JP5332252B2 - Transparent conductive film, organic electroluminescence element, and method for producing transparent conductive film - Google Patents

Description

  The present invention relates to a transparent conductive film, an organic electroluminescence element, and a method for producing a transparent conductive film.

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to increasing demand for thin TVs. In any of these displays having different display methods, a transparent electrode using a transparent conductive film is an essential constituent technology.

  In addition to the TV, the transparent conductive film is an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.

Conventionally, as a transparent conductive film, various metal thin films such as Au, Ag, Pt, Cu, indium oxide doped with tin or zinc (ITO, IZO), zinc oxide doped with aluminum or gallium (AZO, GZO), fluorine And metal oxide thin films such as tin oxide (FTO, ATO) doped with antimony, conductive nitride thin films such as TiN, ZrN, and HfN, and conductive boride thin films such as LaB ₆ are also known. Various electrodes such as combined Bi ₂ O ₃ / Au / Bi ₂ O ₃ and TiO ₂ / Ag / TiO ₂ are also known.

  In addition to inorganic substances, transparent conductive films using CNT (carbon nanotubes) or conductive polymers have also been proposed (see, for example, Non-Patent Document 1).

  However, since the above metal thin film, nitride thin film, boron thin film and conductive polymer thin film cannot have both light transmission properties and conductive properties, special technical fields such as electromagnetic shielding and the like are relatively high. It was used only in the touch panel field where resistance values are allowed.

  On the other hand, metal oxide thin films are becoming mainstream of transparent conductive films because they can achieve both light transmission and conductivity and are excellent in durability.

  In particular, ITO is widely used as a transparent electrode for various optoelectronics because it has a good balance between light transmittance and conductivity and it is easy to form an electrode fine pattern by wet etching using an acid solution.

  However, in recent years, with the increase in the area of the transparent electrode for lighting applications and the like, further reduction in resistance has been demanded, and ITO is still insufficient as conductivity.

  Other transparent conductive films include transparent conductive films in which a fine mesh structure is formed by a metal pattern typified by an electromagnetic wave shielding film of a plasma display (see, for example, Patent Documents 1 and 2).

  In particular, in a metal mesh pattern using silver, both good conductivity and transparency can be achieved due to the inherent high conductivity of silver.

  However, although the metal mesh portion has high conductivity, there is a drawback that the portion that transmits light does not have conductivity because of the mesh structure.

  Furthermore, a transparent conductive film having a smooth surface is required for an electrode for an organic electroluminescence element. In particular, in the case of an electrode for an organic electroluminescence element, an ultra-thin film of an organic compound is formed thereon, so that the transparent conductive film is required to have excellent surface smoothness.

  In the organic electroluminescence element, when the surface height difference (surface unevenness) of the anode is large, the electric field concentrates on the protrusion (protrusion) and the EL element is destroyed, or the protrusion is short-circuited with the cathode, Non-light emitting points (points that do not emit light on the surface of the electroluminescence element) may occur.

  When these phenomena occur, the durability of the organic electroluminescent element is remarkably lowered. Therefore, excellent smoothness is required for the transparent conductive film as the anode.

  Moreover, although there exists what is described about the inorganic electroluminescent element using the transparent conductive sheet which apply | coated ITO on the metal fine wire mesh pattern (for example, refer patent document 3), it is still more than an inorganic electroluminescent element. No mention has been made of organic electroluminescence elements that require high smoothness.

In addition, the first conductive layer made of metal having a large number of fine lines combined with a large number of openings, and the first conductive layer is flattened or substantially flattened by being embedded in the openings of the first conductive layer. An electrode substrate for a dye-sensitized solar cell, comprising: a flattened transparent layer; and a second conductive layer made of a metal oxide formed on the first conductive layer and the flattened transparent layer. Although there are some which are described (for example, refer to Patent Document 4), the use is limited to solar cells, and it is insufficient as a use requiring high smoothness such as an organic electroluminescence element.
JP 2003-46293 A JP 2004-221564 A JP 2006-352073 A JP 2005-158727 A "Technology of transparent conductive film", page 80 (Ohm Publishing Co.)

  An object of the present invention is to provide a transparent conductive film excellent in conductivity and transparency and having high smoothness, an organic electroluminescence device having the film, and a method for producing the transparent conductive film.

1 . In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
A conductive layer containing a metal pattern, a conductive polymer or a metal oxide is laminated in this order on the first support in advance, and then the metal pattern and the conductive layer are connected to the second support via an adhesive layer. After bonding, the first support is peeled off. At this time, the surface roughness R of the first support
a is 5 nm or less, The manufacturing method of the transparent conductive film characterized by the above-mentioned.

2 . In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
After providing a metal pattern on the first support in advance, the metal pattern is bonded onto the second support through an adhesive layer, and then the first support is peeled off. A step of laminating a conductive layer containing a conductive polymer or metal oxide on the release surface of the adhesive layer;
Under the present circumstances, surface roughness Ra of a 1st support body is 5 nm or less, The manufacturing method of the transparent conductive film characterized by the above-mentioned.

3 . In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
A conductive layer containing a metal pattern, a conductive polymer or a metal oxide is previously laminated on the first support in this order, and then the metal pattern and the conductive layer are placed on the second support via an adhesive layer. After the first support is peeled off, and further, a conductive layer containing a conductive polymer or a metal oxide is laminated on the peeled surface of the metal pattern, conductive layer and adhesive layer. In this case, the method for producing a transparent conductive film is characterized in that the surface roughness Ra of the first support is 5 nm or less.

  According to the present invention, a transparent conductive film having excellent conductivity and transparency and high smoothness, an organic electroluminescence device having the film, and a method for producing the transparent conductive film can be provided.

  In the transparent conductive film of this invention, the structure prescribed | regulated to Claim 1 was able to provide the transparent conductive film excellent in electroconductivity and transparency, and high smoothness.

  Moreover, the organic electroluminescent element which has this film, and the manufacturing method of a transparent conductive film were able to be provided collectively.

  Hereinafter, details of each component according to the present invention will be described.

《Transparent support》
The transparent support according to the present invention will be described.

  As the transparent support according to the present invention, for example, a plastic film, a plastic plate, glass or the like can be used.

  Here, “transparent” of the transparent support according to the present invention means that the total light transmittance of the support is 50% or more, but the transparent support according to the present invention has a total light transmittance of A film of 80% or more is preferable, and a film of 90% or more is more preferable.

  Said total light transmittance measured the total light transmittance using Tokyo Denshoku AUTOMATICHAZEMETER (MODEL TC-HIIIDP).

  Examples of the raw material for the plastic film and plastic plate used as an example of the transparent support according to the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyethylene (PE), polypropylene (PP), polystyrene, Polyolefins such as EVA, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic Resin, triacetyl cellulose (TAC), or the like can be used.

(Surface roughness of conductive surface )
The surface roughness Ra of the conductive surface according to the present invention will be described.

The surface roughness Ra of the conductive surface according to the present invention, while indicating the smoothness of the conductive surface is an exposed surface of the metal pattern or conductive layer (uneven) in the present invention, an atomic force microscope (AFM) The surface roughness Ra was determined from the measurement by the above.

  Here, regarding the definition of the surface roughness Ra according to the present invention, JIS B 0601- JIS Handbook 41, page 15 (surface roughness definition and display) of Metal Surface Treatment 2001 (Japan Standards Association), page 16 The description of 1994 was used.

《Metallic pattern》
The formation method of the metal pattern which has the opening part which concerns on this invention is not specifically limited, For example, the metal grid pattern formation method of the fine mesh structure represented by the electromagnetic wave shielding film of a plasma display can be used.

  As a method for forming the metal grid pattern, for example, any method such as a photolithography method, a silver salt method, an ink jet method, and a screen printing method used for forming an electromagnetic wave shielding film of a plasma display can be used. As a metal pattern forming method having other openings, a self-organizing network pattern forming method described in JP-T-2005-530005 may be used.

  The metal forming the metal pattern having the opening according to the present invention preferably contains silver from the viewpoint of conductivity. The metal may be silver alone, an alloy of silver and a metal other than silver, or the silver surface may be plated with a metal other than silver. The plating can be performed by a known method such as electrolytic plating or electroless plating.

  In the metal pattern having an opening according to the present invention, the shape of the opening is not particularly limited. For example, a square such as a triangle, square, rectangle, rhombus, parallelogram, trapezoid, (positive) hexagon, (positive) Examples include a mesh-like pattern composed of geometric figures combining octagons and the like.

  Further, the opening may be not a regular shape but a random shape such as a mesh.

  The metal pattern having an opening according to the present invention preferably has a line width of 20 μm or less and a line interval of 50 μm or more. Further, the metal pattern may have a portion whose line width is larger than 20 μm for the purpose of ground connection or the like.

  Further, from the viewpoint of making the metal pattern inconspicuous, the line width of the metal pattern is more preferably less than 15 μm.

  The aperture ratio is preferably 80% or more from the viewpoint of transparency, more preferably 90% or more, and still more preferably 95% or more.

  Here, the aperture ratio according to the present invention is the ratio of the entire portion of the transparent support that does not have a thin line forming a metal pattern. For example, the aperture of a square grid mesh having a line width of 10 μm and a pitch of 200 μm. The rate is 90%.

《Conductive layer》
The conductive layer according to the present invention contains at least a conductive polymer or a metal oxide. Either one or both of the conductive polymer and the metal oxide contained in the conductive layer according to the present invention may be used, and in the case of containing both, the same layer may be used. However, it may be a separate layer.

  Examples of the conductive polymer according to the present invention include polypyrrole, polyindole, polycarbazole, polythiophene (including basic polythiophene, the same shall apply hereinafter), polyaniline, polyacetylene, polyfuran, polyparaphenylene vinylene, polyazulene, Chain conductive polymers such as polyparaphenylene, polyparaphenylene sulfide, polyisothianaphthene, and polythiazyl, and polyacene conductive polymers can also be used. Of these, polyethylene dioxythiophene (PEDOT) and polyaniline are preferable from the viewpoints of conductivity and transparency.

Moreover, in this invention, in order to raise the electroconductivity of the said conductive polymer more, it is preferable to perform a doping process. As a dopant for the conductive polymer, for example, a sulfonic acid having a hydrocarbon group having 6 to 30 carbon atoms (hereinafter also referred to as “long-chain sulfonic acid”) or a polymer thereof (for example, polystyrene sulfonic acid), halogen Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, alkaline earth metal, MClO ₄ (M = Li ⁺ , Na ⁺ ), R ₄ N ⁺ (R = CH ₃ , C ₄ H ₉ , C ₅₆ ), or R ₄ P ⁺ (R═CH ₃ , C ₄ H ₉ , C ₅₆ ). Of these, the long-chain sulfonic acid is preferable.

Examples of the long chain sulfonic acid include dinonyl naphthalene disulfonic acid, dinonyl naphthalene sulfonic acid, and dodecylbenzene sulfonic acid. Examples of the halogen include Cl ₂ , Br ₂ , I ₂ , ICl ₃ , IBr, IF _{5 and the} like.

Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO ₃ , and GaCl ₃ .

Examples of the protonic acid include HF, HCl, HNO ₃ , H ₂ SO ₄ , HBF ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, and the like.

The transition metal _{halide, NbF 5, TaF 5, MoF} 5, WF 5, RuF 5, BiF 5, TiCl 4, ZrCl 4, MoCl 5, MoCl 3, WCl 5, FeCl 3, TeCl 4, SnCl 4, SeCl ₄ , FeBr ₃ , SnI _{5 and the} like.

The transition metal _{compound, AgClO 4, AgBF 4, La} (NO 3) 3, Sm (NO 3) 3 and the like.

  Examples of the alkali metal include Li, Na, K, Rb, and Cs. Examples of the alkaline earth metal include Be, Mg, Ca, Sc, and Ba.

  The dopant for the conductive polymer may be introduced into fullerenes such as hydrogenated fullerene, hydroxylated fullerene, and sulfonated fullerene.

  The dopant is preferably contained in an amount of 0.001 part by mass or more, more preferably 0.5 part by mass or more, relative to 100 parts by mass of the conductive polymer.

In addition, the transparent conductive composition of the present embodiment is a long-chain sulfonic acid, a polymer of long-chain sulfonic acid (for example, polystyrene sulfonic acid), halogen, Lewis acid, proton acid, transition metal halide, transition metal compound, Both at least one dopant selected from the group consisting of alkali metals, alkaline earth metals, MClO ₄ , R ₄ N ⁺ , and R ₄ P ⁺ and fullerenes may be included.

  The conductive layer of the present invention has 2nd. A water-soluble organic compound may be contained as a dopant. There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably.

  The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable.

  Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide.

  These may be used alone or in combination of two or more, but it is particularly preferable to use at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol.

  In the conductive layer according to the present invention, the 2nd. The content of the dopant is preferably 0.001% by mass or more, more preferably in the range of 0.01% by mass to 50% by mass, and particularly preferably in the range of 0.01% by mass to 10% by mass. .

  The metal oxide according to the present invention is not particularly limited, but preferably contains a metal oxide selected from indium, zinc, and tin. Specifically, ITO in which indium oxide is doped with tin or zinc oxide. It is preferable to contain AZO or GZO doped with aluminum or gallium, and metal oxide selected from ATO or FTO doped with antimony or fluorine in tin oxide.

  The average particle size of the metal oxide is preferably 1 nm to 100 nm, and particularly preferably 3 nm to 50 nm.

  The method for forming a conductive layer according to the present invention is preferably a liquid phase film forming method in which a dispersion containing a conductive polymer or a metal oxide is applied and dried to form a film. Among these, a roll coating method, a bar coating method, Application methods such as dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, letterpress (letterpress) printing method, It is preferable to use a printing method such as a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, or an ink jet printing method.

  The dispersion containing the conductive polymer or metal oxide according to the present invention may contain a transparent binder material or additive.

  The transparent binder material can be selected from a wide range of natural polymer resins or synthetic polymer resins.

  For example, transparent thermoplastic resin (eg, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride), heat, light, electron beam A transparent curable resin that is cured by radiation (for example, melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, silicone resin such as acrylic-modified silicate) can be used.

  Examples of the additive include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments.

  Furthermore, from the viewpoint of improving workability such as coating properties, solvents (for example, water, organic solvents such as alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.

  Moreover, in the manufacturing method of the electroconductive film of this invention mentioned later, since it finally forms in a conductive layer, a metal pattern, etc. on a 2nd support body, the transparent support body which concerns on the electroconductive film of this invention These are synonymous with the 2nd support body which concerns on the manufacturing method of the electroconductive film of this invention.

《Transparent conductive film》
The transparent conductive film of the present invention will be described.

  The total light transmittance of the transparent conductive film of the present invention is 60% or more, preferably 70% or more, and particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.

The electrical resistance value in the transparent conductive film of the present invention is preferably 10 ³ Ω / □ or less, more preferably 10 ² Ω / □ or less, and more preferably 10 Ω / □ or less as surface resistivity as surface resistivity. It is particularly preferred that The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

  An anchor coat, a hard coat, etc. can also be provided to the transparent conductive film of the present invention. If necessary, a conductive layer containing a conductive polymer or a metal oxide may be further provided.

  The transparent conductive film of the present invention can be used for transparent electrodes such as LCDs, electroluminescence elements, plasma displays, electrochromic displays, solar cells, touch panels, electronic papers, electromagnetic wave shielding materials, etc. In addition, since it is excellent in smoothness, it can be suitably used for an organic EL device.

<< Method for producing transparent conductive film >>
The manufacturing method of the transparent conductive film of this invention is demonstrated.

<First support, second support>
The 1st support body and 2nd support body which concern on the manufacturing method of the electroconductive film of this invention are demonstrated.

As a manufacturing method of the transparent conductive film of this invention, there are three types of manufacturing methods as described in said 3, 4, and 5. Here, from the above 3, 4 or 5, in the method for producing a transparent conductive film of the present invention,
(A) After a metal pattern and a conductive layer are sequentially laminated on the first support in advance, the metal pattern and the conductive layer are adhered to the second support via the adhesive layer, and then the first support is peeled off. Process,
(B) a step in which a metal pattern is provided on the first support in advance and then the first support is peeled off after the metal pattern is bonded onto the second support via an adhesive layer;
(C) A conductive layer containing a metal pattern, a conductive polymer or a metal oxide is previously laminated on the first support in this order, and then the metal pattern and the conductive layer are connected to the second support through an adhesive layer. A step of peeling off the first support after bonding on the support;
As shown in FIG. 1, the conductive material containing a metal pattern, a conductive polymer or a metal oxide to be peeled off in a later step is formed on the first support according to the method for producing a transparent conductive film of the present invention. In order to make the release surfaces of the layer and the adhesive layer smooth, it is preferable to use one having excellent surface smoothness.

  Here, as a 1st support body which concerns on the manufacturing method of the transparent conductive film of this invention, what has smoothness (unevenness | corrugation) whose surface roughness Ra is 5 nm or less is preferable. The surface roughness Ra is the same as the definition described in the surface roughness Ra of the transparent support.

  As a means for setting the surface roughness Ra of the first support according to the present invention to 5 nm or less, an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or a radiation curable resin is provided. It may be applied and smoothed, or may be smoothed by machining such as polishing.

  Moreover, since the 1st support body which concerns on the manufacturing method of the electroconductive film of this invention will peel in a manufacturing process, either a transparent support body and a non-transparent (opaque) support body can be used. .

  In the manufacturing process, a release layer may be formed in order to facilitate the peeling of the first support, and as a material for forming the release layer, a polymer or wax that forms a known release layer is appropriately selected. Can be used.

  For example, paraffin wax, acrylic, urethane, silicone, melamine, urea, urea-melamine, cellulose, benzoguanamine, and other organic solvents and surfactants alone or mixtures thereof Alternatively, a paint dissolved in water is applied onto the base film by a normal printing method such as gravure printing, screen printing, or offset printing, and dried (thermosetting resin, ultraviolet curable resin, electron beam curable resin). And curable coatings such as radiation curable resins are cured).

  There is no restriction | limiting in particular as thickness of a mold release layer, It employ | adoptes suitably from the range of about 0.1 micrometer-3 micrometers.

  Moreover, as shown by said (a), (b) or (c), on the 2nd support body which concerns on the manufacturing method of the transparent conductive film of this invention, an electroconductive layer is interposed through an adhesive layer. A metal pattern or the like is formed.

  From the above, the 2nd support body which concerns on the manufacturing method of the electroconductive film of this invention comprises the transparent support body of the electroconductive film of this invention.

  The second support according to the method for producing a transparent conductive film of the present invention is preferably provided with a gas barrier layer for the purpose of blocking oxygen and moisture in the atmosphere. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used.

  These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having favorable barrier properties, solvent resistance, and transparency are preferable. In addition, the barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material.

  The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, and more preferably 10 nm to 200 nm per layer.

  The gas barrier layer is provided on at least one surface of the second support and is preferably provided on the adhesive layer side, more preferably on both surfaces of the second support.

<Adhesive layer>
The adhesive layer according to the method for producing a conductive film of the present invention will be described.

  The adhesive constituting the adhesive layer according to the method for producing a transparent conductive film of the present invention is not particularly limited as long as it is transparent in the visible region (that is, has sufficient transmittance). As long as it is transparent, a curable resin or a thermoplastic resin may be used.

  Here, the adhesive layer being transparent in the visible region is defined in the same manner as “transparent” of the transparent support according to the present invention.

  Examples of the curable resins include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these curable resins, the equipment for resin curing is simple and excellent in workability. Therefore, an ultraviolet curable resin is preferable.

  The adhesive layer is preferably composed of an acrylic polymer from the viewpoint of transparency. The adhesive layer according to the present invention may be provided on the metal pattern and the conductive layer formed on the first support, or may be provided on the second support, and the metal pattern is bonded to the adhesive layer side. Then, after being buried, the curing process is performed.

  The bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine. The roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated. A roll press applies pressure uniformly and is more suitable for productivity than a sheet press.

  The first support is peeled off after bonding. For example, a metal pattern formed by the silver salt method contains gelatin as a binder, and therefore, for the purpose of facilitating peeling, for example, a liquid containing a proteolytic enzyme. Or may be immersed in a strong alkaline solution.

<< Organic electroluminescence element (hereinafter also referred to as organic EL element) >>
The organic electroluminescence element (organic EL element) of the present invention will be described.

  The organic EL element of the present invention has the transparent conductive film of the present invention. The organic EL device of the present invention uses the transparent conductive film of the present invention as an anode, and a light emitting layer (also referred to as an organic light emitting layer) and a cathode are made of materials and structures generally used in organic EL devices. Any thing can be used.

As an element configuration of the organic EL element,
(I) Anode / light emitting layer / cathode,
(II) Anode / hole transport layer / light emitting layer / electron transport layer / cathode,
(III) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode,
(IV) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode,
(V) Anode / hole injection layer / light emitting layer / electron injection layer / cathode,
The thing of various structures, such as these, can be mentioned.

  Examples of the light emitting material or doping material that can be used for the light emitting layer of the organic EL device of the present invention include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, and 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, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacrid Emissions, rubrene, distyrylbenzene derivatives, di still arylene derivatives, and various fluorescent dyes and rare earth metal complex, there is a phosphorescent material, and the like.

  It is also preferable to contain 90% to 99.5% by mass of a light emitting material selected from these compounds and 0.5% to 10% by mass of a doping material.

  The light emitting layer can be produced by a known method using the above materials, and examples thereof include vapor deposition, coating, and transfer. The thickness of the light emitting layer is preferably 0.5 nm to 500 nm, and particularly preferably 0.5 nm to 200 nm.

  The organic EL device of the present invention can be used for a self-luminous display, a liquid crystal backlight, illumination, and the like. Moreover, since the organic EL element of this invention can be made to light-emit uniformly, it is preferable to use for an illumination use.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

  Moreover, the structure of the compound used for an Example is shown below.

  In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1
<< Preparation of Transparent Conductive Film TCF-1; Comparative Example 1 >>
On a polyethylene terephthalate film support having a thickness of 100 μm, ITO (indium tin oxide) was vapor-deposited with a film thickness of 150 nm to produce a transparent conductive film TCF-1.

<< Preparation of Transparent Conductive Film TCF-2; Comparative Example 2 >>
A transparent conductive film TCF-2 was produced by the silver salt method shown below.

(Preparation of silver halide emulsion)
The following solution A was kept at 34 ° C. in a reaction vessel, and the pH was adjusted to 2.95 using nitric acid (concentration 6%) while stirring at high speed using a mixing and stirring device described in JP-A-62-2160128. It was adjusted. Subsequently, the following solution B and the following solution C were added at a constant flow rate over 8 minutes and 6 seconds using the double jet method. After completion of the addition, the pH was adjusted to 5.90 using sodium carbonate (concentration 5%), and then the following solution D and solution E were added.

(Solution A)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
Solution I (below) 1.59ml
Pure water 1246ml
(Solution B)
169.9g of silver nitrate
Nitric acid (concentration 6%) 5.89ml
Finish to 317.1 ml with pure water (Solution C)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
Solution I (below) 0.85ml
Solution II (below) 2.72 ml
Finish to 317.1 ml with pure water (Solution D)
2-Methyl-4hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
(Solution E)
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
Solution I (below) 0.40ml
128.5 ml of pure water
(Solution I)
Surfactant: 10% by weight methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution II)
10 mass% aqueous solution of rhodium hexachloride complex.

  After completion of the above operation, desalting and washing with water using a flocculation method are performed at 40 ° C. according to a conventional method, and the solution F and an anti-bacterial agent are added and dispersed well at 60 ° C. To 90.90 to obtain a silver chlorobromide cubic grain emulsion finally containing 10 mol% of silver bromide and having an average grain size of 0.09 μm and a coefficient of variation of 10%.

(Solution F)
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
The silver chlorobromide cubic grain emulsion was subjected to chemical sensitization at 40 ° C. for 80 minutes using 20 mg of sodium thiosulfate per mole of silver halide, and after completion of chemical sensitization, 4-hydroxy-6-methyl- 1,3,3a, 7-tetrazaindene (TAI) was added in an amount of 500 mg per mole of silver halide and 1-phenyl-5-mercaptotetrazole was added in an amount of 150 mg per mole of silver halide to obtain a silver halide emulsion. . This silver halide emulsion had a volume ratio of silver halide grains to gelatin (silver halide grains / gelatin) of 0.625.

  Further, a hardening agent (H-1: tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 200 mg per 1 g of gelatin, and a surfactant (SU-2: sulfosuccinate disulfate) was applied as a coating aid. (2-ethylhexyl) .sodium) was added to adjust the surface tension.

The coating solution thus obtained was applied onto a 100 μm thick polyethylene terephthalate film support with an undercoat layer so that the amount of silver applied was 0.625 g / m ^2, and then cured at 50 ° C. for 24 hours. Processing was carried out to obtain a photosensitive material.

〔exposure〕
The obtained photosensitive material was exposed with a UV exposure device through a mesh photomask (pitch / line width = 300 μm / 5 μm).

[Chemical development]
The exposed photosensitive material is developed for 60 seconds at 25 ° C. using the following developer (DEV-1), and then fixed for 120 seconds at 25 ° C. using the following fixing solution (FIX-1). It was.

(DEV-1)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1 liter (FIX-1)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to bring the total volume to 1 liter [Physical development]
Next, physical development was performed at 30 ° C. for 10 minutes using the following physical developer (PDEV-1), followed by washing with water and drying.

(PDEV-1)
900ml pure water
Citric acid 10g
Trisodium citrate 1g
Ammonia water (28%) 1.5g
Hydroquinone 2.3g
Silver nitrate 0.23g
Add water to bring the total volume to 1000 ml.

[Washing and drying]
The washing process was performed with tap water for 10 minutes. Moreover, the drying process was dried until it became a dry state using drying air (50 degreeC).

(Electrolytic copper plating)
Then, the electrolytic copper plating process was performed at 25 degreeC using the following electrolytic copper plating solution. Current control in electrolytic copper plating was performed at 3A for 1 minute, then at 1A for 9 minutes, for a total of 10 minutes, to obtain a metal mesh transparent conductive film TCF-2.

(Electrolytic copper plating solution)
Copper sulfate (pentahydrate) 200g
50g of sulfuric acid
Sodium chloride 0.1g
Add water to bring the total volume to 1000 ml.

<< Preparation of Transparent Conductive Film TCF-3; Comparative Example 3 >>
On the obtained transparent conductive film TCF-2, an ITO dispersion (product name: EI) manufactured by Gemco Co., Ltd. was applied so that the dry film thickness was 150 nm, thereby producing a transparent conductive film TCF-3. did.

<< Preparation of Transparent Conductive Film TCF-4; Comparative Example 4 >>
First, a flattening transparent layer forming coating solution (viscosity: 480 mPa · s) in which an acrylic resin (Tg: 100 ° C., weight average molecular weight: 240,000) was diluted to 40% with methyl ethyl ketone was prepared.

  Next, 10 g of a flattened transparent layer-forming coating solution is placed on a part of the metal surface of the transparent conductive film TCF-2, and a squeegee (trade name: Mino Fine Squeegee, hardness: 60) manufactured by Mino Shoji Co., Ltd. is used. The flattening transparent layer forming coating solution was applied to the entire surface of the transparent substrate while scraping off the excess coating solution.

  Then, this transparent base material was heated, and the planarizing transparent layer was formed by drying the apply | coated coating liquid for planarization transparent layer formation. After forming the flattened transparent layer, the ITO dispersion liquid was applied so that the dry film thickness was 150 nm to produce a transparent conductive film TCF-4.

<< Preparation of Transparent Conductive Film TCF-5; Present Invention >>
(Preparation of adhesive layer)
On one side of a polyethylene terephthalate film support having a thickness of 100 μm, an ultraviolet curable resin (UVPOT medium 0, manufactured by Teikoku Ink Co., Ltd.) was applied as an adhesive layer to a thickness of 30 μm to prepare an adhesive layer.

  ITO is applied on the metal pattern side of the transparent conductive film TCF-2 so that the film thickness is 150 nm, and the adhesive layer of the produced adhesive film and the metal pattern of the transparent conductive film TCF-2 and the ITO side face each other. Crimped so that

  Next, ultraviolet rays were irradiated from the adhesive layer side to cure the ultraviolet curable resin, and the adhesive layer and the transparent conductive film TCF-2 were joined.

  The bonded adhesive film and transparent conductive film TCF-2 were immersed in the following enzyme solution at 40 ° C. for 5 minutes, washed with water and dried. The pH of the enzyme solution was 7.0.

(Enzyme solution)
900ml water
7.4 g of 85% orthophosphoric acid
20g triethanolamine
Proteolytic enzyme * 2g
Add water to bring the total volume to 1000 ml.

(*): Bacterial proteinase: Biolase AL15, manufactured by Nagase & Co., Ltd.
After performing the enzyme solution treatment, the polyethylene terephthalate film support on the transparent conductive film TCF-2 side was peeled off to produce a transparent conductive film TCF-5.

<< Preparation of Transparent Conductive Film TCF-6; Present Invention >>
In the transparent conductive film TCF-5, instead of applying the ITO dispersion liquid to a dry film thickness of 150 nm, Baytron PH510 (H, which is a dispersion liquid of PEDOT: PSS (polystyrene sulfonic acid) = 1: 2.5 A transparent conductive film TCF-6 was prepared in the same manner as TCF-5 except that a solution obtained by adding 5% dimethyl sulfoxide to C. Stark) was applied so that the dry film thickness was 150 nm.

<< Preparation of Transparent Conductive Film TCF-7; Present Invention >>
In the transparent conductive film TCF-6, after applying PEDOT: PSS dispersion liquid, joining the adhesive film and the transparent conductive film and performing enzyme treatment, the polyethylene terephthalate film support on the transparent conductive film side is A transparent conductive film TCF-7 was produced in the same manner as TCF-6 except that it was performed after peeling.

<< Preparation of Transparent Conductive Film TCF-8; Present Invention >>
In the transparent conductive film TCF-5, after peeling the polyethylene terephthalate film support on the transparent conductive film side, the PEDOT: PSS dispersion is further applied so as to have a dry film thickness of 100 nm. Thus, a transparent conductive film TCF-8 was produced.

<< Preparation of Transparent Conductive Film TCF-9; Present Invention >>
Transparent conductive film TCF-9 was produced by the printing method shown below.

  On a releasable polyethylene terephthalate film support subjected to corona discharge treatment, a palladium colloid-containing paste was printed using a screen mask having a mesh pattern of L / S = 5/300 (μm), and this was printed. It was immersed in an electroless copper plating solution and subjected to electroless copper plating by a known method, followed by electrolytic copper plating to form a metal pattern. Further, PEDOT: PSS was applied onto the formed metal pattern so that the dry film thickness was 150 nm, and the adhesive layer with the adhesive film produced in the same manner as TCF-5, the metal pattern, and the PEDOT: PSS side faced each other. Crimped as follows. Next, the ultraviolet curable resin is cured by irradiating ultraviolet rays from the adhesive film side, and after bonding the adhesive film and the transparent conductive film, the polyethylene terephthalate film support on the transparent conductive film side is peeled off to obtain a transparent conductive film. Film TCF-8 was produced.

<< Preparation of Transparent Conductive Film TCF-10; Present Invention >>
PEDOT: PSS dispersion is applied in the same manner as TCF-9 except that the adhesive film and the transparent conductive film are joined and the polyethylene terephthalate film support on the transparent conductive film side is peeled off. Film TCF-10 was produced.

<< Preparation of Transparent Conductive Film TCF-11; Present Invention >>
A transparent conductive film TCF-11 was produced in the same manner as TCF-10 except that the metal pattern was formed as follows.

<Metal pattern formation method>
The following metal colloid solution for spontaneous pattern formation was applied with a wet film thickness of 40 μm on a releasable polyethylene terephthalate film support subjected to corona discharge treatment, and then dried at 50 ° C. This was immersed in a formic acid aqueous solution and dried, and then subjected to electrolytic copper plating to form a random mesh-like metal pattern having an average line width of 5 μm, an average interval of 200 μm, and an average height of 3 μm.

(Metal colloid solution) Mass%
BYK-410 (manufactured by BYK Chemie) 0.11
SPAN-80 (manufactured by Tokyo Chemical Industry) 0.11
Dichloroethane 75.63
Cyclohexanone 0.42
Silver powder (average particle size 70 nm) 3.59
BYK-348 (0.02% aqueous solution; manufactured by BYK Chemie) 19.98
ZonylFSH (DuPont) 0.08
Butver B-76 (Solutia) 0.08
<Measurement and evaluation>
The transmittance, surface specific resistance measurement, and surface roughness of the obtained transparent conductive films TCF-1 to 11 were evaluated as follows.

(Surface resistivity)
The surface specific resistance was measured by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.

(Transmittance)
The transmittance was determined by measuring the total light transmittance using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

(Surface roughness)
The surface roughness was determined by arithmetic mean roughness Ra by measuring the conductive surface with an atomic force microscope (AFM).

  The results of measurement and evaluation are shown in Table 1.

Example 2
<< Production of Organic EL Elements OLED-1 to OLED-11 >>
The transparent conductive films TCF-1 to 11 produced in Example 1 were cut into 100 mm × 100 mm squares, and used as the first electrode, and organic EL elements OLED-1 to OLED-11 were produced according to the following procedure.

(Formation of hole transport layer)
On the first electrode, 1.2. Coating for forming a hole transport layer in which 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD) as a hole transport material is dissolved in dichloroethane so as to be 1% by mass. The solution was applied by a spin coater and then dried at 80 ° C. for 60 minutes to form a 40 nm thick hole transport layer.

(Formation of light emitting layer)
On each film on which the hole transport layer is formed, the red dopant material Btp ₂ Ir (acac) is 1 mass% and the green dopant material Ir (ppy) ₃ is 2 mass with respect to the polyvinylcarbazole (PVK) as the host material. % And the blue dopant material FIr (pic) are mixed so as to be 3% by mass, respectively, so that the total solid concentration of PVK and the three dopants is 1% by mass. A coating solution for forming a light emitting layer dissolved in dichloroethane was applied by a spin coater and then dried at 100 ° C. for 10 minutes to form a light emitting layer having a thickness of 60 nm.

(Formation of electron transport layer)
On the formed light emitting layer, LiF was deposited as an electron transport layer forming material under a vacuum of 5 × 10 ⁻⁴ Pa to form an electron transport layer having a thickness of 0.5 nm.

(Formation of second electrode)
On the formed electron transport layer, Al was evaporated as a second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa to form a second electrode having a thickness of 100 nm.

(Formation of sealing film)
On the formed electron transport layer, a polyethylene terephthalate as a substrate, using a flexible sealing member which is deposited to a thickness 300nm of Al ₂ O _3. Applying an adhesive around the second electrode except for the ends so that external lead terminals for the first electrode and the second electrode can be formed, bonding a flexible sealing member, and then curing the adhesive by heat treatment It was.

《Light emission brightness unevenness》
The obtained organic EL elements OLED-1 to OLED-11 were evaluated for light emission luminance unevenness.

  Using a source measure unit 2400 type manufactured by KEITHLEY, a direct current voltage was applied to the organic EL elements OLED-1 to OLED-11 produced to emit light.

  About each organic EL element made to light-emit by 200cd, the light emission nonuniformity of the whole light emission surface at the time of lighting was evaluated by the following reference | standard by visual observation.

◎: 90% or more emits uniformly ○: 80% or more emits uniformly △: 70% or more emits uniformly ×: Less than 70% emits XX: no Table 2 shows the evaluation results.

  From Table 2, it is clear that the organic EL element having the transparent conductive film of the present invention having excellent conductivity and transparency and high smoothness as an electrode, as compared with the comparison, has significantly less uneven luminance. .

Claims (3)

In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
A conductive layer containing a metal pattern, a conductive polymer or a metal oxide is laminated in this order on the first support in advance, and then the metal pattern and the conductive layer are connected to the second support via an adhesive layer. After bonding, the first support is peeled off. At this time, the surface roughness R of the first support
a is 5 nm or less, The manufacturing method of the transparent conductive film characterized by the above-mentioned. In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
After providing a metal pattern on the first support in advance, the metal pattern is bonded onto the second support through an adhesive layer, and then the first support is peeled off. A step of laminating a conductive layer containing a conductive polymer or metal oxide on the release surface of the adhesive layer;
Under the present circumstances, surface roughness Ra of a 1st support body is 5 nm or less, The manufacturing method of the transparent conductive film characterized by the above-mentioned. In a method for producing a transparent conductive film having a metal pattern having an opening on a transparent support and a conductive layer containing a conductive polymer or metal oxide,
A conductive layer containing a metal pattern, a conductive polymer or a metal oxide is previously laminated on the first support in this order, and then the metal pattern and the conductive layer are placed on the second support via an adhesive layer. After the first support is peeled off, and further, a conductive layer containing a conductive polymer or a metal oxide is laminated on the peeled surface of the metal pattern, conductive layer and adhesive layer. In this case, the method for producing a transparent conductive film is characterized in that the surface roughness Ra of the first support is 5 nm or less.