to evaluate the stability of the transparent conductive film, the total light transmittance, surface resistivity, and surface roughness (Ra, Ra) of the transparent conductive film sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 14 days Ry) Evaluation was performed. The results are shown in Table 2.
  • the transparent conductive films TC-201 to TC-205 are superior in smoothness, conductivity and light transmission to the transparent conductive films TC-206 to TC-209, as well as high temperature, high It can be seen that even in a humidity environment, there is little deterioration in smoothness, conductivity, and light transmittance, and the stability is excellent.
  • Example 3 [Preparation of transparent conductive film] Production of transparent conductive film TC-301 (present invention) A transparent conductive film was produced according to a preferable manufacturing process of the transparent conductive film of the present invention.
  • the silver nanowire dispersion is applied and dried so that the basis weight of the silver nanowire is 80 mg / m 2.
  • a first conductive layer containing was provided.
  • an ultraviolet curable resin manufactured by JSR, NN803 was applied as an adhesive layer on a transparent substrate (PET film (total light transmittance 90%)) having a barrier layer and an easy-adhesion layer, and the solvent component was vaporized. Then, the 1st electroconductive layer containing silver nanowire and the contact bonding layer were bonded. Subsequently, after the ultraviolet ray was irradiated to sufficiently cure the adhesive layer, the releasable PET film as the releasable substrate was peeled off.
  • PET film total light transmittance 90%
  • DMSO dimethyl sulfoxide
  • the total light transmittance, surface resistivity, and surface smoothness (Ra, Ry) were determined by the method described in Example 1. Further, in order to evaluate the stability of the transparent conductive film, the total light transmittance, surface resistivity, and surface roughness (Ra, Ra) of the transparent conductive film sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 14 days Ry) Evaluation was performed. The results are shown in Table 3.
  • the transparent conductive films TC-301 to TC-305 are superior in smoothness, conductivity and light transmittance to the transparent conductive films TC-306 to TC-309, as well as high temperature, high It can be seen that even in a humidity environment, there is little deterioration in smoothness, conductivity, and light transmittance, and the stability is excellent.
  • Example 4 [Preparation of transparent electrode] ⁇ Formation of first conductive layer>
  • the transparent electrode was produced according to the preferable manufacturing process of the transparent electrode of this invention.
  • a fine wire grid (metal material) was produced by gravure printing as follows.
  • the following coating liquid A is extruded on the transparent electrode in which a first conductive layer is formed by gravure printing on a film substrate for a transparent electrode having gas barrier properties, using an extrusion method so as to have a dry film thickness of 300 nm.
  • the slit gap was adjusted and applied, dried by heating at 110 ° C. for 5 minutes to form a second conductive layer comprising a conductive polymer compound and CP-1, and the obtained electrode was cut into 8 ⁇ 8 cm. .
  • the obtained electrode was heated in an oven at 110 ° C. for 30 minutes to produce a transparent electrode TC-101.
  • Second conductive layer ⁇ Formation of second conductive layer> (Coating liquid A) To the dispersion D-11 of the present invention, 5% by mass of DMSO (dimethyl sulfoxide) is added with respect to the mass of the conductive polymer compound, and the release PET film is peeled off so that the dry film thickness becomes 100 nm. The surface of the first conductive layer was overcoated and dried, followed by heat treatment at 80 ° C. for 3 hours to produce the transparent conductive film TC-401 of the present invention.
  • DMSO dimethyl sulfoxide
  • the total light transmittance, surface resistivity, and surface smoothness (Ra, Ry) were determined by the method described in Example 1. Moreover, in order to evaluate the stability of the transparent electrode, the total light transmittance, surface resistivity, and surface roughness (Ra, Ry) of the transparent electrode sample after the forced deterioration test placed in an environment of 80 ° C. and 90% RH for 14 days. Evaluation was performed.
  • the transparent electrodes TC-401 to 405 are superior to the transparent electrodes TC-406 to TC-409 in that they are excellent in smoothness, conductivity and light transmittance, and in a high temperature and high humidity environment. It can be seen that there is little deterioration in smoothness, conductivity, and light transmittance, and the stability is excellent.
  • Example 5 [Production of organic electroluminescence element (organic EL element)] Using the produced transparent conductive films TC-101 to 109 as the first electrode, organic EL elements OEL-501 to 509 were produced in the following procedure.
  • the red dopant material Btp 2 Ir (acac) is 1% by mass and the green dopant material Ir (ppy) 3 is 2% with respect to polyvinylcarbazole (PVK) as the host material.
  • % And blue dopant material FIr (pic) are mixed so as to be 3% by mass, respectively, and dissolved in 1,2-dichloroethane so that the total solid concentration of PVK and the three dopants is 1% by mass.
  • the coating liquid for layer formation was applied with a spin coater and then dried at 100 ° C. for 10 minutes to form a light emitting layer having a thickness of 60 nm.
  • LiF was deposited as an electron transport layer forming material under a vacuum of 5 ⁇ 10 ⁇ 4 Pa to form an electron transport layer having a thickness of 0.5 nm.
  • Second electrode On the formed electron transport layer, Al was deposited as a second electrode forming material under a vacuum of 5 ⁇ 10 ⁇ 4 Pa to form a second electrode having a thickness of 100 nm.
  • the comparative organic EL elements OEL-506 to OEL-509 are significantly deteriorated in light emission uniformity after heating at 80 ° C. for 30 minutes, whereas the organic EL elements OEL-501 to OEL-505 of the present invention It can be seen that the light emission uniformity is stable even after heating and has excellent durability.
  • Example 6 [Production of organic electroluminescence element (organic EL element)] Organic EL elements OEL-601 to 609 were fabricated in the same manner as in the procedure of Example 5, using the transparent conductive films TC-201 to 209 fabricated in the same manner as in the procedure of Example 2 as the first electrode.
  • Table 6 shows that the comparative organic EL elements OEL-606 to OEL-609 are significantly deteriorated in light emission uniformity after heating (forced deterioration) at 60% RH and 80 ° C. for 30 minutes. It can be seen that the light emission uniformity of OEL-601 to OEL-605 is stable even after heating (forced deterioration) and is excellent in durability.
  • Example 7 [Production of organic electroluminescence element (organic EL element)] Organic EL elements OEL-701 to 709 were manufactured in the same manner as in the procedure of Example 5, using the transparent conductive films TC-301 to 309 manufactured in the same manner as in the procedure of Example 3 as the first electrode.
  • the comparative organic EL elements OEL-706 to OEL-709 are significantly deteriorated in light emission uniformity after heating (forced deterioration) at 60% RH and 80 ° C. for 30 minutes, whereas the organic EL elements of the present invention It can be seen that the light emission uniformity of OEL-701 to OEL-705 is stable even after heating (forced deterioration) and has excellent durability.
  • Example 8 [Production of organic electroluminescence element (organic EL element)] Organic EL elements OEL-801 to 809 were produced in the same manner as in the procedure of Example 4 using the transparent electrodes TC-401 to 409 produced in the same manner as in the procedure of Example 4 as the first electrode.
  • the comparative organic EL elements OEL-806 to OEL-809 are significantly degraded in light emission uniformity after heating (forced deterioration) at 60% RH and 80 ° C. for 30 minutes, whereas the organic EL elements of the present invention It can be seen that the light emission uniformity of OEL-801 to OEL-805 is stable even after heating (forced deterioration) and has excellent durability.
  • Example 9 Preparation of Transparent Conductive Film TC-901 (Invention Example)] Except for changing the silver nanowire to SWCNT (manufactured by Unidym, HiPcoR single-walled carbon nanotube) and adjusting the weight of SWCNT to 50 mg / m 2 , the same method for producing TC-101 shown in Example 1 Thus, TC-901 was produced.
  • organic electroluminescence element (organic EL element)
  • organic EL element OLE-901 was fabricated and evaluated in the same manner as in Example 5.
  • OLE-101 the entire EL element emitted light uniformly. I was able to confirm. Further, even after heating the organic EL device at 60% RH and 80 ° C. for 30 minutes (forced deterioration), uniform light emission was observed throughout the device.
  • Example 10 Preparation of Transparent Conductive Film TC-1001 (Invention)]
  • the silver nanowire was changed to SWCNT (Unipym, HiPcoR single-walled carbon nanotube), and the dispersion was applied from the top of the plate on which the printed pattern of 10 mm stripe pattern was formed on the support without using the silver nanowire remover.
  • SWCNT Unipym, HiPcoR single-walled carbon nanotube
  • organic electroluminescence element (organic EL element)
  • organic EL element OLE-1001 was fabricated and evaluated in the same manner as in Example 5.
  • OLE-201 the entire EL element emitted light uniformly. I was able to confirm. Further, even after heating the organic EL device at 60% RH and 80 ° C. for 30 minutes (forced deterioration), uniform light emission was observed throughout the device.
  • SYMBOLS 1 1st conductive layer which consists of metal material formed in pattern shape 2 2nd conductive layer containing binder resin and conductive polymer 3 Base material 11 Conductive fiber 21 Conductive polymer compound and water-soluble binder resin 31 1st Transparent conductive film 32 second transparent conductive film 41 transparent substrate

Abstract

La présente invention concerne un film conducteur transparent et un élément électroluminescent (EL) organique. Le film conducteur transparent comprend : un substrat transparent ; et une fibre conductrice et une couche composée organique qui sont disposées sur le substrat transparent. En outre, le film conducteur transparent est caractérisé en ce que : la couche composée organique comprend un composé polymère conducteur et une résine liante hydrosoluble, ledit composé polymère conducteur étant constitué d'un composé polymère qui comprend des unités structurales répétées représentées par la formule générale (I) et d'un polyanion, et ladite résine liante hydrosoluble comprenant des unités structurales représentées par la formule générale (1) ; la couche composée organique est une couche formée en appliquant une dispersion qui comprend le composé polymère conducteur et la résine liante hydrosoluble et en séchant le revêtement résultant ; et les particules présentes dans la dispersion possèdent un diamètre moyen des particules de 5 à 100 nm.
PCT/JP2011/051179 2010-02-24 2011-01-24 Film conducteur transparent et élément électroluminescent organique WO2011105148A1 (fr)

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WO2013061967A1 (fr) * 2011-10-27 2013-05-02 コニカミノルタホールディングス株式会社 Film conducteur transparent et élément électroluminescent organique
JP2013101893A (ja) * 2011-11-10 2013-05-23 Konica Minolta Holdings Inc 有機ｅｌ素子
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WO2010018733A1 (fr) * 2008-08-11 2010-02-18 コニカミノルタホールディングス株式会社 Électrode transparente, élément électroluminescent organique et procédé de production d’une électrode transparente
WO2010082428A1 (fr) * 2009-01-19 2010-07-22 コニカミノルタホールディングス株式会社 Électrode transparente, son procédé de production et élément électroluminescent organique
JP2010244757A (ja) * 2009-04-02 2010-10-28 Furukawa Electric Co Ltd:The スルークリップ

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JP2012069381A (ja) * 2010-09-24 2012-04-05 Konica Minolta Holdings Inc 透明導電膜、および有機エレクトロルミネッセンス素子
WO2013061967A1 (fr) * 2011-10-27 2013-05-02 コニカミノルタホールディングス株式会社 Film conducteur transparent et élément électroluminescent organique
JPWO2013061967A1 (ja) * 2011-10-27 2015-04-02 コニカミノルタ株式会社 透明導電膜及び有機エレクトロルミネッセンス素子
JP2013101893A (ja) * 2011-11-10 2013-05-23 Konica Minolta Holdings Inc 有機ｅｌ素子
FR2996358A1 (fr) * 2012-10-03 2014-04-04 Hutchinson Electrode transparente et procede de fabrication associe
WO2014167960A1 (fr) * 2013-04-09 2014-10-16 長岡産業株式会社 Film conducteur transparent
JP2014203775A (ja) * 2013-04-09 2014-10-27 長岡産業株式会社 透明導電性フィルム
WO2015033882A1 (fr) * 2013-09-03 2015-03-12 日東電工株式会社 Film conducteur transparent

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