WO2012117812A1 - Transparent conductive film, substrate with transparent conductive film, and organic electroluminescent element using same - Google Patents

Transparent conductive film, substrate with transparent conductive film, and organic electroluminescent element using same Download PDF

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WO2012117812A1
WO2012117812A1 PCT/JP2012/052692 JP2012052692W WO2012117812A1 WO 2012117812 A1 WO2012117812 A1 WO 2012117812A1 JP 2012052692 W JP2012052692 W JP 2012052692W WO 2012117812 A1 WO2012117812 A1 WO 2012117812A1
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conductive film
transparent conductive
substrate
metal wires
transparent
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PCT/JP2012/052692
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French (fr)
Japanese (ja)
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太祐 松井
辻本　光
横川　弘
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パナソニック株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines

Definitions

  • the present invention relates to a transparent conductive film used for various optical devices, a substrate with a transparent conductive film, and an organic electroluminescence element using the same.
  • organic EL element is an organic light emitting layer sandwiched between a pair of electrodes formed on a transparent substrate. It passes through the electrode and is taken out from the substrate side.
  • organic EL element a material having conductivity and translucency is used as an electrode material on the substrate side, and indium tin oxide (hereinafter referred to as ITO) is widely used.
  • ITO indium tin oxide
  • electrodes using ITO as a material are vulnerable to bending and physical stress and are fragile.
  • high vapor deposition temperature and / or high annealing temperature are needed, and there exists a possibility that it may become high cost in manufacture of the device using an organic EL element.
  • the base material 101 with a transparent conductive film includes a base material 102 having translucency and a transparent conductive film 103 formed on the base material 102.
  • the transparent conductive film 103 includes a plurality of fine metal wires 103a and a transparent resin layer 103b as a binder. The plurality of fine metal wires 103a are bonded onto the base material 102 by the transparent resin layer 103b.
  • the substrate 101 with the transparent conductive film the plurality of fine metal wires 103a protrude from one surface opposite to the surface facing the substrate 102 of the transparent resin layer 103b.
  • the smoothness is poor. Therefore, when the substrate 101 with a transparent conductive film is used in an organic EL element, for example, when a functional layer such as a hole injection layer, a hole transport layer, or an organic light emitting layer is formed on the transparent conductive film 103, These functional layers may not be formed to a uniform thickness.
  • the above-mentioned organic EL element is expected to be used as a surface light emitter, and it is desired that the thickness of the functional layer is uniform in order to achieve uniform surface light emission, and the transparent where the functional layer is formed. It is necessary to smooth one surface of the conductive film 103. In order to smooth one surface of the transparent conductive film 103, it is conceivable to reduce the amount of the fine metal wires 103a. However, when the amount of the fine metal wires 103a is reduced, the conductivity of the transparent conductive film 103 is lowered.
  • the present invention has been made in order to solve the above problems, and without reducing the conductivity, a transparent conductive film capable of smoothing one surface on which a functional layer is formed, a substrate with a transparent conductive film, Another object of the present invention is to provide an organic electroluminescence device including the same.
  • the transparent conductive film of the present invention is a transparent conductive film provided on a substrate and provided with a transparent resin layer containing fine metal wires, on one surface opposite to the surface facing the substrate of the transparent resin layer.
  • the existence ratio P1 of the fine metal wires and the existence ratio P2 of the fine metal wires in a cross section that is parallel to the base material of the transparent resin layer and closer to the base material than the one surface have a relationship of P1 ⁇ P2. It is comprised as follows.
  • the cross section is a cross section that bisects the transparent resin layer in parallel with the base material, and the existence ratios P1 and P2 of the fine metal wires have a relationship of P1 ⁇ 0.7P2. Is preferred.
  • the existence ratios P1 and P2 of the fine metal wires have a relationship of 0.1P2 ⁇ P1.
  • the fine metal wire is preferably a metal nanowire.
  • the metal nanowire preferably contains silver.
  • this transparent conductive film is formed on a substrate and configured as a substrate with a transparent conductive film.
  • This substrate with a transparent conductive film is preferably used for an organic electroluminescence element.
  • the ratio of the thin metal wires on the surface opposite to the surface facing the substrate of the transparent resin layer is small, and the number of protruding metal wires is small.
  • electroconductivity can be improved.
  • the transparent conductive film of the present embodiment is formed on a light-transmitting substrate and is configured as a substrate with a transparent conductive film, and is used for, for example, an organic electroluminescence (hereinafter referred to as organic EL) element.
  • FIG. 1 shows a cross-sectional configuration of an organic EL element.
  • the organic EL element 1 includes a substrate 2, a transparent conductive film 3, an organic light emitting layer 4 as a functional layer, and a conductor layer 5, and the transparent conductive film 3, the organic light emitting layer 4, And the conductor layer 5 are sequentially laminated.
  • a hole injection layer that promotes injection of holes from the transparent conductive film 3 is provided between the organic light emitting layer 4 and the transparent conductive film 3, and promotes injection of electrons from the conductor layer 5.
  • An electron injection layer is preferably provided between the conductor layer 5.
  • a hole transport layer that efficiently transports holes or an electron transport layer that efficiently transports electrons may be provided.
  • the organic EL element 1 configured as described above, when a voltage is applied between the transparent conductive film 3 and the conductor layer 5 with the transparent conductive film 3 side as a positive potential, holes are emitted from the transparent conductive film 3 to organic light emission. Electrons are injected into the layer 4 and electrons are injected from the conductor layer 5 into the organic light emitting layer 4. Then, the holes and electrons injected into the organic light emitting layer 4 are recombined in the organic light emitting layer 4 so that the organic light emitting layer 4 emits light. The light emitted from the organic light emitting layer 4 passes through the substrate 6 with the transparent conductive film (the transparent conductive film 3 and the substrate 2), and is taken out of the organic EL element 1. The light irradiated on the conductor layer 5 is reflected on the surface of the conductor layer 5, passes through the substrate 6 with a transparent conductive film, and is taken out of the organic EL element 1.
  • the material of the base material 2 will not be specifically limited if it has translucency.
  • a base material 2 for example, a rigid transparent glass plate such as soda glass or non-alkali glass, or a flexible transparent plastic plate such as polycarbonate or ethylene terephthalate is used.
  • a rigid transparent glass plate such as soda glass or non-alkali glass
  • a flexible transparent plastic plate such as polycarbonate or ethylene terephthalate
  • the strength of the device using the substrate 2 is excellent, and the formation of the transparent conductive film 3 on the substrate 2 can be facilitated.
  • a flexible transparent plastic plate is used as the substrate 2, the device using the substrate 2 can be reduced in weight, and the device can have flexibility.
  • Examples of the material of the organic light emitting layer 4 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, and cyclopentadiene.
  • a compound or a polymer is used.
  • a light-emitting material such as an iridium complex, an osmium complex, a platinum complex, or a europium complex, or a phosphorescent light-emitting material such as a compound or polymer having these in a molecule can be used. These materials can be appropriately selected and used as necessary.
  • a material of the conductor layer 5 for example, aluminum or the like is used.
  • a laminated structure may be formed by combining aluminum and another material. Examples of such combinations include a laminate of an alkali metal and aluminum, a laminate of an alkali metal and silver, a laminate of an alkali metal halide and aluminum, a laminate of an alkali metal oxide and aluminum, and an alkali.
  • a laminate of an earth metal or rare earth metal and aluminum, or an alloy of these metal species with another metal can be used.
  • the substrate 6 with a transparent conductive film includes a substrate 2 and a transparent conductive film 3 formed on the substrate 2.
  • the transparent conductive film 3 includes a plurality of fine metal wires 3a having conductivity and a transparent resin layer 3b as a binder.
  • the organic light emitting layer 4 is laminated on the surface 3c on the opposite side of the surface of the transparent resin layer 3b facing the substrate 2, and the organic light emitting layer 4 is laminated. Therefore, in the following description, this surface is referred to as a working surface 3c.
  • the plurality of fine metal wires 3a are bonded onto the base material 2 by the transparent resin layer 3b in a state in which a part protrudes from the action surface 3c. For this reason, on the base material 2, a three-dimensional conductive network of a plurality of fine metal wires 3a is formed. Thereby, the transparent conductive film 3 has electroconductivity.
  • the three-dimensional conductive network of the plurality of fine metal wires 3a indicates a state in which the plurality of fine metal wires 3a are in contact with or close to each other in three dimensions.
  • the fine metal wire 3a protruding from the working surface 3c of the transparent resin layer 3b comes into contact with the organic light emitting layer 4, and a voltage is applied to the organic EL element 1. Then, holes are injected into the organic light emitting layer 4 from the plurality of fine metal wires 3a.
  • the existence ratio P1 of the plurality of fine metal wires 3a on the working surface 3c of the transparent resin layer 3b is parallel to the base material 2 of the transparent resin layer 3b and is present on the base material 2 side with respect to the working surface 3c.
  • the existence ratio P2 of the thin metal wires 3a in the cross section 3d is adjusted to satisfy P1 ⁇ P2.
  • the abundance ratio P1 of the metal fine wires 3a is not zero, and a predetermined amount of the metal fine wires 3a is present on the working surface 3c of the transparent resin layer 3b.
  • a plurality of fine metal wires 3a are continuously present from the working surface 3c of the transparent resin layer 3b to the surface facing the substrate 2.
  • These thin metal wires 3a form a three-dimensional conductive network as described above, whereby the transparent conductive film 3 can obtain high conductivity.
  • the abundance ratios P1 and P2 of the fine metal wires 3a are P1 ⁇ 0.7P2. It is preferable to satisfy the relationship. Thereby, the smoothness of the action surface 3c of the transparent conductive film 3 can be improved. Further, it is preferable that the existence ratios P1 and P2 of the fine metal wires 3a satisfy the relationship of 0.1P2 ⁇ P1. Thereby, it is possible to prevent the conductivity of the working surface 3c of the transparent conductive film 3 from being lowered and the surface resistance value on the working surface 3c from becoming unstable.
  • the following methods can be mentioned. That is, in the step of forming the transparent conductive film 3 on the substrate 2, a plurality of coating agent compositions having different concentrations of the fine metal wires 3a are prepared. And these coating agent compositions are apply
  • the coating agent composition that is finally applied onto the substrate 2 is a coating agent composition having the lowest concentration of the fine metal wires 3a among the plurality of coating agent compositions.
  • the existence ratio P2 of the metal fine wire 3a becomes large gradually toward the surface which opposes the base material 2 from the action surface 3c of the transparent resin layer 3b in the transparent resin layer 3b.
  • the fine metal wire 3a is made of a fibrous metal, metal, or metal fine particle having a line width of several nm to several tens of ⁇ m.
  • the length of the fine metal wire 3a is sufficiently longer than the diameter of the cross section perpendicular to the length direction of the fine metal wire 3a.
  • the amount of the plurality of fine metal wires 3a contained in the transparent conductive film 3 is preferably 0.1 mg / m 2 or more and 1000 mg / m 2 or less, more preferably 1 mg / m 2 or more and 100 mg / m 2 or less. preferable.
  • the length of each of the plurality of fine metal wires 3a is preferably 300 nm or less in consideration of the translucency of the transparent conductive film 3, and the average diameter of the plurality of fine metal wires 3a is 0.3 nm or more and 200 nm or less. Preferably there is. For the same reason, the average aspect ratio of the plurality of fine metal wires 3a is preferably 10 or more and 10,000 or less. Furthermore, considering the conductivity of the transparent conductive film 3, the thickness of the transparent resin layer 3b is preferably not less than the average diameter of the plurality of fine metal wires 3a and not more than 500 nm.
  • the material of the metal thin wire 3a for example, a metal mesh, a metal nanowire, an aggregate of metal fine particles, or the like is used, but it is preferable to use a metal nanowire excellent in transparency and conductivity of the transparent conductive film 3.
  • the metal used for the thin metal wire 3a include gold, silver, copper, aluminum, zinc, cobalt, nickel, and tungsten.
  • gold, silver, or copper having high conductivity is preferably used, and silver having the highest conductivity is more preferably used.
  • the length of the metal nanowires is preferably 3 ⁇ m or more, more preferably 3 ⁇ m or more and 500 ⁇ m or less in consideration of the conductivity of the transparent conductive film 8. More preferably, it is 300 ⁇ m or less.
  • the average diameter of the metal nanowires is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 200 nm or less in consideration of the translucency and conductivity of the transparent conductive film 8.
  • the manufacturing method of metal nanowire is not specifically limited, For example, well-known methods, such as a liquid phase method or a gaseous-phase method, are used.
  • Examples of the material for the transparent resin layer 3b include polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and a saponified product thereof partially or entirely, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer.
  • Polymers ethylene-vinyl acetate-methyl methacrylate copolymers, olefin resins such as polypropylene and propylene- ⁇ -olefin copolymers, vinyl chloride resins such as polyvinyl chloride resins, and acrylonitrile such as acrylonitrile-styrene copolymers Resin, polystyrene, styrene resin such as styrene-methyl methacrylate copolymer, acrylate polymer such as polyethyl acrylate, methacrylate polymer such as polymethyl methacrylate, copolymers thereof and others (Meth) acrylic with added copolymer component Ester resin, a polyester resin such as polyethylene terephthalate, polyamide resins such as nylon, polycarbonate resin, ethyl cellulose, cellulose resins such as acetyl cellulose, polyurethane resins, and silicone resins.
  • Ester resin a polyester resin such as polyethylene
  • thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, or polysiloxane resin can be used.
  • thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, or polysiloxane resin can be used.
  • curing agent, a hardening accelerator, or a solvent to these thermosetting resins as needed.
  • the ionizing radiation curable resin preferably has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal. Resins, polybutadiene resins, polythiol polyene resins, oligomers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, prepolymers, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl Monofunctional monomers such as styrene and N-vinylpyrrolidone, as well as polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate A relatively large amount of diethylene glycol di (me
  • the ionizing radiation curable resin an ultraviolet curable resin
  • a photopolymerization initiator acetophenones, benzophenones, ⁇ -amyloxime esters, thioxanthones or the like are used.
  • a photosensitizer may be used.
  • the photosensitizer n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone, or the like is used.
  • the coating method of the transparent conductive film 3 is not particularly limited, and a known coating method such as spin coating, screen printing, dip coating, die coating, casting, spray coating, or gravure coating is used. Further, in order to smooth the working surface 3c of the transparent resin layer 3b and stabilize the surface resistance value on the working surface 3c, a pressurizing step using, for example, a roller press may be performed.
  • the existence ratio of the thin metal wires 3a on the working surface 3c of the transparent resin layer 3b is small, and the protruding fine metal wires 3a are small.
  • the surface 3c can be smoothed.
  • the conductivity can be improved.
  • Silver nanowires were produced as thin metal wires according to a known paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanorods with high yield by polyol process ””. In this case, the average diameter of the silver nanowire was 50 nm, and the average length of the silver nanowire was 5 ⁇ m.
  • Example 1 3 parts by mass of methyl cellulose “M7140” manufactured by Sigma-Aldrich was dissolved in 200 parts by mass of water to prepare a methylcellulose solution. Next, a dispersion liquid in which the above-mentioned silver nanowire was dispersed as a metal thin wire and water was used as a dispersion medium at a solid content of 3.0% by mass was prepared. Next, 100 parts by mass of this dispersion was added to the methylcellulose solution and mixed well. Thereby, the 1st coating agent composition was produced. Moreover, the dispersion liquid which disperse
  • the first coating composition was applied on a glass substrate BK7 having dimensions of 100 mm in length, 100 mm in width, and 0.7 mm in height by a spin coater so as to have a thickness of 100 nm. And after drying the glass base material with which the 1st coating agent composition was apply
  • Example 2 A third coating agent composition was prepared in the same manner as in Example 1 above by adding a dispersion liquid in which silver nanowires were dispersed in water with a solid content of 1.8% by mass to a methylcellulose solution. Then, instead of the second coating agent composition, a third transparent conductive film is formed on the first transparent conductive film using the third coating agent composition, and the same as in Example 1 above. Thus, a sample of Example 2 was produced.
  • Comparative Example 1 A sample of Comparative Example 1 was produced in the same manner as in Example 1 except that only the first coating agent composition was applied onto a substrate with a spin coater so that the thickness was 150 nm.
  • Comparative Example 2 A dispersion obtained by dispersing silver nanowires with water as a dispersion medium at a solid content of 2.1% by mass was added to the methylcellulose solution to prepare a fourth coating agent composition in the same manner as in Example 1 above. Then, instead of the second coating agent composition, a fourth transparent conductive film is formed on the first transparent conductive film using the fourth coating agent composition, and the same as in Example 1 above. Thus, a sample of Comparative Example 2 was produced.
  • Comparative Example 3 A fifth coating agent composition was prepared in the same manner as in Example 1 above by adding a dispersion liquid in which silver nanowires were dispersed in water with a solid content of 0.3% by mass to a methylcellulose solution. Then, instead of the second coating agent composition, a fifth transparent conductive film is formed on the first transparent conductive film using the fifth coating agent composition, and the same as in Example 1 above. Thus, a sample of Comparative Example 3 was produced.
  • the surface resistance value, the surface roughness Ra, and the leakage current were measured for the samples of Examples 1 and 2 and Comparative Examples 1 to 3. Hereinafter, these measurements will be described in order.
  • the surface resistance value of the transparent conductive film of each sample was measured using Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Corporation.
  • N, N-diphenyl-N, N-bis3-methyl-phenyl-1,1-diphenyl-4,4 diamine manufactured by Doujin Chemical Laboratory Co., Ltd. is 50 nm thick on the transparent conductive film of each sample produced. Vacuum deposition was performed. This formed the positive hole transport layer on the transparent conductive film of each sample. Next, an aluminum quinolinol complex (tris (8-hydroquinoline) aluminum) manufactured by Doujin Chemical Laboratory Co., Ltd. was vacuum-deposited on the hole transport layer so as to have a thickness of 50 nm. This formed the organic light emitting layer on the positive hole transport layer.
  • the presence ratios P1 and P2 of the silver nanowires are 0.1P2 ⁇ P1 ⁇ 0.7P2. It is shown that it is preferable to satisfy this relationship.
  • the transparent conductive film 3 can be used as a transparent electrode such as a liquid crystal display, a plasma display, or a solar organic battery.
  • carbon nanotubes may be used as the material of the fine metal wires 3a
  • conductive polymers may be used as the material of the transparent resin layer 3b.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
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Abstract

A substrate (6) with a transparent conductive film comprises a substrate (2) and the transparent conductive film (3) formed on top of the substrate (2). The transparent conductive film (3) includes a plurality of conductive fine metal wires (3a) and a transparent resin layer (3b). Some of the plurality of fine metal wires (3a) protrude from an action surface (3c) of the transparent resin layer (3b). The proportion (P1) of the plurality of fine metal wires (3a) present in the action surface (3c) and the proportion (P2) of the fine metal wires (3a) present in a cross-sectional surface (3d) parallel to the transparent resin layer (3b) substrate (2) and further on the substrate (2) side than the action surface (3c) fulfill P1<P2. As a result, the number of protruding fine metal wires (3a) decreases and the action surface (3c) can be smoothed. In addition, the proportion of fine metal wires (3a) present further on the substrate (2) side than the action surface (3c) increases and the conductivity can be increased.

Description

透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子Transparent conductive film, substrate with transparent conductive film, and organic electroluminescence device using the same
　本発明は、種々の光学デバイスに用いられる透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子に関する。 The present invention relates to a transparent conductive film used for various optical devices, a substrate with a transparent conductive film, and an organic electroluminescence element using the same.
　一般的な有機エレクトロルミネッセンス（以下、有機ＥＬという）素子は、一対の電極で挟持された有機発光層が透明な基材上に形成されたものであり、有機発光層からの光は、一方の電極を透過して基材側から取り出される。この種の有機ＥＬ素子において、基材側の電極の材料として、導電性及び透光性を有するものが用いられ、インジウムスズ酸化物（以下、ＩＴＯという）が広く用いられる。しかし、ＩＴＯを材料として用いた電極は曲げや物理的な応力に対して脆弱で壊れやすい。また、ＩＴＯを用いた電極の導電性を向上させるためには、高い蒸着温度及び／又は高いアニール温度が必要となり、有機ＥＬ素子を用いたデバイスの製造において、コスト高となる虞がある。 A general organic electroluminescence (hereinafter referred to as “organic EL”) element is an organic light emitting layer sandwiched between a pair of electrodes formed on a transparent substrate. It passes through the electrode and is taken out from the substrate side. In this type of organic EL element, a material having conductivity and translucency is used as an electrode material on the substrate side, and indium tin oxide (hereinafter referred to as ITO) is widely used. However, electrodes using ITO as a material are vulnerable to bending and physical stress and are fragile. Moreover, in order to improve the electroconductivity of the electrode using ITO, high vapor deposition temperature and / or high annealing temperature are needed, and there exists a possibility that it may become high cost in manufacture of the device using an organic EL element.
　そこで、ＩＴＯに代えて、複数の金属細線を含む透明導電膜を電極として用いた技術が知られている（例えば、日本国公表特許２００９－５０５３５８号公報参照）。この種の透明導電膜付き基材の構成例について、図３を参照して説明する。透明導電膜付き基材１０１は、透光性を有する基材１０２と、この基材１０２上に形成される透明導電膜１０３と、を備える。透明導電膜１０３は、細線状の複数の金属細線１０３ａと、バインダとしての透明樹脂層１０３ｂと、を含む。複数の金属細線１０３ａは、透明樹脂層１０３ｂによって、基材１０２上に接着されている。 Therefore, a technique using a transparent conductive film including a plurality of fine metal wires as an electrode instead of ITO is known (see, for example, Japanese Patent Publication No. 2009-505358). A configuration example of this type of substrate with a transparent conductive film will be described with reference to FIG. The base material 101 with a transparent conductive film includes a base material 102 having translucency and a transparent conductive film 103 formed on the base material 102. The transparent conductive film 103 includes a plurality of fine metal wires 103a and a transparent resin layer 103b as a binder. The plurality of fine metal wires 103a are bonded onto the base material 102 by the transparent resin layer 103b.
　上記の透明導電膜付き基材１０１においては、複数の金属細線１０３ａが、透明樹脂層１０３ｂの基材１０２と対向する面と反対側の一面から突出しているので、この一面が凹凸状となり、表面平滑性が悪い。そのため、この透明導電膜付き基材１０１が有機ＥＬ素子に用いられた場合、例えば正孔注入層、正孔輸送層、又は有機発光層等といった機能層を透明導電膜１０３上に形成するとき、これら機能層を均一な厚さに成膜できないことがある。 In the substrate 101 with the transparent conductive film, the plurality of fine metal wires 103a protrude from one surface opposite to the surface facing the substrate 102 of the transparent resin layer 103b. The smoothness is poor. Therefore, when the substrate 101 with a transparent conductive film is used in an organic EL element, for example, when a functional layer such as a hole injection layer, a hole transport layer, or an organic light emitting layer is formed on the transparent conductive film 103, These functional layers may not be formed to a uniform thickness.
　上述した有機ＥＬ素子は、面発光体としての利用が期待されており、均一な面発光をなすためには機能層の厚さが均一であることが望まれると共に、機能層が形成される透明導電膜１０３の一面を平滑化する必要がある。透明導電膜１０３の一面を平滑化するには、金属細線１０３ａの量を減らすことが考えられるが、金属細線１０３ａの量が減ると、透明導電膜１０３の導電性が低下する。 The above-mentioned organic EL element is expected to be used as a surface light emitter, and it is desired that the thickness of the functional layer is uniform in order to achieve uniform surface light emission, and the transparent where the functional layer is formed. It is necessary to smooth one surface of the conductive film 103. In order to smooth one surface of the transparent conductive film 103, it is conceivable to reduce the amount of the fine metal wires 103a. However, when the amount of the fine metal wires 103a is reduced, the conductivity of the transparent conductive film 103 is lowered.
　本発明は、上記課題を解決するためになされたものであり、導電性を低下させることなく、機能層が形成される一面を平滑化することができる透明導電膜、透明導電膜付き基材、及びそれを備えた有機エレクトロルミネッセンス素子を提供することを目的とする。 The present invention has been made in order to solve the above problems, and without reducing the conductivity, a transparent conductive film capable of smoothing one surface on which a functional layer is formed, a substrate with a transparent conductive film, Another object of the present invention is to provide an organic electroluminescence device including the same.
　本発明の透明導電膜は、基材上に設けられ、金属細線を含む透明樹脂層を備えた透明導電膜であって、前記透明樹脂層の前記基材と対向する面と反対側の一面における前記金属細線の存在割合Ｐ１と、前記透明樹脂層の前記基材と平行で、前記一面より前記基材側に存在する断面における前記金属細線の存在割合Ｐ２とが、Ｐ１＜Ｐ２の関係となるように構成されていることを特徴とする。 The transparent conductive film of the present invention is a transparent conductive film provided on a substrate and provided with a transparent resin layer containing fine metal wires, on one surface opposite to the surface facing the substrate of the transparent resin layer. The existence ratio P1 of the fine metal wires and the existence ratio P2 of the fine metal wires in a cross section that is parallel to the base material of the transparent resin layer and closer to the base material than the one surface have a relationship of P1 <P2. It is comprised as follows.
　この透明導電膜において、前記断面は、前記基材と平行に前記透明樹脂層を二等分する断面であり、前記金属細線の存在割合Ｐ１，Ｐ２が、Ｐ１＜０．７Ｐ２の関係となることが好ましい。 In the transparent conductive film, the cross section is a cross section that bisects the transparent resin layer in parallel with the base material, and the existence ratios P1 and P2 of the fine metal wires have a relationship of P1 <0.7P2. Is preferred.
　この透明導電膜において、前記金属細線の存在割合Ｐ１，Ｐ２が、０．１Ｐ２＜Ｐ１の関係となることが好ましい。 In the transparent conductive film, it is preferable that the existence ratios P1 and P2 of the fine metal wires have a relationship of 0.1P2 <P1.
　この透明導電膜において、前記金属細線は、金属ナノワイヤであることが好ましい。 In this transparent conductive film, the fine metal wire is preferably a metal nanowire.
　この透明導電膜において、前記金属ナノワイヤは、銀を含むことが好ましい。 In this transparent conductive film, the metal nanowire preferably contains silver.
　この透明導電膜が基材上に形成されて、透明導電膜付き基材として構成されることが好ましい。 It is preferable that this transparent conductive film is formed on a substrate and configured as a substrate with a transparent conductive film.
　この透明導電膜付き基材は、有機エレクトロルミネッセンス素子に用いられることが好ましい。 This substrate with a transparent conductive film is preferably used for an organic electroluminescence element.
　本発明に係る透明導電膜によれば、透明樹脂層の基材と対向する面と反対側の一面における金属細線の存在割合が少なく、突出する金属細線が少なくなっているので、この面を平滑化することができる。また、この面よりも基材側における金属細線の存在割合が多いので、導電性を向上させることができる。 According to the transparent conductive film of the present invention, the ratio of the thin metal wires on the surface opposite to the surface facing the substrate of the transparent resin layer is small, and the number of protruding metal wires is small. Can be Moreover, since there are many metal fine wire presence ratios in the base material side rather than this surface, electroconductivity can be improved.
本発明の一実施形態に係る透明導電膜付き基材を備えた有機エレクトロルミネッセンス素子の断面図。Sectional drawing of the organic electroluminescent element provided with the base material with a transparent conductive film which concerns on one Embodiment of this invention. 同透明導電膜付き基材の断面図。Sectional drawing of the base material with the said transparent conductive film. 従来の透明導電膜付き基材の断面図。Sectional drawing of the base material with the conventional transparent conductive film.
　以下、本発明の一実施形態に係る透明導電膜について、図面を参照して説明する。本実施形態の透明導電膜は、透光性を有する基材上に形成され、透明導電膜付き基材として構成され、例えば有機エレクトロルミネッセンス（以下、有機ＥＬという）素子に用いられる。図１は、有機ＥＬ素子の断面構成を示す。有機ＥＬ素子１は、基材２と、透明導電膜３と、機能層としての有機発光層４と、導体層５と、を備え、基材２上に透明導電膜３、有機発光層４、及び導体層５が順次積層された構成となっている。基材２と透明導電膜３とが、透明導電膜付き基材６を構成する。透明導電膜３は、有機ＥＬ素子１の陽極として機能し、有機発光層４に正孔（ホール）を注入する。一方、導体層５は、有機ＥＬ素子１の陰極として機能し、有機発光層４に電子を注入する。 Hereinafter, a transparent conductive film according to an embodiment of the present invention will be described with reference to the drawings. The transparent conductive film of the present embodiment is formed on a light-transmitting substrate and is configured as a substrate with a transparent conductive film, and is used for, for example, an organic electroluminescence (hereinafter referred to as organic EL) element. FIG. 1 shows a cross-sectional configuration of an organic EL element. The organic EL element 1 includes a substrate 2, a transparent conductive film 3, an organic light emitting layer 4 as a functional layer, and a conductor layer 5, and the transparent conductive film 3, the organic light emitting layer 4, And the conductor layer 5 are sequentially laminated. The base material 2 and the transparent conductive film 3 constitute a base material 6 with a transparent conductive film. The transparent conductive film 3 functions as an anode of the organic EL element 1 and injects holes into the organic light emitting layer 4. On the other hand, the conductor layer 5 functions as a cathode of the organic EL element 1 and injects electrons into the organic light emitting layer 4.
　有機発光層４は、透明導電膜３からの正孔の注入を促進する正孔注入層が、透明導電膜３との間に設けられることが好ましく、導体層５からの電子の注入を促進する電子注入層が導体層５との間に設けられることが好ましい。さらに、正孔を効率的に輸送する正孔輸送層や、電子を効率的に輸送する電子輸送層が設けられてもよい。 In the organic light emitting layer 4, it is preferable that a hole injection layer that promotes injection of holes from the transparent conductive film 3 is provided between the organic light emitting layer 4 and the transparent conductive film 3, and promotes injection of electrons from the conductor layer 5. An electron injection layer is preferably provided between the conductor layer 5. Furthermore, a hole transport layer that efficiently transports holes or an electron transport layer that efficiently transports electrons may be provided.
　このように構成された有機ＥＬ素子１において、透明導電膜３と導体層５との間に透明導電膜３側を＋電位として電圧が印加されると、正孔が透明導電膜３から有機発光層４に注入され、電子が導体層５から有機発光層４に注入される。そして、有機発光層４に注入された正孔と電子とが、有機発光層４内で再結合することにより、有機発光層４が発光する。有機発光層４から発せられた光は、透明導電膜付き基材６（透明導電膜３及び基材２）を透過して、有機ＥＬ素子１の外へ取り出される。なお、導体層５に照射された光は、導体層５の表面で反射され、透明導電膜付き基材６を透過して、有機ＥＬ素子１の外へ取り出される。 In the organic EL element 1 configured as described above, when a voltage is applied between the transparent conductive film 3 and the conductor layer 5 with the transparent conductive film 3 side as a positive potential, holes are emitted from the transparent conductive film 3 to organic light emission. Electrons are injected into the layer 4 and electrons are injected from the conductor layer 5 into the organic light emitting layer 4. Then, the holes and electrons injected into the organic light emitting layer 4 are recombined in the organic light emitting layer 4 so that the organic light emitting layer 4 emits light. The light emitted from the organic light emitting layer 4 passes through the substrate 6 with the transparent conductive film (the transparent conductive film 3 and the substrate 2), and is taken out of the organic EL element 1. The light irradiated on the conductor layer 5 is reflected on the surface of the conductor layer 5, passes through the substrate 6 with a transparent conductive film, and is taken out of the organic EL element 1.
　なお、基材２の材料は、透光性を有していれば、特に限定されない。このような基材２としては、例えばソーダガラス若しくは無アルカリガラス等のリジッドな透明ガラス板、又はポリカーボネイト若しくはエチレンテレフタレート等のフレキシブルな透明プラスチック板等が用いられる。基材２としてリジッドな透明ガラス板が用いられた場合、この基材２を用いたデバイスの強度が優れると共に、基材２上への透明導電膜３の形成を容易にすることができる。基材２としてフレキシブルな透明プラスチック板が用いられた場合、基材２を用いたデバイスを軽量化できると共に、柔軟性を有するデバイスとすることができる。 In addition, the material of the base material 2 will not be specifically limited if it has translucency. As such a base material 2, for example, a rigid transparent glass plate such as soda glass or non-alkali glass, or a flexible transparent plastic plate such as polycarbonate or ethylene terephthalate is used. When a rigid transparent glass plate is used as the substrate 2, the strength of the device using the substrate 2 is excellent, and the formation of the transparent conductive film 3 on the substrate 2 can be facilitated. When a flexible transparent plastic plate is used as the substrate 2, the device using the substrate 2 can be reduced in weight, and the device can have flexibility.
　また、有機発光層４の材料としては、例えばアントラセン、ナフタレン、ピレン、テトラセン、コロネン、ペリレン、フタロペリレン、ナフタロペリレン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、ビスベンゾキサゾリン、ビススチリル、シクロペンタジエン、クマリン、オキサジアゾール、ビスベンゾキサゾリン、ビススチリル、シクロペンタジエン、キノリン金属錯体、トリス（８－ヒドロキシキノリナート）アルミニウム錯体、トリス（４－メチル－８－キノリナート）アルミニウム錯体、トリス（５－フェニル－８－キノリナート）アルミニウム錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、トリ－（ｐ－ターフェニル－４－イル）アミン、ピラン、キナクリドン、ルブレン、若しくはこれらの誘導体、１－アリール－２，５－ジ（２－チエニル）ピロール誘導体、ジスチリルベンゼン誘導体、スチリルアリーレン誘導体、スチリルアミン誘導体、又はこれらの発光性化合物からなる基を分子の一部分に有する化合物若しくは高分子等が用いられる。また、例えばイリジウム錯体、オスミウム錯体、白金錯体若しくはユーロピウム錯体等の発光材料、又はこれらを分子内に有する化合物若しくは高分子等の燐光発光材料も用いることができる。これらの材料は、必要に応じて、適宜選択して用いることができる。 Examples of the material of the organic light emitting layer 4 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, and cyclopentadiene. , Coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5- Phenyl-8-quinolinato) aluminum complex, aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, pyran, quinacridone, rubrene Alternatively, these derivatives, 1-aryl-2,5-di (2-thienyl) pyrrole derivatives, distyrylbenzene derivatives, styrylarylene derivatives, styrylamine derivatives, or groups composed of these luminescent compounds are included in a part of the molecule. A compound or a polymer is used. In addition, for example, a light-emitting material such as an iridium complex, an osmium complex, a platinum complex, or a europium complex, or a phosphorescent light-emitting material such as a compound or polymer having these in a molecule can be used. These materials can be appropriately selected and used as necessary.
　また、導体層５の材料としては、例えばアルミニウム等が用いられる。また、アルミニウムと他の材料とを組み合わせて積層構造としてもよい。このような組み合わせとしては、アルカリ金属とアルミニウムとの積層体、アルカリ金属と銀との積層体、アルカリ金属のハロゲン化物とアルミニウムとの積層体、アルカリ金属の酸化物とアルミニウムとの積層体、アルカリ土類金属若しくは希土類金属とアルミニウムとの積層体、又はこれらの金属種と他の金属との合金などが挙げられる。具体的には、ナトリウム、ナトリウムとカリウムとの合金、リチウム、若しくはマグネシウム等とアルミニウムとの積層体、マグネシウムと銀との混合物、マグネシウムとインジウムとの混合物、アルミニウムとリチウムとの合金、フッ化リチウムとアルミニウムの混合物との積層体、又はアルミニウムと酸化アルミニウム（Ａｌ２Ｏ３）の混合物との積層体等が挙げられる。 Moreover, as a material of the conductor layer 5, for example, aluminum or the like is used. Alternatively, a laminated structure may be formed by combining aluminum and another material. Examples of such combinations include a laminate of an alkali metal and aluminum, a laminate of an alkali metal and silver, a laminate of an alkali metal halide and aluminum, a laminate of an alkali metal oxide and aluminum, and an alkali. A laminate of an earth metal or rare earth metal and aluminum, or an alloy of these metal species with another metal can be used. Specifically, sodium, an alloy of sodium and potassium, a laminate of lithium or magnesium or the like and aluminum, a mixture of magnesium and silver, a mixture of magnesium and indium, an alloy of aluminum and lithium, lithium fluoride And a laminated body of a mixture of aluminum and aluminum, or a laminated body of a mixture of aluminum and aluminum oxide (Al 2 O 3 ).
　次に、透明導電膜付き基材６の詳細について、図２を参照して説明する。透明導電膜付き基材６は、基材２と、この基材２上に形成されている透明導電膜３と、を備える。透明導電膜３は、導電性を有する複数の金属細線３ａと、バインダとしての透明樹脂層３ｂと、を含む。透明導電膜付き基材６が、有機ＥＬ素子１に用いられる場合、透明樹脂層３ｂの基材２と対向する面と反対側の一面３ｃは、有機発光層４が積層され、有機発光層４に正孔を注入する等の作用をする面であるので、以下の説明においては、この面を作用面３ｃという。複数の金属細線３ａは、この作用面３ｃから一部が突出した状態で、透明樹脂層３ｂによって基材２上に接着されている。このため、基材２上では、複数の金属細線３ａの三次元的な導電ネットワークが形成されている。これにより、透明導電膜３は導電性を有するようになっている。ここで、複数の金属細線３ａの三次元的な導電ネットワークとは、複数の金属細線３ａが三次元的に互いに接触又は近接し合った状態を示す。 Next, details of the substrate 6 with a transparent conductive film will be described with reference to FIG. The substrate 6 with a transparent conductive film includes a substrate 2 and a transparent conductive film 3 formed on the substrate 2. The transparent conductive film 3 includes a plurality of fine metal wires 3a having conductivity and a transparent resin layer 3b as a binder. When the substrate 6 with a transparent conductive film is used for the organic EL element 1, the organic light emitting layer 4 is laminated on the surface 3c on the opposite side of the surface of the transparent resin layer 3b facing the substrate 2, and the organic light emitting layer 4 is laminated. Therefore, in the following description, this surface is referred to as a working surface 3c. The plurality of fine metal wires 3a are bonded onto the base material 2 by the transparent resin layer 3b in a state in which a part protrudes from the action surface 3c. For this reason, on the base material 2, a three-dimensional conductive network of a plurality of fine metal wires 3a is formed. Thereby, the transparent conductive film 3 has electroconductivity. Here, the three-dimensional conductive network of the plurality of fine metal wires 3a indicates a state in which the plurality of fine metal wires 3a are in contact with or close to each other in three dimensions.
　透明導電膜付き基材６が有機ＥＬ素子１に用いられた場合、透明樹脂層３ｂの作用面３ｃから突出した金属細線３ａが有機発光層４と接触し、有機ＥＬ素子１に電圧が印加されると、複数の金属細線３ａから有機発光層４へ正孔が注入される。 When the substrate 6 with a transparent conductive film is used for the organic EL element 1, the fine metal wire 3a protruding from the working surface 3c of the transparent resin layer 3b comes into contact with the organic light emitting layer 4, and a voltage is applied to the organic EL element 1. Then, holes are injected into the organic light emitting layer 4 from the plurality of fine metal wires 3a.
　本実施形態においては、透明樹脂層３ｂの作用面３ｃにおける複数の金属細線３ａの存在割合Ｐ１と、透明樹脂層３ｂの基材２と平行で、作用面３ｃよりも基材２側に存在する断面３ｄにおける金属細線３ａの存在割合Ｐ２とが、Ｐ１＜Ｐ２となるように調整されている。 In the present embodiment, the existence ratio P1 of the plurality of fine metal wires 3a on the working surface 3c of the transparent resin layer 3b is parallel to the base material 2 of the transparent resin layer 3b and is present on the base material 2 side with respect to the working surface 3c. The existence ratio P2 of the thin metal wires 3a in the cross section 3d is adjusted to satisfy P1 <P2.
　ここで、上記の金属細線３ａの存在割合Ｐ１はゼロではなく、所定の量の金属細線３ａが透明樹脂層３ｂの作用面３ｃにおいて存在している。また、透明樹脂層３ｂ内において、複数の金属細線３ａが透明樹脂層３ｂの作用面３ｃから基材２と対向する面にかけて連続的に存在している。これら金属細線３ａが上述したような三次元的な導電ネットワークを形成することにより、透明導電膜３は高い導電性を得ることができる。 Here, the abundance ratio P1 of the metal fine wires 3a is not zero, and a predetermined amount of the metal fine wires 3a is present on the working surface 3c of the transparent resin layer 3b. In the transparent resin layer 3b, a plurality of fine metal wires 3a are continuously present from the working surface 3c of the transparent resin layer 3b to the surface facing the substrate 2. These thin metal wires 3a form a three-dimensional conductive network as described above, whereby the transparent conductive film 3 can obtain high conductivity.
　本実施形態において、透明樹脂層３ｂの断面３ｄが、基材２と平行に透明樹脂層３ｂを二等分する断面であるとき、金属細線３ａの存在割合Ｐ１,Ｐ２が、Ｐ１＜０．７Ｐ２の関係を満たすことが好ましい。これにより、透明導電膜３の作用面３ｃの平滑性を向上させることができる。また、金属細線３ａの存在割合Ｐ１，Ｐ２が、０．１Ｐ２＜Ｐ１の関係を満たすことが好ましい。これにより、透明導電膜３の作用面３ｃの導電性が低下して、作用面３ｃにおける表面抵抗値が不安定となることを防止することができる。 In this embodiment, when the cross section 3d of the transparent resin layer 3b is a cross section that bisects the transparent resin layer 3b in parallel with the substrate 2, the abundance ratios P1 and P2 of the fine metal wires 3a are P1 <0.7P2. It is preferable to satisfy the relationship. Thereby, the smoothness of the action surface 3c of the transparent conductive film 3 can be improved. Further, it is preferable that the existence ratios P1 and P2 of the fine metal wires 3a satisfy the relationship of 0.1P2 <P1. Thereby, it is possible to prevent the conductivity of the working surface 3c of the transparent conductive film 3 from being lowered and the surface resistance value on the working surface 3c from becoming unstable.
　このように金属細線３ａの存在割合Ｐ１，Ｐ２を調整する方法としては、例えば以下のような方法が挙げられる。すなわち、基材２上に透明導電膜３を形成する工程において、金属細線３ａの濃度が異なる複数のコーティング剤組成物を用意する。そして、金属細線３ａの濃度が高いコーティング剤組成物から順に基材２上にそれら複数のコーティング剤組成物を塗布する。この場合、基材２上に最後に塗布されるコーティング剤組成物は、それら複数のコーティング剤組成物のうち金属細線３ａの濃度が最も低いコーティング剤組成物である。そして、金属細線３ａの存在割合Ｐ２は、透明樹脂層３ｂ内において、透明樹脂層３ｂの作用面３ｃから基材２と対向する面に向かって、漸次大きくなる。 As a method of adjusting the existence ratios P1 and P2 of the fine metal wires 3a in this way, for example, the following methods can be mentioned. That is, in the step of forming the transparent conductive film 3 on the substrate 2, a plurality of coating agent compositions having different concentrations of the fine metal wires 3a are prepared. And these coating agent compositions are apply | coated on the base material 2 in an order from the coating agent composition with a high density | concentration of the metal fine wire 3a. In this case, the coating agent composition that is finally applied onto the substrate 2 is a coating agent composition having the lowest concentration of the fine metal wires 3a among the plurality of coating agent compositions. And the existence ratio P2 of the metal fine wire 3a becomes large gradually toward the surface which opposes the base material 2 from the action surface 3c of the transparent resin layer 3b in the transparent resin layer 3b.
　金属細線３ａは、数ｎｍ以上数十μｍ以下の線幅を有する繊維状金属、金属、又は金属微粒子から成る。金属細線３ａの長さは、金属細線３ａの長さ方向に垂直な断面の直径よりも十分に長い。透明導電膜３内に含まれる複数の金属細線３ａの量は、０．１ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下であることが好ましく、１ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であることがより好ましい。複数の金属細線３ａのそれぞれの長さは、透明導電膜３の透光性を考慮して、３００ｎｍ以下であることが好ましく、複数の金属細線３ａの平均直径は、０．３ｎｍ以上２００ｎｍ以下であることが好ましい。また、同様の理由により、複数の金属細線３ａの平均アスペクト比は、１０以上１００００以下であることが好ましい。さらに、透明導電膜３の導電性を考慮して、透明樹脂層３ｂの厚さは、複数の金属細線３ａの平均直径以上５００ｎｍ以下であることが好ましい。 The fine metal wire 3a is made of a fibrous metal, metal, or metal fine particle having a line width of several nm to several tens of μm. The length of the fine metal wire 3a is sufficiently longer than the diameter of the cross section perpendicular to the length direction of the fine metal wire 3a. The amount of the plurality of fine metal wires 3a contained in the transparent conductive film 3 is preferably 0.1 mg / m 2 or more and 1000 mg / m 2 or less, more preferably 1 mg / m 2 or more and 100 mg / m 2 or less. preferable. The length of each of the plurality of fine metal wires 3a is preferably 300 nm or less in consideration of the translucency of the transparent conductive film 3, and the average diameter of the plurality of fine metal wires 3a is 0.3 nm or more and 200 nm or less. Preferably there is. For the same reason, the average aspect ratio of the plurality of fine metal wires 3a is preferably 10 or more and 10,000 or less. Furthermore, considering the conductivity of the transparent conductive film 3, the thickness of the transparent resin layer 3b is preferably not less than the average diameter of the plurality of fine metal wires 3a and not more than 500 nm.
　金属細線３ａの材料としては、例えば金属メッシュ、金属ナノワイヤ、又は金属微粒子の集合体等が用いられるが、透明導電膜３の透明性及び導電性に優れる金属ナノワイヤを用いることが好ましい。このような金属細線３ａに用いられる金属として、例えば金、銀、銅、アルミニウム、亜鉛、コバルト、ニッケル、又はタングステン等が挙げられる。このような金属の中でも、導電率が高い金、銀、又は銅を用いることが好ましく、導電率が最も高い銀を用いることがより好ましい。 As the material of the metal thin wire 3a, for example, a metal mesh, a metal nanowire, an aggregate of metal fine particles, or the like is used, but it is preferable to use a metal nanowire excellent in transparency and conductivity of the transparent conductive film 3. Examples of the metal used for the thin metal wire 3a include gold, silver, copper, aluminum, zinc, cobalt, nickel, and tungsten. Among such metals, gold, silver, or copper having high conductivity is preferably used, and silver having the highest conductivity is more preferably used.
　金属細線３ａとして金属ナノワイヤを用いた場合、金属ナノワイヤの長さは、透明導電膜８の導電性を考慮して、３μｍ以上であることが好ましく、３μｍ以上５００μｍ以下であることがより好ましく、３μｍ以上３００μｍ以下であることがさらに好ましい。また、金属ナノワイヤの平均直径は、透明導電膜８の透光性及び導電性を考慮して、１０ｎｍ以上３００ｎｍ以下であることが好ましく、３０ｎｍ以上２００ｎｍ以下であることがより好ましい。金属ナノワイヤの製造方法は、特に限定されることなく、例えば液相法又は気相法等の公知の方法が用いられる。 When metal nanowires are used as the thin metal wires 3a, the length of the metal nanowires is preferably 3 μm or more, more preferably 3 μm or more and 500 μm or less in consideration of the conductivity of the transparent conductive film 8. More preferably, it is 300 μm or less. The average diameter of the metal nanowires is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 200 nm or less in consideration of the translucency and conductivity of the transparent conductive film 8. The manufacturing method of metal nanowire is not specifically limited, For example, well-known methods, such as a liquid phase method or a gaseous-phase method, are used.
　透明樹脂層３ｂの材料としては、例えばポリエチレン、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体及びその部分又は全部ケン化物、エチレン－アクリル酸エチル共重合体、エチレン－メタクリル酸メチル共重合体、エチレン－酢酸ビニル－メタクリル酸メチル共重合体、ポリプロピレン、プロピレン－α－オレフィン共重合体等のオレフィン系樹脂、ポリ塩化ビニル樹脂等の塩化ビニル系樹脂、アクリロニトリル－スチレン共重合体等のアクリロニトリル系樹脂、ポリスチレン、スチレン－メタクル酸メチル共重合体等のスチレン系樹脂、ポリアクリル酸エチル等のアクリル酸エステル重合体、ポリメタクリル酸メチル等のメタクリル酸エステル重合体、それらの共重合体や他の共重合成分を加えた（メタ）アクリル酸エステル系樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ナイロン等のポリアミド樹脂、ポリカーボネート樹脂、エチルセルロース、アセチルセルロース等のセルロース樹脂、ポリウレタン系樹脂、シリコン系樹脂等が挙げられる。 Examples of the material for the transparent resin layer 3b include polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and a saponified product thereof partially or entirely, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer. Polymers, ethylene-vinyl acetate-methyl methacrylate copolymers, olefin resins such as polypropylene and propylene-α-olefin copolymers, vinyl chloride resins such as polyvinyl chloride resins, and acrylonitrile such as acrylonitrile-styrene copolymers Resin, polystyrene, styrene resin such as styrene-methyl methacrylate copolymer, acrylate polymer such as polyethyl acrylate, methacrylate polymer such as polymethyl methacrylate, copolymers thereof and others (Meth) acrylic with added copolymer component Ester resin, a polyester resin such as polyethylene terephthalate, polyamide resins such as nylon, polycarbonate resin, ethyl cellulose, cellulose resins such as acetyl cellulose, polyurethane resins, and silicone resins.
　また、例えばフェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、アミノアルキッド樹脂、珪素樹脂、又はポリシロキサン樹脂等の熱硬化性樹脂が挙げられる。さらに、これらの熱硬化性樹脂に必要に応じて架橋剤、重合開始剤、硬化剤、硬化促進剤、又は溶剤を加えてもよい。 Also, for example, thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, or polysiloxane resin can be used. Furthermore, you may add a crosslinking agent, a polymerization initiator, a hardening | curing agent, a hardening accelerator, or a solvent to these thermosetting resins as needed.
　また、電離放射線硬化型樹脂としては、好ましくは、アクリレート系の官能基を有するもの、例えば、比較的低分子量のポリエステル樹脂、ポリエーテル樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリチオールポリエン樹脂、多価アルコール等の多官能化合物の（メタ）アクリレート等のオリゴマー、プレポリマー、及び反応性希釈剤としてエチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、スチレン、メチルスチレン、Ｎ－ビニルピロリドン等の単官能モノマー、並びに多官能モノマー、例えばトリメチロールプロパントリ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等を比較的多量に含有するものを使用することができる。さらに、上記の電離放射線硬化型樹脂を紫外線硬化型樹脂とするには、電離放射線硬化型樹脂の中に光重合開始剤を配合することが好ましい。光重合開始剤としてはアセトフェノン類、ベンゾフェノン類、α－アミロキシムエステル、又はチオキサントン類等が用いられる。また、光重合開始剤に加えて光増感剤を用いてもよい。光増感剤としては、ｎ－ブチルアミン、トリエチルアミン、トリ－ｎ－ブチルホスフィン、又はチオキサントン等が用いられる。 The ionizing radiation curable resin preferably has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal. Resins, polybutadiene resins, polythiol polyene resins, oligomers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, prepolymers, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl Monofunctional monomers such as styrene and N-vinylpyrrolidone, as well as polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate A relatively large amount of diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. What is contained can be used. Furthermore, in order to make the ionizing radiation curable resin an ultraviolet curable resin, it is preferable to mix a photopolymerization initiator in the ionizing radiation curable resin. As the photopolymerization initiator, acetophenones, benzophenones, α-amyloxime esters, thioxanthones or the like are used. In addition to the photopolymerization initiator, a photosensitizer may be used. As the photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone, or the like is used.
　透明導電膜３の塗工法としては、特に限定されることなく、例えばスピンコート、スクリーン印刷、ディップコート、ダイコート、キャスト、スプレーコート、又はグラビアコート等の公知の塗工法が用いられる。また、透明樹脂層３ｂの作用面３ｃを平滑化させると共にこの作用面３ｃにおける表面抵抗値を安定させるために、例えばローラープレス等による加圧工程を行ってもよい。 The coating method of the transparent conductive film 3 is not particularly limited, and a known coating method such as spin coating, screen printing, dip coating, die coating, casting, spray coating, or gravure coating is used. Further, in order to smooth the working surface 3c of the transparent resin layer 3b and stabilize the surface resistance value on the working surface 3c, a pressurizing step using, for example, a roller press may be performed.
　このように本実施形態の透明導電膜付き基材６によれば、透明樹脂層３ｂの作用面３ｃにおける金属細線３ａの存在割合が少なく、突出する金属細線３ａが少なくなっているので、この作用面３ｃを平滑化することができる。また、この作用面３ｃよりも基材２側における金属細線３ａの存在割合が多いので、導電性を向上させることができる。 As described above, according to the substrate 6 with a transparent conductive film of the present embodiment, the existence ratio of the thin metal wires 3a on the working surface 3c of the transparent resin layer 3b is small, and the protruding fine metal wires 3a are small. The surface 3c can be smoothed. In addition, since the presence ratio of the fine metal wires 3a on the side of the base material 2 is larger than that of the working surface 3c, the conductivity can be improved.
　次に、実施例１及び実施例２並びに比較例１乃至３について説明する。 Next, Examples 1 and 2 and Comparative Examples 1 to 3 will be described.
　以下に示すように、まず金属細線として銀ナノワイヤを作製した後、実施例１及び実施例２並びに比較例１乃至３のサンプルを作製した。 As shown below, after first producing silver nanowires as metal thin wires, samples of Example 1 and Example 2 and Comparative Examples 1 to 3 were produced.
　（金属細線）
　金属細線として、公知論文「Materials Chemistry and Physics vol.114 p333-338 “Preparation of Ag nanorods with high yield by polyol process”」に準じて銀ナノワイヤを作製した。この場合、銀ナノワイヤの平均直径を５０ｎｍとし、銀ナノワイヤの平均長さを５μｍとした。 (Metal fine wire)
Silver nanowires were produced as thin metal wires according to a known paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanorods with high yield by polyol process ””. In this case, the average diameter of the silver nanowire was 50 nm, and the average length of the silver nanowire was 5 μm.
　（実施例１）
　シグマアルドリッチ社製メチルセルロース「Ｍ７１４０」３質量部を水２００質量部に溶解して、メチルセルロース溶液を作製した。次に、金属細線として上記の銀ナノワイヤを、水を分散媒として固形分３．０質量％で分散した分散液を作製した。次に、メチルセルロース溶液にこの分散液１００質量部を加えてよく混合した。それにより、第１のコーティング剤組成物を作製した。また、銀ナノワイヤを、水を分散媒として固形分０．６質量％で分散した分散液をメチルセルロース溶液に加えて、上記と同様にして、第２のコーティング剤組成物を作製した。 Example 1
3 parts by mass of methyl cellulose “M7140” manufactured by Sigma-Aldrich was dissolved in 200 parts by mass of water to prepare a methylcellulose solution. Next, a dispersion liquid in which the above-mentioned silver nanowire was dispersed as a metal thin wire and water was used as a dispersion medium at a solid content of 3.0% by mass was prepared. Next, 100 parts by mass of this dispersion was added to the methylcellulose solution and mixed well. Thereby, the 1st coating agent composition was produced. Moreover, the dispersion liquid which disperse | distributed silver nanowire by solid content 0.6 mass% using water as a dispersion medium was added to the methylcellulose solution, and the 2nd coating agent composition was produced like the above.
　続いて、寸法が縦１００ｍｍ、横１００ｍｍ、及び高さ０．７ｍｍであるガラス基材ＢＫ７上に第１のコーティング剤組成物を厚さが１００ｎｍとなるようにスピンコーターにより塗布した。そして、第１のコーティング剤組成物が塗布されたガラス基材を２３℃の常温で３分間乾燥させた後、１２０℃で５分間加熱して乾燥させた。それにより、ガラス基材上に第１の透明導電膜を形成した。次に、第１の透明導電膜上に第２のコーティング剤組成物を厚さが５０ｎｍとなるようにスピンコーターにより塗布して、上記と同様にして、第１の透明導電膜上に第２の透明導電膜を形成した。このようにして、実施例１のサンプルを作製した。 Subsequently, the first coating composition was applied on a glass substrate BK7 having dimensions of 100 mm in length, 100 mm in width, and 0.7 mm in height by a spin coater so as to have a thickness of 100 nm. And after drying the glass base material with which the 1st coating agent composition was apply | coated for 3 minutes at normal temperature of 23 degreeC, it heated at 120 degreeC for 5 minutes, and was dried. Thereby, the 1st transparent conductive film was formed on the glass substrate. Next, the second coating agent composition is applied onto the first transparent conductive film by a spin coater so as to have a thickness of 50 nm, and the second coating composition is applied onto the first transparent conductive film in the same manner as described above. A transparent conductive film was formed. Thus, the sample of Example 1 was produced.
　（実施例２）
　銀ナノワイヤを、水を分散媒として固形分１．８質量％で分散した分散液をメチルセルロース溶液に加えて、上記実施例１と同様にして、第３のコーティング剤組成物を作製した。そして、第２のコーティング剤組成物の代わりに、第３のコーティング剤組成物を用いて、第１の透明導電膜上に第３の透明導電膜を形成して、上記実施例１と同様にして、実施例２のサンプルを作製した。 (Example 2)
A third coating agent composition was prepared in the same manner as in Example 1 above by adding a dispersion liquid in which silver nanowires were dispersed in water with a solid content of 1.8% by mass to a methylcellulose solution. Then, instead of the second coating agent composition, a third transparent conductive film is formed on the first transparent conductive film using the third coating agent composition, and the same as in Example 1 above. Thus, a sample of Example 2 was produced.
　（比較例１）
　第１のコーティング剤組成物のみを厚さが１５０ｎｍとなるように基材上にスピンコーターにより塗布した点を除いて、上記実施例１と同様にして、比較例１のサンプルを作製した。 (Comparative Example 1)
A sample of Comparative Example 1 was produced in the same manner as in Example 1 except that only the first coating agent composition was applied onto a substrate with a spin coater so that the thickness was 150 nm.
　（比較例２）
　銀ナノワイヤを、水を分散媒として固形分２．１質量％で分散した分散液をメチルセルロース溶液に加えて、上記実施例１と同様にして、第４のコーティング剤組成物を作製した。そして、第２のコーティング剤組成物の代わりに、第４のコーティング剤組成物を用いて、第１の透明導電膜上に第４の透明導電膜を形成して、上記実施例１と同様にして、比較例２のサンプルを作製した。 (Comparative Example 2)
A dispersion obtained by dispersing silver nanowires with water as a dispersion medium at a solid content of 2.1% by mass was added to the methylcellulose solution to prepare a fourth coating agent composition in the same manner as in Example 1 above. Then, instead of the second coating agent composition, a fourth transparent conductive film is formed on the first transparent conductive film using the fourth coating agent composition, and the same as in Example 1 above. Thus, a sample of Comparative Example 2 was produced.
　（比較例３）
　銀ナノワイヤを、水を分散媒として固形分０．３質量％で分散した分散液をメチルセルロース溶液に加えて、上記実施例１と同様にして、第５のコーティング剤組成物を作製した。そして、第２のコーティング剤組成物の代わりに、第５のコーティング剤組成物を用いて、第１の透明導電膜上に第５の透明導電膜を形成して、上記実施例１と同様にして、比較例３のサンプルを作製した。 (Comparative Example 3)
A fifth coating agent composition was prepared in the same manner as in Example 1 above by adding a dispersion liquid in which silver nanowires were dispersed in water with a solid content of 0.3% by mass to a methylcellulose solution. Then, instead of the second coating agent composition, a fifth transparent conductive film is formed on the first transparent conductive film using the fifth coating agent composition, and the same as in Example 1 above. Thus, a sample of Comparative Example 3 was produced.
　上記実施例１及び実施例２並びに比較例１乃至３のサンプルについて、表面抵抗値、表面粗さＲａ、及びリーク電流の測定を行った。以下、これらの測定について順に説明する。 The surface resistance value, the surface roughness Ra, and the leakage current were measured for the samples of Examples 1 and 2 and Comparative Examples 1 to 3. Hereinafter, these measurements will be described in order.
　（表面抵抗値の測定）
　三菱化学株式会社製ロレスタＥＰ ＭＣＰ－Ｔ３６０を用いて各サンプルの透明導電膜の表面抵抗値を測定した。 (Measurement of surface resistance)
The surface resistance value of the transparent conductive film of each sample was measured using Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Corporation.
　（表面粗さＲａの測定）
　株式会社島津製作所製ナノサーチ顕微鏡ＳＦＴ－３５００を用いて、測定視野を縦３０μｍ及び横３０μｍとして、各サンプルの透明導電膜の表面粗さＲａを測定した。 (Measurement of surface roughness Ra)
Using a nanosearch microscope SFT-3500 manufactured by Shimadzu Corporation, the surface roughness Ra of the transparent conductive film of each sample was measured with a measurement visual field of 30 μm in length and 30 μm in width.
　（リーク電流の測定）
　作製した各サンプルの透明導電膜上に株式会社同人化学研究所製Ｎ，Ｎ－ジフェニル－Ｎ，Ｎ－ビス３－メチル－フェニル－１，１－ジフェニル－４，４ジアミンを厚さが５０ｎｍとなるように真空蒸着した。これにより、各サンプルの透明導電膜上に正孔輸送層を形成した。次に、この正孔輸送層上に株式会社同人化学研究所製アルミキノリノール錯体（トリス（８－ヒドロキノリン）アルミニウム）を厚さが５０ｎｍとなるように真空蒸着した。これにより、正孔輸送層上に有機発光層を形成した。次に、この有機発光層上にアルミニウムを厚さが１５０ｎｍとなるように真空蒸着することにより、有機発光層上にアルミニウムから成る導体層を形成した。このようにして、各サンプルを備えた有機ＥＬ素子を作製した。続いて、各有機ＥＬ素子に、５Ｖの逆電圧を印加して、各サンプルのリーク電流を測定した。 (Measurement of leakage current)
N, N-diphenyl-N, N-bis3-methyl-phenyl-1,1-diphenyl-4,4 diamine manufactured by Doujin Chemical Laboratory Co., Ltd. is 50 nm thick on the transparent conductive film of each sample produced. Vacuum deposition was performed. This formed the positive hole transport layer on the transparent conductive film of each sample. Next, an aluminum quinolinol complex (tris (8-hydroquinoline) aluminum) manufactured by Doujin Chemical Laboratory Co., Ltd. was vacuum-deposited on the hole transport layer so as to have a thickness of 50 nm. This formed the organic light emitting layer on the positive hole transport layer. Next, aluminum was vacuum-deposited on the organic light emitting layer so as to have a thickness of 150 nm, thereby forming a conductor layer made of aluminum on the organic light emitting layer. Thus, the organic EL element provided with each sample was produced. Subsequently, a reverse voltage of 5 V was applied to each organic EL element, and the leakage current of each sample was measured.
　上記の測定の結果を表１に示す。なお、表１中でリーク電流の測定結果として示された「○」はリーク電流値が１０－７Ａよりも小さかったことを示し、「×」はリーク電流値が１０－５Ａよりも大きかったことを示している。また、Ｐ１／Ｐ２は、ガラス基材と平行に透明導電膜を二等分する断面における銀ナノワイヤの存在割合Ｐ２に対する、透明導電膜のガラス基材と対向する面と反対側の一面における銀ナノワイヤの存在割合Ｐ１の比率を示している。 The results of the above measurements are shown in Table 1. In Table 1, “◯” shown as the measurement result of the leakage current indicates that the leakage current value is smaller than 10 −7 A, and “×” indicates that the leakage current value is larger than 10 −5 A. It shows that. Further, P1 / P2 is a silver nanowire on one surface opposite to the surface facing the glass substrate of the transparent conductive film with respect to the silver nanowire existing ratio P2 in the cross section that bisects the transparent conductive film in parallel with the glass substrate. The ratio of the existence ratio P1 is shown.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、透明導電膜内に均一に銀ナノワイヤが含まれる比較例１及び透明導電膜内にほぼ均一に銀ナノワイヤが含まれる比較例２においては、表面粗さＲａが大きく、リーク電流値が１０－５Ａよりも大きかった。透明導電膜の一面における銀ナノワイヤの量が、透明導電膜の断面における銀ナノワイヤの量に比べて極端に少ない比較例３においては、表面抵抗値が不安定となり、有機ＥＬ素子は電気的に絶縁してしまった。これに対して、実施例１及び実施例２は、表面抵抗値が維持されたまま、表面粗さＲａが減少し、リーク電流値が１０－７Ａよりも小さかった。この結果は、透明導電膜の断面が、ガラス基材と平行に透明導電膜を二等分する断面に相当する場合、銀ナノワイヤの存在割合Ｐ１,Ｐ２が、０．１Ｐ２＜Ｐ１＜０．７Ｐ２の関係を満たすことが好ましいということを示している。 As shown in Table 1, in Comparative Example 1 in which the silver nanowires are uniformly contained in the transparent conductive film and in Comparative Example 2 in which the silver nanowires are substantially uniformly contained in the transparent conductive film, the surface roughness Ra is large and leakage occurs. The current value was larger than 10 −5 A. In Comparative Example 3 in which the amount of silver nanowires on one surface of the transparent conductive film is extremely small compared to the amount of silver nanowires in the cross section of the transparent conductive film, the surface resistance value becomes unstable, and the organic EL element is electrically insulated. have done. On the other hand, in Example 1 and Example 2, the surface roughness Ra decreased while the surface resistance value was maintained, and the leakage current value was smaller than 10 −7 A. As a result, when the cross section of the transparent conductive film corresponds to a cross section that bisects the transparent conductive film in parallel with the glass substrate, the presence ratios P1 and P2 of the silver nanowires are 0.1P2 <P1 <0.7P2. It is shown that it is preferable to satisfy this relationship.
　本発明は上記実施形態の構成に限られず、発明の趣旨を変更しない範囲で種々の変更が
可能である。例えば、透明導電膜３は、液晶ディスプレイ、プラズマディスプレイ、又は太陽有機電池等の透明電極として用いることができる。また、金属細線３ａの材料として、カーボンナノチューブを用いてもよく、透明樹脂層３ｂの材料として、導電性を有する高分子を用いてもよい。 The present invention is not limited to the configuration of the embodiment described above, and various modifications can be made without departing from the spirit of the invention. For example, the transparent conductive film 3 can be used as a transparent electrode such as a liquid crystal display, a plasma display, or a solar organic battery. In addition, carbon nanotubes may be used as the material of the fine metal wires 3a, and conductive polymers may be used as the material of the transparent resin layer 3b.
　なお、本出願は、日本国特許出願２０１１－０４６２５７号に基づいており、その特許出願の内容は、参照によって本出願に組み込まれる。 This application is based on Japanese Patent Application No. 2011-046257, and the contents of the patent application are incorporated into this application by reference.
　１　有機エレクトロルミネッセンス素子
　２　基材
　３　透明導電膜
　３ａ　金属細線（金属ナノワイヤ）
　３ｂ　透明樹脂層
　３ｃ　作用面（透明樹脂層の基材と対向する面と反対側の一面）
　３ｄ　基材と平行に透明樹脂層を二等分する断面
　６　透明導電膜付き基材 DESCRIPTION OF SYMBOLS 1 Organic electroluminescent element 2 Base material 3 Transparent electrically conductive film 3a Metal fine wire (metal nanowire)
3b Transparent resin layer 3c Working surface (one surface opposite to the surface facing the substrate of the transparent resin layer)
3d A cross section that bisects the transparent resin layer in parallel with the base material.

Claims (7)

  1. 　基材上に設けられ、金属細線を含む透明樹脂層を備えた透明導電膜であって、
    　前記透明樹脂層の前記基材と対向する面と反対側の一面における前記金属細線の存在割合Ｐ１と、前記透明樹脂層の前記基材と平行で、前記一面より前記基材側に存在する断面における前記金属細線の存在割合Ｐ２とが、Ｐ１＜Ｐ２の関係となるように構成されていることを特徴とする透明導電膜。     A transparent conductive film provided on a substrate and provided with a transparent resin layer containing a thin metal wire,
    The ratio P1 of the thin metal wires on one surface opposite to the surface facing the substrate of the transparent resin layer, and the cross section existing parallel to the substrate of the transparent resin layer and closer to the substrate than the one surface. The transparent conductive film is characterized in that the abundance ratio P2 of the fine metal wires in P is in a relationship of P1 <P2.
  2. 　前記断面は、前記基材と平行に前記透明樹脂層を二等分する断面であり、
    　前記金属細線の存在割合Ｐ１，Ｐ２が、Ｐ１＜０．７Ｐ２の関係となることを特徴とする請求項１に記載の透明導電膜。     The cross section is a cross section that bisects the transparent resin layer in parallel with the base material,
    2. The transparent conductive film according to claim 1, wherein the existence ratios P <b> 1 and P <b> 2 of the thin metal wires have a relationship of P <b> 1 <0.7 P <b> 2.
  3. 　前記金属細線の存在割合Ｐ１，Ｐ２が、０．１Ｐ２＜Ｐ１の関係となることを特徴とする請求項２に記載の透明導電膜。 3. The transparent conductive film according to claim 2, wherein the existence ratios P1 and P2 of the fine metal wires are in a relationship of 0.1P2 <P1.
  4. 　前記金属細線は、金属ナノワイヤであることを特徴とする請求項１乃至請求項３のいずれか一項に記載の透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the metal thin wire is a metal nanowire.
  5. 　前記金属ナノワイヤは、銀を含むことを特徴とする請求項４に記載の透明導電膜。 The transparent conductive film according to claim 4, wherein the metal nanowire contains silver.
  6. 　基材上に請求項１乃至請求項５のいずれか一項に記載の透明導電膜が形成されたことを特徴とする透明導電膜付き基材。 A substrate with a transparent conductive film, wherein the transparent conductive film according to any one of claims 1 to 5 is formed on the substrate.
  7. 　請求項６に記載の透明導電膜付き基材を用いたことを特徴とする有機エレクトロルミネッセンス素子。 An organic electroluminescence device using the substrate with a transparent conductive film according to claim 6.
PCT/JP2012/052692 2011-03-03 2012-02-07 Transparent conductive film, substrate with transparent conductive film, and organic electroluminescent element using same WO2012117812A1 (en)

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