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WO2013061967A1 - Film conducteur transparent et élément électroluminescent organique - Google Patents

Film conducteur transparent et élément électroluminescent organique Download PDF

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Publication number
WO2013061967A1
WO2013061967A1 PCT/JP2012/077363 JP2012077363W WO2013061967A1 WO 2013061967 A1 WO2013061967 A1 WO 2013061967A1 JP 2012077363 W JP2012077363 W JP 2012077363W WO 2013061967 A1 WO2013061967 A1 WO 2013061967A1
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film
transparent
conductive
organic
polymer
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PCT/JP2012/077363
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English (en)
Japanese (ja)
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中村　和明
鈴木　隆行
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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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Publication of WO2013061967A1 publication Critical patent/WO2013061967A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

Definitions

  • the present invention uses 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 the transparent conductive film.
  • the present invention relates to an organic electroluminescence element (hereinafter also referred to as an organic EL element).
  • the transparent electrode is an essential constituent technology.
  • transparent electrodes are an indispensable technical element in touch panels other than televisions, mobile phones, electronic paper, various solar cells, various electroluminescence light control devices, and the like.
  • ITO transparent electrodes in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as glass or transparent plastic film by vacuum deposition or sputtering are mainly used. It has been. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. In addition, with an increase in display screen and productivity, a roll-to-roll production technique using a flexible substrate is desired.
  • ITO indium-tin composite oxide
  • a technique of laminating a conductive polymer on a thin wire structure for example, see Patent Document 3
  • a binder that can be uniformly dispersed in a conductive polymer and an aqueous solvent on a conductive fiber for example, see Patent Document 4.
  • a technique using a resin for example, see Patent Document 4
  • a technique for laminating a conductive polymer and a binder on a conductive layer are disclosed (for example, see Patent Document 5).
  • the present invention has been made in view of the above problems, and is excellent in transparency, conductivity and film strength, and also has a transparent conductive film with little deterioration in transparency, conductivity and film strength even under high temperature and high humidity environments, Another object of the present invention is to provide an organic EL element that uses the conductive film and has excellent light emission uniformity, little deterioration in light emission uniformity even in a high temperature and high humidity environment, and excellent light emission life.
  • the dispersion is formed by coating and drying, and the average particle size of the dispersion containing the conductive polymer compound and the dissociable group-containing self-dispersing polymer is 5 to 100 nm.
  • a transparent conductive film is formed by coating and drying, and the average particle size of the dispersion containing the conductive polymer compound and the dissociable group-containing self-dispersing polymer is 5 to 100 nm.
  • An organic electroluminescence device comprising the transparent conductive film according to any one of 1 to 3 as an electrode.
  • the transparency, conductivity and film strength are excellent, and the transparent conductive film with little deterioration of transparency, conductivity and film strength even under high temperature and high humidity environment, and the transparent conductive film, It is possible to provide an organic EL element that is excellent in light emission uniformity, has little deterioration in light emission uniformity even under a high temperature and high humidity environment, and has an excellent light emission lifetime.
  • a coating liquid for forming a transparent conductive film a water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) and a binder resin are used in order to achieve both conductivity and transmittance. Compositions containing these have been developed.
  • PEDOT / PSS 3,4-polyethylenedioxythiophene polysulfonate
  • binder resin a binder resin
  • a hydrophilic binder resin As such a binder resin, a hydrophilic binder resin has been studied from the viewpoint of compatibility with a water-dispersible conductive polymer.
  • a resin film such as polyethylene terephthalate
  • the drying temperature is lower than that of a glass substrate from the viewpoint of avoiding film deformation.
  • the hydroxyl group-containing binder resin that is known to be compatible with PEDOT / PSS undergoes a dehydration reaction under acidic conditions and crosslinks between polymer chains.
  • the cross-linking reaction progressed during storage and water was generated, and the transparent conductive film and the device performance using the transparent conductive film were significantly deteriorated due to the residual water in the film.
  • a dispersion liquid in which a hydrophobic polymer is uniformly dispersed in an aqueous solvent using a surfactant is used, the transparent conductive film and device performance using the transparent conductive film are adversely affected.
  • the present inventors have used a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent (dissociable group-containing self-dispersing polymer), and coating.
  • the composition of the present invention has been reached in which the average particle size in the dispersion of the conductive polymer compound that forms the organic layer after drying and the self-dispersing polymer is 5 to 100 nm.
  • the object of the present invention is to use a dissociable group-containing self-dispersing polymer as a binder resin mixed with a conductive polymer, and to determine the average particle size of the conductive polymer compound and the self-dispersing polymer in the dispersion. It has been found that the problem can be solved by setting the thickness to 5 to 100 nm, and the present invention has been achieved.
  • the present invention uses a dissociable group-containing self-dispersing polymer as a binder resin, and the average particle size of a dispersion containing a conductive polymer compound and a self-dispersing polymer is 5 to 100 nm.
  • the transparency and conductivity of the transparent conductive film are compatible, and the film strength is excellent, and it has both high conductivity, transparency and good film strength even after environmental testing under high temperature and high humidity environment. It has been found that by suppressing the generation of water, a transparent conductive film excellent in stability and a long-life organic EL element using the transparent conductive film can be obtained.
  • FIG. 1A and 1B are schematic views illustrating an example of a transparent conductive film according to an embodiment of the present invention, in which FIG. 1A is a top view and FIG. 1B is a cross-sectional view taken along the arrow X in FIG.
  • the transparent conductive film 1 includes a base material 11, a first conductive layer 12, and a second conductive layer 13.
  • the first conductive layer 12 is made of a metal material formed in a pattern
  • the second conductive layer 13 contains a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent.
  • a feature of the present invention is that the second conductive layer 13 contains a dissociable group-containing self-dispersing polymer that can be dispersed in an aqueous solvent.
  • the present invention is a transparent conductive film 1 having, as a second conductive layer 13, a transparent conductive layer having a conductive polymer and a binder resin on a transparent substrate 11, wherein the self-dispersing polymer containing a dissociable group is used as the binder resin.
  • the average particle size of the dispersion composed of the conductive polymer compound and the self-dispersing polymer is 5 to 100 nm.
  • the dispersion comprising the conductive polymer compound and the dissociable group-containing self-dispersing polymer according to the present invention comprises a conductive polymer compound dispersed in an aqueous solvent and a dissociable group-containing self-dispersible type dispersible in the aqueous solvent. It consists of a polymer.
  • the aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.
  • the dispersion according to the present invention is preferably transparent, and is not particularly limited as long as it is a medium for forming a film.
  • the dispersion is not limited to a surfactant (emulsifier) or a structure that assists micelle formation. It is preferable not to include a plasticizer or the like for controlling the film temperature.
  • the pH of the dispersion according to the present invention is not particularly problematic as long as desired conductivity is obtained, but is preferably 0.1 to 7.0, more preferably 0.3 to 5.0.
  • an organic solvent may be added to the dispersion.
  • the organic solvent is not particularly limited as long as a desired surface tension can be obtained, but a monovalent, divalent or polyvalent alcohol solvent is preferable.
  • the boiling point of the organic solvent is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.
  • the average particle size of the particles containing the conductive polymer compound and the dissociable group-containing self-dispersing polymer contained in the dispersion according to the present invention is preferably 5 to 100 nm, more preferably 10 to 50 nm. It is.
  • the average particle size of the dispersion is less than 5 nm, the particles are adsorbed and bonded to each other, so that aggregates are easily formed and the stability of the dispersion may be deteriorated.
  • the average particle size of the dispersion exceeds 100 nm, the average roughness of the film surface after coating and drying may be deteriorated, and the performance of the organic electroluminescence device produced by stacking the organic layers may be deteriorated thereafter. is there.
  • the average particle size of the dispersion is 10 to 50 nm, the particle stability of the dispersion is good and the haze value, which is one of the optical performances of the transparent conductive film 1, is good. Even if the average particle size is controlled, if the film-forming temperature of the dissociable group-containing self-dispersing polymer used is too high, the film shape remains without being formed within the drying temperature and the average roughness of the film surface remains. Therefore, it is desirable to control the film forming temperature.
  • Examples of a method for setting the average particle size of the dispersion to a desired range include a homogenizer, an ultrasonic disperser (US disperser), a dispersion technique using a ball mill, a reverse osmosis membrane, an ultrafiltration membrane, and a microfiltration membrane.
  • the classification of the used particles can be used.
  • Dispersion techniques using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, etc. are all likely to increase in particle size at high temperatures. Therefore, the temperature of the dispersion during the dispersion operation is preferably 3 to 50. ° C, more preferably 5 to 30 ° C.
  • the dissociable group-containing self-dispersing polymer particles and the conductive polymer particles in the dispersion according to the present invention are in a state in which each particle is dispersed independently and the particle size is the sum of the particle sizes.
  • the particles having different compositions may be aggregated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.
  • the use amount (solid content) of the dissociable group-containing self-dispersing polymer is preferably 50 to 1000% by mass, more preferably 100 to 900% by mass, and still more preferably based on the solid content of the conductive polymer. Is from 200 to 800% by weight.
  • the particle size measurement method of the dispersion according to the present invention is not particularly limited, but is preferably a dynamic light scattering method, a laser diffraction method or an image imaging method, and more preferably a dynamic light scattering method.
  • the self-dispersing polymer particles and conductive polymer particles containing a dissociable group do not use a surfactant, and the particle size becomes unstable by dilution, so that the measurement can be performed without dilution with a solvent.
  • a concentrated particle size measuring device is preferable, and examples of the concentrated particle size measuring device include a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), the Zetasizer Nano series (manufactured by Malvern), and the like.
  • the dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent does not contain a surfactant or an emulsifier that assists micelle formation, and can be dispersed in an aqueous solvent by itself.
  • “dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration. The size of the colloidal particles is generally about 0.001 to 1 ⁇ m (1 to 1000 ⁇ m).
  • the size of the colloidal particles is preferably 3 to 500 nm, more preferably 5 to 300 nm, and still more preferably 10 to 100 nm.
  • the colloidal particles are large (when the colloidal particles are larger than 500 nm), the smoothness deteriorates when forming a film using the colloidal particles.
  • the colloidal particles are extremely small (smaller than 3 nm), there are limitations on the production of the colloidal particles and the cost is increased.
  • the size of the colloidal particles is measured with a light scattering photometer. be able to.
  • the aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent.
  • the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.
  • the dissociable group-containing self-dispersing polymer according to the present invention is preferably transparent.
  • the dissociable group-containing self-dispersing polymer is not particularly limited as long as it is a medium that forms a film.
  • there is no particular limitation as long as there is no problem in the bleed out to the surface of the transparent conductive film 1 and the element performance when the organic EL element is laminated, but the polymer dispersion controls the surfactant (emulsifier) and the film forming temperature. It is preferable not to contain a plasticizer or the like.
  • the average particle size of the dissociable group-containing self-dispersing polymer according to the present invention is 5 to 100 nm.
  • the glass transition temperature (Tg) of the dissociable group-containing self-dispersing polymer according to the present invention is preferably 25 to 80 ° C., more preferably 50 to 70 ° C.
  • Tg is less than 25 ° C.
  • the surface smoothness of the transparent conductive film 1 is difficult to improve, and the performance of the organic EL element including the transparent conductive film 1 and the transparent conductive film 1 after an environmental test is likely to deteriorate.
  • the temperature exceeds 80 ° C. the melting of the dissociable group-containing self-dispersing polymer particles does not sufficiently proceed at the drying temperature during the production of the transparent conductive film 1, and as a result, a uniform film cannot be obtained.
  • Tg is 50 to 70 ° C.
  • melting of the dissociable group-containing self-dispersing polymer particles sufficiently proceeds at the drying temperature when the transparent conductive film 1 is produced.
  • the glass transition temperature Tg can be measured according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min.
  • the pH of the dispersion of the dissociable group-containing self-dispersing polymer used for the production of the transparent conductive film 1 is preferably 0.1 to 11.0 from the viewpoint of not separating from the conductive polymer solution to be separately compatible, More preferably, it is 3.0 to 9.0, and still more preferably 4.0 to 7.0.
  • Examples of the dissociable group used in the self-dispersing polymer containing a dissociable group include an anionic group (sulfonic acid and its salt, carboxylic acid and its salt, phosphoric acid and its salt, etc.), and a cationic group (ammonium salt, etc.). Etc.
  • the dissociable group is not particularly limited, but an anionic group is preferable from the viewpoint of compatibility with the conductive polymer solution.
  • the amount of the dissociable group is not particularly limited as long as the self-dispersing polymer can be dispersed in the aqueous solvent, and is preferably as small as possible because the drying load is reduced in a suitable manner in the process.
  • the counter species used for the anionic group and the cationic group are not particularly limited, but are hydrophobic and small in amount from the viewpoint of performance when the organic EL device including the transparent conductive film 1 and the transparent conductive film 1 is laminated. It is preferable that
  • the main skeleton of the dissociable group-containing self-dispersing polymer includes polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyamide (nylon), polyvinylidene chloride, polyester.
  • PVA polyethylene-polyvinyl alcohol
  • polyethylene-polyvinyl acetate polyethylene-polyurethane
  • polybutadiene polybutadiene-polystyrene
  • polyamide nylon
  • polyvinylidene chloride polyester.
  • Polysol FP3000 polyethylene resin, anion, core: acrylic, shell: polyester, manufactured by Showa Denko KK
  • Vironal MD1480 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Vironal MD1245 polyyester resin, anion, Toyobo Co., Ltd.
  • Bironal MD1500 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Bironal MD2000 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Bironal MD1930 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Plus Coat RZ105 polyyester resin, anion
  • Plus Coat RZ570 polyyester resin, anion, manufactured by Tatemono Chemical Co., Ltd.
  • Plus Coat RZ571 polyyester resin, anion, manufactured by Tatemono Chemical Co., Ltd.
  • Hitech S-9242 polyethylene resin
  • conductive refers to a state in which electricity flows, and the sheet resistance measured by a method in accordance with JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is 1 ⁇ . It means lower than 10 8 ⁇ / ⁇ .
  • the conductive polymer is a conductive polymer having a ⁇ -conjugated conductive polymer and a polyanion.
  • Such a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a ⁇ -conjugated conductive polymer, which will be described later, in the presence of an appropriate oxidizing agent and an oxidation catalyst, and a poly anion, which will be described later. can do.
  • the ⁇ -conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, or polythiazyl chain conductive polymers can be used. Among these, polythiophenes or polyanilines are preferable from the viewpoint of conductivity, transparency, stability, and the like, and polyethylenedioxythiophene is most preferable.
  • ⁇ -conjugated conductive polymer precursor monomer a precursor monomer used for forming a ⁇ -conjugated conductive polymer has a ⁇ -conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, A ⁇ -conjugated system is formed.
  • precursor monomers include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
  • the precursor monomer examples include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexyl Offene, 3-heptyl
  • the poly anion used for the conductive polymer is substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted. Polyester and any of these copolymers, which are composed of a structural unit having an anionic group and a structural unit having no anionic group.
  • This poly anion is a solubilized polymer that solubilizes the ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • Such an anion group is preferably a mono-substituted sulfate group, a mono-substituted phosphate group, a phosphate group, a carboxy group, a sulfo group, etc. from the viewpoint of ease of production and stability.
  • the anionic group is more preferably a sulfo group, a monosubstituted sulfate group, or a carboxy group from the viewpoint of the doping effect of the functional group on the ⁇ -conjugated conductive polymer.
  • polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. Further, the polyanion may be a homopolymer of these, or two or more kinds of copolymers.
  • the poly anion may further have F (fluorine atom) in the compound.
  • F fluorine atom
  • Specific examples of such a polyanion include Nafion (manufactured by Dupont) containing a perfluorosulfonic acid group, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like. .
  • a heat drying treatment is further performed at 100 to 120 ° C. for 5 minutes or more.
  • the microwaves may be irradiated. Such heat drying treatment and microwave irradiation are preferable from the viewpoint that the crosslinking reaction is accelerated and the washing resistance and solvent resistance of the coating film are remarkably improved.
  • polystyrene sulfonic acid polystyrene sulfonic acid, polyisoprene sulfonic acid, polyethyl acrylate sulfonic acid, or polybutyl acrylate is preferable.
  • These poly anions have high compatibility with the hydroxy group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.
  • the degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units from the viewpoint of dispersibility of the conductive polymer, and from 50 to 10,000 from the viewpoint of solvent solubility and conductivity. A range is more preferred.
  • Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And the like, and the like.
  • Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer.
  • the oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the ⁇ -conjugated conductive polymer.
  • the obtained polymer is a polyanionic salt
  • it is preferably transformed into a polyanionic acid.
  • the method for transforming into polyanionic acid include ion exchange method using ion exchange resin, dialysis method, ultrafiltration method and the like. Among these, ultrafiltration method is preferable from the viewpoint of easy work.
  • Ratio of ⁇ -conjugated conductive polymer and polyanion contained in conductive polymer, “ ⁇ -conjugated conductive polymer”: “poly anion” is preferably a mass ratio from the viewpoint of conductivity and dispersibility The range is from 1: 1 to 20, and more preferably from 1: 2 to 10 by mass ratio.
  • the oxidant used when the precursor monomer forming the ⁇ -conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole.
  • Such oxidants include, for practical reasons, cheap and easy to handle oxidants such as iron (III) salts (eg FeCl 3 , Fe (ClO 4 ) 3 , organic acids and inorganic acids containing organic residues).
  • Iron (III) salt hydrogen peroxide, potassium dichromate, alkali persulfate (eg, potassium persulfate, sodium persulfate), ammonium, alkali perborate, potassium permanganate, or copper salts (eg, tetrafluoride). It is preferable to use copper borate).
  • alkali persulfate eg, potassium persulfate, sodium persulfate
  • ammonium alkali perborate
  • potassium permanganate eg, tetrafluoride
  • copper borate copper borate
  • air or oxygen in the presence of catalytic amounts of metal ions for example, iron ions, cobalt ions, nickel ions, molybdenum ions, vanadium ions
  • metal ions for example, iron ions, cobalt ions, nickel ions, molybdenum ions, vanadium ions
  • iron (III) salts of inorganic acids containing organic residues include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms (for example, lauryl sulfate), alkyl sulfonic acids having 1 to 20 carbon atoms (For example, methane, dodecanesulfonic acid), carboxylic acid having 1 to 20 aliphatic carbon atoms (for example, 2-ethylhexylcarboxylic acid), aliphatic perfluorocarboxylic acid (for example, trifluoroacetic acid, perfluorooctanoic acid), aliphatic dicarboxylic acid Acids (eg oxalic acid), in particular aromatic, optionally alkyl substituted sulfonic acids having 1 to 20 carbon atoms (eg Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid, dodecylbenz
  • a commercially available material can also be preferably used.
  • a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095 and 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.
  • the average particle size of the conductive polymer in the conductive polymer-containing dispersion used in the present invention is 1 to 500 nm, preferably 3 to 300 nm, and more preferably 5 to 100 nm.
  • the conductive polymer may contain an organic compound as the second dopant.
  • an oxygen containing compound is mentioned suitably.
  • the oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound.
  • the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable.
  • Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, ⁇ -butyrolactone, and the like.
  • Examples of the ether group-containing compound include diethylene glycol monoethyl ether.
  • Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.
  • a transparent electrode is formed by further providing a conductive layer made of a metal material on the base material 11 on the transparent conductive film 1 containing a conductive polymer and a binder resin dispersible in an aqueous solvent.
  • the conductive layer made of a metal material is preferably made of a metal material formed in a pattern.
  • a transparent electrode 1 according to an embodiment of the present invention includes a conductive layer (see FIG. 1) containing a conductive polymer compound and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent.
  • the first conductive layer 12 made of a metal material formed in a pattern on the substrate 11.
  • the first conductive layer 12 is preferably formed using metal particles because it is advantageous for ease of pattern formation, stability over time, and densification of the metal pattern.
  • the metal material is not particularly limited as long as it has conductivity, and may be an alloy in addition to a metal such as gold, silver, copper, iron, nickel, or chromium.
  • 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 first conductive layer 12 is formed on the substrate 11 so as to form a pattern having an opening 12a in order to constitute the transparent conductive film 1.
  • the opening part 12a is a part which does not have a metal material on the base material 11, and is a translucent window part. Although there is no restriction
  • the ratio of the opening 12a to the entire surface of the transparent conductive film 1, that is, the opening ratio is preferably 80% or more from the viewpoint of transparency.
  • the aperture ratio is the ratio of the entire portion excluding the light-impermeable conductive portion. For example, when the light-impermeable conductive portion is striped or meshed, the aperture ratio of the striped pattern having a line width of 100 ⁇ m and a line interval of 1 mm is about 90%.
  • the line width of the pattern is preferably 10 to 200 ⁇ m from the viewpoint of transparency and conductivity. If the line width of the fine line is less than 10 ⁇ m, desired conductivity cannot be obtained, and if the line width of the fine line exceeds 200 ⁇ m, the transparency is lowered.
  • the height of the fine wire is preferably 0.1 to 10 ⁇ m. If the height of the fine line is less than 0.1 ⁇ m, the desired conductivity cannot be obtained, and if the height of the fine line exceeds 10 ⁇ m, the cause of current leakage and poor distribution of the thickness of the functional layer in the formation of organic electronic devices It becomes.
  • the method for forming the stripe-shaped or mesh-shaped first conductive layer 12 is not particularly limited, and a conventionally known method can be used. For example, it can be formed by forming a metal layer on the entire surface of the substrate 11 and subjecting the metal layer to a known photolithography method. Specifically, a metal layer is formed on the entire surface of the substrate 11 using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, etc., or a metal foil is used as an adhesive.
  • the first conductive layer 12 processed into a desired stripe shape or mesh shape can be obtained by laminating the substrate 11 on the substrate 11 and then etching using a known photolithography method.
  • the metal species is not particularly limited as long as it can be energized, and copper, iron, cobalt, gold, silver, and the like can be used. From the viewpoint of conductivity, silver or copper is preferable, and silver is more preferable. It is.
  • a method of printing an ink containing metal fine particles in a desired shape by screen printing, a method of applying a plating catalyst ink in a desired shape by gravure printing or an inkjet method, or a plating process, or A method using silver salt photography technology is mentioned.
  • a technique using silver salt photography technology can be implemented with reference to, for example, [0076]-[0112] of Japanese Patent Application Laid-Open No. 2009-140750 and examples. Further, a method for performing a plating process by gravure printing of the catalyst ink can be implemented with reference to, for example, Japanese Patent Application Laid-Open No. 2007-281290.
  • a disordered network structure of conductive fine particles is spontaneously formed by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005. Techniques to do this are available.
  • a random network structure of metal nanowires is formed by applying and drying a coating solution (dispersion) containing metal nanowires as described in JP-T-2009-505358. Techniques are available.
  • Metal nanowire refers to a fibrous structure having a metal element as a main component.
  • the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.
  • the average length is preferably 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, still more preferably 3 to 300 ⁇ m. .
  • the relative standard deviation of the length is preferably 40% or less.
  • the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm.
  • the relative standard deviation of the minor axis is preferably 20% or less.
  • the basis weight of the metal nanowire is preferably 0.005 to 0.5 g / m 2 , and more preferably 0.01 to 0.2 g / m 2 .
  • the metal used for the metal nanowire examples include copper, iron, cobalt, gold, and silver, and silver is preferable from the viewpoint of conductivity.
  • the metal as the main component and one or more other types are used. These metals may be included in any proportion.
  • the method for producing the metal nanowire is not particularly limited, and for example, a known method such as a liquid phase method or a gas phase method can be used. Moreover, there is no restriction
  • a method for producing silver nanowires Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745
  • a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252
  • a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871.
  • the method for producing silver nanowires disclosed in the above-mentioned literature can easily produce silver nanowires in an aqueous solution, and the electrical conductivity of silver is the highest among metals, so it is preferably applied to the present invention. can do.
  • the surface specific resistance of the thin wire portion (first conductive layer 12) made of a metal material is preferably 100 ⁇ / ⁇ or less, and more preferably 20 ⁇ / ⁇ or less in order to increase the area.
  • the surface specific resistance can be measured, for example, according to JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
  • the thin wire portion (first conductive layer 12) made of a metal material is subjected to heat treatment within a range in which the base material 11 is not damaged. As a result, fusion between the metal fine particles and the metal nanowires proceeds, and the thin wire portion made of the metal material becomes highly conductive.
  • the base material 11 is a plate-like body that can carry the conductive layers 12 and 13, and in order to obtain the transparent conductive film 1, JIS K 7361-1: 1997 (Testing method of total light transmittance of plastic-transparent material) ) Having a total light transmittance of 80% or more in the visible light wavelength region measured by a method in accordance with (1) is preferably used.
  • the base material 11 a material that is excellent in flexibility, has a sufficiently low dielectric loss coefficient, and is a material that absorbs microwaves smaller than the conductive layers 12 and 13 is preferably used.
  • the base material 11 for example, a resin substrate, a resin film, and the like are preferably exemplified, but it is preferable to use a transparent resin film from the viewpoint of productivity and performance such as lightness and flexibility.
  • the transparent resin film is a film having a total light transmittance of 50% or more measured in a visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (plastic-transparent material total light transmittance test method).
  • the transparent resin film that can be preferably used is not particularly limited, and the material, shape, structure, thickness, and the like can be appropriately selected from known ones.
  • transparent resin films include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, and cyclic olefin resins.
  • Polyolefin resin film such as polyvinyl chloride, vinyl resin film such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate ( PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. .
  • PEEK polyether ether ketone
  • PSF polysulfone
  • PES polyether sulfone
  • PC polycarbonate
  • PC polyamide resin film
  • polyimide resin film acrylic resin film
  • TAC triacetyl cellulose
  • Any resin film having a total light transmittance of 80% or more is preferably used as a film substrate used as the base material 11 of the present invention.
  • the film substrate is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film from the viewpoint of transparency, heat resistance, ease of handling, strength and cost.
  • An axially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.
  • the base material 11 used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating liquid (dispersion).
  • a conventionally well-known technique can be used about surface treatment and an easily bonding layer.
  • examples of the surface treatment include 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 easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • an inorganic film, an organic film, or a hybrid film of both may be formed on the front or back surface of the film substrate.
  • the film substrate on which such a film is formed conforms to JIS K 7129-1992.
  • the barrier film having a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by the above method is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less
  • water vapor permeability (25 ⁇ 0.5 ° C., relative humidity) (90 ⁇ 2)% RH) is preferably a high barrier film having a value of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • any material may be used as long as it has a function of suppressing invasion of elements such as moisture, oxygen, etc.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the second conductive layer 13 of the present invention is obtained by applying a coating liquid (dispersion) containing the above-described conductive polymer and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent onto the substrate 11. It is formed by heating and drying.
  • a coating liquid disersion
  • the transparent conductive film 1 has a fine wire portion made of a metal material as the first conductive layer 11
  • the above-described coating solution is applied onto the substrate 11 on which the thin wire portion made of the metal material is formed, and is heated and dried.
  • the second conductive layer 13 is formed.
  • the second conductive layer 13 only needs to be electrically connected to the thin metal wire portion that is the first conductive layer 12, and may completely cover the patterned thin metal wire portion. A part of the part may be covered, or may be in contact with the fine metal wire part.
  • the application of the coating liquid comprising the conductive polymer and the dissociable group-containing self-dispersing polymer dispersible in the aqueous solvent is a roll coating method.
  • the second conductive layer 13 containing a conductive polymer and a dissociable group-containing self-dispersing polymer that can be dispersed in an aqueous solvent covers or is in contact with a part of the fine metal wire portion (first conductive layer 12).
  • the first conductive layer 12 is formed on the transfer film by the method described above, and further contains a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent.
  • a method in which the second conductive layer 13 laminated by the method described later is transferred to the substrate 11 described above.
  • a self-dispersing group containing a dissociable group dispersible in a conductive polymer and an aqueous solvent by a known method such as an inkjet method on a non-conductive portion (opening portion 12a) of a thin metal wire portion.
  • a method of forming the second conductive layer 13 containing a mold polymer by a known method such as an inkjet method on a non-conductive portion (opening portion 12a) of a thin metal wire portion.
  • the second conductive layer 13 containing a conductive polymer and a self-dispersing polymer containing a dissociable group dispersible in an aqueous solvent is characterized by containing a self-dispersing polymer.
  • the second conductive layer 13 containing a conductive polymer and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent, a dissociable group-containing self-dispersing polymer dispersible in the conductive polymer and the aqueous solvent
  • the ratio is preferably 30 to 900 parts by mass of the dissociable group-containing non-conductive polymer when the conductive polymer is 100 parts by mass, preventing current leakage and the conductivity of the dissociable group-containing non-conductive polymer.
  • the dissociable group-containing non-conductive polymer is more preferably 100 to 900 parts by mass.
  • the ratio When the ratio is less than 30 parts by weight, it is necessary to reduce the film thickness in order to obtain desired transmittance and conductivity. If the film thickness is thin, the fine metal wire used for the first conductive layer 12 The unevenness on the portion or the thin metal wire portion cannot be covered, causing current leakage. On the other hand, when the ratio exceeds 900 parts by weight, the conductivity of the dispersion composed of the conductive polymer and the dissociable group-containing self-dispersing polymer dispersible in the aqueous solvent decreases, and the transparent conductive film 1 and the organic There is a possibility that desired performance as an EL element cannot be obtained. Further, when the ratio is 100 to 900 parts by weight, it is possible to prevent current leakage by increasing the film thickness, and desired performance as the transparent conductive film 1 and the organic EL element can be suitably obtained.
  • the dry film thickness of the second conductive layer 13 is preferably 30 to 2000 nm.
  • the dry film thickness is less than 30 nm, the metal thin wire portion used for the first conductive layer 12 or the unevenness on the metal thin wire portion cannot be covered, which may cause current leakage.
  • the dry film thickness exceeds 2000 nm, the transmittance and the conductivity are lowered, and the desired performance as the transparent conductive film 1 cannot be obtained, and as a result, a highly efficient organic EL device may not be obtained. is there.
  • the second conductive layer 13 is formed by applying a coating liquid (dispersion liquid) containing a conductive polymer and a dissociable group-containing self-dispersing polymer dispersible in an aqueous solvent, followed by drying treatment.
  • a drying treatment can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes.
  • cleaning tolerance and solvent tolerance of the transparent conductive film 1 improve remarkably, and element performance improves further.
  • effects such as reduction in driving voltage and improvement in life can be obtained.
  • the coating liquid described above contains, as additives, plasticizers, stabilizers (antioxidants, antioxidants, etc.), surfactants, dissolution accelerators, polymerization inhibitors, colorants (dyes, pigments, etc.) and the like. May be. Furthermore, from the viewpoint of improving workability such as coating properties, the coating liquid described above is a solvent (for example, water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons). Or other organic solvents).
  • a solvent for example, water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons. Or other organic solvents).
  • the smoothness of the surface of the second conductive layer 13 which is a transparent conductive layer is Ry ⁇ 50 nm
  • the smoothness of the surface of the second conductive layer 13 which is a transparent conductive layer is It is preferable that Ra ⁇ 10 nm.
  • a commercially available atomic force microscope can be used for the measurement of Ry and Ra.
  • the measurement can be performed by the following method.
  • an SPI 3800N probe station manufactured by Seiko Instruments Inc. and a SPA400 multifunctional unit as the AFM set a sample cut to a size of about 1 cm square on a horizontal sample table on a piezo scanner, and place the cantilever on the sample surface.
  • scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction.
  • a piezo scanner that can scan XY 20 ⁇ m and Z 2 ⁇ m 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 30 nm or less.
  • the value of Ra is more preferably 10 nm or less, and further preferably 5 nm or less. This is because if the surface roughness of the transparent electrode film 1 is smooth, the upper layer can be thinned at the time of manufacturing the organic EL element, and as a result, the organic EL element can be thinned.
  • the transparent conductive film 1 preferably has a total light transmittance of 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • the total light transmittance can be measured according to a known method using a spectrophotometer or the like.
  • the electrical resistance value of the second conductive layer 13 which is a transparent conductive layer in the transparent conductive film 1 of the present invention is preferably 1000 ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less as the surface resistivity. preferable.
  • the surface resistivity is preferably 50 ⁇ / ⁇ or less, and more preferably 10 ⁇ / ⁇ or less.
  • the surface resistivity is 10 3 ⁇ / ⁇ or less because the transparent conductive film 1 can suitably function as an electrode in various optoelectronic devices.
  • the second conductive layer 13 can be thinned if the smoothness of the surface of the thin metal wire portion which is the first conductive layer 12 is very good.
  • An organic EL element can be thinned.
  • the above-mentioned surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method by conductive probe four-probe method) or the like, or using a commercially available surface resistivity meter. It can be easily measured.
  • the thickness of the transparent conductive film 1 which concerns on this invention, although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and a softness
  • An organic EL device includes a transparent conductive film 1 as an electrode, and includes an organic layer including an organic light emitting layer and the transparent conductive film 1.
  • the organic EL element according to the embodiment of the present invention preferably includes the transparent conductive film 1 as an anode, and the organic light-emitting layer and the cathode are arbitrarily selected from materials, configurations, and the like generally used for the organic EL element. Things can be used.
  • the element configuration of the organic EL element is as follows: anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / electron transport layer / cathode, anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / Cathode, anode / hole injection layer / organic light emitting layer / electron transport layer / electron injection layer / cathode, anode / hole injection layer / organic light emitting layer / electron injection layer / cathode, etc. it can.
  • the light emitting material or doping material that can be used for the organic light emitting layer includes anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bis.
  • the film When the light emitting material exceeds 90 parts by weight, the film may be thickened and the flexibility may be lowered. When the light emitting material is less than 9.5 parts by weight, a desired luminance may not be obtained. Further, when the doping material is less than 0.5 parts by weight, the desired luminance may not be obtained, and when it exceeds 10 parts by weight, the dopant concentration may increase and the concentration may be quenched.
  • An organic light emitting layer is manufactured by well-known methods, such as vapor deposition, application
  • the transparent conductive film 1 has both high conductivity and transparency, and various optical options such as a liquid crystal display device, an organic light emitting device, an inorganic electroluminescent device, electronic paper, an organic solar cell, and an inorganic solar cell. It can be suitably used in the fields of electronics devices, electromagnetic wave shields, touch panels and the like. Among them, it can be particularly preferably used as a transparent electrode of an organic EL device or an organic thin film solar cell device in which the smoothness of the transparent electrode surface is strictly required.
  • the organic EL element according to the present invention can emit light uniformly and without unevenness, it is preferably used for lighting applications, and can be used for self-luminous displays, liquid crystal backlights, lighting, and the like. .
  • ⁇ GPC measurement conditions Device: Waters 2695 (Separations Module) Detector: Waters 2414 (Refractive Index Detector) Column: Shodex Asahipak GF-7M HQ Eluent: Dimethylformamide (containing 20 mM LiBr) Flow rate: 1.0 ml / min Temperature: 40 ° C
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Co., Ltd. was applied to a non-undercoated surface of a polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 ⁇ m, and dried. After coating with a wire bar so that the average film thickness becomes 4 ⁇ m, after drying at 80 ° C. for 3 minutes, curing is performed under a curing condition of 1.0 J / cm 2 using a high-pressure mercury lamp in an air atmosphere, and a smooth layer Formed. Next, a gas barrier layer was formed on the sample provided with the smooth layer under the following conditions.
  • the dried sample was further dehumidified by being held for 10 minutes in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature ⁇ 8 ° C.).
  • Modification A The sample subjected to the dehumidification treatment was modified under the following conditions to form a gas barrier layer.
  • the dew point temperature during the reforming process was -8 ° C.
  • Example 1> ⁇ Preparation of transparent electrode> ⁇ Preparation of transparent electrode TC-101>
  • the following coating liquid A was applied to a non-barrier surface on a transparent electrode film substrate having gas barrier properties by adjusting the slit gap of the extrusion head so as to have a dry film thickness of 300 nm using an extrusion method.
  • a second conductive layer made of a binder resin dispersible in a conductive polymer and an aqueous solvent was formed by heating and drying at 110 ° C. for 5 minutes, 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.
  • Conductive polymer PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
  • Binder Vylonal MD1245 (solid content 54.4% aqueous solution) 0.13 g
  • the transparent electrode TC- of the comparative example was prepared in the same manner as the production of the transparent electrode TC-101, except that the binder of coating liquid A, Vylonal MD1245, was changed to the binder shown in Table 1. 108 to TC-112 were produced. Note that the binders used in TC-108 to TC-110, Nypol LX430, LX433C, and LX435, are not a dissociable group-containing self-dispersing polymer according to the present invention, and a surfactant is used for dispersion.
  • the glass transition temperature (Tg) of the binder resin was measured as follows.
  • the film shape, transparency, surface resistance (conductivity), surface roughness and film strength of the obtained transparent electrode were evaluated as follows.
  • evaluation of the film shape, transparency, surface resistance, surface roughness and film strength of the transparent electrode sample after a forced deterioration test placed in an environment of 80 ° C. and 90% RH for 5 days was done.
  • particle size measurement Using a particle size measuring machine (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.), the solution was measured as it was without dilution.
  • the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.).
  • the surface resistance is preferably 100 ⁇ / ⁇ or less, and preferably 30 ⁇ / ⁇ or less in order to increase the area of the organic electronic device.
  • Evaluation criteria Samples evaluated as 30 ⁇ / ⁇ or less after forced deterioration pass the present invention.
  • the transparent electrodes TC-101 to 109 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.
  • Example 2> Preparation of transparent electrode> ⁇ Formation of first conductive layer> The 1st conductive layer was formed with the following method in the surface without the barrier on the film substrate (base material 11) for transparent electrodes (transparent conductive film 1) which has the gas barrier property obtained above.
  • the fine wire lattice (metal material) was produced by gravure printing or silver nanowire as shown below.
  • ⁇ Preparation of transparent electrode TC-201> The following coating liquid A is extruded on the transparent electrode in which the first conductive layer is formed by gravure printing on the film substrate for the transparent electrode having gas barrier properties, using an extrusion method so as to have a dry film thickness of 300 nm.
  • the slit gap was adjusted and applied, dried by heating at 110 ° C. for 5 minutes to form a second conductive layer composed of a conductive polymer and a binder resin dispersible in an aqueous solvent, and the obtained electrode was 8 ⁇ 8 cm. Cut out.
  • the obtained electrode was heated in an oven at 110 ° C. for 30 minutes to produce a transparent electrode TC-101.
  • Second Conductive Layer 13> (Coating liquid A) Conductive polymer: PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g Binder: Polysol FP3000 (solid content 54.4% aqueous solution) 0.13 g Dimethyl sulfoxide (DMSO, 1/10 of the conductive polymer solution mass) 0.16 g
  • the silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m 2 , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate.
  • a second coating solution is prepared in the same manner as in the production of the transparent electrode TC-201 using a coating solution in which Polysol FP3000, which is a binder of coating solution A, is changed to plus coat RZ570.
  • a conductive layer was formed and 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-208.
  • a copper mesh was produced on the substrate as an auxiliary electrode by the following method, and patterned with a metal fine particle removing liquid BF to produce a copper mesh substrate.
  • the catalyst ink JISD-7 manufactured by Morimura Chemical Co. containing palladium nanoparticles is used, and the CAB-O-JET300 self-dispersing carbon black solution manufactured by Cabot is used, and the carbon black ratio to the catalyst ink becomes 10.0% by mass.
  • Surfynol 465 (Nisshin Chemical Industry Co., Ltd.) was further added to prepare a conductive ink having a surface tension at 25 ° C. of 48 mN / m.
  • Conductive ink as an ink jet recording head has a pressure applying means and an electric field applying means, and has a nozzle diameter of 25 ⁇ m, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi (dpi is 1 inch, that is, 2.54 cm per 2.54 cm).
  • Fig. A-6 shows a grid-like conductive thin wire with a line width of 10 ⁇ m, a dried film thickness of 0.5 ⁇ m, and a line spacing of 300 ⁇ m on the substrate. After forming into parts, it was dried.
  • the substrate was immersed for 10 minutes at a temperature of 55 ° C., washed, and subjected to electroless plating to produce an auxiliary electrode having a plating thickness of 3 ⁇ m. .
  • a second conductive layer is formed by the same method as the production of the transparent electrode TC-201, using the coating liquid A in which Vylonal MD1245, which is the binder of the coating liquid A, is changed to the plus coat RZ570. And 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-209.
  • the transparent electrode TC-101 was prepared in the same manner as the production of the transparent electrode TC-101, except that the binder of coating liquid A, Vylonal MD1245, was changed to the binder shown in Table 1. 210 to TC-214 were produced. Note that the binders used for TC-110 to TC-112, Nypol LX430, LX433C, and LX435, are not dissociable group-containing self-dispersing polymers according to the present invention, and a surfactant is used for dispersion.
  • a transparent electrode TC-215 was produced in the same manner as the production of the transparent electrode TC-201 except that the binder in the coating solution A was not used.
  • the transparent electrodes TC-201 to 109 of the present invention are excellent in smoothness, conductivity, light transmittance and film strength, It can be seen that even in a high humidity environment, there is little deterioration in smoothness, conductivity, light transmission and film strength, and the stability is excellent.
  • Example 3> ⁇ Production of organic EL device> After the transparent electrode substrate produced in Example 2 was washed with ultrapure water, it was cut into a 30 mm square so that one square tile-shaped transparent pattern with a pattern side length of 20 mm was placed in the center, and used for the anode electrode. The organic EL device was produced respectively. The hole transport layer and subsequent layers were formed by vapor deposition. Organic EL elements OEL-301 to OEL-315 were fabricated using transparent electrodes TC-201 to TC-215, respectively.
  • Each crucible for vapor deposition in a commercially available vacuum vapor deposition apparatus was filled with a constituent material of each layer in a necessary amount for device production.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • an organic EL layer including a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.
  • each light emitting layer was provided in the following procedures.
  • Compound 2, Compound 3 and Compound 5 are deposited on the formed hole transport layer so that Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass.
  • Co-evaporation was performed in the same region as the hole transport layer at a speed of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
  • compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass.
  • Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.
  • a hole blocking layer was formed by depositing compound 6 in a thickness of 5 nm on the same region as the formed organic light emitting layer.
  • CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm.
  • a transparent electrode is used as an anode, an anode external takeout terminal and Al as a 15 mm ⁇ 15 mm cathode forming material are mask-deposited under a vacuum of 5 ⁇ 10 ⁇ 4 Pa, and a 100 nm thick anode Formed.
  • a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al 2 O 3 is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed.
  • the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm ⁇ 15 mm was produced.
  • emission uniformity For light emission uniformity, a KEITHLEY source measure unit 2400 type was used to apply a DC voltage to the organic EL element to emit light. With respect to the organic EL elements OEL-201 to OEL-217 that emitted light at 1000 cd / m 2 , each light emission luminance unevenness was observed with a 50 ⁇ microscope. Further, the organic EL elements OEL-201 to OEL-217 were heated in an oven at 60% RH and 80 ° C. for 2 hours, and then conditioned again in the environment of 23 ⁇ 3 ° C. and 55 ⁇ 3% RH for 1 hour or more. Thereafter, the emission uniformity was observed in the same manner.
  • the obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m 2 , the voltage was fixed, and the time until the luminance was reduced by half was determined.
  • An organic EL element having an anode electrode made of ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. 100% or more is preferable, and 150% or more is more preferable. ⁇ : 150% or more ⁇ : 100 to less than 150% ⁇ : less than 80 to 100% ⁇ : less than 80% Evaluation Criteria: Samples evaluated as ⁇ , ⁇ , ⁇ after forced deterioration pass the present invention.
  • Table 3 shows the evaluation results.
  • “Invention” in the remarks indicates that it corresponds to an example of the present invention, and “Comparison” indicates that it is a comparative example.
  • the comparative organic EL elements OEL-310 to OEL-315 are significantly deteriorated in light emission uniformity after heating at 80 ° C. for 30 minutes, whereas the organic EL elements OEL-301 to OEL-309 of the present invention It can be seen that the light emission uniformity is stable even after heating and is excellent in durability.

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  • Nanotechnology (AREA)
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Abstract

La présente invention concerne un film conducteur transparent présentant une excellente transparence, une conductivité électrique, une solidité et dont la détérioration de la transparence, de la conductivité électrique et de la solidité est supprimée, y compris dans un environnement à haute température et à taux d'humidité élevé. Un film conducteur transparent (1) présente une seconde couche conductrice transparente (13) composée d'une couche de composition organique, sur une base transparente (11). La couche de composition organique est formée par application et séchage d'un liquide de dispersion contenant un composé polymère conducteur et un polymère auto-dispersible contenant un groupe dissociatif pouvant être dispersé dans un solvant aqueux. Dans le liquide de dispersion, le diamètre moyen des particules contenant le composé polymère conducteur et le polymère auto-dispersible contenant un groupe dissociatif est 5-100 nm.
PCT/JP2012/077363 2011-10-27 2012-10-23 Film conducteur transparent et élément électroluminescent organique WO2013061967A1 (fr)

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WO2014167960A1 (fr) * 2013-04-09 2014-10-16 長岡産業株式会社 Film conducteur transparent
JP2014229397A (ja) * 2013-05-20 2014-12-08 コニカミノルタ株式会社 導電膜の製造方法、導電膜、有機電子素子及びタッチパネル
JP2017036375A (ja) * 2015-08-07 2017-02-16 信越ポリマー株式会社 導電性高分子分散液、常温延伸用導電性フィルムの製造方法及び導電性延伸フィルムの製造方法
KR20180091906A (ko) * 2015-12-10 2018-08-16 센젠 차이나 스타 옵토일렉트로닉스 테크놀로지 컴퍼니 리미티드 Oled 디스플레이 패널 및 oled 디스플레이 장치
JP2018181579A (ja) * 2017-04-12 2018-11-15 株式会社ジャパンディスプレイ 有機ｅｌ表示装置
CN115362409A (zh) * 2020-03-31 2022-11-18 日东电工株式会社 高分子分散型液晶膜、乳液、以及高分子分散型液晶膜的制造方法

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WO2014167960A1 (fr) * 2013-04-09 2014-10-16 長岡産業株式会社 Film conducteur transparent
JP2014229397A (ja) * 2013-05-20 2014-12-08 コニカミノルタ株式会社 導電膜の製造方法、導電膜、有機電子素子及びタッチパネル
JP2017036375A (ja) * 2015-08-07 2017-02-16 信越ポリマー株式会社 導電性高分子分散液、常温延伸用導電性フィルムの製造方法及び導電性延伸フィルムの製造方法
KR20180091906A (ko) * 2015-12-10 2018-08-16 센젠 차이나 스타 옵토일렉트로닉스 테크놀로지 컴퍼니 리미티드 Oled 디스플레이 패널 및 oled 디스플레이 장치
JP2018538673A (ja) * 2015-12-10 2018-12-27 深▲せん▼市華星光電技術有限公司Ｓｈｅｎｚｈｅｎ Ｃｈｉｎａ Ｓｔａｒ Ｏｐｔｏｅｌｅｃｔｒｏｎｉｃｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ． Ｏｌｅｄ表示パネル及び表示装置
KR102183710B1 (ko) * 2015-12-10 2020-11-27 티씨엘 차이나 스타 옵토일렉트로닉스 테크놀로지 컴퍼니 리미티드 Oled 디스플레이 패널 및 oled 디스플레이 장치
JP2018181579A (ja) * 2017-04-12 2018-11-15 株式会社ジャパンディスプレイ 有機ｅｌ表示装置
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CN115362409A (zh) * 2020-03-31 2022-11-18 日东电工株式会社 高分子分散型液晶膜、乳液、以及高分子分散型液晶膜的制造方法

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