JPWO2017056814A1 - Transparent organic electroluminescence device and method for producing the same - Google Patents

Abstract

The subject of this invention is providing the transparent organic electroluminescent element which has a low resistance and highly transparent electrode, and its manufacturing method.
The transparent organic electroluminescent element of the present invention is a transparent organic electroluminescent element having a total light transmittance of 45% or more in the visible light region of the organic electroluminescent element when not emitting light, the anode being a thin metal wire and a metal oxide And a cathode is selected from a combination of a metal wire and a metal oxide layer, or a combination of a metal wire and a metal thin film layer. To do.

Description

  The present invention relates to a transparent organic electroluminescence device and a method for producing the same. More specifically, the present invention relates to a transparent organic electroluminescence device having a low resistance and highly transparent electrode and a method for producing the same.

  At present, a light-emitting element using electroluminescence (EL) of an organic material has attracted attention as a thin light-emitting device.

  A so-called organic electroluminescence element (hereinafter also referred to as an organic EL element) is a thin-film type complete solid-state element that can emit light at a low voltage of about several V to several tens V, and has high luminance, high luminous efficiency, thin thickness, It has many excellent features such as light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.

  Such an organic EL element has a configuration in which a light emitting layer made of an organic material is disposed between two opposing electrodes, and emitted light generated in the light emitting layer passes through the electrode and is extracted to the outside. For this reason, at least one of the two electrodes is configured as a transparent electrode, and emitted light is extracted from the transparent electrode side.

  On the other hand, the demand for a substantially transparent organic EL element capable of emitting light on both sides is increasing due to tiling and high design.

  As an organic EL element capable of emitting light on both sides, in Patent Document 1, in addition to a conventional transparent anode (also referred to as an anode) using ITO (indium tin oxide) or the like, a cathode (also referred to as a cathode) is used as a silver thin film. It has been reported that an organic EL element that can improve transparency by taking out and emit light from both sides has been reported. According to this technology, it is possible to improve a conventional organic EL element whose light transmittance in the visible light region is less than 40% to a light transmittance of 50% or more. However, there is a high demand for transparent organic EL elements.

  On the other hand, it is known to use a fine metal wire to improve the transparency of a transparent electrode, and a technique of forming a fine metal wire containing fine metal particles on a cathode and using it in an organic EL element is disclosed (for example, patents). Reference 2).

  However, when combined with the conventional transparent anode, the light transmittance required by the market is still insufficient, and the conductivity when combined with the transparent electrode is limited to 5Ω / □, Furthermore, a low resistance electrode configuration is desired.

JP2013-04245A JP 2010-198935 A

  The present invention has been made in view of the above problems and circumstances, and a solution to the problem is to provide a transparent organic electroluminescent device having a low resistance and a highly transparent electrode and having uniform light emission and a method for manufacturing the same. It is to be.

  In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the total light transmittance in the visible light region when not emitting light is 45% or more, and the anode and the cathode are each a thin metal wire It has been found that the above-mentioned problems can be achieved by a transparent organic electroluminescence element characterized by having a specific configuration including:

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A transparent organic electroluminescence device having a total light transmittance of 45% or more in the visible light region of the organic electroluminescence device when not emitting light, wherein the anode is a metal fine wire and a metal oxide layer, a metal fine wire and a metal thin film layer, or A transparent organic electroluminescence device, wherein the transparent organic electroluminescent device is selected from a combination of a metal fine wire and a conductive polymer layer, and a cathode is selected from a combination of a metal fine wire and a metal oxide layer, or a combination of a metal fine wire and a metal thin film layer.

  2. 2. The transparent organic electroluminescence device according to item 1, wherein the anode has at least a fine metal wire and a metal oxide layer.

  3. The transparent organic electroluminescence device according to item 1 or 2, wherein the cathode has at least a thin metal wire and a metal thin film layer.

  4). The transparent organic electroluminescence device according to any one of items 1 to 3, wherein the metal thin film layer of the cathode is a silver thin film layer.

  5. It is a manufacturing method of the transparent organic electroluminescent element which manufactures the transparent organic electroluminescent element as described in any one of Claim 1 to 4, Comprising: The metal thin wire of the said cathode is printed under inert gas A method for producing a transparent organic electroluminescent element, characterized by comprising:

  6). 6. The method for producing a transparent organic electroluminescent element according to claim 5, wherein the metal thin wire of the cathode is fired by flash firing.

  7). Item 5 or Item 6 wherein the metal fine wire of the cathode is formed on a base material constituting a sealing layer and then adhered to the metal oxide layer, metal thin film layer or conductive polymer layer. The manufacturing method of the transparent organic electroluminescent element of description.

  By the above means of the present invention, it is possible to provide a transparent organic electroluminescent device having a low resistance and highly transparent electrode and having uniform light emitting properties and a method for producing the same.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  In the organic electroluminescence device of the present invention, the anode is a conductive layer selected from a metal fine wire and a metal oxide layer, a metal fine wire and a metal thin film layer, or a metal fine wire and a conductive polymer layer, and the cathode is a metal fine wire. By using an electrode which is a metal oxide layer or a conductive layer selected from a metal thin wire and a metal thin film layer, the resistance can be reduced by the metal thin wire and each of the conductive layers, and the opening of the metal thin wire Therefore, it is presumed that an electrode having high transparency can be formed by improving the light transmittance. Therefore, an organic electroluminescence device having high transparency can be obtained by providing the highly transparent electrode as an anode and a cathode.

Sectional drawing of the transparent electrode which comprises the anode and cathode which concern on this invention Sectional drawing which shows schematic structure of the transparent organic EL element of this invention Sectional drawing which shows the layer structure of the transparent organic EL element of this invention

  The transparent organic electroluminescent element of the present invention is a transparent organic electroluminescent element having a total light transmittance of 45% or more in the visible light region of the organic electroluminescent element when not emitting light, the anode being a thin metal wire and a metal oxide And a cathode is selected from a combination of a metal wire and a metal oxide layer, or a combination of a metal wire and a metal thin film layer. To do. This feature is a technical feature common to the claimed invention.

  As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the anode preferably has at least a metal fine wire and a metal oxide layer, and the cathode has at least a metal fine wire and a metal thin film layer. Is preferable from the viewpoint of achieving both light transmittance and low resistance.

  Furthermore, the metal thin film layer of the cathode is preferably a silver thin film layer from the viewpoint of further improving the light transmittance and obtaining a low-resistance cathode.

  In the method for producing a transparent organic electroluminescence device according to the present invention, forming the metal thin wire of the cathode by a printing method under an inert gas reduces the influence on the device in the lower layer, and prevents impurities in the metal thin wire. It is preferable from the viewpoint of suppressing the generation and forming fine lines and improving efficiency. Specifically, the inert gas refers to a gas such as nitrogen, argon, or helium.

  Furthermore, it is preferable from the viewpoint of avoiding thermal damage to the base material and the organic functional layer to fire the metal thin wire of the cathode by flash firing.

  Moreover, after forming the metal thin wire of the cathode on the base material constituting the sealing layer, adhering to the metal oxide layer, the metal thin film layer or the conductive polymer layer may damage the organic functional layer. It is preferable from the viewpoint of reducing and improving productivity.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Transparent Organic Electroluminescence Element of the Present Invention >>
The transparent organic electroluminescent element of the present invention is a transparent organic electroluminescent element having a total light transmittance of 45% or more in the visible light region of the organic electroluminescent element when not emitting light, the anode being a thin metal wire and a metal oxide The cathode is selected from a combination of a metal wire and a metal oxide layer, or a combination of a metal wire and a metal thin film layer. With such a configuration, a transparent organic electroluminescent element having a low resistance and highly transparent electrode and having uniform light emitting properties can be obtained. Further, regarding the anode and the cathode, both are also referred to as transparent electrodes in the present application.

  The “organic electroluminescence element” to be measured for the total light transmittance in the visible light region according to the present invention includes, as a minimum configuration, an anode, a first carrier functional layer group, a light emitting layer, a second carrier functional layer group, and An element in which a cathode is laminated. The first carrier functional layer group includes, for example, a hole injection layer, a hole transport layer, and an electron blocking layer, and the second carrier functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer. Etc.

  The total light transmittance is a light transmittance in the visible light wavelength region measured using a spectrophotometer in accordance with JIS K 7361-1: 1997 (a test method for the total light transmittance of plastic-transparent material). The visible light region refers to a light wavelength region of 400 to 700 nm. The “transparent” in the present invention means that the total light transmittance is 45% or more, preferably 50% or more.

<Configuration of Transparent Organic Electroluminescence Element of the Present Invention>
In FIG. 1, sectional drawing of the transparent electrode which comprises the anode and cathode used for the transparent organic electroluminescent element (henceforth an organic EL element) of this invention is shown.

  A transparent electrode 10 shown in FIG. 1 includes a resin base material 11 that is preferable as a transparent base material, a metal fine wire pattern 13, and a conductive layer provided on the metal fine wire pattern 13, for example, a conductive layer composed of a metal oxide layer 14. 12. The metal oxide layer 14 may be a metal thin film layer or a conductive polymer layer according to the present invention, and is exemplified as a metal oxide layer in FIG. 1 and FIG. 2 described later.

  The metal fine line pattern 13 is formed on one surface of the resin base material 11 so that a fine line pattern containing a metal has a constant pattern shape. A metal oxide layer 14 is formed as a continuous layer in the plane direction on the thin metal wire pattern 13. That is, the metal oxide layer 14 is formed so as to cover the fine metal wire pattern and the surface of the resin base material exposed from the opening of the fine metal wire. By covering the fine metal wire pattern 13 and forming the metal oxide layer 14, the conductive layer 12 having a low resistance and a uniform surface resistance can be formed.

  The transparent electrode 10 may be provided with a base layer 15 between the resin base material 11 and the conductive layer 12. The underlayer 15 is a functional layer that improves the adhesion between the resin base material 11 and the fine metal wire pattern 13 constituting the conductive layer 12 and the metal oxide layer 14.

  Furthermore, the particle | grain containing layer 16 which suppresses generation | occurrence | production of the damage | wound to a resin base material or a conductive layer may be provided in the surface (back surface) by which the conductive layer 12 of the resin base material 11 is not provided. The particle-containing layer 16 is preferably disposed in the outermost layer on the surface (back surface) opposite to the surface (front surface) on which the conductive layer 12 of the transparent electrode 10 is formed.

  Further, a gas barrier layer 17 may be provided on the resin base 11 on the surface on which the conductive layer 12 is formed. The gas barrier layer 17 is formed on the resin base material 11 and is provided closer to the resin base material 11 than each layer formed on one surface of the resin base material 11 such as the conductive layer 12 and the base layer 15. It is preferable. In addition, a resin base material 11 with the gas barrier layer 17 in which the gas barrier layer 17 is formed on the resin base material 11, such as a gas barrier film, can be used as a support substrate for the transparent electrode 10.

  FIG. 2 is a cross-sectional view showing a schematic configuration of the transparent organic EL element of the present invention. Here, an example using the metal oxide layer 14 as in FIG. 1 is shown.

  The organic EL element 20 shown in FIG. 2 includes the conductive layer 12 as an anode 12A and a cathode 12B, and a light emitting unit 21 is provided as an organic functional layer between the electrodes. The conductive layer 12 has the same configuration as that in FIG.

  Moreover, after forming the metal oxide layer 14, the cathode 12B is an aspect which forms the metal fine wire 13 pattern on it.

  In addition, when forming a metal fine wire and a silver thin film layer as the anode 12A and the cathode 12B, in order to promote uniform formation of a silver thin film layer, the organic compound containing layer 18 can also be provided as a lower layer.

[1] Structure of anode and cathode The anode according to the present invention is selected from a combination of a metal fine wire and a metal oxide layer, a metal fine wire and a metal thin film layer, or a combination of a metal fine wire and a conductive polymer layer, and the cathode is a metal fine wire and a metal oxide layer. It is characterized by being selected from a physical layer or a combination of a fine metal wire and a thin metal film layer.

  As the anode and the cathode, electrodes having the same configuration or different electrodes may be used in the combination. Moreover, even when the transparent organic EL element of the present invention has a plurality of electrodes such as an intermediate electrode in addition to the anode and the cathode, the structure including the intermediate electrode may be an electrode having the same configuration in the combination. You may use the electrode of a different structure.

  The anode and cathode according to the present invention (both are collectively referred to as a transparent electrode in the present application) preferably have a total light transmittance of 70% or more, more preferably 80% or more.

  As an embodiment of the present invention, it is preferable that the anode is composed of a fine metal wire and a metal oxide layer, and that the cathode is composed of a fine metal wire and a metal thin film layer. It is preferable from the viewpoint of achieving compatibility.

  In an organic EL device, when used as an anode, it is preferable to select a metal, an alloy, an electrically conductive compound, and a mixture thereof having a high work function (for example, 4 eV or more) as an electrode material.

  When used as a cathode, it is preferable to use a metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof having a low work function (for example, 4 eV or less) as an electrode material.

[1.1] Fine metal wire The fine metal wire pattern 13 constituting the conductive layer 12 is formed with a metal content ratio that is mainly composed of metal and can obtain conductivity. The ratio of the metal in a metal fine wire pattern becomes like this. Preferably it is 50 mass% or more.

  The surface resistance value of the conductive layer provided with the fine metal wires is preferably 100Ω / □ or less, more preferably 10Ω / □ or less, and further preferably 3Ω / □ or less. 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.

  The fine metal wire pattern 13 constituting the conductive layer 12 contains a metal material and is formed in a pattern so as to have an opening on the resin base material 11 or the base layer 15. When a transparent base material is used, an opening part is a part which does not have a metal fine wire pattern, and is a translucent part of a metal fine wire pattern. For example, the aperture ratio of a stripe pattern having a line width of 100 μm and a line interval of 1 mm is approximately 90%.

  There is no restriction | limiting in particular in the pattern shape of the metal fine wire pattern 13. FIG. Examples of the pattern shape of the metal fine line pattern 13 include a stripe shape (parallel line shape), a lattice shape, a honeycomb shape, and a random mesh shape. However, moire due to polarization may occur depending on the fine line pattern. From the viewpoints of transparency and polarization control, a lattice shape and a honeycomb shape are more preferable.

  When a transparent substrate is used, it is necessary to optimally design the ratio occupied by the openings, that is, the opening ratio, from the viewpoint of transparency. The feature of the present application is that a fine metal wire is used to adjust the total light transmittance of the transparent organic EL element, but the control can be adjusted by the aperture ratio. That is, the transmittance of the electrode can be adjusted by a combination of the aperture ratio formed by the metal fine wire pattern (generally also referred to as “grid”) and the transmittance of the surface electrode such as a metal oxide used together with the metal fine wire.

  The line width of the fine metal line pattern 13 is preferably in the range of 10 to 200 μm, more preferably in the range of 10 to 100 μm, and particularly preferably in the range of 10 to 30 μm. Desired conductivity is obtained when the line width of the metal fine line pattern is 10 μm or more, and electrode transparency is improved when the line width is 200 μm or less.

  In the stripe-like and grid-like patterns, the interval between the fine metal line patterns is preferably in the range of 0.5 to 4 mm. In general, when the line width is thick, the interval is wide, and when the line width is thin, it is preferable to adjust the total aperture ratio by narrowing the interval, and the line width is 30 μm or less and the interval is less than 300 μm. When a line is arranged, it can be felt as a film having a uniform concentration without observing the line when observed.

  The height (thickness) of the fine metal wire pattern 13 is preferably in the range of 0.1 to 5.0 μm, and more preferably in the range of 0.1 to 2.0 μm. When the metal fine line pattern 13 has a height of 0.1 μm or more and desired conductivity is obtained, and when the thickness is 5.0 μm or less, the unevenness difference is caused in the layer thickness distribution of the functional layer. Can reduce the impact.

  The metal fine line pattern 13 is prepared by preparing a metal ink composition containing a metal or a metal forming material and applying it, and then selecting a post-treatment such as a drying process or a firing process as appropriate to form the metal fine line pattern 13. It is preferable to do.

  The metal (single metal or alloy) blended in the metal ink composition is preferably in the form of particles or fibers (tube shape, wire shape, etc.), and more preferably metal nanoparticles. Moreover, it is preferable to form from the metal formation material which has a metal atom (element) and produces a metal by structural changes, such as decomposition | disassembly. The metal and the metal forming material in the metal ink composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily adjusted.

  The metal nanoparticle as used in the present invention refers to a metal or metal oxide in the form of fine particles having a particle diameter from the atomic scale to the nm size.

  As a metal used for a metal nanoparticle, metals, such as gold | metal | money, silver, copper, and platinum, or an alloy which has these as a main component is mentioned, for example. Among these, gold and silver are preferable from the viewpoints of excellent light reflectance and further improvement in the efficiency of the obtained organic EL device. These metals or alloys can be used alone or in combination of two or more.

  The metal ink composition is preferably a metal colloid or metal nanoparticle dispersion liquid in which the surface of metal nanoparticles is coated with a protective agent and stably dispersed in a solvent.

  As an average particle diameter of the metal nanoparticles in the metal ink composition, those having an atomic scale of 1000 nm or less can be preferably applied. In particular, the metal nanoparticles preferably have an average particle size in the range of 3 to 300 nm, and more preferably in the range of 5 to 100 nm. In particular, silver nanoparticles having an average particle diameter of 3 to 100 nm are preferable. The metal nanowire is preferably a silver wire having a width of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm.

  Here, the average particle diameter of the metal nanoparticles and the metal colloid and the width of the metal nanowire are obtained by measuring the particle diameter of the metal nanoparticles and the width of the metal nanowire in the dispersion using a transmission electron microscope (TEM). be able to. For example, the average particle diameter can be calculated by measuring the particle diameters of 300 independent metal nanoparticles that are not overlapped among the particles observed in the TEM image.

  In the metal colloid, the protective agent for coating the surface of the metal nanoparticles is preferably an organic π-junction ligand. Conductivity is imparted to the metal colloid by π-junction of the organic π-conjugated ligand to the metal nanoparticles.

  As said organic (pi) junction ligand, the 1 type, or 2 or more types of compound chosen from the group which consists of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative is preferable.

  In addition, as the organic π-junction ligand, in order to improve coordination to metal nanoparticles and dispersibility in a dispersion medium, an amino group, an alkylamino group, a mercapto group, a hydroxyl group, At least one selected from a carboxyl group, a phosphine group, a phosphonic acid group, a sulfonic acid group, a halogen group, a selenol group, a sulfide group, a selenoether group, an amide group, an imide group, a cyano group, a nitro group, and salts thereof It is preferable to have a substituent.

  Moreover, the organic (pi) conjugated ligand as described in international publication 2011/114713 can be used as an organic (pi) junction ligand.

  As a specific compound of the organic π-junction ligand, one or more selected from the following OTAN, OTAP, and OCAN are preferable.

OTAN: 2,3,11,12,20,21,29,30-octakis [(2-N, N-dimethylaminoethyl) thio] naphthalocyanine OTAP: 2,3,9,10,16,17,23 , 24-octakis [(2-N, N-dimethylaminoethyl) thio] phthalocyanine OCAN: 2,3,11,12,20,21,29,30-naphthalocyanine octacarboxylic acid containing organic π-junction ligand Examples of the method for preparing the metal nanoparticle dispersion liquid include a liquid phase reduction method. In addition, the production of the organic π-junction ligand of this embodiment and the preparation of the metal nanoparticle dispersion containing the organic π-junction ligand are described in paragraphs [0039] to [0060] of International Publication No. 2011/114713. It can be performed according to the method described.

  The average particle diameter of the metal colloid is usually in the range of 3 to 500 nm, preferably in the range of 5 to 50 nm. When the average particle diameter of the metal colloid is within the above range, fusion between the particles is likely to occur, and the conductivity of the obtained fine metal wire pattern 13 can be improved.

  In the metal nanoparticle dispersion liquid, as the protective agent for coating the surface of the metal nanoparticles, it is preferable to use a protective agent that removes the ligand at a low temperature of 200 ° C. or lower. As a result, the protective agent is detached by low temperature or low energy, the metal nanoparticles are fused, and conductivity can be imparted.

  Specific examples include metal nanoparticle dispersions described in JP2013-142173A, JP2012-162767A, JP2014-139343A, Patent No. 5606439, and the like.

  Examples of the metal forming material include metal salts, metal complexes, organometallic compounds (compounds having a metal-carbon bond), and the like. The metal salt and metal complex may be either a metal compound having an organic group or a metal compound having no organic group. By using a metal forming material for the metal ink composition, a metal is generated from the material, and a metal fine line pattern 13 including the metal is formed.

As a material for forming metallic silver, an organic silver complex compound produced by reacting a silver compound represented by “Ag _n X” with an ammonium carbamate compound is preferably used. In “Ag _n X”, n is an integer of 1 to 4, and X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrate, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, A substituent selected from the group consisting of acetylacetonate and carboxylate.

  Examples of the silver compound include silver oxide, thiocyanate silver, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoroborate, acetylacetate. Examples thereof include silver nitrate, silver acetate, silver lactate, and silver oxalate permeation. As the silver compound, use of silver oxide or silver carbonate is preferable in terms of reactivity and post-treatment.

  Examples of ammonium carbamate compounds include ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, t-butyl ammonium t-butyl carbamate, 2-ethylhexyl ammonium 2 -Ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutyl ammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl decyl Examples include rubamate, hexamethylene iminium hexamethylene imine carbamate, morpholium morpholine carbamate, pyridinium ethylhexyl carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropyl carbamate, etc. Can do. Of the ammonium carbamate compounds, alkylammonium alkyl carbamates substituted with primary amines are preferred because they are superior to secondary or tertiary amines in terms of reactivity and stability.

  The organic silver complex compound can be produced by the method described in JP2011-48795A. For example, one or more of the above silver compounds and one or more of the above ammonium carbamate compounds can be directly reacted without using a solvent at normal pressure or under pressure in a nitrogen atmosphere. Also, alcohols such as methanol, ethanol, isopropanol and butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate and carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane , Ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, and halogen substituted solvents such as chloroform, methylene chloride and carbon tetrachloride Can be reacted.

The structure of the organic silver complex compound can be represented by “Ag [A] _m ”. In “Ag [A] _m ”, A is the ammonium carbamate compound, and m is 0.7 to 2.5.

  The organic silver complex compound is well soluble in various solvents including a solvent for producing an organic silver complex compound, such as alcohols such as methanol, esters such as ethyl acetate, and ethers such as tetrahydrofuran. For this reason, the organic silver complex compound can be easily applied to a coating or printing process as a metal ink composition.

  In addition, examples of the metal silver forming material include silver carboxylate having a group represented by the formula “—COOAg”. The carboxylate silver is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be only one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.

  The silver carboxylate is preferably at least one selected from the group consisting of silver β-ketocarboxylate and silver carboxylate (4) described in JP-A-2015-66695. As a material for forming metallic silver, not only silver β-ketocarboxylate and silver carboxylate (4), but also silver carboxylate having a group represented by the formula “—COOAg” including them can be used. it can.

  Further, when the metal ink composition contains the above-mentioned silver carboxylate as a metal forming material, the amine compound and quaternary ammonium salt having 25 or less carbon atoms, ammonia, and the amine compound or ammonia react with the acid together with the silver carboxylate. It is preferable that one or more nitrogen-containing compounds selected from the group consisting of ammonium salts are blended.

The amine compound has 1 to 25 carbon atoms and may be any of primary amine, secondary amine, and tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain or cyclic. The number of nitrogen atoms constituting the amine moiety or ammonium salt moiety (for example, the nitrogen atom constituting the amino group “—NH ₂ ” of the primary amine) may be one or two or more.

<Method of forming fine metal wire pattern>
An example in which the fine metal wire pattern 13 is formed on the resin substrate 11 as an anode will be described. The metal thin line pattern 13 is formed using, for example, the metal ink composition. There is no restriction | limiting in particular as a formation method of the metal fine wire pattern 13, A conventionally well-known method can be utilized. As a conventionally known method for forming the fine metal wire pattern 13, for example, a method using a photolithography method, a coating method, a printing method, or the like can be used. Of these, the printing method is preferably used.

  The metal ink composition contains the metal nanoparticles described above and a solvent, and may contain additives such as a dispersant, a viscosity modifier, and a binder. Although there is no restriction | limiting in particular as a solvent contained in a metal nanoparticle containing composition, The compound which has OH group is preferable at the point which can volatilize a solvent efficiently by mid-infrared irradiation, and water, alcohol, and glycol ether are preferable.

  Solvents used in the composition containing metal nanoparticles include water, methanol, ethanol, propanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, hexane Diol, heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalool, geraniol, nerol, heptadienol, tetradecenol, hexadecenol, phytol, oleyl alcohol, dedecenol, decenol, undecylenyl alcohol, nonenol , Citronellol, octenol, heptenol, methylcyclohexanol, menthol, dimethylcyclohex Nord, methylcyclohexenol, terpineol, dihydrocarbeveol, isopulegol, cresol, trimethylcyclohexenol, glycerin, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, hexylene glycol, propylene glycol, dipropylene glycol , Tripropylene glycol, neopentyl glycol, butanediol, pentanediol, heptanediol, propanediol, hexanediol, octanediol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and the like.

  When forming a pattern of the metal nanoparticle-containing composition by a printing method, a method generally used for electrode pattern formation is applicable. Specific examples of the gravure printing method include those described in JP 2009-295980 A, JP 2009-259826 A, JP 2009-96189 A, and JP 2009-90662 A, and the like. The methods described in Japanese Patent Application Laid-Open Nos. 2004-268319 and 2003-168560 are disclosed, and the screen printing methods are described in Japanese Patent Application Laid-Open Nos. 2010-34161, 2010-10245, and 2009-302345. Examples of the method described in JP-A No. 2011-180562, JP-A No. 2000-127410, and JP-A No. 8-238774 are examples of the ink jet printing method.

  In the present invention, in particular, in forming the cathode, it is preferable to carry out in an inert gas atmosphere such as nitrogen, argon, helium, etc., when forming the fine metal wire by the printing method. By performing in an inert gas atmosphere, the influence on the element in the lower layer can be reduced, and the generation of impurities in the fine metal wire can be suppressed, which is preferable.

  When the pattern of the metal nanoparticle-containing composition is formed by the photolithography method, specifically, the metal ink composition is formed on the entire surface of the underlayer 15 by printing or coating, followed by drying treatment and baking described later. After the treatment, the film is processed into a desired pattern by etching using a known photolithography method.

  Next, the drying process of the metal nanoparticle containing composition apply | coated on the resin base material 11 is performed. The drying process can be performed using a known drying method. Drying methods include, for example, air cooling drying, convection heat transfer drying using hot air, radiant heat drying using infrared rays, conductive heat transfer drying using a hot plate, vacuum drying, internal using microwaves Exothermic drying, IPA vapor drying, Marangoni drying, Rotagoni drying, freeze drying, and the like can be used.

  The heat drying is preferably performed at a temperature in a temperature range of 50 to 200 ° C. at which the resin base material 11 is not deformed. It is more preferable to heat the resin base material 11 under conditions where the surface temperature is 50 to 150 ° C. When a PET substrate is used as the substrate, it is particularly preferable to heat in a temperature range of 100 ° C. or lower. Although the firing time depends on the temperature and the size of the metal nanoparticles used, it is preferably in the range of 10 seconds to 30 minutes, and from the viewpoint of productivity, it should be in the range of 10 seconds to 15 minutes. More preferably, it is in the range of 10 seconds to 5 minutes.

  In the drying process, it is preferable to perform a drying process by infrared irradiation. In particular, it is preferable to selectively irradiate a specific wavelength region with a wavelength control infrared heater or the like. By selectively using a specific wavelength region, it is possible to selectively irradiate a specific wavelength effective for the cutting of the absorption region of the resin substrate 11 or the solvent of the metal ink composition. It is particularly preferable to use an infrared heater in which the filament temperature of the light source is in the range of 1600 to 3000 ° C.

  Next, the dried metal ink composition pattern is baked. Depending on the type of metal composition contained in the metal ink composition (for example, silver colloid having the above-described π-junction organic ligand), the drying process may sufficiently exhibit conductivity, so the firing step is not performed. May be.

  Firing the pattern of the metal ink composition by light irradiation using a flash lamp (also referred to as flash firing) reduces damage to the resin substrate and the lower layer, and improves the conductivity of the transparent electrode 10. Therefore, it is preferable. As a discharge tube of a flash lamp used in flash firing, a discharge tube of xenon, helium, neon, argon or the like can be used, but a xenon lamp is preferably used.

  A preferable spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. Within this range, there is little damage such as thermal deformation of the resin base material 11 due to flash firing.

Light irradiation conditions of the flash lamp is arbitrary, it is preferable that total irradiation energy in the range of 0.1~50J / cm ^2, in a range of 0.5~10J / cm ² More preferred. The light irradiation time is preferably within a range of 10 μsec to 100 msec, and more preferably within a range of 100 μsec to 10 msec. Further, the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1-50 times. By performing flash light irradiation in these preferable condition ranges, a fine metal wire pattern can be formed without damaging the resin substrate 11.

  The flash lamp irradiation on the resin base material 11 is preferably performed from the side of the resin base material 11 on which the pattern of the metal ink composition is formed. When the resin base material 11 is transparent, it may be irradiated from the resin base material 11 side or from both surfaces of the resin base material 11.

  Further, the surface temperature of the resin base material 11 at the time of flash firing includes the heat resistance temperature of the resin base material 11, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the metal ink composition, the type and pressure of the atmospheric gas, The determination may be made in consideration of the thermal behavior such as dispersibility and oxidation of the metal ink composition, and it is preferably performed at room temperature or higher and 200 ° C. or lower.

  The light irradiation device of the flash lamp may be any device that satisfies the above irradiation energy and irradiation time. Moreover, although flash baking may be performed in air | atmosphere, it can also be performed in inert gas atmosphere, such as nitrogen, argon, and helium, as needed. In particular, it is preferable to form the cathode in an inert gas atmosphere from the viewpoint of reducing the influence on the underlying element and suppressing the generation of impurities in the metal thin wire.

  Moreover, a plating layer can also be formed on a metal fine wire pattern. The plating layer can be formed by applying a plating layer coating solution by an intaglio printing method, a stencil printing method, an ink jet method, or the like, and performing a plating treatment. As the plating process, there are an electroplating process in which a metal in the coating solution is deposited by energization to form a metal film, and an electroless plating process in which the metal in the coating solution is deposited by an oxidizing action of a reducing agent instead of energization.

  As the coating solution for the plating layer, for example, a coating solution containing a conductive substance serving as a plating nucleus in a solvent can be used. As the conductive substance, a transition metal or a compound thereof can be used. Among them, ionic transition metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt are preferable, and since a plating layer having low resistance and high corrosion resistance can be formed, silver, gold, copper, and the like are more preferable. .

  The conductive material is preferably in the form of particles having an average particle diameter of about 1 to 50 nm. An average particle diameter is an average value when a center particle diameter (D50) is measured with a laser diffraction scattering type particle size distribution measuring apparatus.

  It is preferable that content of the electroconductive substance in a coating liquid exists in the range of 10-60 mass%.

  In the case of electrolytic plating treatment, after applying a coating solution containing plating nuclei in the shape of the fine metal wire pattern 13, it is immersed in the electrolytic plating solution, or is applied with an electrolytic plating solution and energized. The metal can be deposited on the fine metal wire pattern 13 connected to the negative electrode to form a metal film. The temperature of the electrolytic plating solution at the time of application can be in the range of 20 to 98 ° C.

  As the electrolytic plating solution, one containing a conductive substance such as copper, nickel, chromium, cobalt, tin, sulfuric acid, an aqueous medium, or the like can be used.

  In the case of electroless plating treatment, after applying a coating solution containing plating nuclei in the shape of the fine metal wire pattern 13, by further applying an electroless plating solution containing a reducing agent, the metal in the electroless plating solution is removed. It can be deposited to form a metal coating. The temperature of the electroless plating solution at the time of application can be in the range of about 20 to 98 ° C.

  As the electroless plating solution, for example, one containing a conductive material such as copper, nickel, chromium, cobalt, tin, a reducing agent, an aqueous medium, a solvent, or the like can be used. As the reducing agent, for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenols and the like can be used.

  In addition, the electroless plating solution may contain a complexing agent such as carboxylic acid such as acetic acid, formic acid, malonic acid, and succinic acid, soluble salts thereof, and amines such as ethylenediamine, if necessary.

  On the other hand, when forming the fine metal wire pattern 13 on the cathode side, the same method as described above can be used, and in consideration of the influence on the device performance, it should be formed in a volatile gas environment or a vacuum environment. Is preferred. Moreover, when formation in a volatile gas environment is difficult, after forming a metal fine wire pattern in a sealing material or a transfer film, you may bond to the metal oxide layer or metal thin film layer by the side of a cathode.

[1.2] Metal oxide layer On the anode side, the metal oxide layer 14 constituting the conductive layer 12 is formed on one main surface of the resin base material 11 or the base layer 15 so as to cover the surface of the metal fine wire pattern 13. Is provided. On the other hand, on the cathode side, a fine metal wire pattern 13 is provided on one main surface of the metal oxide layer 14 constituting the conductive layer 12.

The metal oxide layer 14 is preferably formed using a conductive metal oxide having a volume resistivity lower than 1 × 10 ¹ Ω · cm. The volume resistivity can be obtained by measuring the sheet resistance and the film thickness measured in accordance with the resistivity test method by the 4-probe method of conductive plastics of JIS K 7194-1994. The film thickness can be measured using a contact-type surface shape measuring device (for example, DECTAK) or an optical interference surface shape measuring device (for example, WYKO).

  From the viewpoint of constituting the conductive layer 12 of the transparent electrode 10, the metal oxide layer 14 preferably has a sheet resistance of 10,000Ω / □ or less, and more preferably 2000Ω / □ or less.

  The thickness of the metal oxide layer 14 can be in the range of 10 to 500 nm. From the viewpoint of increasing conductivity, the thickness is preferably in the range of 100 to 500 nm. From the viewpoint of enhancing the smoothness of the surface, the thickness is preferably 50 nm or more.

  The metal oxide that can be used for the metal oxide layer 14 is not particularly limited as long as the material is excellent in transparency, conductivity, and flexibility. Examples of the metal oxide that can be used for the metal oxide layer 14 include IZO (indium oxide / zinc oxide), IGO (gallium doped indium oxide), IWZO (indium oxide / tin oxide), ZnO (zinc oxide), GZO ( Ga-doped zinc oxide), IGZO (indium gallium zinc oxide) and the like.

In particular, IZO, IGO, and IWZO are preferable as the metal oxide. Among these, as IZO, the mass ratio _{In 2 O 3: ZnO = 80~95} : composition is preferably represented by 5-20. The IGO, mass ratio _{In 2 O 3: Ga 2 O} 3 = 70~95: Preferably composition represented by 5-30. As IWZO, a composition represented by In ₂ O ₃ : WO ₃ : ZnO = 95 to 99.8: 0.1 to 2.5: 0.1 to 2.5 is preferable.

  In the transparent electrode 10, the metal oxide layer 14 is preferably a layer that does not have a metal oxide crystal phase (crystal grains), and the metal oxide does not have a crystal phase, and only an amorphous phase. It is preferable that it is a layer formed by having.

  In the metal oxide layer 14, the phase state of the metal oxide can be examined by X-ray diffraction (XRD) measurement. Specifically, X-ray diffraction measurement is performed on the metal oxide layer 14, and the phase state of the metal oxide is determined depending on the presence or absence of the crystalline diffraction peak due to the crystal phase (crystal grains) in the total X-ray scattering intensity. Can be judged.

  When the metal oxide layer is composed only of an amorphous phase, there is no crystalline diffraction peak in the X-ray diffraction spectrum. On the other hand, when the metal oxide layer has a crystal phase (crystal grains), a crystalline diffraction peak is generated in the X-ray diffraction spectrum.

  The metal oxide layer is less flexible in the crystal phase than the amorphous phase. The cause is considered to be that the crystal phase is likely to break due to crystal grains or defects. For this reason, in the transparent electrode 10 using the resin base material 11 and requiring flexibility, it is desirable that no crystal phase exists in the metal oxide layer.

  Further, when crystal grains are present in the metal oxide layer, the smoothness of the surface of the metal oxide layer is reduced by the crystal grain lump.

  When the smoothness of the surface of the conductive layer 12 is lowered, it causes a defect when the transparent electrode 10 is incorporated into an organic EL element. For example, when the transparent electrode 10 is applied to a transparent electrode of an organic EL element, problems such as deterioration of the rectification ratio due to current leakage and current concentration on the protruding part of the agglomerate, which easily causes a short circuit in this part. To do. Therefore, it is desirable that the metal oxide layer 14 of the transparent electrode 10 has no metal oxide crystal phase.

  The metal oxide layer 14 preferably has an arithmetic average roughness Ra of 5 nm or less. Furthermore, Ra is preferably 3 nm or less. The arithmetic average roughness Ra is measured using, for example, an atomic force microscope (manufactured by Digital Instruments).

  The metal oxide layer is formed by sputtering a material (including reactive sputtering such as magnetron cathode sputtering, flat-plate magnetron sputtering, 2-pole AC flat-plate magnetron sputtering, 2-pole AC rotary magnetron sputtering), or vapor deposition (eg, Resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), photo CVD method, plasma It is preferable to form a layer by a chemical vapor deposition method such as a CVD method (PE-CVD), an epitaxial growth method or an atomic layer growth method.

[1.3] Metal Thin Film Layer On the anode side, the metal thin film layer 14 constituting the conductive layer 12 is provided on one main surface of the resin base material 11 or the base layer 15 so as to cover the surface of the metal fine wire pattern 13. ing. On the other hand, on the cathode side, a thin metal wire pattern 13 is provided on one main surface of the metal thin film layer 14 constituting the conductive layer 12.

  As the metal used for the metal thin film layer that can be combined with the metal thin wire, nickel, cobalt, silver, copper, gold, aluminum, tungsten, palladium, molybdenum, or an alloy thereof is preferably used. These may be used individually by 1 type and may use 2 or more types together. Among these, nickel, silver, and copper are preferable. In order to prevent the surface oxidation of these metals, particles having gold or palladium on the surface may be used. Furthermore, you may use what gave the metal film and the insulating film with the organic substance on the surface.

  Examples of the metal-coated resin particles include particles in which the surface of the resin core is coated with any metal of nickel, copper, gold, and palladium. Similarly, particles obtained by applying gold or palladium to the outermost surface of the resin core may be used. Further, a resin core whose surface is coated with a metal protrusion or an organic material may be used.

  Among them, the metal is preferably silver or an alloy containing silver as a main component. When silver is used as the main component, the purity of silver is preferably 99% or more. Further, palladium (Pd), copper (Cu), gold (Au), or the like may be added to ensure the stability of silver.

  In the case of constituting silver as a main component, specifically, it may be formed of silver alone or an alloy containing silver (Ag). Examples of such alloys include silver / magnesium (Ag / Mg), silver / copper (Ag / Cu), silver / palladium (Ag / Pd), silver / palladium / copper (Ag / Pd / Cu), silver -Indium (Ag.In) etc. are mentioned.

  The layer composed mainly of silver means that the silver content in the metal thin film layer is 60% by mass or more, preferably the silver content is 80% by mass or more, more preferably The silver content is 90% by mass or more, and the silver content is particularly preferably 98% by mass or more.

  Moreover, the structure by which the layer comprised as a main component was divided | segmented into the some layer as needed, and may be sufficient.

  In the case of constituting silver as a main component, the thickness is preferably in the range of 2 to 20 nm, more preferably in the range of 4 to 12 nm, from the viewpoint of transparency. A thickness of 20 nm or less is preferable because the absorption component and reflection component of the transparent electrode can be kept low and high light transmittance can be maintained.

  The metal thin film layer can be formed by a known vapor deposition method. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. Especially, it is more preferable to form by a sputtering method.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.

  In the present invention, when silver is used as the main component, it is preferable to provide an organic compound-containing layer underneath from the viewpoint of improving the uniformity of the silver film of the transparent electrode to be formed. Although there is no restriction | limiting in particular as an organic compound content layer, It is preferable from a viewpoint which prevents aggregation of silver that it is a layer containing the organic compound which has a nitrogen atom or a sulfur atom, On the said organic compound content layer, a metal thin film The method of forming the layer is a preferred embodiment.

  The organic compound-containing layer is preferably a layer containing a nitrogen-containing organic compound. As a method for forming the film, a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, or a vapor deposition method is used. (Resistance heating, EB method, etc.), a method using a dry process such as a sputtering method, a CVD method, or the like. Of these, the vapor deposition method is preferably applied.

  The nitrogen-containing organic compound constituting the organic compound-containing layer is not particularly limited as long as it is a compound having a nitrogen atom in the molecule, but a compound having a nitrogen-containing heterocycle is preferable. The nitrogen-containing heterocycle includes aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, isoindole, benzimidazole. , Purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and the like.

  Furthermore, as specific organic compounds, compounds described in paragraphs [0097] to [0221] of JP-A-2015-046364 can be referred to.

[1.4] Conductive polymer layer On the anode side, the conductive polymer layer 14 constituting the conductive layer 12 is formed on one main surface of the resin base material 11 or the base layer 15 so as to cover the surface of the fine metal wire pattern 13. Is provided.

  As a conductive polymer that can be combined with a fine metal wire, it is preferable to use a π-conjugated conductive polymer containing a polyanion.

  Examples of π-conjugated conductive polymers that can be used include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, Examples include polyparaphenylene sulfides, polyisothianaphthenes, and polythiazyl compounds. Of these, polythiophenes or polyanilines are preferable and polyethylenedioxythiophene is more preferable from the viewpoint of improving conductivity, transparency, stability, and the like.

  The π-conjugated conductive polymer can be easily produced by subjecting a precursor monomer that forms a π-conjugated conductive polymer to chemical oxidative polymerization in the presence of an oxidizing agent, an oxidation catalyst, and a polyanion. The precursor monomer used for forming the π-conjugated conductive polymer has a π-conjugated system in the molecule, and has a π-conjugated system in the main chain even when polymerized by the action of an oxidizing agent. Examples of such precursor monomers include pyrroles, thiophenes, anilines, and derivatives thereof.

  Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

  The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, or a copolymer thereof. It is a compound composed of a structural unit having a group and a structural unit having no anionic group. The polyanion solubilizes or disperses the π-conjugated conductive polymer in a solvent, and the anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer. Improve sexiness.

  The anion group of the polyanion may be any functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. However, from the viewpoint of facilitating production and improving stability, a monosubstituted sulfate group, A substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Among these, a sulfo group, a monosubstituted sulfate group or a carboxy group is more preferable from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Examples include acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . Furthermore, these homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  A fluorinated polyanion having a fluorine atom in the molecule can also be used. Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of improving solubility in a solvent and conductivity.

  The ratio of the π-conjugated system conductive polymer and the polyanion in the conductive polymer, that is, the mass ratio of the π-conjugated system conductive polymer: polyanion can be 1: 1 to 20 to enhance conductivity and dispersibility. Is preferably 1: 2 to 10.

  As the conductive polymer, a commercially available product may be used. For example, as a commercial product of a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (hereinafter abbreviated as PEDOT / PSS), Heraeus Clevios series, Aldrich's PEDOT-PSS 483095 and 560596, Nagase Chemtex's Denatron series. Further, as a commercially available product of polyaniline, ORMECON series manufactured by Nissan Chemical Industries, Ltd. can be used.

  The transparent electrode can be formed by applying a coating solution containing a conductive polymer onto a fine metal wire to form a coating film, and irradiating the coating film with infrared rays and drying.

  As the method of forming the coating film, gravure printing method, flexographic printing method, screen printing method, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, Coating methods such as a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.

  Infrared irradiation is preferably performed in a drying treatment tank having a moisture concentration of 100 ppm or less. The moisture concentration in the drying treatment tank refers to the moisture concentration at the end of drying in the tank where the drying treatment is performed. It is preferable to irradiate infrared rays having a ratio of the light radiance having a wavelength of 5.8 μm to the light radiance having a wavelength of 3.0 μm of 5% or less.

  Furthermore, the extraction electrode preferably contains a non-conductive polymer together with a conductive polymer from the viewpoint of enhancing transparency, and the non-conductive polymer further comprises at least one of a self-dispersing polymer and a hydroxy group-containing polymer. It is more preferable to contain. By using a non-conductive polymer, the content of the conductive polymer can be reduced without impairing the conductivity of the extraction electrode.

  Self-dispersing polymers that can be used in combination with conductive polymers have dissociable groups, and colloidal particles formed by self-dispersing polymers do not aggregate even without surfactants or emulsifiers that assist micelle formation. The self-dispersing polymer is a non-conductive polymer that can be dispersed in an aqueous medium. When the self-dispersing polymer has high transparency, the transparency of the first conductive layer 4 can be increased, which is preferable.

  The amount of the self-dispersing polymer used can be in the range of 50 to 1000% by mass with respect to the conductive polymer.

  The main skeleton of the self-dispersing polymer includes polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyamide (nylon), polyvinylidene chloride, polyester, polyacrylate, Polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone-polyacrylate, polyvinylidene fluoride-polyacrylate, Examples include polyfluoroolefin-polyvinyl ether. Further, copolymers based on these skeletons and further using other monomers may be used. Among these, a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, an acrylic resin emulsion having an acrylic skeleton, or a polyethylene resin emulsion having an ethylene skeleton is preferable.

  Commercially available self-dispersing polymers include iodosol AD-176, AD-137 (acrylic resin: manufactured by Henkel Japan), Vironal MD-1200, MD-1245, MD-1500 (polyester resin: manufactured by Toyobo), plus A coat RZ570, a plus coat Z561, a plus coat Z565, a plus coat Z687, a plus coat Z690 (polyester resin: manufactured by Kyodo Chemical Co., Ltd.), or the like can be used. One type or a plurality of types of self-dispersing polymer dispersions containing dissociable groups that can be dispersed in the aqueous medium can be used.

  The hydroxy group-containing polymer is a non-conductive polymer having a hydroxy group.

  The ratio of the conductive polymer to the hydroxy group-containing polymer, that is, the mass ratio of the conductive polymer: hydroxy group-containing polymer is preferably 100: 30 to 900. From the viewpoint of preventing current leakage and increasing transparency, the ratio is 100: 100. More preferably, it is -900.

  Examples of the hydroxy group-containing polymer include a polymer containing a structural unit represented by the following general formula (1).

〔上記一般式（１）において、Ｒは、水素原子又はメチル基を表す。Ｑは、−Ｃ（＝Ｏ）Ｏ−、又は−Ｃ（＝Ｏ）ＮＲａ−を表す。Ｒａは、水素原子又はアルキル基を表す。Ａは、置換若しくは無置換のアルキレン基、又は−（ＣＨ_２ＣＨＲｂＯ）_ｘＣＨ_２ＣＨＲｂ−を表す。Ｒｂは、水素原子又はアルキル基を表す。ｘは、平均繰り返しユニット数を表す。〕
こうした樹脂は導電性ポリマーと容易に混合可能で、また、前述の第二ドーパント的な効果も有するため、該水溶性バインダ樹脂を併用することにより、導電性、透明性を低下させることなく、導電性ポリマー含有層の膜厚を上げることが可能となる。

[In the above general formula (1), R represents a hydrogen atom or a methyl group. Q represents -C (= O) O- or -C (= O) NRa-. Ra represents a hydrogen atom or an alkyl group. A is a substituted or unsubstituted alkylene group, or _- represents a _{(CH 2 CHRbO) x CH 2} CHRb-. Rb represents a hydrogen atom or an alkyl group. x represents the average number of repeating units. ]
Since such a resin can be easily mixed with a conductive polymer and also has the effect of the second dopant described above, by using the water-soluble binder resin in combination, the conductivity and transparency are not lowered. The film thickness of the conductive polymer-containing layer can be increased.

  The water-soluble binder resin is a water-soluble binder resin, and means a binder resin in which 0.001 g or more of the water-soluble binder resin is dissolved in 100 g of water at 25 ° C. The dissolution can be measured with a haze meter or a turbidimeter.

  The water-soluble binder resin is preferably transparent.

  The water-soluble binder resin preferably has a structure including the structural unit represented by the general formula (1). The homopolymer represented by the general formula (1) may be used, or other components may be copolymerized. When copolymerizing other components, the structural unit represented by the general formula (1) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.

  The water-soluble binder resin is preferably contained in the conductive polymer-containing layer in an amount of 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.

  In the structural unit having a hydroxy group represented by the general formula (1), R represents a hydrogen atom or a methyl group. Q represents -C (= O) O- or -C (= O) NRa-, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl , Aryloxy sulfonyl group, alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxy group and an alkyloxy group are preferable.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.

  The number of carbon atoms in the cycloalkyl group is preferably 3-20, more preferably 3-12, and even more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkoxy group may have a branch, the number of carbon atoms is preferably 1-20, more preferably 1-12, still more preferably 1-6, and 1-4 Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group.

  The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1-20, more preferably 1-12, even more preferably 1-6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group.

  The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.

  The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

  The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

  The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.

  The heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the heteroaryl group include a thienyl group and a pyridyl group.

  The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.

  The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group.

  The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like.

  The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include a methanesulfonamide group.

  The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group.

  The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.

  The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.

  The acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.

  The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group.

  The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.

  The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.

  The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.

  The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

In the structural unit having a hydroxy group represented by the general formula (1), A represents a substituted or unsubstituted alkylene group, or — (CH ₂ CHRbO) _x —CH ₂ CHRb—. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent described above. Rb represents a hydrogen atom or an alkyl group. The alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with the above-mentioned substituent. Furthermore, x represents the average number of repeating units, preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.

  Below, the typical example of the structural unit represented by General formula (1) is shown, However, This invention is not limited by these.

本発明に用いられる水溶性バインダ樹脂は、汎用的な重合触媒を用いたラジカル重合により得ることができる。重合様式としては、塊状重合、溶液重合、懸濁重合、乳化重合等が挙げられ、好ましくは溶液重合である。重合温度は、使用する開始剤によって異なるが、一般に−１０〜２５０℃の範囲、好ましくは０〜２００℃の範囲、より好ましくは１０〜１００℃の範囲で実施される。

The water-soluble binder resin used in the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The polymerization temperature varies depending on the initiator used, but is generally in the range of −10 to 250 ° C., preferably in the range of 0 to 200 ° C., more preferably in the range of 10 to 100 ° C.

  The number average molecular weight (Mn) of the water-soluble binder resin used in the present invention is preferably in the range of 3000 to 2000000, more preferably in the range of 4000 to 500000, and still more preferably in the range of 5000 to 100,000.

The number average molecular weight (Mn) and molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the water-soluble binder resin used in the present invention are measured by generally known gel permeation chromatography (GPC). ). The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, THF and DMF are more preferable, and DMF is more preferable. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

[2] Underlayer The underlayer 15 is preferably formed of a polymer material or a polymer material containing metal oxide fine particles.

  The thickness of the underlayer 15 is preferably in the range of 0.01 to 1.0 μm, and more preferably in the range of 0.05 to 0.3 μm. When the layer thickness of the underlayer 15 is 0.01 μm or more, the underlayer 15 itself becomes a continuous film, the surface becomes smooth, and the organic EL element is hardly affected. On the other hand, when the thickness of the underlayer 15 is 1.0 μm or less, the transparency of the transparent electrode 10 caused by the underlayer 15 and the adsorbed gas derived from the underlayer 15 can be reduced. Resistance deterioration can be suppressed. Moreover, if the thickness of the base layer 15 is 1.0 μm or less, the damage of the base layer 15 when the transparent electrode 10 is bent can be suppressed.

  The transparency of the underlayer 15 can be arbitrarily selected depending on the use, but the higher the transparency, the better the application to the transparent electrode 10, which is preferable from the viewpoint of expanding the use. The total light transmittance of the underlayer 15 is at least 50% or more, preferably 70% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.

<Metal oxide fine particles>)
The metal oxide fine particles constituting the underlayer 15 are not particularly limited as long as they can be applied to the transparent electrode 10. By adding metal oxide fine particles to the polymer material, physical properties such as film strength, stretchability, refractive index and the like of the underlayer 15 can be adjusted as appropriate, and adhesion to the metal fine wire pattern is also improved. Examples of the metal oxide fine particles include metal oxides such as magnesium, aluminum, silicon, titanium, zinc, yttrium, zirconium, molybdenum, tin, barium, and tantalum. In particular, the metal oxide fine particles are preferably titanium oxide or any of aluminum oxide, silicon oxide, and zirconium oxide. Furthermore, since the lifetime of the organic EL element is more excellent, it is preferable that at least one kind of fine particles of titanium oxide and zirconium oxide is contained as the metal oxide fine particles.

  The average particle diameter of the metal oxide fine particles is preferably in the range of 10 to 300 nm, and particularly preferably in the range of 10 to 100 nm because it can be suitably used for the transparent electrode 10. When metal oxide fine particles having an average particle diameter in the above range are used, sufficient irregularities can be formed on the surface of the underlayer 15 and the adhesion to the metal fine line pattern is improved. When the average particle size is 300 nm or less, the surface becomes smooth and the influence on the organic EL element is small.

  The average particle diameter of the metal oxide fine particles can be easily measured using a commercially available measuring device using a light scattering method. Specifically, a value measured by a laser Doppler method at 25 ° C. and a sample dilution amount of 1 ml using a Zetasizer 1000 (manufactured by Malvern) can be used.

  The metal oxide fine particles are preferably contained in the base layer 15 in an amount of 10 to 70% by volume, and more preferably 20 to 60% by volume.

<Polymer material>
The polymer material constituting the underlayer 15 is not particularly limited as long as the underlayer 15 can be formed alone or together with the metal oxide fine particles. For example, a known natural polymer material having a monomer repeating structure or a synthetic polymer material can be used. These can use organic polymer materials, inorganic polymer materials, organic-inorganic hybrid polymer materials, and mixtures thereof. The dispersion state of metal oxide fine particles in the polymer material, various coating films It can be selected according to physical properties. These polymer materials can be used in a mixture of two or more.

  Specifically, the natural polymer material is preferably a natural organic polymer material, and examples thereof include natural fibers such as cotton, hemp, cellulose, silk, and wool, proteins such as gelatin, and natural rubber. Synthetic polymer materials include polyolefin resin, polyacrylic resin, polyvinyl resin, polyether resin, polyester resin, polyamide resin, polyurethane resin, polyphenylene resin, polyimide resin, polyacetal resin, polysulfone resin, fluorine resin, epoxy resin, silicon resin Phenol resin, melamine resin, polyurethane resin, polyurea resin, polycarbonate resin, polyketone resin, and the like.

  Examples of the inorganic polymer material include polysiloxane, polyphosphazene, polysilane, polygermane, polystannane, borazine-based polymer, polymetalloxane, polysilazane, titanium oligomer, and silane coupling agent. Specific examples of the polysiloxane include silicone, silsesquioxane, and silicone resin.

  As organic / inorganic hybrid polymer materials, polycarbosilane, polysilylene arylene, polysilole, polyphosphine, polyphosphine oxide, poly (ferrocenylsilane), silsesquioxane derivatives based on silsesquioxane Examples thereof include a resin in which silica is combined with a resin.

  Specific examples of silsesquioxane derivatives having silsesquioxane as a basic skeleton include photo-curing type SQ series (Toagosei Co., Ltd.), Composelan SQ (Arakawa Chemical Co., Ltd.), Sila-DEC (Chisso Corporation). And so on. Specific examples of the resin in which silica is combined with the resin include the Composelan series (Arakawa Chemical).

  Further, as the polymer material, a curable resin such as an ionizing radiation curable resin or a thermosetting resin can be used. The ionizing radiation curable resin is a resin that can be cured by an ordinary curing method of an ionizing radiation curable resin composition, that is, by irradiation with an electron beam or ultraviolet rays.

  For example, in the case of electron beam curing, 10 to 1000 keV emitted from various electron beam accelerators such as a cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy within a range of preferably 30 to 300 keV is used.

  In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. Specific examples of the ultraviolet irradiation device include a rare gas excimer lamp that emits vacuum ultraviolet rays within a range of 100 to 230 nm. Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light having a long wavelength that causes a temperature rise is not emitted and energy is emitted at a single wavelength in the ultraviolet region, the temperature rise of the irradiation object due to the irradiation light itself is suppressed.

  The thermosetting resin is a resin that is cured by heating, and it is more preferable that a crosslinking agent is contained in the resin. As a heating method of the thermosetting resin, a conventionally known heating method can be used, and heater heating, oven heating, infrared heating, laser heating and the like can be used.

  Further, a low molecular compound containing N (nitrogen) atoms or S (sulfur) atoms may be added to the polymer material used for the underlayer 15. By adding N (nitrogen) atoms or S (sulfur) atoms to the underlayer 15, the adhesion between the fine metal wire pattern 13 and the underlayer 15 is improved.

  Any appropriate method can be selected as a method for forming the underlayer 15. For example, as a coating method, various printing methods such as a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, and an inkjet printing method can be used. In addition, various coating methods such as a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used. . When forming the underlayer 15 in a predetermined pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, or an inkjet printing method.

  The underlayer 15 is formed by depositing the above coating method on the resin substrate 11 and then drying it by a known heat drying method such as warm air drying or infrared drying, or natural drying. The temperature at which the heat drying is performed can be appropriately selected according to the resin substrate 11 to be used. It is preferable to carry out at a temperature of 200 ° C or lower. Further, depending on the polymer material to be selected, a treatment such as curing with light energy such as ultraviolet rays or thermal curing with little damage to the resin substrate 11 may be performed.

[3] Particle-containing layer The particle-containing layer 16 is provided on the surface (back surface) opposite to the surface (front surface) on which the conductive layer 12 is formed in the resin base material 11. In the case where the transparent electrodes 10 are in direct contact with each other, such as when the transparent electrodes 10 are stacked or the long transparent electrodes 10 are wound into a roll, the transparent electrodes 10 are in the particle-containing layer 16. Therefore, charging, sticking of the transparent electrodes 10 and the like can be suppressed.

  In the transparent electrode 10, the particle-containing layer 16 is composed of particles and a binder resin. The particle-containing layer 16 preferably contains particles in the range of 1 to 900 parts by mass with respect to 100 parts by mass of the binder resin.

The particles constituting the particle-containing layer 16 are preferably inorganic fine particles, inorganic oxide particles, conductive polymer particles, conductive carbon fine particles and the like. Among these, metal oxide particles such as ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₂ , V ₂ O ₅ , and inorganic oxide particles such as SiO ₂ are used. preferable. In particular, SnO ₂ and SiO ₂ are preferable.

  Examples of the binder resin constituting the particle-containing layer 16 include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, and polybutylene terephthalate. Or polyesters such as copolybutylene / tere / isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate , Polypropyltyl methacrylate, polybutyl methacrylate, polymethyl Can be used a copolymer of acrylic resin or an acrylic resin and other resins such as acrylates, it is not particularly limited to these exemplified a resin material. Among these, cellulose derivatives or acrylic resins are preferable, and acrylic resins are most preferably used.

  The particle-containing layer 16 is formed by dissolving the above-described particles and binder resin in an appropriate organic solvent to prepare a coating solution for forming a particle-containing layer in a solution state. It is formed by coating and drying.

[4] Configuration of Organic Electroluminescence Device and Manufacturing Method FIG. 3 is a cross-sectional view showing the layer configuration of the transparent organic EL device of the present invention.

  The organic EL element 30 is configured by laminating an anode 32, a first carrier functional layer group 33, a light emitting layer 34, a second carrier functional layer group 35, and a cathode 36 on a transparent substrate 31. The first carrier functional layer group includes, for example, a hole injection layer, a hole transport layer, and an electron blocking layer, and the second carrier functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer. Etc. Each of the first carrier functional layer group and the second carrier functional layer group may be composed of only one layer, or the first carrier functional layer group and the second carrier functional layer group may not be provided.

  Further, the organic EL element is sealed with a sealing material 38 through an adhesive 37 so as to cover the anode 32 to the cathode 36.

  Lights L and L ′ emitted from the light emission center h of the light emitting layer are extracted from both surfaces of the organic EL element 30.

  Below, the typical example of a structure of the organic EL element of this invention is shown. Since the anode and cathode shown below are the transparent electrodes 10 according to the present invention, detailed description thereof will be omitted.

(I) Anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (ii) Anode / hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iii) Anode / Hole injection / transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iv) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / Cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (vi) Anode / hole injection layer / hole transport layer / electron blocking Layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode Furthermore, the organic EL element 1 may have a non-light emitting intermediate layer. The intermediate layer may be a charge generation layer or a multi-photon unit configuration.

  Regarding the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A, JP JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A, JP 2013-235994 A, JP 2013-243234 A, JP 2013-243236 A, JP 2013-2013 A. JP 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-014933 Gazette, JP, 2014-017494, A It can be mentioned configurations described in.

[4.1] Transparent base material Examples of the transparent base material applicable to the organic EL device of the present invention include transparent materials such as glass and plastic. Examples of the transparent substrate preferably used include glass, quartz, and resin film, and a resin substrate using a resin film is particularly preferable for providing a flexible organic EL element.

  Examples of the glass material include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass. On the surface of these glass materials, from the viewpoint of adhesion with adjacent layers, durability, and smoothness, a physical treatment such as polishing, a coating made of an inorganic material or an organic material, or these coatings, if necessary. A combined hybrid coating can be formed.

  Examples of the material constituting the resin substrate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose. Cellulose esters such as acetate propionate (CAP), cellulose acetate phthalate, cellulose nitrate and their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, Polyether ketone, polyimide, polyether sulfone (PES), polyphenylene sulfide, police Phones, polyether imides, polyether ketone imides, polyamides, fluororesins, nylon, polymethyl methacrylate, acrylics and polyarylates, cyclones such as Arton (trade name, manufactured by JSR) and Appel (trade name, manufactured by Mitsui Chemicals) An olefin resin etc. can be mentioned.

  In an organic EL element, the structure which provides a gas barrier layer on the transparent base demonstrated above as needed may be sufficient.

  The organic light emitting layer is very sensitive to oxygen, moisture, and the like, and needs an oxygen / water blocking ability like glass. When the substrate is not glass (in the case of the resin film or the like), or the outermost layer of the layer that does not have the substrate itself and is in contact with the outside world, a protective layer having oxygen and moisture barrier properties is required.

On the surface of the resin film, a film made of an inorganic material or an organic material or a hybrid film combining these films may be formed. Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / ( m ² · 24 hours) or less of a barrier film (also referred to as a gas barrier film) is preferable. Furthermore, the oxygen permeability measured by a method according to JIS-K-7126-1987 is 10 ⁻³ / (m ² · 24 hours · atm) or less, and the water vapor permeability is 10 ⁻⁵ g / (m ^2. -24 hours) It is preferable that it is the following highly barrier film.

  The material for forming the gas barrier film as described above may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen, and examples thereof include silicon oxide, silicon dioxide, and silicon nitride. Can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In particular, a polysilazane having a structure represented by the following general formula (A) is applied on a substrate by a coating method, subjected to a heat treatment within a range of 50 to 200 ° C., and then a noble gas excimer lamp having an irradiation wavelength of about 172 nm. (For example, Xe excimer lamp MODEL: MECL-M-1-200 manufactured by M.D.Com) is preferably used to perform a modification treatment with vacuum ultraviolet light to form a barrier layer. Although the thickness of a barrier layer can be suitably set according to the objective, generally it can be in the range of 10 nm-10 micrometers.

Formula (A)-[Si (R ¹ ) (R ² ) -N (R ³ )]-
[In the above general formula (A), R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. Represent. ]
The polysilazane in which all of R ¹ , R ² and R ^{3 in} the general formula (A) are hydrogen atoms is perhydropolysilazane. Perhydropolysilazane is preferable in that a dense film can be obtained.

  Examples of the coating film forming method include a roll coating method, a flow coating method, a spray coating method, a printing method, a dip coating method, a bar coating method, a casting film forming method, an ink jet method, and a gravure printing method.

  For the preparation of the coating solution, it is preferable to avoid the use of an alcohol-based organic solvent that easily reacts with polysilazane or an organic solvent containing moisture. Accordingly, examples of the organic solvent that can be used for preparing the coating liquid include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. And ethers. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

As the coating solution, a commercial product in which polysilazane is dissolved in an organic solvent can be used. Commercial products that can be used include AQUAMICA manufactured by AZ Electronic Materials.
NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 etc. are mentioned.

The illuminance of the vacuum ultraviolet light can be in the range of 1 mW / cm ^{2 to} 10 W / cm ² . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that may occur in the coating film, damage to the resin substrate 11, and the like can be reduced.

The irradiation energy amount (irradiation amount) of the vacuum ultraviolet light can be set within a range of 0.1 to 10.0 J / cm ² . If it is this range, generation | occurrence | production of the crack by excessive modification | reformation, the thermal deformation of the resin base material 11, etc. can be prevented, and productivity will also improve.

[4.2] Light-Emitting Layer The light-emitting layer constituting the organic EL element preferably has a configuration containing a phosphorescent compound as a light-emitting material.

  This light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

  As such a light emitting layer, there is no restriction | limiting in particular in the structure, if the light emitting material contained satisfy | fills the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer between the light emitting layers.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between light emitting layers.

  For the light emitting layer as described above, a light emitting material and a host compound to be described later may be used by publicly known methods such as a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir-Blodget, Langmuir Broadgett method), and an ink jet method. Can be formed.

  The light-emitting layer may be a mixture of a plurality of light-emitting materials, and a phosphorescent light-emitting material and a fluorescent light-emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light-emitting layer. . The structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound) and emits light from the light-emitting material.

[4.2.1] Host Compound As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Furthermore, it is preferable that the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As a host compound, a well-known host compound may be used independently, or multiple types of host compounds may be mixed and used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used in the light emitting layer may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). )

  Examples of the host compound applicable to the present invention include, for example, JP-A Nos. 2001-257076, 2001-357777, 2002-8860, 2002-43056, 2002-105445, 2002-352957, 2002-231453, 2002-234888, 2002-260861, 2002-305083, US Patent Publication No. 2005/0112407, US Patent Publication No. 2009 No./0030202, International Publication No. 2001/039234, International Publication No. 2008/056746, International Publication No. 2005/089025, International Publication No. 2007/063754, International Publication No. 2005/030900, International Publication No. 2009. / 086 No. 28, International Publication No. 2012/023947, may be mentioned JP 2007-254297, JP-European compounds described in Japanese Patent No. 2034538 Pat like.

[4.2.2] Luminescent Material As the luminescent material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material, or a phosphorescent dopant) and a fluorescent compound. (Also referred to as a fluorescent compound or a fluorescent material).

<Phosphorescent compound>
A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescent quantum yield can be measured by the method described in HIkari II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. The phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds) or rare earth complexes, and most preferred are iridium compounds.

  In the present invention, at least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.

  Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents.

  Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Publication No. 2006/835469, US Patent Publication No. 2006/020202194. The compounds described in the specification, US Patent Publication No. 2007/0087321, US Patent Publication No. 2005/0244673, and the like can be mentioned.

  Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42,1248 (2003), International Publication No. 2009/050290, International Publication No. 2009/000673, US Pat. No. 7,332,232, US Patent Publication No. 2009/0039776, US Pat. No. 6,687,266, US Pat. As described in Japanese Patent Publication No. 2006/0008670, US Patent Publication No. 2008/0015355, US Pat. No. 7,396,598, US Patent Publication No. 2003/0138667, US Pat. No. 7090928, etc. A compound can be mentioned.

  Also, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2006/056418, International Publication No. 2005/123873, International Publication No. 2005/123873, International Publication No. 2006/082742, US Patent Publication No. 2005/0260441, Compounds described in U.S. Pat. No. 7,534,505, U.S. Patent Publication No. 2007/0190359, U.S. Pat. No. 7,338,722, U.S. Pat. No. 7,279,704, U.S. Pat. Publication No. 2006/103874, etc. Can also be mentioned.

  Furthermore, International Publication No. 2005/076380, International Publication No. 2008/140115, International Publication No. 2011/134013, International Publication No. 2010/086089, International Publication No. 2012/020327, International Publication No. 2011/051404. Further, compounds described in International Publication No. 2011/073149, JP2009-114086, JP2003-81988, JP2002-363552, and the like can also be mentioned.

  In the present invention, preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, or a metal-sulfur bond is preferable.

The phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of
It can be synthesized by applying the methods disclosed in Organic Chemistry, Vol. 4, pages 695-709 (2004), and references and the like described in these documents.

<Fluorescent compound>
Fluorescent compounds include, for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

[4.3] Injection layer, transport layer, blocking layer [4.3.1] Hole injection layer, electron injection layer The injection layer is interposed between the electrode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. For the layer to be provided, see “Organic EL device and its industrialization front line (November 30, 1998, issued by NTT)”, Chapter 2, Chapter 2, “Electrode materials” (pages 123-166). Details are described. In general, a hole injection layer can exist between an anode and a light emitting layer or a hole transport layer, and an electron injection layer can exist between a cathode and a light emitting layer or an electron transport layer.

  The details of the hole injection layer are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. Examples of the material used for the hole injection layer include: , Porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives, Inrocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinylcarbazole, aromatic amines introduced into the main chain or side chain Material or oligomer, polysilane, a conductive polymer or oligomer (e.g., PEDOT (polyethylene dioxythiophene): PSS (polystyrene sulfonic acid), aniline copolymers, polyaniline, polythiophene, etc.) and the like can be mentioned.

  Examples of the triarylamine derivative include benzidine type represented by α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), and MTDATA (4,4 ′, 4 ″). Examples include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine) and a compound having fluorene or anthracene in the triarylamine-linked core.

  There is no restriction | limiting in particular about the layer thickness of a positive hole injection layer, Usually, it exists in the range of about 0.1-100 nm, However, It is preferable in the range of 2-50 nm, and it exists in the range of 2-30 nm. Is more preferable.

  The details of the electron injection layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specific examples of materials preferably used for the electron injection layer are as follows. Metals represented by strontium and aluminum, alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metal halide layers represented by magnesium fluoride, calcium fluoride, etc. Examples thereof include an alkaline earth metal compound layer typified by magnesium, a metal oxide typified by molybdenum oxide and aluminum oxide, and a metal complex typified by lithium 8-hydroxyquinolate (Liq).

  The electron injection layer is desirably a very thin film, and although depending on the constituent material, the layer thickness is preferably in the range of 1 nm to 10 μm.

[4.3.2] Hole transport layer, electron transport layer The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer and the electron blocking layer are also positive. Functions as a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, and thiophene oligomers.

  As the hole transport material, those described above can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amine compounds can be used. preferable.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) c Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N- Examples include diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like.

  For the hole transport layer, known methods such as vacuum deposition, spin coating, casting, printing including ink jet, and LB (Langmuir Brodget, Langmuir Broadgett) are used as the hole transport material. Thus, it can be formed by thinning. Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Moreover, p property can also be made high by doping the material of a positive hole transport layer with an impurity. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer because an element with lower power consumption can be manufactured.

  The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer structure or a stacked structure of a plurality of layers.

  In the electron transport layer having a single-layer structure and the electron transport layer having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc. and the central metal of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as a material for the electron transport layer.

  The electron transport layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, and an LB method. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

[4.3.3] Blocking layer Examples of the blocking layer include a hole blocking layer and an electron blocking layer. In addition to the above-described layers of the organic EL element, the blocking layer is provided as necessary. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). Hole blocking (hole block) layer and the like.

  The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of an electron carrying layer can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense. The electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made. Moreover, the structure of a positive hole transport layer can be used as an electron blocking layer as needed.

The layer thickness of the hole blocking layer and the electron blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
[4.4] Manufacturing method of organic EL element As a manufacturing method of the organic EL element, an anode, a first carrier functional layer group, a light emitting layer, a second carrier functional layer group, and a cathode are laminated on a transparent substrate. A laminate is formed.

  First, a transparent substrate is prepared, and the anode according to the present invention is formed on the transparent substrate. At the same time, a connection electrode portion connected to an external power source is formed at the anode end portion.

  Next, a hole injection layer and a hole transport layer constituting the first carrier functional layer group, a light emitting layer, an electron transport layer constituting the second carrier functional layer group, and the like are sequentially laminated thereon.

As a method for forming each of these layers, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a printing method, or the like is used, but a uniform layer is easily obtained and pinholes are not easily generated. From the point of view, a vacuum deposition method or a spin coating method is particularly preferable. Furthermore, different formation methods may be applied for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 × 10 ⁻⁶ to 1 × 10 ⁻² Pa. It is desirable to appropriately select the respective conditions within the ranges of the deposition rate of 0.01 to 50 nm / second, the substrate temperature of −50 to 300 ° C., and the layer thickness of 0.1 to 5 μm.

  After forming the first carrier functional layer group, the light emitting layer, and the second carrier functional layer group as described above, the cathode according to the present invention is formed. At this time, the cathode is patterned in a shape in which a terminal portion is drawn from the upper side of the second carrier functional layer group to the periphery of the transparent substrate while maintaining an insulating state with respect to the anode by the organic functional layer group.

  An extraction electrode is connected to the transparent electrode. The extraction electrode is for electrically connecting the conductive layer 12 of the transparent electrode 10 and an external power source, and the material thereof is not particularly limited and a known material can be preferably used. A metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) having a layer structure can be used.

  As described above, the transparent organic EL device of the present invention can be produced.

  After forming the cathode, the anode, the first carrier functional layer group, the light emitting layer, the second carrier functional layer group, and the cathode are sealed on the transparent substrate with a sealing pattern.

[5] Sealing Examples of the sealing means used for sealing the organic EL element include a method of adhering a sealing member on a transparent substrate with an adhesive.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and it may be concave plate shape or flat plate shape. In the present invention, the same degree of transparency as that of the transparent substrate is required.

  Specifically, a glass plate, a polymer plate, a film, a metal plate, a film, etc. are mentioned. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

As the sealing member, a resin film with a gas barrier layer can be preferably used from the viewpoint of making the organic EL element thin and transparent. Therefore, the resin film with a gas barrier layer has a water vapor permeability of 1 × 10 ⁻³ g at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% RH measured by a method according to JIS K 7129-1992. is preferably / ^m 2 · 24h or less, more, oxygen permeability measured in compliance with the method provided in JIS K 7126-1987 ^{is, 1 × 10 -3 mL / m} 2 · 24h · atm (1atm is 1.01325 × 10 ⁵ Pa) or less, and the water vapor permeability at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% RH is 1 × 10 ⁻³ g / m ² · 24 h or less. It is preferable.

  In the gap between the sealing member and the display area (light emitting area) of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorocarbon or silicon oil is injected in the gas phase and liquid phase. It is preferable to do. Further, the gap between the sealing member and the display area of the organic EL element can be evacuated, or a hygroscopic compound can be sealed in the gap.

  An adhesive is appropriately used for sealing, and the adhesive layer is formed on the sealing member. As a material constituting the adhesive layer, a conventionally known sealing adhesive can be used. For example, a thermosetting adhesive, an ultraviolet curable resin, or the like is used, and preferably an epoxy resin, an acrylic resin, or silicone. A thermosetting adhesive such as a resin, more preferably an epoxy thermosetting adhesive resin that is excellent in moisture resistance and water resistance and has little shrinkage during curing. As thickness of an adhesive bond layer, it can be set as the range of 10-30 micrometers, for example.

  Further, after forming the metal thin wire of the cathode on the sealing member, it is possible to reduce the metal fine wire by adhering to the metal oxide layer, the conductive polymer layer or the metal thin film layer previously formed on the light emitting unit. Since it can avoid damaging the said light emission unit by the heating at the time of resistance-izing, it is a preferable embodiment.

  For example, when a resin film with a gas barrier layer is used as the sealing member, a fine metal wire pattern is formed on the resin film by using the above-described metal nano ink or the like, and is fired by flash firing or the like. On the other hand, a metal oxide layer, a metal thin film layer, or a conductive polymer layer is formed on the organic functional layer prepared in advance by the vapor deposition method or the coating method.

  Subsequently, the said metal fine wire pattern surface of the sealing member in which the metal fine wire pattern was formed is adhere | attached on the said metal oxide layer, a metal thin film layer, or a conductive polymer layer surface.

  As the adhesive, a thermosetting adhesive such as the epoxy resin, acrylic resin, or silicone resin is used.

  Moreover, it can also adhere | attach through the following conductive adhesive.

  For example, as the conductive adhesive, for example, an anisotropic conductive film (ACF), an anisotropic conductive paste (ACP), a metal paste, or the like is used.

  As an anisotropic conductive film, for example, fine conductive particles having conductivity are mixed with a thermosetting resin film. There is no restriction | limiting in particular as electroconductive particle, According to the objective, it can select suitably, For example, a metal particle, a metal covering resin particle, etc. are mentioned. Examples of the commercially available anisotropic conductive film include a low-temperature curing type that can also be applied to a resin film, such as MF-331 (manufactured by Hitachi Chemical).

  As a metal particle, nickel, cobalt, silver, copper, gold | metal | money, palladium etc. are mentioned, for example. These may be used individually by 1 type and may use 2 or more types together. Among these, nickel, silver, and copper are preferable. In order to prevent these surface oxidations, particles having gold or palladium on the surface may be used. Furthermore, you may use what gave the metal film and the insulating film with the organic substance on the surface.

  Examples of the metal-coated resin particles include particles in which the surface of the resin core is coated with any metal of nickel, copper, gold, and palladium. Similarly, particles obtained by applying gold or palladium to the outermost surface of the resin core may be used. Further, a resin core whose surface is coated with a metal protrusion or an organic material may be used.

  Further, the anisotropic conductive paste is configured by mixing the conductive particles with a paste-like thermosetting resin. Examples of the commercially available anisotropic conductive paste include NIR-30E manufactured by Sanyu Rec.

  When an anisotropic conductive paste is used as the conductive adhesive, an adhesive layer can be provided by a printing process such as a screen printing method. Specifically, the anisotropic conductive paste is provided with a thickness of 5 to 30 μm by a screen printing method or the like and then dried. Although the anisotropic conductive paste after drying can be stored at room temperature, since it has slight adhesiveness, it is preferable to protect it by covering with a slip sheet or a transparent protective film.

  Moreover, as a metal paste, the silver particle paste, silver-palladium particle paste, gold particle paste, copper particle paste, etc. which are commercially available metal nanoparticle pastes can be selected suitably and used. Examples of the metal paste include silver pastes for organic EL element substrates (CA-6178, CA-6178B, CA-2500E, CA-2503-4, CA-2503N, CA-271, etc. sold by Daiken Chemical Co., Ltd. , Specific resistance value: 15-30 mΩ · cm, formed by screen printing method, curing temperature: 120-200 ° C., LTCC paste (PA-88 (Ag), TCR-880 (Ag), PA-Pt (Ag · Pt)), silver paste for glass substrates (US-201, UA-302, firing temperature: 430 to 480 ° C.), and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
[Production of Organic EL Element 1]
(Formation of anode)
As an anode, IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) is 110 nm thick on an alkali-free glass substrate 60 mm × 80 mm in length and width 0.7 mm, L-430S- Using an FHS sputtering apparatus, Ar: 20 sccm, O ₂ : ₂ sccm, sputtering pressure: 0.25 Pa, room temperature, target-side power: 1000 W, and target-substrate distance: 86 mm were formed by RF sputtering. After forming a film by patterning, the transparent support substrate provided with the IZO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

(Formation of hole injection layer to electron injection layer)
The support substrate provided with this IZO layer is fixed to a substrate holder of a commercially available vacuum deposition apparatus, and α-NPD, compound H4, compound Ir-4, BAlq, Alq ₃ , and lithium fluoride are respectively added to each tantalum resistance heating boat. And attached to the first vacuum chamber of the vacuum deposition apparatus. The structures of Compound H4, Compound Ir-4, α-NPD, BAlq, and Alq ₃ are as follows.

さらに、各タングステン製抵抗加熱ボートにＡｇを入れ、真空蒸着装置の第２真空槽に取り付けた。

Furthermore, Ag was put into each resistance heating boat made from tungsten, and it attached to the 2nd vacuum chamber of a vacuum evaporation system.

First, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and deposited on the IZO layer at a deposition rate of 0.1 to 0.2 nm / sec. A hole transport layer serving also as a 20 nm thick hole injection layer was provided.

  Further, the heating boat containing H4 and the heating boat containing Ir-4 are energized independently so that the deposition rate of H4 as a light emitting host and Ir-4 as a light emitting dopant becomes 100: 6. And a light emitting layer having a thickness of 30 nm was provided.

  Next, the heating boat containing BAlq was energized and heated to provide a 10 nm thick hole blocking layer at a deposition rate of 0.1 to 0.2 nm / sec.

Furthermore, the heating boat containing Alq ₃ was heated by energization to provide an electron transport layer having a film thickness of 20 nm at a deposition rate of 0.1 to 0.2 nm / second.

  Furthermore, it supplied with electricity to the said heating boat containing lithium fluoride, and it heated, and provided the electron injection layer with a film thickness of 1 nm with the vapor deposition rate of 0.01-0.02 nm / sec.

(Formation of cathode)
Next, the element formed up to the electron injection layer is transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing Ag is energized and heated. Then, a layer made of Ag having a film thickness of 10 nm was formed at a deposition rate of 0.1 to 0.1 to 0.2 nm / second to form a cathode electrode (cathode).

(Element sealing)
Finally, the device obtained above is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (Lux Track LC0629B, manufactured by Toagosei Co., Ltd.) is used as a sealing material around it. The organic EL device 1 was obtained by applying it, bringing it into intimate contact with the support substrate of the device, irradiating UV light from the glass substrate side, curing and sealing.

[Production of Organic EL Element 2]
In the production of the organic EL element 1, a layer made of Ag (hereinafter referred to as an Ag layer) is formed using Ag as an anode at a deposition rate of 0.1 to 0.1 to 0.2 nm / second and a thickness of 10 nm. IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) with a thickness of 110 nm using an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar: 20 sccm, O ₂ : ₂ sccm, sputtering pressure: 0. Organic EL element 2 was produced in the same manner except that it was formed by RF sputtering at 25 Pa, room temperature, target-side power: 1000 W, target-substrate distance: 86 mm.

[Production of Organic EL Element 3]
In the production of the organic EL element 1, an organic EL element 3 was produced in the same manner except that a conductive polymer (PEDOT / PSS) -containing liquid was applied and patterned as an anode to form a conductive polymer layer.

  The conductive polymer layer was formed to a thickness of 500 nm by printing the following conductive polymer-containing liquid by an ink jet method and then baking it at 120 ° C. for 30 minutes using a hot plate.

  The conductive polymer-containing liquid is 0.40 g of a water-soluble binder resin aqueous solution (solid content 20% aqueous solution), 1.90 g of PEDOT-PSS CLEVIOS PH750 (solid content 1.03%) (manufactured by Heraeus), and dimethyl sulfoxide. 0.10 g was mixed and adjusted. In addition, the water-soluble binder resin aqueous solution is prepared by dissolving the water-soluble binder resin in pure water to a solid content of 20%.

  The water-soluble binder resin was cooled to room temperature under nitrogen after adding 200 ml of tetrahydrofuran (THF) to a 300 ml three-necked flask and heating to reflux for 10 minutes. Next, 2-hydroxyethyl acrylate (10.0 g, 86.2 mmol, molecular weight 116.12) and azobisbutyronitrile (AIBN) (2.8 g, 17.2 mmol, molecular weight 164.11) were added, and 5 hours. Heated to reflux. Subsequently, after cooling to room temperature, the reaction solution was dripped in 2000 ml methyl ethyl ketone (MEK), and it stirred for 1 hour. Subsequently, this MEK solution was decanted and then washed with 100 ml of MEK three times, the polymer was dissolved with THF, and transferred to a 100 ml flask. Next, the THF solution was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 9.0 g (yield 90%) of a water-soluble binder resin having a number average molecular weight of 22100 and a molecular weight distribution of 1.42 was obtained.

Here, the structure and molecular weight of the water-soluble binder resin were measured by 1H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.
(GPC measurement conditions)
Device: Waters 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
[Production of Organic EL Element 4]
First, a fine metal wire pattern was formed on the substrate by the following procedure.

(Metallic fine wire pattern)
On the alkali-free glass substrate, a silver nanoparticle dispersion (Flow Metal SR6000, manufactured by Bando Chemical Co., Ltd.) is applied as a metal ink composition in a stripe pattern with a width of 50 μm and a pitch of 1 mm using an inkjet printing method. did. The area for printing the pattern was 150 mm × 150 mm. As an ink jet printing method, an ink jet head having an ink droplet ejection amount of 4 pl was used, and a coating speed and an ejection frequency were adjusted to print a pattern. As the ink jet printing apparatus, a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an ink jet head (manufactured by Konica Minolta Co., Ltd.) was used and controlled by an ink jet evaluation apparatus EB150 (manufactured by Konica Minolta Co., Ltd.).

  Next, wavelength control infrared rays in which two quartz glass plates that absorb infrared rays having a wavelength of 3.5 μm or more are attached to an infrared irradiation device (ultimate heater / carbon, manufactured by Meimitsu Kogyo Co., Ltd.) and cooling air is allowed to flow between the glass plates. The pattern of the formed metal ink composition was dried using a heater.

Next, using a xenon flash lamp 2400WS (manufactured by COMET) equipped with a short wavelength cut filter of 250 nm or less, flash light with a total light irradiation energy of 3.5 J / cm ² was irradiated with metal ink in an irradiation time of 2 ms. Irradiate once from the pattern side of the composition. The dried metal ink composition pattern was baked.

Next, on the formed thin metal wire pattern, IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) as a conductive layer is 110 nm thick, using an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar : 20 sccm, O ₂ : ₂ sccm, sputtering pressure: 0.25 Pa, room temperature, target side power: 1000 W, target-substrate distance: 86 mm.

  Next, a hole injection layer to an electron injection layer were formed in the same manner as in the production of the organic EL element 1.

  Next, in the same procedure as the anode, the cathode is formed using Ag as a conductive layer so as to have a thickness of 10 nm under the vapor deposition conditions, and then the ink jet printing method is used thereon in an Ar atmosphere. The silver nanoparticle dispersion was applied in a stripe pattern with a width of 50 μm and a pitch of 1 mm to form a fine metal wire pattern made of Ag, and fired in the same manner with flash light, and then an epoxy photocurable adhesive (Toagosei Co., Ltd.) The organic EL element 4 was produced by sealing through a manufactured Luxtrack LC0629B).

  At this time, the patterns of the anode and the cathode were drawn so as to overlap each other well.

[Production of Organic EL Element 5]
In the production of the organic EL element 4, the compound H4, which is a nitrogen-containing compound, is put in a resistance heating boat made of tantalum, the first vacuum tank is depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the compound is energized. Then, an organic compound layer having a thickness of 5 nm composed of compound H4 was formed on the glass substrate at a deposition rate of 0.1 nm / second to 0.2 nm / second.

Next, an Ag layer having a thickness of 10 nm was formed as a conductive layer on the organic compound layer to form an anode. Moreover, the organic EL element 5 was produced in the same manner except that an IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) layer having a thickness of 110 nm was formed on the metal fine wire pattern as the cathode.

[Production of Organic EL Element 6]
In the production of the organic EL element 4, the organic EL element 6 was similarly prepared except that a conductive polymer (PEDOT / PSS) layer having a thickness of 500 nm was used as the anode conductive layer and an Ag layer was used as the cathode conductive layer. Was made.

[Production of Organic EL Element 7]
In the production of the organic EL element 4, the metal thin wire pattern of the cathode was baked by heating at 120 ° C. for 30 minutes using a hot air circulation type oven, and then IZO (mass ratio In ₂ O ₃ having a thickness of 110 nm as a conductive layer. : ZnO = 90: 10) layer was used to produce the organic EL device 7 in the same manner.

[Production of Organic EL Element 8]
In the production of the organic EL element 4, the organic EL element 8 was produced in the same manner except that the fine metal wire pattern of the cathode was formed by the ink jet printing method in the atmosphere.

[Production of Organic EL Element 9]
In the production of the organic EL element 4, the organic EL element 9 was prepared in the same manner except that an IGO (mass ratio In ₂ O ₃ : Ga ₂ O ₃ = 90: 10) layer having a thickness of 110 nm was used as the anode conductive layer. Produced.

For the IGO layer, an L-430S-FHS sputtering apparatus manufactured by Anerva is used. Ar: 20 sccm, O ₂ : ₂ sccm, sputtering pressure: 0.25 Pa, room temperature, target-side power: 1000 W, target-substrate distance: 86 mm It was formed by RF sputtering.

[Production of Organic EL Element 10]
In the production of the organic EL element 4, the organic EL element 10 was produced in the same manner except that an Al layer having a thickness of 10 nm was used as the cathode conductive layer.

[Production of Organic EL Element 11]
In the production of the organic EL element 4, the organic EL element 11 was produced in the same manner except that the following resin base material was used as the substrate.

<Resin substrate>
A polyethylene terephthalate (PET / CHC) film (G1SBF, thickness 125 μm, refractive index 1.59, hereinafter referred to as a CHC-PET film) manufactured by Kimoto Co., Ltd. was prepared as a resin base material.

<Particle-containing layer>
Next, a particle-containing layer was produced on the back surface (surface on which the conductive layer is not formed) of the prepared resin base material.

  For the particle-containing layer, a colloidal silica-containing monomer was prepared by the following method, and then a particle-containing layer preparation solution was prepared from the colloidal silica-containing monomer. And the particle | grain content layer was formed using the particle content layer preparation liquid.

(Preparation of colloidal silica-containing monomer)
2-Methacryloyloxyethyl isocyanate (abbreviation: MOI, molecular weight 155) is added to 130 parts by mass of colloidal silica (SiO ₂ component 30% by mass, average particle size 20 nm, manufactured by Nissan Chemical Co., Ltd.) dispersed using ethyl acetate as a solvent. , Manufactured by Showa Denko KK) and 0.1 parts by mass of di-n-butyltin dilaurate (abbreviation: DBTDL) as a catalyst were added and stirred at room temperature for 24 hours. The reaction of the isocyanate group was confirmed by infrared spectroscopy (IR), and ethyl acetate as a solvent was removed with an evaporator to obtain a colloidal silica-containing monomer.

(Preparation of particle-containing layer preparation solution)
To 100 parts by mass of the colloidal silica-containing monomer produced above (non-volatile content: 36% by mass), a methyl ethyl ketone solution of Li / CF ₃ SO ₃ ^— (non-volatile content: 50% by mass, manufactured by Sanko Chemical Co., Ltd.) Were mixed and stirred. As an initiator, 1 part by mass of Irgacure 907 (manufactured by BASF Japan) was added to prepare a particle-containing layer preparation solution.

(Formation of particle-containing layer)
Next, the prepared particle-containing layer preparation liquid was applied and dried on a resin base material under the condition that the thickness after curing was 10 μm. Thereafter, an ultraviolet irradiation treatment was performed using an 80 W / cm mercury lamp under the condition of 300 mJ to form a particle-containing layer.

<Gas barrier layer>
Next, a gas barrier layer was produced on the surface of the resin substrate (surface on the side where the conductive layer is formed).

  The resin base material was set in a discharge plasma chemical vapor deposition apparatus (Plasma CVD apparatus Precision 5000 manufactured by Applied Materials) and continuously conveyed by roll-to-roll. Next, a magnetic field was applied between the film forming rollers, and electric power was supplied to each film forming roller to generate plasma between the film forming rollers to form a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas) is supplied as a film forming gas from a gas supply pipe to the formed discharge region. Then, a gas barrier layer having a layer thickness of 120 nm was formed under the following conditions.

(Deposition conditions)
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Reaction gas (O ² ) supply amount: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.8 m / min
[Production of Organic EL Element 12]
In the production of the organic EL element 11, using the prepared PET film with a gas barrier layer as a substrate, in the same manner as the organic EL element 1, an anode (IZO), a hole injection layer to an electron injection layer, and a cathode (Ag layer) Formed.

  As a sealing substrate, a thermosetting liquid adhesive (epoxy photocurable adhesive: Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) is applied to the gas barrier layer side of the PET film with the gas barrier layer produced as described above at a thickness of 30 μm. And dried at 80 ° C. for 30 minutes.

  Next, a thin metal wire pattern was formed on the epoxy-based photocurable adhesive under atmospheric pressure in the same manner as in the production of the organic EL element 4 and fired with flash light.

  Next, the adhesive surface on which the fine metal wire pattern of the sealing member was formed and the cathode (Ag layer) of the organic EL element were superposed and bonded by a dry laminating method to produce the organic EL element 12.

[Production of Organic EL Element 13]
In the production of the organic EL element 12, the organic EL element 13 was produced in the same manner except that the anode was formed under the production conditions of the organic EL element 2 using Ag instead of IZO.

[Production of Organic EL Element 14]
In the production of the organic EL element 12, a metal fine wire pattern was formed on a sealing substrate with a silver nanoparticle dispersion, and then applied to the cathode (Ag) after applying curable PEDOT. An organic EL element 14 was produced.

[Production of Organic EL Element 15]
In the production of the organic EL element 14, a metal fine wire pattern is formed on the sealing substrate with a silver nanoparticle dispersion liquid, and then an anisotropic conductive adhesive (NIR-30E manufactured by Sanyu Rec Co., Ltd.) is formed by screen printing. An organic EL element 15 was produced in the same manner except that it was bonded to the cathode (Ag) using a dried sealing substrate after being provided with a thickness of 5 μm.

[Production of Organic EL Element 16]
In the production of the organic EL element 4, first, IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) is formed as a conductive layer on the above-described glass substrate at a thickness of 110 nm, and L-430S-FHS sputtering manufactured by Anelva. Using an apparatus, it was formed by RF sputtering with Ar: 20 sccm, O ₂ : ₂ sccm, sputtering pressure: 0.25 Pa, room temperature, target-side power: 1000 W, and target-substrate distance: 86 mm.

  Next, a silver nanoparticle dispersion (Flow Metal SR6000, manufactured by Bando Chemical Co., Ltd.) is applied onto the IZO layer in an Ar atmosphere using an ink-jet printing method in a 50 μm width and 1 mm pitch to form a metal fine line pattern. did.

  Further, only on the metal thin wire pattern, a silicon oxide dispersion having a thickness of 100 nm is formed as an insulating layer using an ink jet printing method, and then a hole injection layer to an electron injection layer and a cathode (Ag) are formed. Thus, an organic EL element 16 was produced.

  The following evaluation was performed using the produced organic EL elements 1 to 16.

≪Evaluation≫
<Total light transmittance>
A commercially available spectrophotometer was used for the total light transmittance of the produced organic EL device when not emitting light in accordance with JIS K 7361-1: 1997 (a test method for the total light transmittance of plastic-transparent material). The total light transmittance in the light wavelength region of 400 to 700 nm was measured.

<Luminescent efficiency>
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated.

  Here, the measurement of emission luminance was performed using CS-1000 (manufactured by Konica Minolta Sensing), the external extraction quantum efficiency was set to 100 for the organic EL element 1, and the following ranking was performed for the relative values of each sample.

◎: 90 or more and 100 or less ○: 80 or more and less than 90 <Sheet resistance value>
The conductivity of each anode and cathode is made on a glass substrate so that it has the same structure as a square, and an extraction electrode is attached to each, and the resistance value (Ω) is measured. This is the sheet resistance of each electrode. Value (Ω / □) was used.

<Uniform luminescence>
The produced organic EL element was made to emit light, and it was visually evaluated whether or not the light emission state of the entire element was uniform.

  Table 1 shows the configuration and evaluation results of the above organic EL elements.

表１から、陽極は金属細線と金属酸化物層、金属細線と金属薄膜層、又は金属細線と導電性ポリマー層の組み合わせから選択され、陰極は金属細線と金属酸化物層、又は金属細線と金属薄膜層の組み合わせから選択される電極を用いることで、シート抵抗値が低下し、均一発光が可能な透明有機エレクトロルミネッセンス素子が得られることが分かる。

From Table 1, the anode is selected from metal wire and metal oxide layer, metal wire and metal thin film layer, or a combination of metal wire and conductive polymer layer, and the cathode is metal wire and metal oxide layer, or metal wire and metal oxide layer. It can be seen that by using an electrode selected from a combination of thin film layers, a sheet resistance value is reduced, and a transparent organic electroluminescence element capable of uniform light emission is obtained.

  In addition, after forming the metal fine line pattern on the sealing substrate, it is also found that bonding the metal fine line pattern to the cathode formed of the metal oxide layer and the metal thin film layer with an adhesive is also a preferable manufacturing method. It was.

  Since the transparent organic electroluminescent element of this invention is an element which has a low resistance and highly transparent electrode, it is suitable for the organic electroluminescent element by which high transparency is requested | required. Moreover, it is suitable for a double-sided light emitting organic electroluminescence element.

DESCRIPTION OF SYMBOLS 10 Transparent electrode 11 Resin base material 12 Conductive layer 12A Anode 12B Cathode 13 Metal fine wire pattern 14 Metal oxide layer, metal thin film layer, or conductive polymer layer 15 Underlayer 16 Particle-containing layer 17 Gas barrier layer 18 Organic compound-containing layer 21 Light-Emitting Unit 30 Organic EL Element 31 Transparent Substrate 32 Anode 33 First Carrier Functional Layer Group 34 Light-Emitting Layer 35 Second Carrier Functional Layer Group 36 Cathode 37 Adhesive 38 Sealant h Luminous Center L, L ′ Light

Claims (7)

  A transparent organic electroluminescence device having a total light transmittance of 45% or more in the visible light region of the organic electroluminescence device when not emitting light, wherein the anode is a metal fine wire and a metal oxide layer, a metal fine wire and a metal thin film layer, or A transparent organic electroluminescence device, wherein the transparent organic electroluminescent device is selected from a combination of a metal fine wire and a conductive polymer layer, and a cathode is selected from a combination of a metal fine wire and a metal oxide layer, or a combination of a metal fine wire and a metal thin film layer.   The transparent organic electroluminescent element according to claim 1, wherein the anode has at least a thin metal wire and a metal oxide layer.   The transparent organic electroluminescent element according to claim 1, wherein the cathode has at least a thin metal wire and a thin metal film layer.   The transparent organic electroluminescence device according to any one of claims 1 to 3, wherein the metal thin film layer of the cathode is a silver thin film layer.   It is a manufacturing method of the transparent organic electroluminescent element which manufactures the transparent organic electroluminescent element as described in any one of Claim 1- Claim 4, Comprising: The metal thin wire of the said cathode is printed under inert gas A method for producing a transparent organic electroluminescent element, characterized by comprising:   6. The method for producing a transparent organic electroluminescent element according to claim 5, wherein the metal thin wire of the cathode is fired by flash firing.   The metal thin wire of the cathode is formed on a base material constituting a sealing layer, and then adhered to the metal oxide layer, the metal thin film layer, or the conductive polymer layer. The manufacturing method of the transparent organic electroluminescent element of description.

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