WO2016152822A1 - Film électroconducteur et élément électroluminescent organique - Google Patents

Film électroconducteur et élément électroluminescent organique Download PDF

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WO2016152822A1
WO2016152822A1 PCT/JP2016/058887 JP2016058887W WO2016152822A1 WO 2016152822 A1 WO2016152822 A1 WO 2016152822A1 JP 2016058887 W JP2016058887 W JP 2016058887W WO 2016152822 A1 WO2016152822 A1 WO 2016152822A1
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layer
conductive
metal oxide
film
silicon
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PCT/JP2016/058887
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English (en)
Japanese (ja)
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小島　茂
健 波木井
和央 吉田
隼 古川
井　宏元
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コニカミノルタ株式会社
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Priority to JP2017508341A priority Critical patent/JPWO2016152822A1/ja
Publication of WO2016152822A1 publication Critical patent/WO2016152822A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • 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

Definitions

  • the present invention relates to a conductive film and an organic electroluminescence device, and more particularly, to a conductive film having a low resistance and a high stability in electrical conductivity and an organic electroluminescence device having a high stability in light emission performance.
  • a conductive film including a conductive layer formed using a conductive substance on a resin film is a thin film such as an organic electroluminescence (EL) element used in a display or a lighting panel, a solar cell, or electronic paper.
  • EL organic electroluminescence
  • a large-area electronic device, for example, an organic EL element for illumination, a solar cell for power generation, and the like require high light emission efficiency or power generation efficiency, and thus a low resistance conductive film has been desired.
  • a low-resistance conductive film using a carbon material such as graphene and silver nanowires for a conductive layer containing a conductive polymer has been proposed (see, for example, Patent Document 1).
  • the conductive layer easily deteriorates due to the infiltrated gas, the resistivity changes, and the stability of the conductive performance is low.
  • the stability of the light emitting performance has been lowered, such as a change in luminance due to long-term use under high temperature and high humidity.
  • a silicon compound layer having a high gas barrier property can also be formed under the conductive layer so that it can withstand use under high temperature and high humidity (see, for example, Patent Document 2).
  • a conductive film in which a silicon compound layer is formed under a conductive layer using a conductive polymer has a large resistance, and cannot achieve both low resistance and stability of conductive performance.
  • an organic EL element used for a backlight of a liquid crystal display is desired to have less chromaticity angle dependency.
  • the present invention has been made in view of the above problems and circumstances, and the problem to be solved is a conductive film having low resistance and high stability of conductive performance, and an organic electroluminescence device having high stability of light emission performance and less angular dependency of chromaticity. Is to provide.
  • the present inventor has a transition metal oxide layer under a conductive layer containing a conductive polymer or a metal oxide in the process of examining the cause of the above problem, and further includes a transition metal oxide. It has been found that when a silicon-containing polymer modified layer is provided under the physical layer, a very high gas barrier property can be obtained without impairing the conductive performance of the conductive layer, resulting in the present invention. That is, the subject concerning this invention is solved by the following means.
  • a conductive film comprising a conductive layer containing a conductive polymer or metal oxide on a resin film, A silicon-containing polymer modified layer containing a modified product of the silicon-containing polymer; A transition metal oxide layer located on the silicon-containing polymer modified layer and containing a transition metal oxide; and The conductive film is located on the transition metal oxide layer.
  • the conductive film according to claim 1 comprising a metal layer containing a metal nanomaterial on the transition metal oxide layer when the conductive layer is a conductive layer containing the conductive polymer.
  • the conductive layer is a conductive layer containing the conductive polymer
  • a carbon layer containing a carbon material is provided on the transition metal oxide layer. Conductive film.
  • the conductive layer is a conductive layer containing the conductive polymer
  • the conductive layer containing a metal oxide is further provided on the conductive layer containing the conductive polymer.
  • the conductive layer is a conductive layer containing the metal oxide
  • a light scattering layer is provided under the conductive layer, or the conductive film according to claim 1 or 5.
  • An organic electroluminescence device comprising the conductive film according to any one of items 1 to 9 as an electrode.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • a silicon-containing polymer modified layer with excellent gas barrier properties and a transition metal oxide layer that prevents oxidation of the silicon-containing polymer modified layer are combined and placed under the conductive layer, making the transition instead of the silicon-containing polymer modified layer. It is presumed that by making the metal oxide layer adjacent to the conductive layer, very high gas barrier properties could be obtained without impairing the conductivity of the conductive layer. The reason is not clear, but the d-electron of the transition metal acts to affect the film quality of the conductive layer formed on the transition metal oxide layer. As a result, the film quality of the conductive layer becomes uniform and the conductivity is improved.
  • Sectional drawing which shows the structure of the electroconductive film of embodiment of this invention Front view showing the outline of vacuum ultraviolet light irradiation equipment Sectional drawing which shows the structure of the electroconductive film further provided with a silicon compound layer Sectional drawing which shows the structure of the electroconductive film further provided with a silicon-containing polymer modified layer Enlarged cross-sectional view of a conductive layer comprising a conductive polymer layer, carbon layer, metal layer, grid and plating layer Sectional drawing which shows the structure of the conductive film further provided with the conductive layer containing a metal oxide on the conductive layer containing a conductive polymer Enlarged sectional view of a conductive layer comprising a metal oxide layer, a grid and a plating layer Sectional drawing which shows the structure of the electroconductive film further provided with a light-scattering layer Sectional drawing which shows the structure of the organic electroluminescent element of this Embodiment
  • the conductive film of the present invention is a conductive film comprising a conductive layer containing a conductive polymer or a metal oxide on a resin film, the silicon-containing polymer modified layer containing a modified product of a silicon-containing polymer And a transition metal oxide layer containing a transition metal oxide located on the silicon-containing polymer modified layer, wherein the conductive layer is located on the transition metal oxide layer, To do.
  • This feature is a technical feature common to the claimed invention.
  • a metal nanomaterial is contained on the transition metal oxide layer. It is preferable to provide a metal layer or a carbon layer containing a carbon material.
  • a conductive layer containing a metal oxide is further provided on the conductive layer containing the conductive polymer. It is preferable.
  • the metal oxide is preferably indium-zinc / oxide from the viewpoint of enhancing conductivity.
  • the said conductive layer is a conductive layer containing the said metal oxide
  • the transition metal oxide is preferably an oxide of a Group 5 metal in the periodic table.
  • niobium oxide is more preferable because it provides not only gas barrier properties but also a conductive film having a smaller angle dependency of transmittance.
  • the conductive layer preferably includes a grid on the transition metal oxide layer.
  • the conductive film of the present invention can be preferably used as an electrode of an organic electroluminescence element.
  • the stability of the light emitting performance of the organic electroluminescence element can be improved, and the angle dependency of chromaticity can be reduced.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • a conductive film according to a first embodiment of the present invention is a conductive film including a conductive layer containing a conductive polymer on a resin film, the silicon-containing polymer containing a modified product of the silicon-containing polymer A modified layer and a transition metal oxide layer located on the silicon-containing polymer modified layer and containing a transition metal oxide, wherein the conductive layer is located on the transition metal oxide layer.
  • FIG. 1 shows a configuration of a conductive film 10a according to an embodiment of the present invention.
  • the conductive film 10 a includes a silicon-containing polymer modified layer 2 and a transition metal oxide layer 3 in this order on the resin film 1, and a conductive layer 4 on the transition metal oxide layer 3. ing.
  • resin film There is no restriction
  • polyester-type resin such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester
  • polyethylene (PE) resin polypropylene (PP) resin
  • polystyrene resin polystyrene resin
  • cyclic olefin Resins such as polyolefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin, polycarbonate (PC) resin , Polyamide resin, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin and the like.
  • PET polyethylene terephthalate
  • PP polypropylene
  • Pstyrene resin polystyrene resin
  • cyclic olefin Resins such as polyo
  • Resin film 1 having high transparency is preferable because it can be used as a transparent electrode in an electronic device.
  • High transparency means that the total light transmittance in the visible light wavelength region measured by a method based on JIS K 7361-1: 1997 (plastic-transparent material total light transmittance test method) is 50% or more. This is more preferably 80% or more.
  • the resin film 1 may be subjected to a surface activation treatment or may be provided with a base layer in order to improve the adhesion with the silicon-containing polymer modified layer 2 or the like formed on the resin film 1.
  • a hard coat layer may be provided.
  • the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • the material for the underlayer and the hard coat layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer, and the like. Of these, ultraviolet curable resins can be preferably used.
  • the underlayer may be a single layer, but the adhesiveness is further improved when it has a multilayer structure.
  • the silicon-containing polymer modified layer 2 contains a modified product of a silicon-containing polymer having a bond of silicon and oxygen (Si—O), silicon and nitrogen (Si—N), etc. in a repetitive structure.
  • the thickness of the silicon-containing polymer modified layer 2 can be appropriately set according to the purpose, but generally can be in the range of 10 nm to 10 ⁇ m.
  • silicon-containing polymer examples include polysiloxane having a Si—O bond (including polysilsesquioxane), polysilazane having a Si—N bond, Si—O bond and Si—N bond in a repeating structure.
  • examples include polysiloxazan containing both. These can be used in combination of two or more. It is also possible to laminate layers of different types of silicon-containing polymers.
  • the polysiloxane contains-[RaSiO 1/2 ]-,-[RbSiO]-,-[RcSiO 3/2 ]-,-[SiO 2 ]-and the like in the repeating structure.
  • Ra, Rb and Rc are each independently a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), an aryl group (eg, a phenyl group, an unsaturated alkyl group) And the like.
  • Polysilsesquioxane is a compound that includes the same structure as silsesquioxane among the polysiloxanes in its repeated structure.
  • Silsesquioxane is a compound having a structure represented by the above-[RcSiO 3/2 ]-.
  • the structure of polysilazane can be represented by the following general formula (A).
  • Formula (A) [Si (R 1 ) (R 2 ) —N (R 3 )] —
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • the polysilazane in which all of R 1 , R 2 and R 3 in the general formula (A) are hydrogen atoms is perhydropolysilazane.
  • Perhydropolysilazane is preferable in that a dense film can be obtained.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring.
  • the number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • a polysilane in which a part of hydrogen atoms bonded to Si is substituted with an alkyl group or the like is an organopolysilazane.
  • Organopolysilazane improves adhesion to the underlying resin film 1 by an alkyl group such as a methyl group, and can impart toughness to a polysilazane having hard and brittle properties, so even if the film is thickened, There is an advantage that generation is suppressed. Therefore, perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, or both may be used in combination.
  • Polysiloxazan includes a structure represented by — [(SiH 2 ) n (NH) r ] — and — [(SiH 2 ) m O] — in a repeating structure.
  • n, m and r each independently represent 1 to 3.
  • a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the above general formula (A) (for example, Japanese Patent Laid-Open No. Hei. No.
  • glycidol-added polysilazanes obtained by reacting glycidol see, for example, JP-A-6-122852
  • alcohol-added polysilazanes obtained by reacting with alcohol see, for example, JP-A-6-6 240208
  • a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate see, for example, JP-A-6-299118
  • Acetylacetonate complex-added polysilazane (in example, JP-A 6-306329 JP reference.), Fine metal particles of the metal particles added polysilazane obtained by adding (e.g., JP-A-7-196986 JP reference.), And the like.
  • the silicon-containing polymer modified layer 2 can be formed by forming a coating film using the coating liquid containing the silicon-containing polymer described above and subjecting the coating film to a modification treatment.
  • the silicon-containing polymer is converted to silica or the like by the modification treatment to obtain a modified treatment product, it is not necessary to modify all of the silicon-containing polymer, and at least a part, for example, the ultraviolet irradiation surface side is modified. Just do it.
  • the coating film forming method include a roll coating method, a flow coating method, a spray coating method, a printing method, a dip coating method, a bar coating method, a casting film forming method, an ink jet method, and a gravure printing method.
  • examples of the organic solvent that can be used for preparing the coating liquid include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. And ethers.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
  • a commercial product in which polysilazane is dissolved in an organic solvent can be used.
  • examples of commercially available products that can be used include Aquamica® NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.
  • the coating solution can also contain a catalyst from the viewpoint of promoting the reforming treatment.
  • the catalyst is preferably a basic catalyst, for example, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetra Amine catalysts such as methyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, Pd compounds such as propionic acid Pd, Examples thereof include metal catalysts such as Rh compounds such as Rh acetylacetonate, N-heterocyclic compounds, and the like.
  • the content of the silicon-containing polymer in the coating solution varies depending on the thickness of the silicon-containing polymer modified layer 2 to be formed and the pot life of the coating solution, but is preferably in the range of 0.2 to 35.0% by mass. .
  • the formed coating film can be subjected to a drying treatment by heating.
  • the temperature during heating can be in the range of 50 to 200 ° C.
  • the heating time is preferably set to a short time in order to prevent deformation of the resin film 1 and the like.
  • the temperature during the drying treatment can be set to 150 ° C. or lower in order to prevent deformation of the resin film.
  • the formed coating film can be subjected to a drying process for dehumidification while maintaining a low humidity environment. Since humidity in a low-humidity environment varies with temperature, the relationship between temperature and humidity can be determined by defining the dew point temperature.
  • a preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is ⁇ 8 ° C. (temperature 25 ° C./humidity 10%) or lower, and a more preferable dew point temperature is ⁇ 31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less.
  • the pressure for drying under reduced pressure can be selected within the range of normal pressure to 0.1 MPa.
  • a known method for modifying the coating film a known method with little damage to the resin film 1 can be used, and plasma treatment capable of low temperature treatment, ozone treatment, ultraviolet ray or vacuum ultraviolet ray irradiation treatment, etc. are used. be able to.
  • the irradiation treatment with vacuum ultraviolet rays is preferable because the gas barrier property is not easily lowered by the influence of the environment from the formation of the silicon-containing polymer modified layer 2 to the formation of the transition metal oxide layer 3. .
  • the vacuum ultraviolet irradiation treatment uses the light energy of vacuum ultraviolet light in the wavelength range of 100 to 200 nm, which is larger than the interatomic bonding force constituting the silicon-containing polymer, and the bonding between atoms is called a photon process by the action of only photons. It is a process of converting directly to silica or the like in a relatively low temperature environment of about 200 ° C. or lower by directly cutting and advancing an oxidation reaction with active oxygen or ozone.
  • the vacuum ultraviolet light source may be any light source that generates light having a wavelength of 100 to 200 nm.
  • the irradiation wavelength is a rare gas excimer lamp having a wavelength of about 172 nm (for example, Xe excimer lamp MODEL manufactured by M.D. : MECL-M-1-200), a low-pressure mercury vapor lamp of about 185 nm, a medium-pressure and high-pressure mercury vapor lamp of 200 nm or less, and the like.
  • the excimer lamp is characterized by the fact that it emits light of a single wavelength, has a very high luminous efficiency, the emitted light has a short wavelength, the temperature of the irradiation target can be kept at a low temperature, and it can be turned on and off instantaneously.
  • This is a light source that can be easily applied to the resin film 1 that is easily affected by heat.
  • vacuum ultraviolet light having a short wavelength of 172 nm emitted from an Xe excimer lamp has a large oxygen absorption coefficient, generates a high concentration of active oxygen or ozone from a small amount of oxygen, and has a high ability to dissociate organic bonds. Therefore, the reforming process can be performed in a short time.
  • the irradiation condition of the vacuum ultraviolet rays may be set within a range in which the resin film 1 and the like below the silicon-containing polymer modified layer 2 are not deteriorated.
  • the irradiation time of ultraviolet rays depends on the composition and concentration of the resin film 1 and the coating solution, it is generally in the range of 0.1 second to 10 minutes and in the range of 0.5 seconds to 3 minutes. It is preferable.
  • the illuminance of the vacuum ultraviolet light can be in the range of 1 mW / cm 2 to 10 W / cm 2 . If it is 1 mW / cm 2 or more, the reforming efficiency is improved, and if it is 10 W / cm 2 or less, ablation that may occur in the coating film, damage to the resin film 1, and the like can be reduced.
  • the irradiation energy amount (irradiation amount) of vacuum ultraviolet rays can be set within a range of 0.1 to 10.0 J / cm 2 . If it is this range, generation
  • the vacuum ultraviolet irradiation treatment may be batch treatment or continuous treatment.
  • it can be processed in an ultraviolet baking furnace (for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd.) equipped with a vacuum ultraviolet light source.
  • an ultraviolet baking furnace for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd.
  • the resin film 1 may be conveyed and irradiated with ultraviolet rays continuously in a zone having a vacuum ultraviolet light source.
  • Oxygen is required for the reaction at the time of irradiation with vacuum ultraviolet rays, but since vacuum ultraviolet rays are absorbed by oxygen and the reforming efficiency tends to decrease, irradiation with vacuum ultraviolet rays is performed in an atmosphere with low oxygen concentration and water vapor concentration as much as possible. It is preferable to carry out.
  • the oxygen concentration during vacuum ultraviolet irradiation can be in the range of 10 to 20000 ppm by volume (0.001 to 2% by volume).
  • the water vapor concentration is preferably in the range of 1000 to 4000 ppm by volume.
  • dry inert gas particularly dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by adjusting the flow ratio of oxygen gas and inert gas introduced into the room.
  • FIG. 2 shows an example of a vacuum ultraviolet irradiation apparatus that can be used for the modification treatment.
  • the vacuum ultraviolet irradiation apparatus 100 places the resin film 1 on the stage 104 and conveys the inside of the chamber 101.
  • the stage 104 includes a heater and can heat the resin film 1.
  • the chamber 101 is divided into three zones in the transport direction V of the resin film 1 by the shielding plate 106, and a plurality of Xe excimer lamps 102 are installed in the central zone.
  • the Xe excimer lamp 102 is supported by a holder 103 containing a power supply and is controlled to be lit.
  • a silicon compound layer containing a silicon compound such as silicon oxide, silicon nitride, silicon oxynitride, or silicon carbide may be further disposed under the silicon-containing polymer modified layer 2.
  • FIG. 3 shows a cross-sectional configuration of a conductive film 10 b including the silicon compound layer 5 under the silicon-containing polymer modified layer 2.
  • the layer adjacent to the transition metal oxide layer 3 is the silicon-containing polymer modified layer 2
  • the lower layer than the silicon-containing polymer modified layer 2 is a multilayer structure of the silicon compound layer 5 and the silicon-containing polymer modified layer.
  • FIG. 4 shows a cross-sectional configuration of the conductive film 10 c in the case of having a multilayer structure of the silicon-containing polymer modified layer 2, the silicon compound layer 5, and the silicon-containing polymer modified layer 2.
  • the silicon compound layer 5 includes a silicon-containing polymer used for the silicon-containing polymer modified layer 2 such as polysilazane, in addition to a vacuum deposition method using silicon oxide as a raw material, a magnetron sputtering method using a target containing silicon, and an ion plating method.
  • a silicon-containing polymer used for the silicon-containing polymer modified layer 2 such as polysilazane
  • silicon oxide as a raw material
  • a magnetron sputtering method using a target containing silicon such as a raw material
  • ion plating method for example, hexamethyldisiloxane, perhydropolysilazane, etc.
  • silicon dioxide or the like can be used as a raw material by a plasma CVD (Chemical Vapor Deposition) method or the like.
  • a layer of a metal oxide other than silicon, such as aluminum oxide, or a metal nitride may be provided as long as the gas barrier property is high.
  • the transition metal oxide layer 3 is located on the silicon-containing polymer modified layer 2 and below the conductive layer 4 and contains a transition metal oxide.
  • the transition metal oxide layer 3 is adjacent to the silicon-containing polymer modified layer 2 to suppress oxidation of the silicon-containing polymer modified layer 2, and is adjacent to the conductive layer 4 without impairing the conductivity of the conductive layer 4.
  • the silicon-containing polymer modified layer 2 can exhibit very high gas barrier properties.
  • the transition metal oxide used for the transition metal oxide layer 3 is an oxide of a metal from Group 3 to Group 12 in the periodic table, and one of them may be used alone, You may use multiple types together. From the viewpoint of obtaining higher stability, the transition metal oxide is preferably an oxide of a Group 5 metal in the periodic table.
  • the Group 5 metal include vanadium (V), niobium (Nb), and tantalum (Ta).
  • the transition metal oxide is preferably niobium oxide.
  • the conductive film 10a in which the transition metal oxide layer 3 using niobium oxide and the silicon-containing polymer modified layer 2 are combined not only improves the stability of the conductive performance but also depends on the angle dependency of the transmittance of incident light. Sex can be reduced. This is because, by laminating a low refractive index layer and a high refractive index layer, multiple interference of light occurs, the reflectance is reduced, and the optical behavior due to the difference in refractive index is changed. Inferred to be a factor.
  • By using such a conductive film 10a it is possible to obtain an organic EL element with little change in the color of the luminescent color depending on the angle, and the reliability of the luminescent performance can be improved.
  • the transition metal oxide content in the transition metal oxide layer 3 is preferably in the range of 50 to 100% by mass. Within this range, the transition metal in the transition metal oxide layer 3 can interact with the silicon-containing polymer modified layer 2, and sufficient gas barrier properties can be obtained.
  • PVD Physical vapor deposition
  • a CVD method such as a plasma CVD method, an atomic layer deposition (ALD) method, and the like.
  • ALD atomic layer deposition
  • a bipolar sputtering method As a sputtering method, a bipolar sputtering method, a magnetron sputtering method, a dual magnetron (DM) sputtering method, a reactive sputtering method, an ion beam sputtering method, an electron cyclotron resonance (ECR) electron sputtering method, or the like is used. One of these may be used alone, or two or more may be used in combination.
  • the target application method can be appropriately selected depending on the target type.
  • a transition metal oxide thin film can be formed by using a transition metal as a target and introducing oxygen as a source gas.
  • RF high frequency
  • a transition metal oxide target can be used.
  • the inert gas He, Ne, Ar, Kr, Xe, or the like can be used, and among these, Ar is preferable.
  • the transition metal oxide layer 3 may be a single layer or a multilayer structure of two or more layers. In the case of a multilayer structure, the transition metal oxide used for each layer may be the same or different.
  • the thickness of the transition metal oxide layer 3 is preferably in the range of 1 to 200 nm from the viewpoint of exhibiting uniform gas barrier properties regardless of the position.
  • the conductive layer 4 contains a conductive polymer having a resistivity lower than 1 ⁇ 10 6 ⁇ / ⁇ .
  • the resistivity refers to a sheet resistance measured in accordance with a resistivity test method based on a four-probe method for conductive plastics of JIS K 7194-1994.
  • the conductive layer 4 preferably has a resistivity of 10000 ⁇ / ⁇ or less, and more preferably 2000 ⁇ / ⁇ or less.
  • the thickness of the conductive layer 4 can be in the range of 30 to 2000 nm. From the viewpoint of enhancing conductivity, the thickness is preferably 100 nm or more. From the viewpoint of increasing the smoothness of the surface, the thickness is preferably 200 nm or more, and from the viewpoint of increasing transparency, the thickness is more preferably 1000 nm or less.
  • a ⁇ -conjugated conductive polymer containing a polyanion can be used as the conductive polymer.
  • ⁇ -conjugated conductive polymers that can be used include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, Examples include polyparaphenylene sulfides, polyisothianaphthenes, and polythiazyl compounds.
  • polythiophenes or polyanilines are preferable and polyethylenedioxythiophene is more preferable from the viewpoint of improving conductivity, transparency, stability, and the like.
  • the ⁇ -conjugated conductive polymer can be easily produced by subjecting a precursor monomer that forms a ⁇ -conjugated conductive polymer to chemical oxidative polymerization in the presence of an oxidizing agent, an oxidation catalyst, and a polyanion.
  • the precursor monomer used for forming the ⁇ -conjugated conductive polymer has a ⁇ -conjugated system in the molecule, and has a ⁇ -conjugated system in the main chain even when polymerized by the action of an oxidizing agent.
  • Examples of such precursor monomers include pyrroles, thiophenes, anilines, and derivatives thereof.
  • 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 polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, or a copolymer thereof. It is a compound composed of a structural unit having a group and a structural unit having no anionic group.
  • the polyanion solubilizes or disperses the ⁇ -conjugated conductive polymer in a solvent, and the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer. Improve sexiness.
  • the anion group of the polyanion may be any functional group that can undergo chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate group, A substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable.
  • a sulfo group, a monosubstituted sulfate group or a carboxy group is more preferable 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, polyisoprene sulfone. Acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . Furthermore, these homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
  • Fluorinated polyanions having further fluorine atoms in the molecule can also be used. Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.
  • the fluorinated polyanion is preferable because it can form a transparent electrode with a hole injection function by using it together with the non-fluorinated polyanion, and the productivity is increased.
  • the degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of improving solubility in a solvent and conductivity.
  • the ratio of the ⁇ -conjugated system conductive polymer to the polyanion in the conductive polymer that is, the mass ratio of the ⁇ -conjugated system conductive polymer: polyanion can be 1: 1-20, and the viewpoint of improving conductivity and dispersibility Is preferably 1: 2 to 10.
  • a commercially available conductive polymer may be used.
  • a commercially available conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid includes Heraeus. Clevios series of the company, PEDOT-PSS 483095 and 560596 of Aldrich, and the Denatron series of Nagase Chemtex. Further, as a commercially available product of polyaniline, ORMECON series manufactured by Nissan Chemical Industries, Ltd. can be used.
  • the conductive layer 4 preferably contains a non-conductive polymer together with a conductive polymer, and the non-conductive polymer further contains at least one of a self-dispersing polymer and a hydroxy group-containing polymer. More preferably.
  • the content of the conductive polymer can be reduced without impairing the conductivity of the conductive layer 4, and the conductive film 10a can be used as a transparent electrode having both high conductivity and transparency. Can be used.
  • Self-dispersing polymers that can be used in combination with conductive polymers have dissociable groups, and colloidal particles formed by self-dispersing polymers do not aggregate even without surfactants or emulsifiers that assist micelle formation.
  • the self-dispersing polymer is a non-conductive polymer that can be dispersed in an aqueous medium. It is preferable that the self-dispersing polymer has high transparency because the transparency of the conductive layer 4 can be increased.
  • the amount of the self-dispersing polymer used can be in the range of 50 to 1000% by mass with respect to the conductive polymer.
  • the main skeleton of the self-dispersing polymer includes polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyamide (nylon), polyvinylidene chloride, polyester, polyacrylate, Polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone-polyacrylate, polyvinylidene fluoride-polyacrylate, Examples thereof include polyfluoroolefin-polyvinyl ether.
  • copolymers based on these skeletons and further using other monomers may be used.
  • a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, an acrylic resin emulsion having an acrylic skeleton, or a polyethylene resin emulsion having an ethylene skeleton is preferable.
  • self-dispersing polymers include iodosol AD-176, AD-137 (acrylic resin: manufactured by Henkel Japan), Vironal MD-1200, MD-1245, MD-1500 (polyester resin: manufactured by Toyobo), plus A coat RZ570, a plus coat Z561, a plus coat Z565, a plus coat Z687, a plus coat Z690 (polyester resin: manufactured by Kyodo Chemical Co., Ltd.), or the like can be used.
  • One type or a plurality of types of self-dispersing polymer dispersions containing dissociable groups that can be dispersed in the aqueous medium can be used.
  • the hydroxy group-containing polymer is a non-conductive polymer having a hydroxy group.
  • the ratio of the conductive polymer to the hydroxy group-containing polymer in the conductive layer 4, that is, the mass ratio of the conductive polymer: hydroxy group-containing polymer is preferably 100: 30 to 900, from the viewpoint of preventing current leakage and increasing transparency. 100: 100 to 900 is more preferable.
  • Examples of the hydroxy group-containing polymer include a polymer containing a structural unit represented by the following general formula (1). [In the above general formula (1), R represents a hydrogen atom or a methyl group.
  • —Q— represents —C ( ⁇ O) O— or —C ( ⁇ O) NRd—
  • Rd represents a hydrogen atom or an alkyl group.
  • A represents a substituted or unsubstituted alkylene group or — (CH 2 CHReO) x CH 2 CHRe—, and Re represents a hydrogen atom or an alkyl group.
  • x represents the average number of repeating units.
  • the hydroxy group-containing polymer has an absorbance within the same wavelength range of 2.5 to 3.0 ⁇ m as the infrared ray because the solvent can be easily removed when infrared rays are used for drying the coating film. It is preferable to have an absorption of 0.1 or more.
  • the absorbance here refers to the absorbance in the coating film having the thickness of the conductive layer 4 to be formed. Further, by having absorption in a wavelength region different from that of the resin film 1, infrared rays having a wavelength with little damage to the resin film 1 can be selectively used.
  • the conductive layer 4 can be formed by applying a coating solution containing a conductive polymer on the transition metal oxide layer 3 to form a coating film, and irradiating the coating film with infrared rays and drying.
  • a coating solution containing a conductive polymer on the transition metal oxide layer 3 to form a coating film
  • irradiating the coating film with infrared rays and drying.
  • a gravure printing method, flexographic printing method, screen printing method, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, Coating methods such as a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.
  • the infrared irradiation is preferably performed in a drying treatment tank having a moisture concentration of 100 ppm or less.
  • the moisture concentration in the drying treatment tank refers to the moisture concentration at the end of drying in the tank where the drying treatment is performed. It is preferable to irradiate infrared rays with a ratio of the spectral radiance of wavelength 5.8 ⁇ m to the spectral radiance of wavelength 3.0 ⁇ m of 5% or less.
  • the conductive layer 4 containing a conductive polymer includes a metal layer containing a metal nanomaterial or a carbon material on the transition metal oxide layer 3 from the viewpoint of increasing resistance by reducing resistance. It is preferred to have a carbon layer or both. From the same viewpoint, the conductive layer 4 containing a conductive polymer preferably includes a grid on the transition metal oxide layer 3.
  • FIG. 5 is an enlarged cross-sectional view showing a configuration example of the conductive layer 4 when a grid is provided together with the metal layer and the carbon layer.
  • the carbon layer 41 and the metal layer 42 are formed on the transition metal oxide layer 3 in this order, and the grid 43 is formed on the metal layer 42.
  • a conductive polymer layer 451 is formed so as to cover the grid 43.
  • the conductive polymer layer 451 is a layer formed using the above-described conductive polymer.
  • the arrangement order of the carbon layer 41, the metal layer 42, and the grid 43 is not limited to the order shown in FIG. 5 as long as it is located on the transition metal oxide layer 3 and below the conductive polymer layer 451.
  • Carbon layer 41 Examples of the carbon material used for the carbon layer 41 include graphene, carbon nanotube, and fullerene. These carbon materials may be used individually by 1 type, and may use multiple types together. Moreover, the carbon layer 41 may be a single layer or may have a multilayer structure including a plurality of layers having the same or different carbon materials. The thickness of the carbon layer 41 can be in the range of 10 nm to 10 ⁇ m.
  • Graphene is a sheet of carbon atoms bonded in a honeycomb structure, and the carbon layer 41 can be formed by transferring this sheet onto the transition metal oxide layer 3.
  • a method for producing graphene for example, a method of applying and reducing graphene oxide described in JP2011-241479A, a method of using epitaxial growth on a SiC substrate, and graphene by thermal CVD using Cu or Ni as a catalyst metal It can produce
  • the carbon nanotube is a carbon fiber made of hollow graphene.
  • Carbon nanotubes can be produced by catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure and grown in the gas phase.
  • fullerenes fullerene C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 84 , fullerene C 240 , fullerene C 540 , mixed fullerene, fullerene nanotubes and the like can be used.
  • the carbon layer 41 can be formed by preparing a coating liquid containing these and applying them on the transition metal oxide layer 3.
  • the metal nanomaterial used for the metal layer 42 is a metal material having a nanoscale size, and is also called a nanotube, nanowire, nanofiber, or the like depending on the shape.
  • the metal include silver (Ag), aluminum (Al), copper (Cu), gold (Au), tungsten (W), molybdenum (Mo), and alloys thereof.
  • silver is preferable because it has low resistance, high conductivity, and can be easily processed into a desired shape.
  • the metal layer 42 can be formed by preparing a coating solution containing a metal nanomaterial and applying it on the transition metal oxide layer 3.
  • the thickness of the metal layer 42 can be in the range of 10 nm to 10 ⁇ m.
  • the grid 43 is composed of conductive fine metal wires.
  • the shape of the grid 43 is not limited to a lattice shape, and various shapes of grids such as a stripe shape, a honeycomb structure shape, and a mesh shape can be used. From the viewpoint of obtaining uniform conductivity regardless of the position, a periodically-shaped grid 43 located on the entire surface of the conductive layer 4 is preferable.
  • the line width dw of the fine metal wires constituting the grid 43 is preferably in the range of 10 to 200 ⁇ m. If the line width dw is 10 ⁇ m or more, sufficient conductivity is obtained, and if it is 200 ⁇ m or less, a decrease in transparency can be suppressed.
  • the height dh of the fine metal wires constituting the grid 43 is preferably in the range of 0.1 to 10.0 ⁇ m. If the height dh is 0.1 ⁇ m or more, sufficient conductivity is obtained, and if it is 10.0 ⁇ m or less, current leakage can be prevented when used in an electronic device.
  • the resistivity of the grid 43 is preferably 100 ⁇ / ⁇ or less, and more preferably 20 ⁇ / ⁇ or less for increasing the area.
  • the resistivity of the grid 43 can be measured according to JIS K 7194-1994 described above.
  • the aperture ratio of the grid 43 is preferably 80% or more from the viewpoint of increasing transparency.
  • the aperture ratio is the ratio of the area occupied by the region where the fine metal wires forming the grid 43 are not arranged in the total area of the conductive layer 4.
  • the aperture ratio of the grid 43 in which fine metal wires having a line width of 100 ⁇ m and a line interval of 1 mm are formed in a stripe shape or a lattice shape is about 90%.
  • Examples of conductive metal materials that can be used for the fine metal wires of the grid 43 include gold, silver, copper, iron, cobalt, nickel, chromium, and alloys thereof. From the viewpoint of low resistance, silver or copper is preferable, and silver is more preferable.
  • the grid 43 is formed by applying a coating solution containing metal nanoparticles, metal complexes, and the like using the above metal material by a relief printing method, an intaglio printing method, a stencil printing method, a screen printing method, an inkjet method, an inkjet parallel line drawing method, and the like. It can form by apply
  • the ink jet parallel line drawing method uses a coffee stain phenomenon in which when the coating liquid is applied in a line shape, the coating liquid flows from the center to the end of the line and solidification of the end proceeds. This is a method of forming two parallel lines from a line. In the case of forming a random network shape, as described in Japanese Patent Application Publication No.
  • a coating solution containing metal fine particles is applied and then dried, whereby the metal particles are spontaneously disordered.
  • the method of forming can be used. Among these, an inkjet method that allows easy shape control or an inkjet parallel line drawing method that is highly accurate in forming a thin line is preferable.
  • the coating solution containing a metal complex is sufficient if the metal forming the complex is dispersed or dissolved in the solvent.
  • the solvent ketocarboxylic acid, behenic acid, stearic acid and the like can be used.
  • JP-T-2008-530001 also discloses a silver complex compound derived by reacting a silver compound and an ammonium carbonate compound.
  • the coating liquid can also contain an amine compound as a reducing agent.
  • the grid 43 When the grid 43 is formed, it is preferable to perform heat treatment in a range that does not damage the resin film 1. Thereby, fusion of metal materials such as metal nanoparticles and metal complexes proceeds, and the conductivity of the grid 43 increases.
  • a general oven or hot plate heating method can be used.
  • local heat treatment may be performed by flash pulse light irradiation treatment, microwave treatment, plasma treatment, dielectric heating treatment, excimer light irradiation treatment, ultraviolet ray treatment, infrared heater treatment, hot air heater treatment, etc. You may use together with heat processing by oven etc.
  • the grid 43 may include a plating layer 44 that covers the grid 43.
  • the plating layer 44 By covering the grid 43 with the plating layer 44, it is possible to smooth the nanoscale unevenness caused by a metal material such as metal nanoparticles or metal complexes forming the grid 43.
  • the maximum cross-sectional height Rt (p) measured in accordance with JIS B 0601-2013 is preferably 500 nm or less, more preferably 200 nm or less, and 100 nm or less. Is more preferable. The higher the smoothness, the better the yield and continuous drivability of the organic EL element when used as an electrode.
  • the plating layer 44 can be formed by applying a coating solution of the plating layer 44 on the grid 43 by an intaglio printing method, a stencil printing method, an ink jet method, or the like, and performing a plating process.
  • a plating process there are an electroplating process in which a metal in the coating solution is deposited by energization to form a metal film, and an electroless plating process in which the metal in the coating solution is deposited by an oxidizing action of a reducing agent instead of energization.
  • a coating solution containing a conductive substance serving as a plating nucleus in a solvent can be used.
  • a conductive substance a transition metal or a compound thereof can be used.
  • ionic transition metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt are preferable. Since the plating layer 44 having low resistance and high corrosion resistance can be formed, silver, gold, copper, and the like are more preferable. preferable.
  • the conductive substance is preferably in the form of particles having an average particle diameter of about 1 to 50 nm.
  • An average particle diameter is an average value when a center particle diameter (D50) is measured with a laser diffraction scattering type particle size distribution measuring apparatus.
  • the content of the conductive substance in the coating solution is preferably in the range of 10 to 60% by mass.
  • a coating solution containing plating nuclei is applied in the shape of the grid 43, and then immersed in the electrolytic plating solution, or applied with an electrolytic plating solution and energized, so that the metal in the electrolytic plating solution Can be deposited on the grid 43 connected to the negative electrode to form a metal film.
  • the temperature of the electrolytic plating solution at the time of application can be in the range of 20 to 98 ° C.
  • the electrolytic plating solution one containing a conductive substance such as copper, nickel, chromium, cobalt, tin, sulfuric acid, an aqueous medium, or the like can be used.
  • a metal in the electroless plating solution is deposited by further applying an electroless plating solution containing a reducing agent.
  • a metal film can be formed.
  • the temperature of the electroless plating solution during application can be in the range of about 20 to 98 ° C.
  • the electroless plating solution for example, one containing a conductive material such as copper, nickel, chromium, cobalt, tin, a reducing agent, an aqueous medium, a solvent, or the like can be used.
  • reducing agent for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenols and the like can be used.
  • the electroless plating solution may contain a complexing agent such as carboxylic acid such as acetic acid, formic acid, malonic acid, and succinic acid, soluble salts thereof, and amines such as ethylenediamine, if necessary.
  • a complexing agent such as carboxylic acid such as acetic acid, formic acid, malonic acid, and succinic acid, soluble salts thereof, and amines such as ethylenediamine, if necessary.
  • FIG. 6 shows a configuration example of a conductive film 10d including a conductive layer 6 containing a metal oxide.
  • the same reference numerals are assigned to the same layers as the conductive film 10d.
  • the metal oxide that can be used for the conductive layer 6 include highly transparent indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO 2 ), indium gallium zinc, and the like. Examples thereof include oxides (IGZO: Indium Gallium Zinc Oxide), IDIXO (In 2 O 3 —ZnO), and the like.
  • a conductive film according to a second embodiment of the present invention is a conductive film including a conductive layer containing a metal oxide on a resin film, the silicon-containing polymer containing a modified product of a silicon-containing polymer A modified layer and a transition metal oxide layer located on the silicon-containing polymer modified layer and containing a transition metal oxide, wherein the conductive layer is located on the transition metal oxide layer.
  • the conductive film of the second embodiment has the same layer structure as the conductive film of the first embodiment except that the conductive layer is a conductive layer containing a metal oxide instead of a conductive polymer.
  • the conductive layer is a conductive layer containing a metal oxide instead of a conductive polymer.
  • a silicon-containing polymer modified layer 2 and a transition metal oxide layer 3 are provided in this order on a resin film 1, and a conductive layer 4 is provided on the transition metal oxide layer 3. . Only the conductive layer 4 made of different materials will be described below.
  • the conductive layer 4 contains a conductive metal oxide having a resistivity lower than 1 ⁇ 10 6 ⁇ / ⁇ .
  • the resistivity refers to a sheet resistance measured in accordance with a resistivity test method based on a four-probe method for conductive plastics of JIS K 7194-1994.
  • the conductive layer 4 containing a metal oxide preferably has a resistivity of 10000 ⁇ / ⁇ or less, more preferably 2000 ⁇ / ⁇ or less.
  • Examples of the metal oxide that can be used for the conductive layer 4 include indium-tin-oxide (ITO), zinc oxide (ZnO), tin oxide (SnO 2 ), indium-gallium-zinc-oxide (IGZO), IDIXO ( In 2 O 3 —ZnO) and the like. Of these, indium-tin oxide is preferable because of its high transparency.
  • the thickness of the conductive layer 4 containing a metal oxide can be in the range of 10 to 500 nm. From the viewpoint of increasing the conductivity, the thickness is preferably in the range of 100 to 500 nm. From the viewpoint of enhancing the smoothness of the surface, the thickness is preferably 50 nm or more.
  • the conductive layer 4 containing a metal oxide preferably includes a grid on the transition metal oxide layer 3 from the viewpoint of reducing resistance and increasing conductivity.
  • FIG. 7 is an enlarged cross-sectional view illustrating a configuration example of the conductive layer 4 in the case where a grid is provided. As shown in FIG. 7, a grid 43 is formed on the transition metal oxide layer 3. A plating layer 44 that covers the grid 43 may be formed on the grid 43. A metal oxide layer 452 is formed so as to cover the grid 43 including the plating layer 44. The metal oxide layer 452 is a layer containing a metal oxide such as ITO. Since the grid 43 and the plating layer 44 have the same configuration as the grid 43 and the plating layer 44 of the first embodiment, detailed description thereof is omitted.
  • the conductive film 10 a can also include a light scattering layer below the conductive layer 4.
  • the light scattering layer can be provided between the conductive layer 4 and the transition metal oxide layer 3 as long as the silicon-containing polymer modified layer 2 and the transition metal oxide layer 3 can be adjacent to each other. It can also be provided between the containing polymer modified layer 2 and the resin film 1.
  • FIG. 8 shows an enlarged cross-sectional view of the conductive layer 4 provided with the light scattering layer 7 below.
  • the light scattering layer 7 is preferably a high refractive index layer having a refractive index measured at a light wavelength of 550 nm in a range of 1.7 or more and less than 2.5.
  • the refractive index can be measured with a multiwavelength Abbe refractometer, a prism camera, a Mickelson interferometer, a spectroscopic ellipsometer, or the like.
  • the light scattering layer 7 may be composed of a single material having such a high refractive index, or a mixture of two or more materials may have a high refractive index. When two or more kinds of materials are mixed, a calculated refractive index calculated by a total value obtained by multiplying a refractive index specific to each material by a mixing ratio is used as the refractive index of the light scattering layer 7.
  • the light scattering layer 7 in the case of mixing two or more materials contains light scattering particles having a refractive index higher than that of the layer medium, using a binder such as polyacrylate ester and polyethylene terephthalate (PET) as a layer medium, It is preferable to scatter incident light using the difference in refractive index.
  • the light scattering particles are not particularly limited and may be organic fine particles such as polymethyl methacrylate beads and acrylic-styrene copolymer beads, or inorganic fine particles made of oxides such as zirconium, titanium, indium and zinc. Good. Among these, inorganic fine particles having a high refractive index are preferable.
  • the content of the light scattering particles in the light scattering layer 7 is preferably in the range of 1 to 70%, more preferably in the range of 5 to 50% in terms of volume filling factor. Thereby, the density distribution of the refractive index distribution can be made at the interface between the light scattering layer 7 and the smooth layer 22, and the light extraction efficiency can be improved by increasing the amount of light scattering.
  • the thickness of the light scattering layer 7 is preferably in the range of 100 to 2000 nm from the viewpoint of efficiently extracting light by scattering light from the light emitting layer.
  • the thickness of the light-scattering layer 7 means an average thickness.
  • the light scattering layer 7 may be a high refractive index layer having a refractive index in the range of 1.7 or more and less than 2.5 by controlling the shape of the layer to an uneven structure that diffracts or diffuses light. .
  • the concavo-convex structure is a structure in which concave and convex portions are arranged at a constant pitch (period), and acts as a diffraction grating.
  • the concavo-convex structure acting as a diffraction grating is described in, for example, Japanese Patent Application Laid-Open Nos. 11-283951 and 2003-115377.
  • the stripe-shaped diffraction grating does not have a diffraction effect in the direction parallel to the stripe, and therefore preferably functions as a diffraction grating uniformly from any direction two-dimensionally.
  • the thickness of the light scattering layer 7 is preferably in the range of 100 to 2000 nm, as in the case of containing light scattering particles.
  • the organic EL device of the present invention includes at least an organic functional layer and a pair of electrodes that sandwich the organic functional layer.
  • the pair of electrodes are an anode that supplies holes to the light emitting layer in the organic functional layer and a cathode that supplies electrons, and the conductive layer of the conductive film of the present invention described above can be used as an anode or a cathode. .
  • the transparency of the conductive film is high, it can be used as a transparent electrode disposed on the light extraction side.
  • FIG. 9 shows, as an example, a configuration of an organic EL element 20 using the conductive film 10a shown in FIG. 1 as an anode.
  • the organic EL element 20 includes a conductive film 10a in which a silicon-containing polymer modified layer 2, a transition metal oxide layer 3, and a conductive layer 4 are positioned in this order on a resin film 1, and this conductive
  • the organic functional layer 25, the cathode 26 and the gas barrier layer 27 are provided on the conductive film 10a.
  • the organic EL element 20 includes two electrode connection layers 24 for connecting the conductive layer 4 and the cathode 26 to an external device such as a power source, and a sealing film bonded on the gas barrier layer 27 via an adhesive layer 29. 28.
  • the two electrode connection layers 24 are formed so as to be exposed from the silicon-containing polymer modified layer 2 and the gas barrier layer 27.
  • the material of the electrode connection layer 24 is not particularly limited as long as it is a conductive material excellent in heat resistance and moisture resistance, and a known material can be suitably used. Specifically, metals such as aluminum, titanium, molybdenum, copper, and tantalum, highly transparent metal oxides such as ITO, IGZO, tin oxide, zinc oxide, and gallium-zinc oxide (GZO) MAM electrodes (Mo / Al ⁇ Nd alloy / Mo) or the like can be used.
  • the organic functional layer 25 includes at least a light emitting layer, and may include an organic layer other than the light emitting layer, for example, a hole injection layer, a hole transport layer, a blocking layer, an electron transport layer, an electron injection layer, and the like as necessary. .
  • Each organic layer is laminated in the order of anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.
  • the light-emitting layer containing a light-emitting organic compound holes injected from the anode side and electrons injected from the cathode side recombine to emit light.
  • a known host compound also referred to as a light-emitting host
  • a light-emitting material also referred to as a light-emitting dopant
  • organic compounds include phosphorescent materials (also called phosphorescent compounds or phosphorescent compounds) such as carbazole derivatives such as dibenzofuran compounds, iridium complexes, osmium complexes, platinum complexes, and rare earth complexes, and coumarin-based compounds.
  • Dye pyran dye, cyanine dye, croconium dye, squalium dye, oxobenzanthracene dye, fluorescein dye, rhodamine dye, pyrylium dye, perylene dye, stilbene dye, polythiophene dye, rare earth complex
  • fluorescent light emitting materials such as system fluorescent materials.
  • the cathode 26 is formed using, for example, a metal (electron-injecting metal), an alloy, a conductive compound such as a metal oxide such as ITO, IGZO, GZO, tin oxide, zinc oxide, and aluminum oxide, a mixture thereof, or the like. be able to.
  • the gas barrier layer 27 can be formed by a PVD method, a CVD method, or the like using an inorganic material having a high gas barrier property such as a silicon compound or an aluminum compound.
  • the sealing film 28 preferably has flexibility, such as a thin film glass, a thin film ceramic, a resin film, a resin film having glass fiber or carbon fiber, a Ni—Fe alloy such as SUS or Invar, aluminum, titanium or the like.
  • a metal film or the like can be used.
  • a thermosetting resin such as an epoxy resin, an ultraviolet curable resin, or the like can be used.
  • a conductive layer including a conductive polymer layer is referred to as a first conductive layer
  • a conductive layer including a metal oxide layer is referred to as a second conductive layer.
  • PET polyethylene terephthalate
  • UV coating agent Z731L manufactured by Aika Kogyo Co., Ltd.
  • UV curable resin was applied onto a PET film so that the thickness after drying was 0.5 ⁇ m.
  • a curing treatment was performed by irradiating ultraviolet rays having an irradiation energy amount of 0.5 J / cm 2 using a high-pressure mercury lamp in the atmosphere.
  • UV curable resin OPSTAR registered trademark
  • Z7527 manufactured by JSR
  • the PET film on which the underlayer was formed was cut out in a size of 150 mm ⁇ 150 mm.
  • a drying treatment is performed to form a first conductive layer consisting only of a conductive polymer layer having a size of 130 mm ⁇ 100 mm and a thickness of 100 nm, A conductive film 101a was manufactured.
  • radiant heat transfer drying using an infrared heater was performed for 5 minutes.
  • Clevios PH1000 PEDOT / PSS made by Heraeus, solid content concentration 1.2%): 70 parts by mass
  • Ethylene glycol 15 parts by mass
  • Ethylene glycol monobutyl ether 8 parts by mass Pure water: 7 parts by mass
  • a conductive film 101b was produced in the same manner as the conductive film 101a except that a silicon-containing polymer-modified layer having a thickness of 300 nm was formed instead of the silicon compound layer.
  • the silicon-containing polymer modified layer was formed as follows. Non-catalytic perhydropolysilazane 20% by weight dibutyl ether solution (Aquamica NN120-20, manufactured by AZ Electronic Materials) and amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane) ) Is mixed with a 20% by weight dibutyl ether solution of perhydropolysilazane containing 5% by weight of a solid content (Aquamica NAX120-20, manufactured by AZ Electronic Materials) at a ratio of 4: 1, and the thickness is adjusted. Therefore, it was diluted appropriately with dibutyl ether to prepare a coating solution.
  • the coating solution prepared on the underlayer was coated with a die coater so that the thickness after drying was 300 nm, and dried at 80 ° C. for 2 minutes.
  • the coating film after drying was subjected to a modification treatment to irradiate 2.5 mJ / cm 2 of vacuum ultraviolet radiation.
  • a silicon-containing polymer modified layer was formed.
  • substitution with nitrogen was performed so that an atmosphere with an oxygen concentration of 0.1% by volume was obtained.
  • the temperature of the stage on which the PET film was placed was 80 ° C., and the stage conveyance speed was 0.5 m / min.
  • a conductive film 102 was produced in the same manner as the conductive film 101b except that a transition metal oxide layer was formed on the silicon-containing polymer layer.
  • the transition metal oxide layer was formed as follows. Next, a transition metal oxide layer having a thickness of 15 nm was formed on the silicon-containing polymer modified layer by RF sputtering using oxygen-deficient niobium oxide (Nb 2 O 5 ) as a target. At the time of formation, Ar gas and O 2 gas were supplied so that the film composition was Nb 2 O 5, and a transition metal oxide layer was formed on the entire surface of the silicon-containing polymer modified layer. A first conductive layer was formed on the transition metal oxide layer.
  • Conductive films 103 and 104 In the production of the conductive film 102, except that the transition metal oxide layer was formed by changing niobium oxide used for the target to titanium oxide (TiO 2 ) and tantalum oxide (Ta 2 O 5 ), respectively.
  • the conductive films 103 and 104 were manufactured in the same manner as the film 102.
  • a dispersion of silver nanowires was prepared with reference to the method described in the document “Adv. Mater., 2002, 14, 833-837”.
  • ethylene glycol manufactured by Kanto Chemical Co., Ltd.
  • polyvinylpyrrolidone manufactured by Aldrich, average molecular weight of 1.3 million
  • the reaction solution in which the silver nanowires are formed is subjected to desalting water washing treatment using an ultrafiltration membrane having a molecular weight cut off of 0.2 ⁇ m, and then the solvent is replaced with toluene to obtain a toluene dispersion of silver nanowires. It was.
  • a conductive polymer layer was formed in the same manner as the conductive film 102 to obtain a conductive film 105 in which the first conductive layer was composed of a metal layer and a conductive polymer layer.
  • the conductive film 105 In the production of the conductive film 105, the conductive film except that the silver nanowire dispersion was changed to a graphene dispersion and a carbon nanotube dispersion to form a carbon layer instead of the metal layer. In the same manner as in 105, the conductive films 106 and 107 were manufactured.
  • the graphene dispersion a dispersion obtained by dispersing graphene Grade C (manufactured by XG Science Co., Ltd.) in toluene and filtering with a 2 ⁇ m filter was used.
  • the carbon nanotube dispersion P3 SWCNT (manufactured by Carbon Solutions) was used.
  • the film forming conditions for the silicon compound layer are as follows.
  • Source gas hexamethyldisiloxane: HMDSO
  • supply amount 50 sccm
  • each of the conductive films 112 to 115 was formed in the same manner as the conductive films 112 to 115, except that a second conductive layer having a thickness of 110 nm containing ITO was further formed on the first conductive layer.
  • Conductive films 116-119 were produced.
  • the second conductive layer was formed using ITO by a commercially available sputtering apparatus.
  • the conductive films 120 to 123 are formed in the same manner as the conductive films 116 to 119, except that the ITO used for forming the second conductive layer is changed to IZO. Manufactured.
  • a sample in which a sealing film was bonded and sealed so as to cover the first conductive layer and the second conductive layer of the conductive film was produced.
  • an adhesive was applied to a non-alkali glass substrate having a thickness of 0.7 mm and dried at 120 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 ⁇ m.
  • the adhesive layer was laminated with a release treatment surface of a polyethylene terephthalate film having been subjected to a release treatment with a thickness of 38 ⁇ m as a release sheet to obtain a sealing film.
  • the release sheet After leaving this sealing film in a nitrogen atmosphere for 24 hours or more, the release sheet is removed, and the first conductive layer and the second conductive layer of the conductive film are covered with a vacuum laminator heated to 80 ° C. Pasted together. Furthermore, it sealed by heating for 30 minutes at 120 degreeC.
  • Opanol B50 polyisobutylene resin manufactured by BASF Japan, Mw 340,000
  • 100.0 parts by mass Nisseki Polybutene Grade HV-1900 manufactured by Nippon Oil Corporation, Mw: 1900
  • 30 parts by mass TINUVIN765 a hindered amine light stabilizer having a tertiary hindered amine group manufactured by BASF Japan
  • IRGANOX1010 manufactured by BASF Japan, both of the ⁇ -positions of the hindered phenol groups are tert-butyl groups
  • Hindered phenolic antioxidants 0.5 parts by mass Eastotac H-100L Resin (cyclic olefin polymer manufactured by Eastman Chemical Co.): 50.0 parts by mass
  • Resistance change rate (%) (resistance value after storage / resistance value before storage) ⁇ 100
  • the visible light transmittance obtained by the measurement is normalized to the maximum value, and the normalized visible light transmittance (B) / normalized visible light transmittance (A) is obtained and averaged for each wavelength of 1 nm. Was determined as the angle dependency (%) of transmittance.
  • NW in the table represents a nanowire
  • NT represents a nanotube
  • PEDOT represents PEDOT / PSS.
  • the silicon-containing polymer modification under the first conductive layer compared to the conductive film 101a or 101b having only the silicon compound layer or only the silicon-containing polymer layer under the first conductive layer.
  • the conductive films 102 to 123 each having a layer and a transition metal oxide layer have little change in resistance value and are excellent in stability of conductive performance.
  • the conductive films 102 to 123 have little change in the total light transmittance, stable not only the conductive performance but also the light transmittance, and the angle dependency of the transmittance is also low.
  • the use of niobium oxide improved the stability of the conductive performance and lowered the angle dependency of the transmittance.
  • Example I-II [Conductive films 201a and 201b]
  • a grid was formed on the transition metal oxide layer and a first conductive layer made of a conductive polymer layer was formed on the formed grid.
  • the conductive films 201a and 201b were manufactured in the same manner as the conductive films 101a and 101b.
  • the grid was formed by the inkjet method as follows.
  • an ink jet nano paste NPS-JL manufactured by Harima Chemicals
  • the coating liquid was applied in layers so that a sufficient height was obtained.
  • a desktop robot SHOTMASTER 300 manufactured by Musashi Engineering
  • an ink jet head KM512SHX manufactured by Konica Minolta was used, and this was controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta).
  • firing was performed by irradiating with xenon light using PulseForge 1300 manufactured by NovaCentrix to form a grid.
  • Xenon light was irradiated by pulse light emission of 250 ⁇ s at a cycle of 500 ⁇ s, and the irradiation amount was adjusted so that the applied energy was 1500 mJ / cm 2 .
  • the size of the fine metal wires of the formed grid was measured several times by changing the position with a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100 (manufactured by Nihon Beco).
  • the average value of the line width was 60 ⁇ m and the height The average value was 1 ⁇ m, and the interval was 1 mm.
  • Example I-III [Organic EL element 301a] An organic functional layer was formed on the conductive film 101a produced in Example II as follows.
  • the conductive film 101a was dried in a glove box having a dew point of ⁇ 80 ° C. or lower and an oxygen concentration of 1 ppm or lower, and then placed in a vacuum evaporation apparatus for forming an organic functional layer without exposing the glove box to the atmosphere.
  • Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten. After reducing the vacuum to 1 ⁇ 10 ⁇ 4 Pa, the deposition crucible containing the compound M-2 was heated and energized, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection transport layer was formed.
  • Compound BD-1 and Compound H-1 are co-deposited at a deposition rate of 0.1 nm / second so that the concentration of Compound BD-1 is 5% in volume ratio, and fluorescence that exhibits blue light emission with a thickness of 15 nm is obtained. A light emitting layer was formed.
  • the vapor deposition rate of 0.1 nm is applied so that the compound GD-1, RD-1, and the compound H-2 are at a concentration of 17% by volume of the compound GD-1 and 0.8% by volume of RD-1.
  • the phosphorescent light emitting layer having a thickness of 15 nm and having a yellow color was formed.
  • Compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 30 nm.
  • LiF was formed at a thickness of 1.5 nm
  • aluminum was deposited at 110 nm to form a cathode.
  • the compounds M-2, BD-1, H-1, GD-1, RD-1, H-2 and E-1 are compounds having the following structures.
  • the organic EL element 301a was manufactured by bonding and sealing a sealing film so as to cover the formed anode to cathode.
  • the conductive film obtained when the rate of change in resistance was obtained in Example II, except that 50 ⁇ m thick polyethylene terephthalate was used as the sealing film, which was bonded to an aluminum foil having a thickness of 100 ⁇ m. Sealing was performed in the same manner as the sealing method.
  • Organic EL element 301b In the manufacture of the organic EL element 301a, an organic EL element 301b was manufactured in the same manner as the organic EL element 301a except that the conductive film 101b was used instead of the conductive film 101a.
  • Organic EL elements 302 to 323 were manufactured in the same manner as the organic EL element 301a except that the conductive films 102 to 123 were used instead of the conductive film 101a in the manufacture of the organic EL element 301a.
  • the organic EL element was connected to a DC voltage / current source 6243 (manufactured by ADC), and a current of 50 A / m 2 was applied to emit light, and the driving voltage at the time of light emission was measured by the DC voltage / current source 6243.
  • the angle dependency of the chromaticity of the emission color of each organic EL element 301a, 301b and 302 to 323 was evaluated as follows.
  • the organic EL element is connected to a DC voltage / current source 6243 (manufactured by ADC), and a current of 25 A / m 2 is allowed to flow to emit light.
  • the chromaticity x and y of the light emitted from the organic EL element are expressed as chromaticity. It was measured with a measuring instrument CS-2000 (manufactured by Konica Minolta).
  • the organic EL element is arranged and colored so that the optical axis of the measurement light and the light emitting surface of the organic EL element are perpendicular, that is, the angle formed by the optical axis of the measuring light and the light emitting surface is 90 degrees. The degree was measured. Thereafter, the angle formed between the optical axis of the measurement light and the light emitting surface was changed by 5 degrees within a range of 0 to 90 degrees, and the chromaticities x and y were respectively measured.
  • NW in the table represents a nanowire
  • NT represents a nanotube
  • PEDOT represents PEDOT / PSS.
  • the organic EL elements 302 to 323 in which the first conductive layer is formed on the silicon-containing polymer modified layer and the transition metal oxide have only the silicon compound layer or silicon below the first conductive layer.
  • the change in driving voltage and luminance is small, and the stability of the light emission performance is high.
  • the organic EL elements 302 to 323 have small angle dependency of chromaticity, and it can be seen that the change in emission color is small depending on the observation position. This is presumed to be because the conductive films 102 to 123 having a small angle dependency of transmittance are used.
  • the use of a conductive film using niobium oxide further improved the stability of light emission performance, and the angle dependency of chromaticity was further reduced.
  • Examples I-IV The conductive films 101a, 101b, and 102 to 123 used in the manufacture of the organic EL elements 301a, 301b, and 302 to 323 of Example I-III were replaced with the conductive films 201a and 201b manufactured in Example I-II, respectively.
  • the organic EL elements 401a, 401b, and 402 to 423 were manufactured in the same manner as the organic EL elements 301a, 301b, and 302 to 323, except that the organic EL elements were changed to 202 and 223.
  • Example II-I [Conductive film 2101] 100 ⁇ m thick polyethylene terephthalate (hereinafter abbreviated as “PET”) film (Lumirror (registered trademark) U48 manufactured by Toray Industries, Inc.) having a surface activation treatment on both sides, a clear hard coat with a thickness of 0.5 ⁇ m A layer was formed. Specifically, UV coating agent Z731L (manufactured by Aika Kogyo Co., Ltd.), which is an ultraviolet curable resin, was applied onto a PET film so that the thickness after drying was 0.5 ⁇ m. After the coating film was dried at 80 ° C., a curing treatment was performed by irradiating ultraviolet rays having an irradiation energy amount of 0.5 J / cm 2 using a high-pressure mercury lamp in the atmosphere.
  • PTT polyethylene terephthalate
  • UV curable resin OPSTAR registered trademark
  • Z7527 manufactured by JSR
  • the PET film on which the underlayer was formed was cut out in a size of 150 mm ⁇ 150 mm.
  • a metal oxide layer having a size of 130 mm ⁇ 100 mm and a thickness of 150 nm is formed on the silicon compound layer by using a commercially available sputtering apparatus using ITO, and a conductive film 2101 in which the conductive layer is composed only of the metal oxide layer is formed. Manufactured.
  • a conductive film 2102 was produced in the same manner as the conductive film 2101 except that a silicon-containing polymer-modified layer having a thickness of 100 nm was formed instead of the silicon compound layer.
  • the silicon-containing polymer modified layer was formed as follows. Non-catalytic perhydropolysilazane 20% by weight dibutyl ether solution (Aquamica NN120-20, manufactured by AZ Electronic Materials) and amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane) ) Is mixed with a 20% by weight dibutyl ether solution of perhydropolysilazane containing 5% by weight of a solid content (Aquamica NAX120-20, manufactured by AZ Electronic Materials) at a ratio of 4: 1, and the thickness is adjusted. Therefore, it was diluted appropriately with dibutyl ether to prepare a coating solution.
  • the coating solution prepared on the underlayer was coated with a die coater so that the thickness after drying was 100 nm, and dried at 80 ° C. for 2 minutes.
  • the coating film after drying was subjected to a modification treatment to irradiate 2.5 mJ / cm 2 of vacuum ultraviolet radiation.
  • a silicon-containing polymer modified layer was formed.
  • substitution with nitrogen was performed so that an atmosphere with an oxygen concentration of 0.1% by volume was obtained.
  • the temperature of the stage on which the PET film was placed was 80 ° C., and the stage conveyance speed was 0.5 m / min.
  • Source gas hexamethyldisiloxane: HMDSO
  • supply amount 50 sccm
  • a silicon-containing polymer modified layer having a thickness of 100 nm was formed on the formed silicon compound layer in the same manner as the silicon polymer modified layer formed in the conductive film 2102.
  • a transition metal oxide layer having a thickness of 15 nm was formed on the silicon-containing polymer modified layer by RF sputtering using oxygen-deficient niobium oxide (Nb 2 O 5 ) as a target.
  • Ar gas and O 2 gas were supplied so that the film composition was Nb 2 O 5, and a transition metal oxide layer was formed on the entire surface of the silicon-containing polymer modified layer.
  • a conductive layer was formed on the transition metal oxide layer in the same manner as the conductive film 2101 to manufacture a conductive film 2103.
  • each conductive film 2106 was produced in the same manner as the conductive film 2103 except that the thickness of the silicon compound layer was changed to 150 nm and IZO was used to form the conductive layer. did.
  • the transition metal oxide layer was formed by changing the niobium oxide used for the target to titanium oxide (TiO 2 ) and tantalum oxide (Ta 2 O 5 ), respectively.
  • the conductive films 2107 and 2108 were produced.
  • Conductive film 2109 to 2112 In the production of the conductive films 2103 to 2106, the same as the conductive films 2103 to 2106, except that a silicon-containing polymer-modified layer having a thickness of 50 nm was further formed between the base layer of the PET film and the silicon compound layer. Thus, conductive films 2109 to 2112 were manufactured.
  • the silicon-containing polymer modified layer between the underlayer and the silicon compound layer was formed in the same manner as the silicon-containing polymer modified layer between the silicon compound layer and the transition metal oxide layer.
  • the resistance values of the conductive films 2101 to 2112 were measured as follows. A sample in which a sealing film was bonded and sealed so as to cover the conductive layer of the conductive film was produced. Specifically, an adhesive was applied to a non-alkali glass substrate having a thickness of 0.7 mm and dried at 120 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 ⁇ m. The adhesive layer was laminated with a release treatment surface of a polyethylene terephthalate film having been subjected to a release treatment with a thickness of 38 ⁇ m as a release sheet to obtain a sealing film.
  • the release sheet was removed, and the conductive film of the conductive film was bonded to cover the conductive layer with a vacuum laminator heated to 80 ° C. Furthermore, it sealed by heating for 30 minutes at 120 degreeC.
  • Opanol B50 polyisobutylene resin manufactured by BASF Japan, Mw 340,000
  • 100.0 parts by mass Nisseki Polybutene Grade HV-1900 manufactured by Nippon Oil Corporation, Mw: 1900
  • 30 parts by mass TINUVIN765 a hindered amine light stabilizer having a tertiary hindered amine group manufactured by BASF Japan
  • IRGANOX1010 manufactured by BASF Japan, both of the ⁇ -positions of the hindered phenol groups are tert-butyl groups
  • Hindered phenolic antioxidants 0.5 parts by mass Eastotac H-100L Resin (cyclic olefin polymer manufactured by Eastman Chemical Co.): 50.0 parts by mass
  • the resistance value of the prepared sample was measured by a 4-terminal 4-probe method constant current application method using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) in accordance with JIS-K7194.
  • the transmittance of each of the conductive films 2101 to 2112 was measured as follows. An unsealed conductive film was cut into a size of 30 mm ⁇ 30 mm to prepare a sample. The total light transmittance (%) of this sample was measured according to JIS K7361 using NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the angle dependency of the transmittance of each of the conductive films 2101 to 2112 was determined as follows. An unsealed conductive film was cut into a size of 30 mm ⁇ 30 mm to prepare a sample. The visible light transmittance (A) in the wavelength range of 400 to 800 nm of this sample was measured using a spectrophotometer U-3310 manufactured by Hitachi. The baseline was measured with air and the reference was also air. Next, the arrangement position of the sample was changed so that the angle of the sample with respect to the optical axis of the measurement light was 45 degrees, and the visible light transmittance (B) in the wavelength range of 400 to 800 nm was measured in the same manner.
  • A visible light transmittance
  • U-3310 manufactured by Hitachi.
  • the baseline was measured with air and the reference was also air.
  • the arrangement position of the sample was changed so that the angle of the sample with respect to the optical axis of the measurement light was 45 degrees, and the visible light transmittance (B) in the wavelength range of 400 to 800
  • the visible light transmittance obtained by the measurement is normalized to the maximum value, and the normalized visible light transmittance (B) / normalized visible light transmittance (A) is obtained and averaged for each wavelength of 1 nm. Was determined as the angle dependency (%) of transmittance.
  • the silicon-containing polymer modified layer is formed under the conductive layer as compared with the conductive film 2101 or 2102 having only the silicon compound layer or the silicon-containing polymer modified layer under the conductive layer.
  • the conductive films 2103 to 2112 provided with the transition metal oxide layer have little change in resistance value and are excellent in stability of conductive performance.
  • the conductive films 2103 to 2112 have little change in transmittance, are stable in light transmission as well as conductive performance, and have low angle dependency of transmittance.
  • the use of niobium oxide improved the stability of the conductive performance and lowered the angle dependency of the transmittance.
  • Example II-II [Conductive films 2201 to 2203]
  • the respective conductive films 2201 to 2203 are similar to the respective conductive films 2101 to 2103 except that a grid is formed on the transition metal oxide layer. Manufactured.
  • the grid was formed by the inkjet method as follows.
  • a coating solution containing silver nanoparticles an inkjet nanopaste NPS-JL (manufactured by Harima Chemicals) was used to form fine metal wires having a line width of 50 ⁇ m and an interval of 1 mm in stripes.
  • the coating liquid was applied in layers so that a sufficient height was obtained.
  • a desktop robot SHOTMASTER300 manufactured by Musashi Engineering Co., Ltd.
  • an ink jet head KM512SHX manufactured by Konica Minolta Co., Ltd. was used, and this was controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta Co., Ltd.).
  • PulseForge 1300 manufactured by NovaCentrix firing was performed by irradiating with xenon light to form a grid.
  • Xenon light was irradiated by pulse light emission of 250 ⁇ s at a cycle of 500 ⁇ s, and the irradiation amount was adjusted so that the applied energy was 1500 mJ / cm 2 .
  • the size of the fine metal wires of the formed grid was measured several times by changing the position with a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100 (manufactured by Nihon Beco Co., Ltd.). The average value of was 1.0 ⁇ m.
  • a conductive film 2204 was produced in the same manner as the conductive film 2203 except that the material of the conductive layer was changed to IZO.
  • the conductive film 2205 was formed in the same manner as the conductive film 2204 except that the transition metal oxide layer was formed by changing niobium oxide used for the target to titanium oxide and tantalum oxide, respectively. And 2206 were produced.
  • a conductive film 2207 was produced in the same manner as the conductive film 2204 except that the thickness of the silicon compound layer was changed to 150 nm and a plating layer was formed on the grid.
  • the grid was formed in the same manner as the conductive film 2204 except that the coating was performed only once and the height of the fine metal wires of the grid was changed to 0.3 ⁇ m.
  • the plating layer was formed by an electrolytic plating method so that the total thickness of the metal thin wires of the grid and the thickness of the plating layer was 1 ⁇ m. Specifically, after applying an electrolytic plating solution containing silver cyanide, potassium cyanide and potassium carbonate on the fine metal wires of the grid, the fine metal wires of the grid were energized as power supply electrodes, and 0.7 ⁇ m thick silver was formed on a thin metal wire.
  • each conductive film 2208 was produced in the same manner as the conductive film 2207, except that a grid was formed by a screen printing method using a screen printing apparatus.
  • a conductive film 2209 was produced in the same manner as the conductive film 2207, except that a grid was formed by a relief printing method. Specifically, a relief plate having the same convex shape as the shape of the grid to be formed was pressed onto a blanket coated with a coating solution containing silver nanoparticles, and the coating solution was transferred in the shape of a grid onto the blanket. Next, the blanket was brought into contact with the transition metal oxide layer, and the silver nanoparticles transferred onto the blanket were transferred to the transition metal oxide layer.
  • the respective conductive films 2212 and 2213 were produced in the same manner as the conductive film 2211 except that the grid formation method was changed to the screen printing method and the relief printing method, respectively.
  • the grid formation method by the screen printing method and the relief printing method is the same as that of the conductive films 2208 and 2209.
  • the conductive films 2215 and 2211 are the same as the conductive films 2215 and 2211 except that the electroplating method is changed to an electroless plating method to form a plated layer of copper film. 2216 was formed.
  • the formation of the plating layer by the electroless plating method was performed by applying an activating agent A-screen A220 (Okuno Pharmaceutical Co., Ltd.) on the thin metal wire and activating the plating nucleus.
  • an electroless copper plating agent OPC-750 electroless copper M (Okuno Pharmaceutical Co., Ltd.) was applied to the surface subjected to activation treatment, and electroless plating treatment was performed at a temperature of 20 ° C. for 20 minutes. .
  • a conductive film 2217 was produced in the same manner as the conductive film 2211 except that the material of the conductive layer was changed to GZO. Further, in the production of the conductive film 2211, a conductive film 2218 is produced in the same manner as the conductive film 2211 except that the thickness of the silicon compound layer is changed to 150 nm and the material of the conductive layer is changed to ZnO. did.
  • the resistance was reduced by providing a grid, and the resistance was further reduced by providing a plating layer on the grid. Also, a lower transmittance angle dependence was obtained.
  • Example II-III [Organic EL element 2301]
  • An organic functional layer was formed on the conductive film 2101 produced in Example II-I as follows. Note that the conductive film 2101 was dried in a glove box having a dew point of ⁇ 80 ° C. or lower and an oxygen concentration of 1 ppm or lower, and then placed in a vacuum evaporation apparatus for forming an organic functional layer without exposing the glove box to the atmosphere.
  • Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten. After reducing the vacuum to 1 ⁇ 10 ⁇ 4 Pa, the deposition crucible containing the compound M-2 was heated and energized, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection transport layer was formed.
  • Compound BD-1 and Compound H-1 are co-deposited at a deposition rate of 0.1 nm / second so that the concentration of Compound BD-1 is 5% in volume ratio, and fluorescence that exhibits blue light emission with a thickness of 15 nm is obtained. A light emitting layer was formed.
  • the vapor deposition rate of 0.1 nm is applied so that the compound GD-1, RD-1, and the compound H-2 are at a concentration of 17% by volume of the compound GD-1 and 0.8% by volume of RD-1.
  • the phosphorescent light emitting layer having a thickness of 15 nm and having a yellow color was formed.
  • Compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 30 nm.
  • LiF was formed at a thickness of 1.5 nm
  • aluminum was deposited at 110 nm to form a cathode.
  • An organic EL element 2301 was manufactured by attaching and sealing a sealing film so as to cover the formed anode to cathode.
  • a sealing film For sealing, except for using polyethylene terephthalate having a thickness of 50 ⁇ m bonded to a 100 ⁇ m thick aluminum foil as the sealing film, sealing the conductive film when obtaining the resistance value in Example II-I. Sealing was performed in the same manner as the method.
  • Organic EL elements 2302 to 2312 were manufactured in the same manner as the organic EL element 2301 except that the conductive films 2102 to 2112 were used instead of the conductive film 2101 in the manufacture of the organic EL element 2301.
  • Organic EL element 2313 In manufacturing the conductive film 2112, a light scattering layer was formed between the transition metal oxide layer and the conductive layer. An organic EL element 2313 was produced in the same manner as the organic EL element 2312 except that the conductive film 2112 having this light scattering layer was used. The light scattering layer was formed as follows.
  • the mixture was mixed so that the solid content concentration of the coating solution was 15% by mass to prepare a coating solution for the light scattering layer having a total amount of 10 mL.
  • hexylene glycol, propylene glycol monomethyl ether and isopropyl alcohol were used as solvents, and the solvent ratio (mass ratio) in these coating solutions was set to 30:50:20.
  • the above-mentioned TiO 2 particles and the above-mentioned solvent are mixed and cooled at room temperature, with an ultrasonic disperser UH-50 (manufactured by SMT Co., Ltd.) of Microchip Step MS-3 3 mm ⁇ (manufactured by SMT Co., Ltd.).
  • Dispersion of TiO 2 particles was prepared by dispersing for 10 minutes under standard conditions. While stirring this dispersion at 100 rpm, the organic-inorganic hybrid resin solution was added little by little.
  • the stirring speed was increased to 500 rpm, mixed for 10 minutes, and filtered through a hydrophobic PVDF 0.45 ⁇ m filter (manufactured by Whatman) to obtain a coating solution for the light scattering layer.
  • the obtained coating solution was applied on the transition metal oxide layer by an inkjet method. Thereafter, simple drying was performed at a temperature of 80 ° C. for 2 minutes, and further, baking was performed at a temperature of 120 ° C. for 6 minutes to form a light scattering layer.
  • the thickness of the light scattering layer was 500 nm.
  • the organic EL element was connected to a DC voltage / current source 6243 (manufactured by ADC), and a current of 50 A / m 2 was applied to emit light, and the driving voltage at the time of light emission was measured by the DC voltage / current source 6243.
  • the angle dependency of the chromaticity of the emission color of each of the organic EL elements 2301 to 2313 was evaluated as follows.
  • the organic EL element is connected to a DC voltage / current source 6243 (manufactured by ADC), and a current of 25 A / m 2 is allowed to flow to emit light.
  • the chromaticity x and y of the light emitted from the organic EL element are expressed as chromaticity. It was measured with a measuring instrument CS-2000 (manufactured by Konica Minolta).
  • the organic EL element is arranged and colored so that the optical axis of the measurement light and the light emitting surface of the organic EL element are perpendicular, that is, the angle formed by the optical axis of the measuring light and the light emitting surface is 90 degrees. The degree was measured. Thereafter, the angle formed between the optical axis of the measurement light and the light emitting surface was changed by 5 degrees within a range of 0 to 90 degrees, and the chromaticities x and y were respectively measured.
  • the organic EL elements 2303 to 2313 in which a conductive layer is formed on a silicon-containing polymer modified layer and a transition metal oxide have a silicon compound layer only or a silicon-containing polymer layer only under the conductive layer.
  • the organic EL elements 2303 to 2313 have small angle dependency of chromaticity, and it can be seen that the change in emission color is small depending on the observation position. This is presumed to be due to the use of a conductive film having a small angle dependency of transmittance.
  • the use of a conductive film using niobium oxide further improved the stability of light emission performance, and the angle dependency of chromaticity was further reduced.
  • Example II-IV [Organic EL elements 2401 to 2418]
  • the same as the organic EL element 2301 except that the conductive films 2201 to 2218 produced in Example II-II were used instead of the conductive film 2101, respectively.
  • each of the organic EL elements 2401 to 2418 was manufactured.
  • the conductive film of the present invention can be used for an electrode of an organic EL element.
  • the organic EL element of this invention can be used for a display, an illuminating device, etc.

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Abstract

L'objectif de la présente invention est de pourvoir à un film électroconducteur présentant une faible résistance et une grande stabilité en ce qui concerne les performances électroconductrices, et à un élément électroluminescent organique présentant une grande stabilité en ce qui concerne les performances d'émission de lumière et une faible dépendance angulaire de la chromaticité. Ce film électroconducteur comporte un film de résine sur lequel est placée une couche électroconductrice contenant un polymère électroconducteur ou un oxyde métallique, le film électroconducteur étant caractérisé en ce qu'il est pourvu : d'une couche de modification de polymère contenant du silicium qui contient une substance de modification pour le polymère contenant du silicium ; et d'une couche d'oxyde de métal de transition positionnée sur la couche de modification de polymère contenant du silicium, la couche d'oxyde de métal de transition contenant un oxyde de métal de transition, et la couche électroconductrice étant positionnée sur la couche d'oxyde de métal de transition.
PCT/JP2016/058887 2015-03-23 2016-03-22 Film électroconducteur et élément électroluminescent organique WO2016152822A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003133080A (ja) * 2001-10-30 2003-05-09 Fuji Photo Film Co Ltd 発光素子
WO2012002113A1 (fr) * 2010-06-29 2012-01-05 コニカミノルタホールディングス株式会社 Conducteur transparent, élément el organique et élément organique de conversion photoélectrique
WO2012147685A1 (fr) * 2011-04-28 2012-11-01 旭硝子株式会社 Élément électroluminescent organique, substrat translucide, et procédé de fabrication d'élément à diodes électroluminescentes organiques
JP2014151571A (ja) * 2013-02-08 2014-08-25 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
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
WO2016039060A1 (fr) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Film barrière aux gaz et élément électroluminescent organique
JP2016046066A (ja) * 2014-08-22 2016-04-04 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003133080A (ja) * 2001-10-30 2003-05-09 Fuji Photo Film Co Ltd 発光素子
WO2012002113A1 (fr) * 2010-06-29 2012-01-05 コニカミノルタホールディングス株式会社 Conducteur transparent, élément el organique et élément organique de conversion photoélectrique
WO2012147685A1 (fr) * 2011-04-28 2012-11-01 旭硝子株式会社 Élément électroluminescent organique, substrat translucide, et procédé de fabrication d'élément à diodes électroluminescentes organiques
JP2014151571A (ja) * 2013-02-08 2014-08-25 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
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
JP2016046066A (ja) * 2014-08-22 2016-04-04 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子
WO2016039060A1 (fr) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Film barrière aux gaz et élément électroluminescent organique

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