JPWO2018190010A1 - Organic electroluminescence device - Google Patents

Abstract

It is an object of the present invention to provide an organic electroluminescent device which has excellent rectification characteristics and suppresses generation of dark spots. The organic electroluminescent element (1) comprises a first electrode (3) including at least a thin metal wire (3a) and a transparent conductive layer (3b), an organic functional layer (4), Two electrodes (5), an inorganic protective layer (6), an adhesive layer (7), and a sealing member (8) are sequentially laminated.

Description

  The present invention relates to an organic electroluminescence device.

2. Description of the Related Art In recent years, organic EL devices such as organic electroluminescent devices (hereinafter, also referred to as “organic EL devices”) and organic solar cells are required to have high efficiency, large area, and flexibility. In an organic EL device, a method of using a transparent electrode using a thin metal wire is known for increasing the area.
For example, a technique has been disclosed in which a conductive electrode such as a metal nanowire is contained in a transparent electrode (for example, see Patent Document 1).

On the other hand, organic EL devices are known to be degraded by impurities such as oxygen and water, and sealing is required to shut them off. As a sealing method corresponding to a flexible substrate, there is known a contact-type sealing method in which a space is not provided on an organic EL element surface and a sealing member is bonded on a second electrode via an adhesive. (For example, see Patent Document 2).
However, when these sealing structures are used for a transparent electrode using a thin metal wire, there has been a problem that the rectification ratio deteriorates and a dark spot occurs in the light emitting portion.

US Patent Application Publication No. 2010/0255323 JP 2008-77855 A

  The present invention has been made in view of the above problems and circumstances, and a problem to be solved is to provide an organic electroluminescent element having excellent rectification characteristics and suppressing generation of dark spots.

  The present inventor has conducted intensive studies and found that, when sealing using an adhesive is used in an organic EL device, the generation of dark spots in the organic EL device is suppressed by laminating an inorganic protective layer on the second electrode. In addition, the inventors have found that the rectification characteristics are improved, leading to the present invention. It is presumed that this was because the damage to the organic functional layer could be reduced. It is considered that the reason why the generation of dark spots is suppressed is that the inorganic protective layer was able to suppress the influence of diffusion of moisture and the like caused by the adhesive. Further, it has been found that by setting the arithmetic average roughness Ra of the fine metal wire in a preferable range, the generation of dark spots is further suppressed. It is presumed that this was because deterioration of the inorganic protective layer due to minute unevenness of the fine metal wire could be suppressed. The rectification characteristic specifically means a rectification ratio.

  That is, the above object according to the present invention is solved by the following means.

1. An organic electroluminescence element in which a first electrode including at least a thin metal wire and a transparent conductive layer, an organic functional layer, a second electrode, an inorganic protective layer, an adhesive layer, and a sealing member are sequentially laminated on a transparent flexible base material.

2. 2. The organic electroluminescence device according to the above 1, wherein the fine metal wire has an arithmetic average roughness Ra of 1 to 20 nm.

3. 3. The organic electroluminescence device according to 1 or 2, wherein the arithmetic average roughness Ra of the thin metal wire is 1 to 10 nm.

4. 4. The organic electroluminescent device according to any one of 1 to 3, wherein the inorganic protective layer has a thickness of 500 to 1500 nm.

5. 5. The organic electroluminescence device according to any one of 1 to 4, wherein the inorganic protective layer is formed from three layers having different film densities.

6. 6. The organic electroluminescence device according to 5, wherein the intermediate layer has the lowest film density among the three inorganic protective layers.

7. 7. The organic electroluminescent device according to the item 6, wherein the thickness of the intermediate layer is 20 to 50% of the total thickness of the inorganic protective layer.

8. 8. The organic electroluminescence device according to any one of 1 to 7, wherein the inorganic protective layer is silicon nitride.

9. 9. The organic electroluminescence device according to any one of 1 to 8, wherein the transparent conductive layer is an amorphous metal oxide.

10. The organic electroluminescence device according to any one of 1 to 9, wherein the transparent conductive layer has a thickness of 50 to 300 nm.

11. The organic electroluminescence device according to any one of 1 to 10, wherein a base layer is provided between the transparent flexible base material and the first electrode.

12. 12. The organic material according to the above item 11, wherein the underlayer contains at least one selected from a compound having a thiol group, poly (meth) acrylate having an aminoethyl group, and poly (meth) acrylamide having an aminoethyl group. Electroluminescence element.

  According to the above-described means of the present invention, it is possible to provide an organic electroluminescence device having excellent rectification characteristics and suppressing generation of dark spots.

FIG. 2 is a schematic cross-sectional view showing a schematic configuration as an example of the organic EL device of the present invention FIG. 3 is a schematic cross-sectional view showing a schematic configuration as another example of the organic EL element of the present invention. FIG. 3 is a schematic cross-sectional view showing a schematic configuration as another example of the organic EL element of the present invention. FIG. 3 is a schematic cross-sectional view showing a schematic configuration as another example of the organic EL element of the present invention. FIG. 3 is a schematic cross-sectional view showing a schematic configuration as another example of the organic EL element of the present invention. FIG. 2 is a schematic cross-sectional view showing a schematic configuration as an example of an inorganic protective layer in the organic EL device of the present invention.

  Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail. In the present application, “to” representing a numerical range is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

<< Organic EL device >>
The organic EL device according to the present invention includes a first electrode, an organic functional layer, a second electrode, an inorganic protective layer, and at least a thin metal wire and a transparent conductive layer on a transparent flexible substrate (hereinafter, also referred to as a substrate). An adhesive layer and a sealing member (sealing layer) are sequentially laminated.

  FIG. 1 shows a schematic configuration of the organic EL device of the present invention. As shown in FIG. 1, an organic EL element 1 has a first electrode 3 as a transparent electrode, an organic functional layer 4, a second electrode 5 as a counter electrode, an inorganic protective layer 6, an adhesive on a transparent flexible substrate 2. The layer 7 and the sealing member 8 are sequentially laminated. The term “transparent (translucent)” as used herein means that the light transmittance at a wavelength of 550 nm is 50% or more.

  In the organic EL element 1 shown in FIG. 1, the first electrode 3 is configured by laminating a thin metal wire 3a and a transparent conductive layer 3b formed in a pattern from the transparent flexible base material 2 in this order. As shown in FIG. 2, a transparent conductive layer 3b and a thin metal wire 3a formed in a pattern may be laminated in this order from the transparent flexible base material 2 side, and further cover the thin metal wire 3a. Thus, an insulating layer (not shown) may be provided. However, from the viewpoint of productivity, it is preferable that the first electrode 3 be configured by sequentially laminating the thin metal wires 3a and the transparent conductive layers 3b formed in a pattern from at least the transparent flexible base material 2 side.

The organic functional layer 4 includes at least a light emitting layer, and may have various organic layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. The hole injection layer and the hole transport layer may be provided as a hole transport injection layer. The electron transport layer and the electron injection layer may be provided as an electron transport injection layer. Further, among these organic layers, for example, the electron injection layer may be made of an inorganic material.
The organic functional layer 4 may have a hole-blocking layer, an electron-blocking layer, and the like, if necessary, in addition to these layers.

  The second electrode 5 may have a laminated structure as needed.

  Further, the inorganic protective layer 6 may have a laminated structure as required. For example, as shown in FIG. 6, the inorganic protective layer 6 may be composed of a first inorganic protective layer 6a, a second inorganic protective layer 6b, and a third inorganic protective layer 6c. The inorganic protective layer 6 may be composed of two layers, or may be composed of four or more layers.

  In the organic EL device 1, only the portion where the organic functional layer 4 is sandwiched between the first electrode 3 and the second electrode 5 becomes the light emitting region in the organic EL device 1. The organic EL element 1 has a configuration in which generated light (hereinafter, also referred to as emission light) is extracted from at least the transparent flexible substrate 2 side.

  Further, in the organic EL element 1, at the end portions of the first electrode 3 and the second electrode 5, an extraction electrode (not shown) is provided. The first electrode 3 and the second electrode 5 are electrically connected to an external power supply (not shown) through the corresponding electrodes.

The organic EL element 1 of the present invention may have other various functional layers as needed.
For example, as shown in FIG. 3, the gas barrier layer 9 may be provided on the transparent flexible base material 2.
Further, as shown in FIG. 4, an underlayer 10 may be provided between the transparent flexible base material 2 and the first electrode 3.
Further, as shown in FIG. 5, a gas barrier layer 9 and a base layer 10 may be provided in this order between the transparent flexible base material 2 and the first electrode 3.
Furthermore, a particle-containing layer may be provided on the surface of the transparent flexible substrate 2 opposite to the first electrode 3. The particle-containing layer is preferably arranged on the outermost layer.
These functional layers can be provided alone or in combination of two or more.

<First electrode (3)>
Hereinafter, each member constituting the first electrode according to the present invention will be described.

(Fine metal wire (3a))
The fine metal wire used in the present invention contains a metal as a main component and is formed with a metal content ratio such that conductivity can be obtained. The ratio of the metal in the thin metal wire is preferably 50% by mass or more.

  The thin metal wire contains a metal material and is formed in a pattern so as to have an opening. The opening is a portion having no thin metal wire and is a light-transmitting portion of the first electrode.

  There is no particular limitation on the pattern shape of the thin metal wire. Examples of the pattern shape of the thin metal wire include a stripe shape (parallel line shape), a lattice shape, a honeycomb shape, a random mesh shape, and the like. From the viewpoint of transparency, the stripe shape is particularly preferable.

  Further, the ratio occupied by the openings (opening ratio) is preferably 80% or more from the viewpoint of transparency.

  The line width of the fine metal wire is preferably in the range of 5 to 100 μm. Desired conductivity is obtained when the line width of the thin metal wire is 5 μm or more, and when the line width is 100 μm or less, the luminous efficiency of the organic EL element can be further improved. Further, in a stripe-like or lattice-like pattern, the interval between the fine metal wires is preferably in the range of 0.01 to 1 mm.

  The height (thickness) of the thin metal wire is preferably in the range of 0.05 to 3.0 μm, and more preferably in the range of 0.1 to 0.6 μm. Desired conductivity is obtained when the height of the thin metal wire is 0.05 μm or more, and when the height is 3.0 μm or less, when the thin metal wire is used for an organic EL device, the height of the thin metal wire is the layer thickness distribution of the functional layer. Can be reduced.

The arithmetic average roughness Ra of the fine metal wire is preferably 1 to 20 nm. The arithmetic average roughness Ra is based on JIS B 0601: 2001.
When forming a thin metal wire on a flexible substrate, the arithmetic average roughness becomes 1 nm or more due to the influence of the material and the forming method of the thin metal wire. The arithmetic average roughness Ra of the thin metal wire is more preferably 10 nm or less from the viewpoint of dark spot generation and rectification characteristics.

The arithmetic average roughness Ra can be measured using, for example, an atomic force microscope (manufactured by Digital Instruments), and is a value obtained by measuring 5 μm squares at the center of a thin metal wire. The central portion of the thin metal wire is a portion within a predetermined range including the center of the cross section cut perpendicular to the line direction of the thin metal wire, that is, the midpoint of the line width (horizontal direction) of the thin metal wire and the center of the thin metal wire. It refers to a part of a predetermined range including a point where the middle point in the height direction (vertical direction) intersects. The central area of 5 μm square of the thin metal wire is a rectangular area of 5 μm × 5 μm centered on the intersection.
Further, the arithmetic average roughness Ra can be controlled by appropriately selecting a material, a forming condition, and a forming method of the thin metal wire.

(1) Metal nanoparticle-containing composition As described below, a metal fine wire is prepared by preparing a metal nanoparticle-containing composition in which a metal or a material for forming a metal is blended, applying the composition, followed by drying treatment, baking treatment, or the like. Processing is performed as appropriate to form.
Examples of the metal used for the metal nanoparticles include metals such as gold, silver, copper, and platinum, and alloys containing these as main components. Among these, gold and silver are preferable from the viewpoint of excellent light reflectance and further improving the luminous efficiency of the obtained organic EL device. These metals or alloys can be used alone or in an appropriate combination of two or more.

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

  As the average particle diameter of the metal nanoparticles in the metal nanoparticle-containing composition, those having an average particle size of 1000 nm or less can be preferably applied. In particular, the metal nanoparticles preferably have an average particle diameter in a range of 3 to 300 nm, and more preferably have an average particle diameter in a range of 5 to 100 nm. In particular, silver nanoparticles having an average particle diameter of 5 to 100 nm are preferable.

  Here, the average particle diameter of the metal nanoparticles and the metal colloid can be determined by measuring the particle diameter of the metal nanoparticles in the dispersion using a transmission electron microscope (TEM). For example, among the particles observed in the TEM image, the average particle diameter can be calculated by measuring the particle diameters of 300 independent non-overlapping metal nanoparticles.

  In the metal colloid, an organic π-junction ligand is preferable as a protective agent for coating the surface of the metal nanoparticle. The π-junction of the organic π-conjugated ligand to the metal nanoparticles imparts conductivity to the metal colloid.

As the organic π-junction ligand, one or more compounds selected from the group consisting of phthalocyanine derivatives, naphthalocyanine derivatives and porphyrin derivatives are preferable.
In addition, as the organic π-junction ligand, the coordination to metal nanoparticles, in order to improve the dispersibility in the dispersion medium, as an amino group, an alkylamino group, a mercapto group, a hydroxyl group as a substituent, 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 of

  Further, as the organic π-junction ligand, an organic π-conjugated ligand described in WO 2011/114713 can be used.

As the 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

  Examples of a method for preparing a metal nanoparticle dispersion containing an organic π-junction ligand include a liquid phase reduction method. In addition, the production of the organic π-junction ligand and the preparation of the metal nanoparticle dispersion containing the organic π-junction ligand of the present embodiment are performed by the method described in paragraphs 0039 to 0060 of WO2011 / 114713. It can be performed according to it.

  The average particle size 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 thin metal wire can be improved.

In the metal nanoparticle dispersion, it is preferable to use, as a protective agent for coating the surface of the metal nanoparticle, a protective agent that releases a ligand at a low temperature of 200 ° C. or lower. Thereby, at low temperature or low energy, the protective agent comes off, the metal nanoparticles are fused, and conductivity can be imparted.
Specifically, metal nanoparticle dispersions described in JP-A-2013-142173, JP-A-2012-162767, JP-A-2014-139343, Japanese Patent No. 5606439, and the like are exemplified.

  Examples of the metal forming material include a metal salt, a metal complex, an organic metal compound (a compound having a metal-carbon bond), and the like. The metal salt and the 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 in the metal nanoparticle-containing composition, a metal is generated from the material, and a thin metal wire containing the metal is formed.

As the material for forming the metallic silver, using a silver compound represented by "Ag n _X", the organic silver complex made by reacting an ammonium carbamate-based compound is preferable. In "Ag _n X", n is an integer from 1 to 4, X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, It is a substituent selected from the group consisting of acetylacetonate and carboxylate.

  Examples of the silver compound include silver oxide, silver thiocyanate, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoride borate, and silver acetylacetate. Silver nitrate, silver acetate, silver lactate, silver oxalate and the like can be mentioned. As the silver compound, silver oxide or silver carbonate is preferably used in terms of reactivity and post-treatment.

  Examples of the 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, and 2-ethylhexylammonium 2 -Ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutylammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyldecyl ammonium methyldecyl Rubamate, hexamethyleneiminium hexamethyleneimine carbamate, morpholium morpholine carbamate, pyridinum ethylhexyl carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzyl carbamate, triethoxysilylpropylammonium triethoxysilylpropyl carbamate, etc. Can be. Among the above-mentioned ammonium carbamate compounds, primary ammonium-substituted alkylammonium alkyl carbamates are preferable because they are superior in reactivity and stability to secondary or tertiary amines.

  The organic silver complex can be produced by the method described in JP-A-2011-148795. For example, it can be synthesized by directly reacting one or more of the above-mentioned silver compounds and one or more of the above-mentioned ammonium carbamate-based compounds at normal pressure or under a nitrogen atmosphere without using a solvent. Also, alcohols such as methanol, ethanol, isopropanol, butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate, carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane Solvents such as benzene, 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. To react.

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

  The organic silver complex is soluble in various solvents including a solvent for producing an organic silver complex, such as an alcohol such as methanol, an ester such as ethyl acetate, and an ether such as tetrahydrofuran. Therefore, the organic silver complex can be easily applied to a coating or printing step as a composition containing metal nanoparticles.

  Examples of the material for forming metallic silver include silver carboxylate having a group represented by the formula “—COOAg”. The silver carboxylate 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 may be 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 described in JP-A-2015-66695 and silver carboxylate (4). As a material for forming metallic silver, not only β-ketocarboxylate and silver carboxylate (4) but also silver carboxylate having a group represented by the formula “—COOAg”, which includes these, may be used. it can.

  When the silver carboxylate is contained as a metal-forming material in the metal nanoparticle-containing composition, the amine compound having 25 or less carbon atoms and a quaternary ammonium salt, ammonia, and the amine compound or ammonia are added together with the silver carboxylate. It is preferable that one or more nitrogen-containing compounds selected from the group consisting of ammonium salts reacted with the compound are blended.

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

(2) Method of Forming Fine Metal Line Pattern Next, a method of forming a fine metal line pattern will be described. The metal fine line pattern is formed using the metal nanoparticle-containing composition. There is no particular limitation on the method for forming the thin metal wire pattern, and a conventionally known method can be used. As a conventionally known method for forming a thin metal wire pattern, for example, a method using a photolithography method, a coating method, a printing method, or the like can be used.

  The metal nanoparticle-containing composition contains the above-described metal nanoparticles and a solvent, and may contain additives such as a dispersant, a viscosity modifier, and a binder. The solvent contained in the metal nanoparticle-containing composition is not particularly limited, but is preferably a compound having a hydroxy group, and is preferably water, alcohol, or glycol ether, in that the solvent can be efficiently volatilized by irradiation with mid-infrared rays.

  As the solvent used for the metal nanoparticle-containing composition, water, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, hexanediol, Heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalool, geraniol, nerol, heptadienol, tetradecenol, hexadecenol, phytol, oleyl alcohol, dedecenol, desenol, undecylenyl alcohol, nonenol, citronellol , Octenol, heptenol, methylcyclohexanol, menthol, dimethylcyclohexanol, methyl Cyclohexenol, terpineol, dihydrocarbeol, 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, Ethylene 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 a pattern of the metal nanoparticle-containing composition is formed by a printing method, a method generally used for forming an electrode pattern can be applied. As a specific example, the gravure printing method described in JP-A-2009-295980, JP-A-2009-259826, JP-A-2009-96189, JP-A-2009-90662, etc. The printing method is described in JP-A-2004-268319, JP-A-2003-168560, and the like, and the screen printing method is described in JP-A-2010-34161, JP-A-2010-10245, and JP-A-2009-2009. Japanese Patent Application Laid-Open No. 2011-180562, Japanese Patent Application Laid-Open No. 2000-127410, Japanese Patent Application Laid-Open No. H8-238774, and the like. The method described in JP-A-146665 is cited as an example. It is.

  When forming a pattern of the metal nanoparticle-containing composition by a photolithographic method, specifically, for example, to form a film of the metal nanoparticle-containing composition by printing or coating on the entire surface of the transparent flexible substrate After performing a drying process and a baking process described later, the film is processed into a desired pattern by etching using a known photolithography method.

  Next, the applied metal nanoparticle-containing composition is dried. The drying treatment can be performed using a known drying method. As a drying method, for example, air cooling drying, convection heat transfer drying using hot air, etc., radiant heat drying using infrared rays or the like, conduction heat transfer drying using a hot plate, etc., vacuum drying, internal drying using microwaves Exothermic drying, IPA vapor drying, Marangoni drying, Rotagoni drying, freeze drying and the like can be used.

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

  In the drying treatment, it is preferable to perform a drying treatment 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 cut the absorption region of the transparent flexible substrate and selectively irradiate a specific wavelength effective for the solvent of the metal nanoparticle-containing composition. In particular, it is 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, a baking treatment of the dried pattern of the metal nanoparticle-containing composition is performed. Depending on the type of the metal composition contained in the metal nanoparticle-containing composition (for example, the above-mentioned silver colloid having an organic π-junction ligand), sufficient conductivity is exhibited by the drying treatment. It does not need to be performed.

  The firing of the pattern of the metal nanoparticle-containing composition is preferably performed by light irradiation (flash firing) using a flash lamp in order to improve the conductivity of the first electrode. 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.

  The preferred spectral band of the flashlamp is preferably in the range of 240-2000 nm. Within this range, damage such as thermal deformation of the transparent flexible substrate due to flash firing is small.

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 in the range of 10 μsec to 100 msec, and more preferably in the range of 100 μsec to 10 msec. The number of times of light irradiation may be one or more, and it is preferable to perform light irradiation within a range of 1 to 50 times. By irradiating the flash light under these preferable conditions, a thin metal wire pattern can be formed without damaging the transparent flexible substrate.

  The flash lamp irradiation on the transparent flexible substrate is preferably performed from the side of the transparent flexible substrate on which the pattern of the metal nanoparticle-containing composition is formed. When the transparent flexible substrate is transparent, the irradiation may be performed from the transparent flexible substrate side or from both surfaces of the transparent flexible substrate.

  In addition, the surface temperature of the transparent flexible substrate during flash firing is determined by the heat-resistant temperature of the transparent flexible substrate, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the metal nanoparticle-containing composition, the type of atmosphere gas, The pressure and the thermal behavior such as the dispersibility and the oxidizing property of the metal nanoparticle-containing composition may be determined in consideration of the pressure, and the temperature is preferably from room temperature (25 ° C.) to 200 ° C.

  The light irradiation device of the flash lamp only needs to satisfy the above irradiation energy and irradiation time. The flash firing may be performed in the air, but may be performed in an atmosphere of an inert gas such as nitrogen, argon, or helium, if necessary.

  Further, the thin metal wire may be formed by using a known vacuum film formation in the same manner as in forming a conventional metal layer. As a conventional method for forming a metal layer, a film can be formed by various vapor deposition methods, sputtering methods, ion plating methods, or the like. In addition, as a method for forming a thin metal wire pattern, a known pattern may be processed by etching using a known photolithography method, or a mask pattern may be used during film formation.

(Transparent conductive layer (3b))
The first electrode used in the present invention includes at least a thin metal wire and a transparent conductive layer. In a preferred embodiment, the transparent conductive layer is provided on the thin metal wire so as to cover the entire surface of the thin metal wire.
It is preferable that a metal oxide layer or an organic conductive layer be used as the transparent conductive layer. The transparent conductive layer is preferably a metal oxide (metal oxide layer) from the viewpoint of further improving luminous efficiency. In addition, “is a metal oxide” includes, for example, a case where a metal oxide is contained as a main component and other impurities are contained.

  The thickness of the transparent conductive layer is preferably from 50 to 300 nm. The first electrode used in the present invention can sufficiently exhibit conductivity even when the thickness of the transparent conductive layer is within the above range. Further, when the thickness of the transparent conductive layer is 50 nm or more, the rectification characteristics are further improved. Further, when the thickness of the transparent conductive layer is 300 nm or less, the generation of dark spots is further suppressed, and the rectification characteristics are further improved.

The metal oxide layer and the organic conductive layer are preferably formed using a highly conductive metal oxide having a volume resistivity in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻² Ω · cm. The volume resistivity can be determined by measuring the sheet resistance and the film thickness measured in accordance with the resistivity test method of the conductive plastic according to JIS K 7194-1994 by the four probe method. The film thickness can be measured using a contact surface profiler (for example, DECTAK) or a light interference surface profiler (for example, WYKO).
In addition, the metal oxide layer and the organic conductive layer have a sheet resistance of 10,000 Ω / sq. From the viewpoint of ensuring the conductivity. Or less, preferably 2000 Ω / sq. It is more preferred that:

(1) Metal oxide layer The metal oxide that can be used for the metal oxide layer is not particularly limited as long as it is a material having excellent transparency and conductivity. Examples of the metal oxide that can be used for the metal oxide layer include ITO (tin-doped indium oxide), IZO (indium oxide / zinc oxide), IGO (gallium-doped indium oxide), IWZO (indium oxide / tin oxide), and ZnO ( Zinc oxide), GZO (gallium-doped zinc oxide), IGZO (indium gallium zinc oxide) and the like.

In particular, as a metal oxide that can be used for the metal oxide layer, IZO, IGO, and IWZO are preferable. Above all, as IZO, a composition represented by a mass ratio of In ₂ O ₃ : ZnO = 80 to 95:20 to 5 is preferable. As IGO, a composition represented by a mass ratio of In ₂ O ₃ : Ga ₂ O ₃ = 70 to 95:30 to 5 is preferable. As IWZO, a composition represented by a mass ratio of In ₂ O ₃ : WO ₃ : ZnO = 95 to 99.8: 2.5 to 0.1: 2.5 to 0.1 is preferable.

  The transparent conductive layer is particularly preferably made of an amorphous metal oxide. That is, the transparent conductive layer is preferably an amorphous metal oxide layer. By using an amorphous metal oxide as a material of the transparent conductive layer, generation of dark spots can be further suppressed. Examples of the amorphous metal oxide include amorphous IZO, amorphous ITO, amorphous IGZO, and the like.

  Note that a plurality of metal oxide layers may be provided in the first electrode.

(1.1) Method for Forming Metal Oxide Layer The metal oxide layer can be formed by various sputtering methods or ion plating methods in the same manner as when forming a conventional metal oxide layer. it can.

Examples of the sputtering method include DC sputtering, RF sputtering, DC magnetron sputtering, RF magnetron sputtering, ECR plasma sputtering, and ion beam sputtering.
Further, in the sputtering method, by examining various conditions as described below, it is possible to adjust the conductivity and the gas barrier property even if the composition is the same as in IZO.

  For example, the metal oxide layer may be formed by DC magnetron sputtering with the distance between target substrates during sputtering being in the range of 50 to 100 mm and the sputtering gas pressure being in the range of 0.5 to 1.5 Pa. Can be.

  Regarding the distance between the target substrates, when the distance between the target substrates is shorter than 50 mm, the kinetic energy of the sputtered particles to be deposited becomes large, so that the damage to the transparent flexible base material becomes large. In addition, the film thickness becomes non-uniform, and the film thickness distribution deteriorates. When the distance between the target substrates is longer than 100 mm, the film thickness distribution is improved, but the kinetic energy of the sputtered particles to be deposited becomes too low, densification hardly occurs due to diffusion, and the density of the metal oxide layer is undesirably low.

  Regarding the sputtering gas pressure, if the sputtering gas pressure is lower than 0.5 Pa, the kinetic energy of the sputtered particles to be deposited becomes large, so that the transparent flexible base material is greatly damaged. When the sputtering gas pressure is higher than 1.5 Pa, not only the film formation rate is reduced, but also the kinetic energy of the sputtered particles to be deposited becomes too low, so that densification by diffusion does not occur and the density of the metal oxide layer is low. Is not preferred.

(2) Organic conductive layer The organic conductive layer is mainly composed of a conductive polymer and a binder. As the conductive polymer and the binder, the compounds described in Japanese Patent No. 5750908 and Japanese Patent No. 5782855 can be used. In addition, the preparation (method) of the organic conductive composition for forming the organic conductive layer, the formation (method) of the organic conductive layer, and the like are performed according to the methods described in Japanese Patent Nos. 5750908 and 5782855. Can be.

<Transparent flexible substrate (2)>
The transparent flexible substrate used in the present invention is not particularly limited as long as it has a high light transmittance, and from the viewpoint of productivity, lightness, and performance such as flexibility, it may be a transparent resin substrate. preferable.

The resin that can be used as the transparent resin substrate is not particularly limited. For example, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, and polystyrene Resins, polyolefin resins such as cyclic olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyetheretherketone (PEEK) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin, and the like. These resins may be used alone or in combination.
The transparent resin substrate may be an unstretched film or a stretched film.

  The transparent flexible base material has a total light transmittance of 50% or more in a visible light wavelength region measured by a method according to JIS K 7361-1: 1997 (test method for total light transmittance of plastic-transparent material). , And more preferably 80% or more.

The transparent flexible base material may have been subjected to a surface activation treatment in order to enhance the adhesion with a base layer, a gas barrier layer and the like described later. Further, a clear hard coat layer may be provided in order to enhance impact resistance. Examples of the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
Examples of the material of the clear hard coat layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. An ultraviolet curable resin can be preferably used.

<Organic functional layer (4)>
The organic functional layer used in the present invention is a layer located between the anode and the cathode, and is composed of an organic layer, a metal layer, and the like, but is not limited thereto.
The organic functional layer includes at least a light emitting layer, and may further include various organic layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. The hole injection layer and the hole transport layer may be provided as a hole transport injection layer. The electron transport layer and the electron injection layer may be provided as an electron transport injection layer. Further, among these organic layers, for example, the electron injection layer may be made of an inorganic material.
The organic functional layer may have a hole-blocking layer, an electron-blocking layer, or the like, if necessary, in addition to these layers.

(I) (anode) / light-emitting layer / (cathode)
(Ii) (anode) / light-emitting layer / electron transport layer / (cathode)
(Iii) (Anode) / Hole transport layer / Emitting layer / (Cathode)
(Iv) (Anode) / Hole transport layer / Emitting layer / Electron transport layer / (Cathode)
(V) (anode) / hole transport layer / emission layer / electron transport layer / electron injection layer / (cathode)
(Vi) (anode) / hole injection layer / hole transport layer / emission layer / electron transport layer / (cathode)
(Vii) (anode) / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / (cathode)

  Among the above, the configuration (vii) is preferable, but not particularly limited.

  The thickness of the organic functional layer is preferably in the range of 100 to 500 nm. When the thickness of the organic functional layer is 500 nm or less, an increase in driving voltage can be suppressed, and when it is 100 nm or more, rectification characteristics can be maintained.

  In the present invention, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, the electron injection layer is not particularly limited, for example, JP-A-2014-120334, Compounds described in JP-A-2013-89608 and the like can be used.

<Second electrode (5)>
The organic EL device according to the present invention has an organic functional layer sandwiched between a pair of electrodes including a first electrode as a transparent electrode and a second electrode that is a counter electrode thereof. One of the first electrode and the second electrode serves as an anode of the organic EL element, and the other serves as a cathode.
In the organic EL device 1 shown in FIG. 1, the transparent conductive layer 3b of the first electrode 3 is made of a transparent conductive material, and the second electrode 5 is made of a highly reflective material. When the organic EL element 1 is of a double-sided emission type, the second electrode 5 is also made of a transparent conductive material.

In the case where the second electrode is used as the anode in the organic EL device, a metal, an alloy, an electrically conductive compound having a large work function (4 eV or more), and a mixture thereof are preferably used as the electrode material. Specific examples of the electrode material that can constitute the anode include metals such as Au and Ag, and conductive transparent materials such as CuI, ITO, SnO ₂ , and ZnO. Alternatively, a material such as IDIXO (In ₂ O ₃ —ZnO) that can form an amorphous and transparent conductive film may be used.

In the case where the second electrode is used as a cathode in an organic EL device, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are used as an electrode material. Used as
The cathode is an electrode film that functions as a cathode (cathode) for supplying electrons to the light emitting layer. The cathode can be manufactured by forming a thin film from these electrode substances by a method such as evaporation or sputtering.

Specific examples of the electrode material include aluminum, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among them, a mixture of an electron-injecting metal and a second metal that is a stable metal having a large work function value, such as a magnesium / silver mixture, from the viewpoint of durability against electron injection and oxidation. Preferred are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like.

  The sheet resistance as a cathode is several hundred Ω / sq. The following is preferred, and the thickness is usually selected in the range of 10 nm to 5 μm, preferably in the range of 50 to 200 nm. In addition, after the above metal is produced in a thickness of 1 to 20 nm as a cathode, a transparent or translucent cathode can be produced by producing a conductive transparent material thereon, and by applying this, An element in which both the anode and the cathode have transparency can be manufactured.

<Extraction electrode>
The extraction electrode electrically connects the conductive layer of the transparent electrode to an external power supply, and the material is not particularly limited and a known material can be suitably used. A metal film such as a MAM electrode made of (Mo / Al.Nd alloy / Mo) can be used.

<Inorganic protective layer (6)>
The inorganic protective layer used in the present invention is provided on the upper surface of the second electrode. The inorganic protective layer may be provided on a part of the second electrode, but is preferably provided on the entire surface.
The material that can be used for the inorganic protective layer is not particularly limited, and examples thereof include silicon compounds such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, and silicon nitride carbide. In particular, from the viewpoint of barrier properties, the inorganic protective layer preferably contains silicon nitride as a main component, and specifically, silicon nitride. That is, the inorganic protective layer is preferably a silicon nitride layer. Further, by using silicon nitride for the inorganic protective layer, the generation of dark spots is further suppressed.
Note that, for example, “is silicon nitride” includes a case where silicon nitride is contained as a main component and other impurities are contained, for example.
In addition, the inorganic protective layer may be formed as a composite film or a stacked film in which films each containing a silicon compound having the same composition or a different composition as a main component are combined. When the inorganic protective layer is formed as a composite film or a laminated film in this manner, the function as the inorganic protective layer as a whole may be exhibited.

Inorganic protective layer, a water vapor transmission rate (25 ± 0.5 ° C., a relative humidity of 90 ± 2% RH) is preferably is less than ^{0.1g / (m 2 · 24h)} , 0.01g / (m 2 · more preferably 24h) or less, and more preferably 0.001g ^/ (m 2 · 24h) or less.
The water vapor permeability of the inorganic protective layer is a value measured by a method according to JIS K 7129-1992.

The thickness of the inorganic protective layer is preferably from 500 to 1500 nm. When the thickness of the inorganic protective layer is 500 nm or more, generation of dark spots due to the thickness of the inorganic protective layer is further suppressed. When the thickness of the inorganic protective layer is 1500 nm or less, the generation of dark spots due to cracks in the inorganic protective layer is further suppressed.
The thickness of the inorganic protective layer can be measured using a contact surface profiler (for example, DECTAK).
Further, the film density of the inorganic protective layer is preferably 4.0 to 10.0 × 10 ²² atoms / cm ³ .

The inorganic protective layer is preferably formed from two or more layers having different film densities. In particular, as shown in FIG. 6, the inorganic protective layer 6 is preferably formed of three layers having different film densities. Here, the inorganic protective layer 6 includes a first inorganic protective layer 6a on the second electrode 5, a second inorganic protective layer 6b as an intermediate layer, and a third inorganic protective layer 6c on the adhesive layer 7 side. It is configured. Note that the three layers having different film densities means that at least one layer may have a different film density from the other two layers, and the other two layers may have the same film density. Further, each of the three layers may have a different film density.
Since the inorganic protective layer is formed from three layers having different film densities, the occurrence of dark spots is further suppressed.

The first inorganic protective layer, the second inorganic protective layer, and the third inorganic protective layer each preferably have a film density of 4.0 to 10.0 × 10 ²² atoms / cm ³ .

Here, as for the inorganic protective layer, the second inorganic protective layer, which is an intermediate layer, among the three inorganic protective layers, preferably has the lowest film density.
According to such a configuration, the rectification characteristics are further improved.
When the number of inorganic protective layers is three or more, the intermediate layer (other than the lowermost layer and the uppermost layer) preferably has a low film density.

When the second inorganic protective layer has the lowest film density, the difference in film density between the second inorganic protective layer and the first inorganic protective layer, and the difference in film density between the second inorganic protective layer and the third inorganic protective layer. Is preferably 0.3 to 3.0 × 10 ²² atoms / cm ³ .

The film density can be measured by measuring the formed single film using Rutherford backscattering analysis and measuring the film thickness of the formed cross section by TEM.
The film density can be controlled by film forming conditions when forming a film.

  When the second inorganic protective layer, which is the intermediate layer, has the lowest film density, the thickness of the second inorganic protective layer, which is the intermediate layer, is 20 to 50% of the total thickness of the inorganic protective layer. Preferably it is 50%. When the thickness of the second inorganic protective layer is 20 to 50% of the total thickness of the inorganic protective layer, the effect of diffusion of moisture and the like due to the adhesive is suppressed, and the generation of dark spots is further suppressed. At the same time, the rectification characteristics become better. In the case of four or more layers, the thickness of the intermediate layer having the lowest film density (other than the lowermost layer and the uppermost layer) is preferably 20 to 50% of the total thickness of the inorganic protective layer.

(Method of forming inorganic protective layer)
Next, an example of a method for forming the inorganic protective layer will be described.
The inorganic protective layer can be formed by a dry process. Examples of the dry process include a film deposition method such as a vacuum deposition method (resistance heating, EB method, etc.), a magnetron sputtering method, an ion plating method, a CVD method, and the like.
In addition, when a barrier layer is formed on a transparent flexible substrate, it can be performed by the same method as the step of forming the inorganic protective layer.

As an example of the step of forming the inorganic protective layer, a plasma CVD method using an organic silicon compound will be described. In the formation of the inorganic protective layer by the plasma CVD method, a silicon compound is formed by a reaction product of an organic silicon compound.
Examples of the organic silicon compound used for the plasma CVD method include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethylsilane. , Diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like. Among them, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoint of handling in film formation and barrier properties of the obtained inorganic protective layer. These organic silicon compounds can be used alone or in combination of two or more.

  For example, when an inorganic protective layer made of a reaction product of hexamethyldisiloxane is formed by using a plasma CVD method, a molar ratio of oxygen as a reaction gas to a molar amount (flow rate) of hexamethyldisiloxane is used as a raw material gas. The amount (flow rate) is preferably 12 times or less (more preferably 10 times or less), which is the stoichiometric ratio. By supplying hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that are not completely oxidized are taken into the inorganic protective layer. For this reason, the obtained inorganic protective layer can have excellent barrier properties and bending resistance. The lower limit of the molar amount of oxygen in the deposition gas is preferably 0.1 times or more, more preferably 0.5 times or more, of the molar amount of hexamethyldisiloxane.

Further, in film formation using a dry process, a trace amount of gas other than the introduced gas is present, so that it is rare that the components become stoichiometric. Specifically, Si ₃ N ₄ is a stoichiometric representative value, but an actual film has a certain ratio of width, and these are treated as SiN. The above atomic ratio can be determined by a conventionally known method. For example, the atomic ratio can be measured by an analyzer using X-ray Photoelectron Spectroscopy (XPS).

  The film density of the inorganic protective layer can be controlled by film formation conditions when forming a film by the CVD method. That is, in the film formation by the CVD method, the film formation proceeds by a surface reaction on a film formation surface and a gas phase reaction in a film formation atmosphere. At this time, for example, by increasing the flow rate of the source gas to increase the gas phase reaction, the film forming speed is increased and the film density is decreased. On the other hand, by increasing the surface reaction by decreasing the flow rate of the source gas, the film formation rate is reduced and the film density is increased.

Here, ammonia (NH ₃ ) gas is used for forming the inorganic protective layer, and silane (SH ₄ ) gas is further used as another source gas. Therefore, the silicon nitride film as the inorganic protective layer is configured as a film having a controlled film density by adjusting the total flow rate of the ammonia gas and the silane gas.

  That is, the high-density inorganic protective layer is a film formed by a CVD method whose film formation rate mainly based on the surface reaction is relatively low. On the other hand, the low-density inorganic protective layer is a film formed by a CVD method in which a film-forming rate mainly based on a gas phase reaction is higher than that of a high-density inorganic protective layer.

  The gas phase reaction and the surface reaction in the CVD film formation are controlled by, for example, the substrate temperature and the gas pressure in the film formation atmosphere, in addition to the flow rate of the raw material gas described above. At this time, for example, by lowering the substrate temperature or increasing the gas pressure in the film formation atmosphere, the gas phase reaction increases, the film formation speed increases, and the film density decreases.

  In the case where the inorganic protective layer is formed of three layers having different film densities, the film densities of the first inorganic protective layer, the second inorganic protective layer, and the third inorganic protective layer may be controlled by the above-described method. . Further, even when the inorganic protective layer has two layers having different film densities or four or more layers, the film density may be controlled by the method described above.

<Adhesive layer (7)>
The adhesive layer used in the present invention is provided on the upper surface of the inorganic protective layer. The adhesive layer may be provided on a part of the inorganic protective layer, but is preferably provided on the entire surface.
The adhesive layer is used as an agent for adhering the sealing member to the organic EL element. Further, the adhesive layer has a role of fixing the sealing member to the base material side.
Specific examples of the adhesive layer include photo-curing and thermosetting adhesives having reactive vinyl groups of acrylic acid-based oligomers and methacrylic acid-based oligomers, and moisture-curable adhesives such as 2-cyanoacrylates. Agents can be mentioned.

  Further, as the adhesive layer, a heat and chemical curing type (two-component mixing) such as an epoxy type can be used. In addition, hot melt type polyamide, polyester, and polyolefin can be used. In addition, a cation-curable ultraviolet-curable epoxy resin adhesive can be used.

<Sealing member (8)>
The organic EL element is sealed with a sealing member for the purpose of preventing deterioration of an organic functional layer made of an organic material or the like. The sealing member is a plate-shaped (film-shaped) member that covers the upper surface of the organic EL element, and is fixed to the substrate side by an adhesive layer. Further, the sealing member may be a sealing film. Such a sealing member is provided so as to expose the electrode terminal portion of the organic EL element and cover at least the organic functional layer. Further, an electrode may be provided on the sealing member, and the electrode terminal portion of the organic EL element may be electrically connected to the electrode of the sealing member.

Specific examples of the plate-shaped (film-shaped) sealing member include a glass substrate, a polymer substrate, and a metal substrate. These substrates may be formed into a thinner film. Examples of the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal substrate include those made of 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.
In particular, it is preferable to use a polymer substrate or a metal substrate in the form of a thin film as a sealing member because the element can be thinned.
Further, the substrate material may be processed into a concave plate shape and used as a sealing member. In this case, a process such as sandblasting or chemical etching is performed on the above-described substrate member to form a concave shape.

Furthermore, the polymer substrate having a film shape, the oxygen permeability was measured by the method based on JIS K 7126-1987 is ^{1 × 10 -3 mL / (m} 2 · 24h · atm) or less, to JIS K 7129-1992 measured in compliance with the method, the water vapor transmission rate (25 ± 0.5 ℃, (90 ± 2)% RH) is preferably at ^{1 × 10 -3 g / (m} 2 · 24h) or less.

The application of the adhesive layer may be performed by using a commercially available dispenser or by printing such as screen printing.
Note that the organic material constituting the organic EL element may be deteriorated by heat treatment. For this reason, the adhesive layer is preferably one that can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Further, a desiccant may be dispersed in the adhesive layer.

<Underlayer (10)>
The underlayer used in the present invention is a layer serving as an underlayer for forming a thin metal wire pattern or a transparent conductive layer, and improves the adhesion between the substrate and the first electrode.
The underlayer preferably contains at least one selected from a compound having a thiol group, a poly (meth) acrylate having an aminoethyl group, and a poly (meth) acrylamide having an aminoethyl group. The above may be used in combination.

  In addition, the underlayer may contain inorganic particles in addition to the above compounds, and is particularly preferably formed to contain oxide particles. When the underlayer contains the oxide particles, the adhesion to the fine metal wire pattern and the metal oxide layer is improved.

Further, the underlayer may be provided with a function other than the improvement of the adhesion to the fine metal wire pattern or the metal oxide layer. As a function other than the adhesion, it is preferable to have a light extraction function. In order to impart a light extraction function to the underlayer, it is preferable to include, together with the resin constituting the underlayer, oxide particles having a higher refractive index than the resin. Oxide particles having a refractive index higher than that of the resin function as light scattering particles in the underlayer, thereby causing light scattering in the underlayer and giving the underlayer a light extraction function.
In addition, fluorine may be contained in the underlayer in order to thin the thin metal wires.

The thickness of the underlayer is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 100 nm. When the thickness of the underlayer is 10 nm or more, the underlayer itself becomes a continuous film, the surface becomes smooth, and the influence on the organic EL element is small. On the other hand, when the thickness of the underlayer is 1000 nm or less, it is possible to reduce the transparency of the transparent electrode due to the underlayer and reduce the amount of gas adsorbed due to the underlayer, and to suppress the deterioration of the resistance of the thin metal wire pattern. Can be. In addition, when the thickness of the underlayer is 1000 nm or less, damage to the underlayer when the transparent electrode is bent can be suppressed.
Note that the thickness of the underlayer can be measured using a contact surface profiler (for example, DECTAK).

  The transparency of the underlayer can be arbitrarily selected depending on the application. However, the higher the transparency, the better the application to the transparent electrode, and this is preferable from the viewpoint of expanding applications. The total light transmittance of the underlayer is at least 40% or more, preferably 50% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.

(Compound having a thiol group)
The compound having a thiol group (also referred to as a mercapto group) (hereinafter, also referred to as a thiol group-containing compound) is not particularly limited as long as the effects of the present invention are not impaired.
The thiol group-containing compound used in the present invention is preferably a polyfunctional thiol group-containing compound having two or more thiol groups. Thereby, the adhesiveness with the thin metal wire containing a more metallic material can be achieved.

  Further, the thiol group-containing compound is preferably a condensate of a compound having a structure represented by the following general formula (I) with a monovalent or polyhydric alcohol or amine.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group having 1 to 10 carbon atoms. m is an integer of 0 to 2, and n is 0 or 1.

The alkyl group having 1 to 10 carbon atoms in R ¹ and R ² may be linear or branched, and specifically, a methyl group, an ethyl group, an n-propyl group, an iso- Examples thereof include a propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group, and preferably a methyl group or an ethyl group.
R ¹ and R ² may have a known substituent as long as the effects of the present invention are not impaired.

m is an integer of 0 to 2, preferably 0 or 1.
n is 0 or 1, but is preferably 0.

  Examples of the compound having a structure represented by the general formula (I) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, and 3-mercaptoisobutyric acid.

  Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl- 1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2 -Pentanol, 1-heptanol, 2-heptanol, 2-methyl-2-heptanol, 2-methyl-3-heptanol Lumpur, and the like.

As the polyhydric alcohol, glycols (however, the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain may be branched), for example, ethylene glycol, diethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane And dipentaerythritol.
Among them, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane, and dipentaerythritol are preferred.

  As the alcohol condensed with the compound having the structure represented by the general formula (I), a polyhydric alcohol is preferable since a polyfunctional thiol group-containing compound is obtained.

  The amine is not particularly limited, and may be any of primary to tertiary amines. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, and dimethylamine. Amine, diethylamine, dipropylamine, dibutylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, isophoronediamine And the like.

  Hereinafter, as specific examples of the thiol group-containing compound applicable to the underlayer according to the present invention, exemplary compounds SH-1 to SH-155, SE-1 to SE-84, and SA-1 to SA-34 are shown.

  In addition, as the thiol group-containing compound, compounds described in Japanese Patent No. 4911666 and Japanese Patent No. 4917294 can also be suitably used.

  The above exemplified compounds SH-1 to SH-155, SE-1 to SE-84 and SA-1 to SA-34 can be synthesized by a known method.

Further, as the thiol group-containing compound, a silsesquioxane derivative having a thiol group (hereinafter, also simply referred to as a silsesquioxane derivative) can be used.
The silsesquioxane derivative is not particularly limited, but is preferably a compound having a cage siloxane structure represented by the following general formula (A).

In the general formula (A), ^{X A} is representative of the following ^{X 1} or ^{X 2,} at least one of ^{X A} is ^{X 2.}

In X ¹ and X ² , R ^{1 to} R ⁵ each independently represent an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon ring group. A represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

The alkyl group having 1 to 8 carbon atoms of R ^{1 to} R ⁵ in X ¹ and X ² may be linear or branched, and specifically, a methyl group, an ethyl group, Examples include an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.

Examples of the aromatic hydrocarbon ring group represented by R ^{1 to} R ⁵ in X ¹ and X ² include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

X ¹ and X ² may have a known substituent as long as the effects of the present invention are not impaired.

Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms A in X ^2, and linear or branched alkylene group having 1 to 8 carbon atoms. Among these, synthesis of silsesquioxane derivative readily _{point, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 - straight-chain alkylene group having a carbon number of 2 or 3 are preferable.
A may have a known substituent as long as the effect of the present invention is not impaired.

  Further, as a commercially available silsesquioxane derivative, Composelan (registered trademark) SQ100 series manufactured by Arakawa Chemical Co., Ltd. can be used.

  In addition, as a silsesquioxane derivative having a thiol group applicable to the present invention and a method for synthesizing the same, reference can be made to JP-A-2015-59108, JP-A-2012-180464, and the like.

(Poly (meth) acrylate having aminoethyl group and poly (meth) acrylamide having aminoethyl group)
The poly (meth) acrylate having an aminoethyl group and the poly (meth) acrylamide having an aminoethyl group are not particularly limited as long as the effects of the present invention are not impaired, but the partial structure represented by the following general formula (II) It is preferable to have

In the general formula (II), R ³ 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 represents a substituted or unsubstituted alkylene group or — (CH ₂ CHRbNH) _x —CH ₂ CHRb—, Rb represents a hydrogen atom or an alkyl group, x represents an average number of repeating units, and a positive integer It is.

  As the alkyl group for Ra, for example, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable.

  Further, these alkyl groups may be substituted with a substituent. Examples of these substituents include an alkyl group, a cycloalkyl group, an aryl group, a heterocycloalkyl group, a heteroaryl group, a hydroxy group, a halogen atom, an alkoxy group, an alkylthio group, an arylthio group, a cycloalkoxy group, an aryloxy group, 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, alkylsulfamoyl, arylsulfamoyl, acyloxy, alkenyl, alkynyl, alkylsulfonyl, arylsulfonyl, alkyloxysulfonyl , Aryloxy sulfonyl group, alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxy group and an alkyloxy group are preferred.

The alkyl group as the substituent may be branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, and an octyl group.
The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
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 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.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkoxy group may be branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 6, and preferably 1 to 4. Is most preferred. 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 an ethoxy group is preferable.
The alkylthio group may be branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Is most preferred. Examples of the alkylthio group include a methylthio group and an ethylthio group.
The arylthio group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.
The cycloalkoxy group preferably has 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy 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 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 alkyl carbon amide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamido 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.
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 a 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, and 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, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, and an 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, 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.

The alkylene group in A preferably has 1 to 5 carbon atoms, and is more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the aforementioned substituents.
As the alkyl group for Rb, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable. These alkyl groups may be substituted with the aforementioned substituents.

  The average repeating unit number x is not particularly limited as long as it is a positive integer, but is preferably in the range of 1 to 20.

  The weight average molecular weight (Mw) of poly (meth) acrylate and poly (meth) acrylamide is preferably in the range of 10,000 to 500,000, and more preferably in the range of 30,000 to 200,000. If the weight average molecular weight (Mw) is 10,000 or more, the underlayer containing poly (meth) acrylate and poly (meth) acrylamide is hard, so that the film thickness changes under aging and forced deterioration conditions, and interface deterioration with other layers. And no electrical or optical failure occurs. In addition, if it is 500,000 or less, the solubility in the coating solution for forming the underlayer and the compatibility with other compounds are good, and further, there is a problem of peeling off from other layers having different hardnesses in a low temperature or high temperature environment. Will not occur.

(1) Poly (meth) acrylate having an aminoethyl group Examples of the poly (meth) acrylate having an aminoethyl group include a polymer or copolymer of (meth) acrylate having an aminoethyl group.
Examples of the (meth) acrylate include a monofunctional or bifunctional (meth) acrylate having one or two (meth) acryloyl groups, and a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups. .

Examples of the monofunctional (meth) acrylate include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate , stearyl (meth) alkyl (meth) acrylates of _{C 1-24} acrylates such as cyclohexyl (meth) cycloalkyl (meth) acrylates such as acrylate, dicyclopentanyl (meth) acrylate, Jishiku Bridged cyclic (meth) acrylates such as lopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and phenyl (meth) ) Acrylates, aryl (meth) acrylates such as nonylphenyl (meth) acrylate, aralkyl (meth) acrylates such as benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate hydroxy _{C 2-10} alkyl (meth) acrylate or _{C 2-10} alkanediol mono (meth) acrylate and the like, trifluoroethyl (meth) acrylate, tetrafluoroethylene-flop Pill (meth) acrylate, fluoroalkyl C _1-10 alkyl (meth) acrylates such as hexafluoroisopropyl (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl Aryloxyalkyl (meth) acrylates such as (meth) acrylate, phenylcarbitol (meth) acrylate, nonylphenylcarbitol (meth) acrylate, and aryloxy (poly) alkoxyalkyl (meta) such as nonylphenoxypolyethylene glycol (meth) acrylate ) Acrylates, polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate Amino groups or substituted amino groups such as alkane polyol mono (meth) acrylates such as acrylates, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and 2-t-butylaminoethyl (meth) acrylate; (Meth) acrylate, glycidyl (meth) acrylate, and the like.

Examples of the bifunctional (meth) acrylate include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, and 1,4-butane Alkanediol di (meth) acrylates such as diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and alkane polyol di (meth) acrylates such as glycerin di (meth) acrylate ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol Poly (alkylene glycol) di (meth) acrylates such as di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) A) di (meth) acrylate of a _C2-4 alkylene oxide adduct of bisphenols (bisphenol A, bisphenol S, etc.) such as propane and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane; Examples thereof include bridged cyclic di (meth) acrylates such as di (meth) acrylate of acid-modified alkane polyol such as modified pentaerythritol, tricyclodecane dimethanol di (meth) acrylate, and adamantane di (meth) acrylate.

  Further, as the bifunctional (meth) acrylate, for example, epoxy di (meth) acrylate (bisphenol A type epoxy di (meth) acrylate, novolak type epoxy di (meth) acrylate), polyester di (meth) acrylate (for example, aliphatic polyester) Type di (meth) acrylate, aromatic polyester type di (meth) acrylate, etc.), (poly) urethane di (meth) acrylate (polyester type urethane di (meth) acrylate, polyether type urethane di (meth) acrylate), silicon (meth) ) Oligomer or resin such as acrylate.

  As the polyfunctional (meth) acrylate, an esterified product of a polyhydric alcohol and (meth) acrylic acid, for example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Further, in these polyfunctional (meth) acrylates, the polyhydric alcohol may be an adduct of an alkylene oxide (for example, a C2-4 alkylene oxide such as ethylene oxide or propylene oxide).

Among these polyfunctional (meth) acrylates, tri- to hexafunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferred, and pentaerythritol Tri- or tetrafunctional (meth) acrylates such as tri (meth) acrylate are more preferred.
Further, the polyfunctional (meth) acrylate is preferably a polyfunctional (meth) acrylate that has not been modified with an amine (an unmodified polyfunctional (meth) acrylate that has no amines added by Michael addition or the like).

  These (meth) acrylates can be used alone or in combination of two or more.

  Hereinafter, exemplary compounds PE-1 to PE-9 are shown as specific examples of the poly (meth) acrylate having an aminoethyl group applicable to the underlayer according to the present invention. In addition, x and y in the following exemplary compounds represent the polymerization ratio of the copolymer. The polymerization ratio can be appropriately adjusted according to the solubility, the electrode performance, and the like. For example, x: y = 10: 90 and the like can be set.

The above exemplified compounds PE-1 to PE-9 can be synthesized by a known method. More specifically, (i) a method of aminoethylating (meth) acrylate followed by polymerization or copolymerization, and (ii) a method of polymerizing (meth) acrylate and then aminoethylating.
Hereinafter, as an example, a method for synthesizing the exemplified compound PE-7 will be described.

Synthesis Example Synthesis of Exemplified Compound PE-7 80 parts by mass of toluene was charged into a glass reactor equipped with a thermometer, a stirrer, and a reflux condenser, and the internal temperature was heated to 110 ° C. 1.2 parts by mass of 2,2-azobis- (2-methylbutyronitrile) was added as an initiator, and a mixed solution consisting of 100 parts by mass of methyl methacrylate and 18 parts by mass of acrylic acid was added dropwise over 3 hours. Heating was continued for hours. After completion of the reaction, toluene was added to obtain a carboxy group-containing polymer solution.

120 parts by mass of the carboxy group-containing polymer solution and 60 parts by mass of toluene were charged, and a mixed solution of 53.8 parts by mass of ethyleneimine and 30 parts by mass of toluene was added dropwise at 40 ° C. with stirring over 30 minutes. After reacting at 40 ° C. for 2 hours after the dropwise addition, the internal temperature was raised to 70 ° C., and the mixture was further stirred for 5 hours to ripen, thereby obtaining Exemplified Compound PE-7.
The rate of modification of the carboxy group to the amino group was 100% as calculated from the amount of consumed ethyleneimine calculated from gas chromatography analysis.
Subsequently, unreacted ethyleneimine was removed by distillation under reduced pressure. When the polymer solution after distillation under reduced pressure was analyzed by gas chromatography having a detection limit of 1 ppm or less, ethyleneimine was not detected.

  In addition, the synthesis methods described in JP-A-4-356448 and JP-A-2003-41000 can be referred to.

(2) Poly (meth) acrylamide having an aminoethyl group Examples of the poly (meth) acrylamide having an aminoethyl group include a polymer or a copolymer of (meth) acrylamide having an aminoethyl group.

  As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-benzyl (meth) Acrylamide, N-hydroxyethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N- (hydroxyphenyl) (meth) acrylamide, N- (sulfamoylphenyl) (meth) acrylamide , N- (phenylsulfonyl) (meth) acrylamide, N- (tolylsulfonyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl- N-methyl Meth) acrylamide.

  Hereinafter, exemplary compounds PA-1 to PA-12 are shown as specific examples of poly (meth) acrylamide having an aminoethyl group applicable to the underlayer used in the present invention. In addition, x and y in the following exemplary compounds represent the polymerization ratio of the copolymer. The polymerization ratio can be, for example, x: y = 10: 90.

  The above exemplified compounds PA-1 to PA-12 can be synthesized by a known method. The aminoethylation of (meth) acrylamide or the aminoethylation of poly (meth) acrylamide (homopolymer) can be performed in the same manner as the above-mentioned aminoethylation of (meth) acrylate or poly (meth) acrylate.

(resin)
The resin constituting the underlayer is not particularly limited as long as it can form the underlayer.
For example, a known natural polymer material having a repeating monomer structure or a synthetic polymer material can be used. As these, organic polymer materials, inorganic polymer materials, organic-inorganic hybrid polymer materials, and mixtures thereof can be used. These resins may be used in combination of two or more.

  The above resin can be synthesized by a known method. Natural polymer materials can be extracted from natural raw materials or synthesized by microorganisms such as cellulose. Synthetic polymers can be obtained by radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, ring-opening polymerization, polycondensation, addition polymerization, addition condensation, and living polymerization thereof.

  These resins may be a homopolymer or a copolymer. When a monomer having an asymmetric carbon is used, the resin can have any one of random, syndiotactic and isotactic properties. Moreover, in the case of a copolymer, it can take forms such as random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization.

  The resin may be liquid or solid. Further, the resin is preferably dissolved in a solvent or dispersed uniformly in the solvent. Further, the resin may be a water-soluble resin or a water-dispersible resin.

  The resin may be an ionizing radiation-curable resin that is cured by an ultraviolet ray or an electron beam, a thermosetting resin that is cured by heat, or a resin produced by a sol-gel method. Further, the resin may be cross-linked.

  In the above-mentioned resins, natural polymers and synthetic polymers are described on pages 1551 and 769 of “Dictionary of Chemistry” edited by Michinori Oki, Toshiaki Osawa, Motoharu Tanaka and Hideaki Chihara (Tokyo Kagaku Dojin, 1989). Can be used as an example.

  Specifically, as the natural polymer material, a natural organic polymer material is preferable, 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, silicone resin Phenolic resin, melamine resin, polyurethane resin, polyurea resin, polycarbonate resin, polyketone resin and the like.

Examples of the polyolefin resin include polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), and polyisoprene. , Polybutadiene, polycyclopentene, polynorbornene and the like.
Examples of the polyacrylic resin include polymethacrylate, polyacrylate, polyacrylamide, polymethacrylamide, polyacrylonitrile, and the like.
Examples of the polyvinyl resin include polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polymethyl vinyl ether, polyethyl vinyl ether, and polyisobutyl vinyl ether.
Examples of the polyether resin include polyalkylene glycols such as polyethylene oxide and polypropylene oxide.
Examples of the polyester resin include polyalkylene phthalate such as polyethylene terephthalate and polybutylene terephthalate, and polyalkylene naphthalate such as polyethylene naphthalate.
Examples of the polyamide resin include polyamide 6, polyamide 6, 6, polyamide 12, polyamide 11, and the like.
Examples of the fluorine resin include polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, and polychlorotrifluoroethylene.

  In addition, the above-mentioned water-soluble resin means a resin that dissolves in an amount of 0.001 g or more in 100 g of water at 25 ° C. The degree of dissolution can be measured with a haze meter, turbidity meter, or the like. The color of the water-soluble resin is not particularly limited, but is preferably transparent. The number average molecular weight of the water-soluble resin is preferably in the range of 3,000 to 2,000,000, more preferably in the range of 4,000 to 500,000, and still more preferably in the range of 5,000 to 100,000.

The number average molecular weight and the molecular weight distribution of the water-soluble resin can be measured by generally known gel permeation chromatography (GPC). The solvent to be used is not particularly limited as long as the binder is dissolved, but is preferably tetrahydrofuran (THF), dimethylformamide (DMF), or dichloromethane (CH ₂ Cl ₂ ), more preferably THF and DMF, and further preferably DMF. It is. The measurement temperature is not particularly limited, but is preferably 40 ° C.

  Specific examples of the water-soluble resin include natural polymer materials and synthetic polymer materials such as acrylic, polyester, polyamide, polyurethane, and fluorine-based resins, such as casein, starch, and agar. , Carrageenan, cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, dextran, dextrin, pullulan, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly (2-hydroxyethyl acrylate), poly ( 2-hydroxyethyl methacrylate), polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, and water-soluble polymers such as polyvinyl butyral.

  The above-mentioned water-dispersible resin is a resin which can be uniformly dispersed in an aqueous solvent, and means a resin in which colloid particles made of a resin are dispersed without being aggregated in the aqueous solvent. The size (average particle diameter) of the colloid particles is generally in the range of 1 to 1000 nm. The average particle diameter of the above colloid particles can be measured by a light scattering photometer.

  The aqueous solvent is not only pure water such as distilled water and deionized water, but also an aqueous solution containing acids, alkalis, salts, etc., a water-containing organic solvent, and a solvent such as a hydrophilic organic solvent. And an alcoholic solvent such as methanol or ethanol, a mixed solvent of water and an alcohol, and the like. The water-dispersible resin is preferably transparent. The water-dispersible resin is not particularly limited as long as it is a medium for forming a film. Examples of the water-dispersible resin include an aqueous acrylic resin, an aqueous urethane resin, an aqueous polyester resin, an aqueous polyamide resin, an aqueous polyolefin resin, and the like.

  Examples of the aqueous acrylic resin include vinyl acetate, acrylic acid, acrylic acid-styrene polymers, and copolymers with other monomers. Further, the acid portion having a function of imparting dispersibility to an aqueous solvent is formed of a copolymer of an anionic, nitrogen-containing monomer which forms a counter salt with ions of lithium, sodium, potassium, ammonium, etc. There is a cationic type in which an atom forms a hydrochloride or the like, or a nonionic type in which a site such as a hydroxy group or ethylene oxide is introduced, but an anionic type is preferable.

  Examples of the aqueous urethane resin include a water-dispersed urethane resin and an ionomer-type aqueous urethane resin (anionic). Examples of the water-dispersed urethane resin include a polyether-based urethane resin and a polyester-based urethane resin, and a polyester-based urethane resin is preferable. For use in optical applications, it is preferable to use a non-yellowing isocyanate having no aromatic ring.

  Examples of the ionomer-type aqueous urethane resin include a polyester-based urethane resin, a polyether-based urethane resin, and a polycarbonate-based urethane resin, and are preferably a polyester-based urethane resin and a polyether-based urethane resin.

The aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
Examples of the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecane diacid, and the like, and these may be used alone. However, two or more kinds may be used in combination, and as the polybasic acid component that can be particularly preferably used, terephthalic acid and isophthalic acid are used because they are industrially produced in large quantities and are inexpensive. Is particularly preferred.
Examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, bisphenol, and the like. Or two or more of them may be used in combination. As a polyol component that can be particularly preferably used, ethylene is mass-produced industrially, is inexpensive, and has various properties such as improved solvent resistance and weather resistance of a resin film. Glycol, propylene glycol or neopentyl glycol is particularly preferred.

  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.

  Organic-inorganic hybrid polymer materials include polycarbosilane, polysilylenearylene, polysilole, polyphosphine, polyphosphine oxide, poly (ferrocenylsilane), and silsesquioxane derivatives having silsesquioxane as a basic skeleton. And a resin obtained by compounding silica with the resin.

  Specific examples of silsesquioxane derivatives having silsesquioxane as a basic skeleton include photocurable SQ series (Toagosei Co., Ltd.), Composelan SQ (Arakawa Chemical Co., Ltd.), and Sila-DEC (Chisso Corporation). And the like. Specific examples of the resin obtained by combining silica with the resin include the COMPOSELLAN series (Arakawa Chemical Co., Ltd.).

  As the resin, a curable resin such as an ionizing radiation curable resin and a thermosetting resin can be used. The ionizing radiation-curable resin is a resin that can be cured by a usual method for curing an ionizing radiation-curable resin composition, that is, 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 Cockrow-Walton type, Bande graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type and High frequency type. Is used, preferably an electron beam having an energy in the range of 30 to 300 keV.

  In the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultrahigh-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. A specific example of the ultraviolet irradiation device is a rare gas excimer lamp that emits vacuum ultraviolet light in the range of 100 to 230 nm. An excimer lamp has a high light generation efficiency, and can be turned on by inputting low power. In addition, since light having a long wavelength that causes a temperature rise is not emitted and energy is irradiated at a single wavelength in the ultraviolet region, the temperature of an irradiation target due to the irradiation light itself can be suppressed.

  The thermosetting resin is a resin that is cured by heating, and more preferably contains a crosslinking agent in the resin. As a method for heating 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 surface energy adjuster may be added to the resin used for the underlayer. By adding the surface energy adjusting agent, the adhesion between the fine metal wire pattern and the underlying layer, the line width of the fine metal wire pattern, and the like can be adjusted.

(Oxide particles)
The oxide particles that can be added to the underlayer are not particularly limited as long as they can be applied to a transparent electrode. By adding oxide particles to the resin, the physical properties such as the film strength, elasticity, and refractive index of the underlayer can be appropriately adjusted, and the adhesion to the fine metal wire pattern can be improved. Examples of the oxide particles include oxides of metals such as magnesium, aluminum, silicon, titanium, zinc, yttrium, zirconium, molybdenum, tin, barium, and tantalum. In particular, the oxide particles are preferably any of titanium oxide, aluminum oxide, silicon oxide, and zirconium oxide.

  The average particle diameter of the oxide particles is preferably in the range of 5 to 300 nm, and particularly preferably in the range of 5 to 100 nm, because it can be suitably used for a transparent electrode. When oxide particles having an average particle diameter within the above range are used, sufficient unevenness can be formed on the surface of the underlayer, and the adhesion to the fine metal wire pattern is improved. When the average particle diameter is 100 nm or less, the surface becomes smooth, and the influence on the organic EL element is small.

The average particle size of the oxide particles can be easily measured using a commercially available measuring device using a light scattering method. Specifically, a value measured using a Zetasizer 1000 (manufactured by Malvern Co., Ltd.) by a laser Doppler method at 25 ° C. and a sample diluent amount of 1 mL can be used.
The oxide particles are preferably contained in the underlayer in the range of 10 to 70 vol%, more preferably in the range of 20 to 60 vol%.

(Method of forming underlayer)
The underlayer is formed by preparing a dispersion for forming an underlayer by dispersing a resin, oxide particles, a thiol group-containing compound, and the like in a solvent, and applying the dispersion for forming an underlayer to a substrate. .

  The dispersion solvent used for the underlayer-forming dispersion is not particularly limited, but it is preferable to select a solvent that does not cause precipitation of the resin and aggregation of the thiol group-containing compound. When the underlayer contains oxide particles, from the viewpoint of dispersibility, a resin, a thiol group-containing compound, and the like, and a liquid obtained by mixing the oxide particles are dispersed by a method such as ultrasonic treatment or bead mill treatment, Filtration with a filter or the like is preferable because generation of metal oxide aggregates on the substrate after coating and drying can be prevented.

The formation method of the underlayer can be selected from any appropriate method. For example, as a coating method, in addition to various printing methods such as gravure printing, flexo printing, offset printing, screen printing, and inkjet printing, 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 the underlayer is formed in a predetermined pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, and an inkjet printing method.

The base layer is formed by forming a film by the above-described coating method on a base material and then drying by a known heat drying method such as hot air drying or infrared drying, or natural drying. The temperature at which the heating and drying are performed can be appropriately selected according to the base material to be used, but the temperature is preferably 200 ° C. or lower.
In addition, depending on the resin selected as described above, treatment such as curing with light energy such as ultraviolet light or excimer light, or heat curing with little damage to the base material may be performed. This is a preferred embodiment.

  When a polar solvent having a hydroxyl group such as water or a low-boiling solvent having a boiling point of 200 ° C. or lower is selected as the dispersion solvent used for the underlayer-forming dispersion, the filament temperature of the light source is set to 1600 to 1600 as a drying method. It is preferable to use an infrared heater in the range of 3000 ° C. Since the hydroxy group has an absorption at a specific wavelength emitted from the infrared heater, the solvent can be dried. On the other hand, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) as a base material has less thermal damage to the base material because it has less absorption of a specific wavelength emitted from an infrared heater.

Examples of the polar solvent having a hydroxy group include water (preferably pure water such as distilled water and deionized water), alcoholic solvents such as methanol and ethanol, glycols, glycol ethers, and mixed solvents of water and alcohol. Is mentioned.
Specific examples of the glycol ether-based organic solvent include ethyl carbitol, butyl carbitol and the like.
Specific examples of the alcohol-based organic solvent include, in addition to the above-mentioned methanol and ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, diacetone alcohol, butoxyethanol, and the like.

<Gas barrier layer (9)>
The organic EL device of the present invention preferably has a configuration in which a gas barrier layer is provided on the transparent flexible substrate used in the present invention.
The transparent flexible substrate on which the gas barrier layer is formed has a water vapor permeability of 1 × 10 ⁻³ at a temperature of 25 ± 0.5 ° C. and a humidity of 90 ± 2% RH measured by a method according to JIS K 7129-1992. is preferably g ^/ m 2 · 24h or less, further, the oxygen permeability was measured by the method based on JIS K 7126-1987 ^{is, 1 × 10 -3 ml / m} 2 · 24h · atm (1atm is a 1.01325 × ¹⁰ 5 Pa.) less a temperature 25 ± 0.5 ° C., water vapor permeability at humidity 90 ± 2% RH is below ^{1 × 10 -3 g / m 2} · 24h Preferably, there is.

As a material for forming the gas barrier layer, any material may be used as long as it has a function of suppressing intrusion of what causes deterioration of the element, such as moisture and oxygen, and for example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. .
Further, in order to improve the brittleness of the gas barrier layer, it is more preferable to have a laminated structure of these inorganic layers and layers made of an organic material. The order of laminating the inorganic layer and the organic layer is not particularly limited, but it is preferable that both are alternately laminated plural times.

  The method for forming the gas barrier layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, a plasma polymerization method, and an atmospheric pressure plasma. A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but a method based on an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is also preferable. Further, the polysilazane-containing liquid is applied and dried by a wet coating method, and the formed coating film is irradiated with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less, and the formed coating film is subjected to a modification treatment, A method of forming a barrier layer is also preferable.

  The thickness of the gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. When the thickness of the gas barrier layer is 1 nm or more, desired gas barrier performance can be exhibited. When the thickness is 500 nm or less, deterioration of film quality such as generation of cracks in a dense silicon oxynitride film can be prevented. Can be.

<Particle-containing layer>
The particle-containing layer is provided on the surface (back surface) of the transparent flexible substrate opposite to the surface (front surface) on which the first electrode is formed.

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

(particle)
The particles constituting the particle-containing layer are preferably inorganic fine particles, inorganic oxide particles, conductive polymer particles, conductive carbon fine particles, and the like. Among them, 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 preferable. Particularly, SnO ₂ and SiO ₂ are preferable.

(Binder resin)
Examples of the binder resin constituting the particle-containing layer include, for example, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose derivatives such as cellulose acetate phthalate and cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, and copolybutylene. / Polyesters such as tele / 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, polypropyl tyl methacrylate , Polybutyl methacrylate, polymethyl acrylate, etc. It can be used a copolymer of acrylic resin or an acrylic resin and other resins, but it is not particularly limited to these exemplified a resin material. Among these, a cellulose derivative and an acrylic resin are preferable, and an acrylic resin is most preferably used.

  As the binder resin, the above-mentioned thermoplastic resin having a weight average molecular weight (Mw) of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. is preferable in terms of optical characteristics and quality of a particle-containing layer to be formed. .

  The glass transition temperature can be determined by the method described in JIS K 7121: 2012. The binder resin used here is 60% by mass or more, more preferably 80% by mass or more of the total resin mass constituting the particle-containing layer, and an actinic ray-curable resin or a thermosetting resin is applied as necessary. You can also.

(Method of forming particle-containing layer)
The formation of the particle-containing layer is preferably performed before the formation of the first electrode, the underlayer, and the gas barrier layer.
In the formation of the particle-containing layer, the above-described particles and the binder resin are dissolved in an appropriate organic solvent to prepare a coating solution for forming the particle-containing layer in a solution state, and the wet coating method is used to form a coating solution on the transparent flexible substrate. To form a particle-containing layer.

  As the organic solvent used for preparing the coating liquid for forming the particle-containing layer, hydrocarbons, alcohols, ketones, esters, glycol ethers and the like can be appropriately mixed and used. It is not limited to these.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, and cyclohexane. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, and tert. -Butanol, pentanol, 2-methyl-2-butanol, cyclohexanol, and the like; ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; and esters, for example, formic acid Methyl, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, methyl lactate, and the like. Examples of glycol ethers (1 to 4 carbon atoms) include methyl cellosolve and ethyl cellosolve. Propylene glycol monomethyl ether (abbreviation: PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol mono (1-4 carbon) alkyl ether esters Examples of the propylene glycol mono (C.sub.1-4) alkyl ether esters include, for example, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Other solvents include, for example, N-methylpyrrolidone. And the like. Although not particularly limited to these, a solvent obtained by appropriately mixing them is also preferably used.

  As a method of applying the coating liquid for forming a particle-containing layer on a transparent flexible substrate, there are doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating, and the United States. An extrusion coating method using a hopper described in Japanese Patent No. 2681294 is exemplified. By appropriately using these wet coating methods, a particle-containing layer having a dry film thickness in the range of 0.1 to 20 μm, preferably in the range of 0.2 to 5 μm can be formed on the transparent flexible substrate. .

<Protective member>
Further, in order to mechanically protect the organic EL element, a protective member (not shown) such as a protective film or a protective plate may be provided. The protection member is disposed at a position where the organic EL element and the sealing member are sandwiched between the first electrodes. In particular, when the sealing member is a sealing film, mechanical protection for the organic EL element is not sufficient, and thus it is preferable to provide such a protection member.

  As the above protective member, a glass plate, a polymer plate, a thinner polymer film, a metal plate, a thinner metal film, a polymer material film or a metal material film is applied. Among them, it is particularly preferable to use a polymer film because of its light weight and thinness.

<Manufacturing method of organic EL element>
Next, an example of a method for manufacturing an organic EL element will be described.
First, a first electrode is manufactured by the above-described manufacturing method.
Next, on the first electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially formed to form an organic functional layer. As a method of forming each of these layers, there are a spin coating method, a casting method, an inkjet method, a vapor deposition method, a printing method, and the like.However, a uniform film is easily obtained, and a pinhole is hardly generated. Vacuum evaporation or spin coating is particularly preferred. Further, a different film formation method may be applied to each layer. When an evaporation method is used for forming each of these layers, the evaporation conditions vary depending on the type of the compound to be used and the like, but generally the boat heating temperature is 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 × 10 ^−2. It is preferable to appropriately select each condition within a range of Pa, a deposition rate of 0.01 to 50 nm / sec, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 to 5 μm.

  After the formation of the organic functional layer, a second electrode is formed thereon by a suitable film forming method such as a vapor deposition method or a sputtering method. At this time, the second electrode is formed in a pattern in which a terminal portion is drawn out from the upper side of the organic functional layer to the periphery of the substrate while maintaining the insulating state with respect to the first electrode by the organic functional layer. Next, an inorganic protective layer is formed by the above-described manufacturing method. Thereafter, an adhesive layer and a sealing member are provided on at least the organic functional layer in a state where the terminal portions of the extraction electrode and the second electrode are exposed.

  Thus, a desired organic EL element is obtained. In manufacturing such an organic EL element, it is preferable to consistently manufacture from the light emitting unit to the second electrode by one evacuation, but the substrate is taken out of the vacuum atmosphere and subjected to a different film forming method in the middle. No problem. At that time, it is necessary to consider that the operation is performed in a dry inert gas atmosphere.

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

<< Preparation of organic EL element >>
Organic EL elements 101 to 136 were produced as follows. The organic EL elements 101 to 105 are comparative examples, and the organic EL elements 106 to 136 are examples.

<Preparation of organic EL element 101>
(1) Preparation of Substrate As a transparent flexible substrate, a polyethylene terephthalate (PET / CHC) film (G1SBF, thickness 125 μm, refractive index 1.59) with a clear hard coat layer manufactured by Kimoto Co., Ltd. was prepared.

(2) Formation of Gas Barrier Layer Next, a gas barrier layer was formed on the surface (hard coat layer surface) of the transparent flexible substrate.

  Specifically, a transparent flexible base material was set in a discharge plasma chemical vapor deposition apparatus (plasma CVD apparatus Precision 5000 manufactured by Applied Materials Co., Ltd.), and was continuously transported by a roll-to-roll. Next, a magnetic field was applied between the film forming rollers and power was supplied to each film forming roller to generate plasma between the film forming rollers, thereby forming a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (also functioning as a discharge gas) as a reaction gas is supplied into the formed discharge region from a gas supply pipe. Then, a gas barrier layer having a thickness of 120 nm was formed under the following conditions.

(Deposition conditions)
Supply amount of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of reaction gas (O ₂ ): 500 sccm
Degree of vacuum in vacuum chamber: 3Pa
Applied power from plasma generation power supply: 0.8 kW
Frequency of power supply for plasma generation: 70 kHz
Film transport speed: 0.8 m / min

(3) Formation of First Electrode (3.1) Formation of Fine Metal Wire For the organic EL element 101, a silver film was formed on the gas barrier layer by a vapor deposition method to a thickness of 0.5 μm. Using a photolithographic method, a grid-like pattern having a width of 50 μm and a pitch of 1 mm was formed. Thus, a fine metal line pattern having an arithmetic average roughness Ra of 1.3 nm was formed.
Note that the arithmetic average roughness Ra is a value obtained by measuring an area of 5 μm square in the center of the thin metal wire using an atomic force microscope (manufactured by Digital Instruments).

(3.2) Formation of transparent conductive layer Amorphous IZO (mass ratio In ₂ O ₃ : ZnO = 90) as a transparent conductive layer (metal oxide layer) was formed on the transparent flexible base material (gas barrier layer) and the fine metal wire pattern. : 10) A film was formed to have a thickness of 150 nm. In addition, the film thickness of the transparent conductive layer is a value measured by a contact type surface profiler (DECTAK).
The amorphous IZO film was formed by using an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar: 20 sccm, O ₂ : 3 sccm, sputtering pressure: 0.25 Pa, room temperature (25 ° C.), target-side power: 1000 W, target-substrate. Distance: 86 mm, produced by RF sputtering.

(4) Formation of Organic Function Layer First, each of the following crucibles constituting the organic function layer was filled in each of the crucibles for vapor deposition in the vacuum vapor deposition apparatus in an optimal amount for producing each element. The crucible for vapor deposition used was made of a molybdenum or tungsten resistance heating material.
After the pressure was reduced to a degree of vacuum of 1 × 10 ⁻⁴ Pa, a current was passed through the crucible for vaporization containing the following compound A-1 and heated, and the film was formed on the first electrode (metal oxide layer side) at a vapor deposition rate of 0.1 nm / sec. To form a hole injection layer having a thickness of 10 nm.
Next, a current was passed through the crucible for vaporization containing the following compound M-2 and heated, and vapor deposition was performed on the hole injection layer at a vapor deposition rate of 0.1 nm / second to form a hole transport layer having a thickness of 30 nm.
Next, the following compound BD-1 and the following compound H-1 are co-evaporated at an evaporation rate of 0.1 nm / sec so that the compound BD-1 has a concentration of 5% by mass, and emit blue light with a thickness of 15 nm. A fluorescent light emitting layer was formed.
Next, the following compound GD-1, the following compound RD-1 and the following compound H-2 were vapor-deposited at a rate of 0% so that the concentration of compound GD-1 was 17% by mass and RD-1 was 0.8% by mass. By co-evaporation at 1 nm / sec, a yellow phosphorescent layer having a thickness of 15 nm was formed.
Thereafter, the following compound E-1 was deposited at a deposition rate of 0.1 nm / sec to form an electron transport layer having a thickness of 30 nm.
As described above, an organic functional layer was formed.

(5) Formation of Second Electrode Further, after forming LiF to a thickness of 1.5 nm, aluminum was deposited to a thickness of 110 nm to form a second electrode and an extraction electrode thereof, whereby an organic EL element 101 was manufactured.

(6) Sealing (6.1) Preparation of Adhesive Composition As polyisobutylene-based resin (A), 100 parts by mass of “Opanol B50 (manufactured by BASF, weight average molecular weight (Mw) = 340000)”, polybutene resin (B) 30 parts by mass of "Nisseki Polybutene Grade HV-1900 (manufactured by Nippon Oil Co., Ltd., weight average molecular weight (Mw) = 1900)", and "TINUVIN 765 (manufactured by BASF Japan) as a hindered amine light stabilizer (C) 0.5 parts by mass of a hindered amine group) and "IRGANOX1010 (manufactured by BASF Japan, both hindered phenol groups having a tertiary butyl group at two β-positions) as a hindered phenolic antioxidant (D). ) "And 0.5 parts by mass of" Eastotac H-1 "as the cyclic olefin polymer (E). The 0L Resin (Eastman Chemical .Co. Ltd.) "50 parts by weight, was dissolved in toluene, to prepare a solid concentration of about 25 wt% of the adhesive composition.

(6.2) Production of Sealing Member First, a 50 μm-thick polyethylene terephthalate film on which an aluminum (Al) foil having a thickness of 100 μm was laminated was prepared and used as a sealing member. Next, the prepared adhesive composition solution is applied on the aluminum side (gas barrier layer side) of the sealing member so that the adhesive layer formed after drying has a thickness of 20 μm. After drying for 2 minutes, an adhesive layer was formed.
Next, as a release sheet, a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment with a thickness of 38 μm was attached to the formed adhesive layer surface to produce a sealing member.

The sealing member produced by the above method was left under a nitrogen atmosphere for 24 hours or more.
After the standing, the release sheet was removed, and the laminate was laminated using a vacuum laminator heated to 80 ° C. so as to cover the second electrode of the organic EL element 101. Further, heating was performed at 120 ° C. for 30 minutes, and the organic EL element 101 was sealed with a sealing member.

<Production of organic EL elements 102 to 105>
Organic EL devices 102 to 105 were produced in the same manner as in the production of organic EL device 101, except that the method for forming the thin metal wires was as follows.

  On the gas barrier layer, a silver nanoparticle dispersion (FlowMetal SR6000, manufactured by Bando Chemical Co., Ltd.) was used as a metal nanoparticle-containing composition, using an inkjet printing method, with a width of 50 μm, a pitch of 1 mm, and a dry film thickness of 0. A pattern was formed by applying a 5 μm grid. As the ink jet printing method, a pattern was printed by using an ink jet head having an ink droplet ejection amount of 4 pl, adjusting the application speed and the ejection frequency. As an inkjet printing apparatus, a desktop robot Shotmaster-300 (manufactured by Musashi Engineering) equipped with an inkjet head (manufactured by Konica Minolta) was used, and controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta).

  Next, two quartz glass plates that absorb infrared light having a wavelength of 3.5 μm or more were attached to an infrared irradiation device (Ultimate heater / carbon, manufactured by Meiryo Kogyo Co., Ltd.), and wavelength-controlled infrared light was supplied between the glass plates by cooling air. Using the heater, the formed pattern of the metal nanoparticle-containing composition was dried.

Next, using a xenon flash lamp 2400WS (manufactured by COMET) equipped with a short-wavelength cut filter of 250 nm or less, a total of 3.5 J / cm ² of light irradiation energy was applied to the metal nanometers for an irradiation time of 2 ms. Irradiation was performed once from the pattern side of the particle-containing composition, and a baking treatment was performed on the pattern of the metal nanoparticle-containing composition after drying to form a fine metal line pattern having an arithmetic average roughness Ra of 9.2 nm (organic EL). Element 102).

  Further, by increasing the total irradiation energy of light, thin metal wire patterns having arithmetic average roughness Ra of 13.5 nm, 19.5 nm, and 30.2 nm were formed (organic EL elements 103 to 105).

<Preparation of organic EL elements 106 to 110>
The organic EL element 106 was produced in the same manner as in the production of the organic EL element 101 except that an inorganic protective layer was formed on the second electrode before sealing in the following manner. did.
The organic EL elements 107 to 110 were prepared in the same manner as in the preparation of the organic EL elements 102 to 105 except that an inorganic protective layer was formed on the second electrode before sealing in the following manner. EL elements 107 to 110 were produced.

(1) Formation of Inorganic Protective Layer On the second electrode, a silicon nitride film was formed as an inorganic protective layer to have a thickness shown in Table 1. The thickness of the inorganic protective layer is a value measured by a contact surface profiler (DECTAK).
The inorganic protective layer had a high density of 7.0 × 10 ²² atoms / cm ³ . The film density was measured by measuring the formed single film using Rutherford backscattering analysis, and measuring the film thickness of the formed cross section by TEM.
Specifically, the substrate was set in a discharge plasma chemical vapor deposition apparatus (Plasma CVD apparatus Precision 5000 manufactured by Applied Materials). As a film forming gas, a mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (also functioning as a discharge gas) as a reaction gas is supplied at 50 sccm (Standard Cubic Centimeter per Minute) and 500 sccm, respectively. The gas was supplied from a gas supply pipe in a quantity, and was formed by plasma CVD under the conditions of a vacuum degree in the chamber of 3 Pa, an applied voltage of 0.8 kW, and a frequency of 70 kHz.

<Production of organic EL elements 111 to 114>
Organic EL elements 111 to 114 were manufactured in the same manner as in the production of organic EL element 107 except that the thickness of the inorganic protective layer was changed to the value shown in Table 1.

<Production of organic EL elements 115 and 116>
In the production of the organic EL element 107, the organic EL element 115 was formed in the same manner except that the inorganic protective layer was made into two layers and the film density and the film thickness were set to the values shown in Table 1 for each of the organic EL elements 115 and 116. 116 was produced.
The film density of the inorganic protective layer is 5.1 × 10 ²² atoms / cm ^{3 for the} low density, 7.0 × 10 ²² atoms / cm ³ for the high density, and the film density of the inorganic protective layer is the gas flow rate. And by controlling the pressure during film formation. Hereinafter, the same applies.

<Production of organic EL elements 117 to 123>
Organic EL devices 117 to 123 were produced in the same manner as in the production of the organic EL device 107 except that the inorganic protective layer was made into three layers, and the film density and the film thickness were respectively set to the values shown in Table 1. When the inorganic protective layer has three layers, the second layer is an intermediate layer.

<Preparation of organic EL elements 124 and 125>
In the production of the organic EL element 121, the organic EL elements 124 and 125 were produced in the same manner as the inorganic protective layer except that the organic EL element 124 was changed to a silicon oxide film and the organic EL element 125 was changed to a silicon oxynitride film. .
Note that the silicon oxide film was formed using tetrahydroxysilane and dinitrogen oxide as source gases. The silicon oxynitride film was formed using dichlorosilane and ammonia as source gases.

<Production of organic EL elements 126 and 127>
In the production of the organic EL element 121, as the transparent conductive layer, the organic EL element 126 was changed to amorphous ITO, and the organic EL element 127 was changed to PEDOT (poly (3,4-ethylenedioxythiophene)). The organic EL elements 126 and 127 were produced in the same manner except that the organic EL elements 126 and 127 were formed.

The amorphous ITO was formed on a thin metal wire so as to have a thickness shown in Table 1 by using the method of International Publication No. 2012/090735.
PEDOT was formed by the following method.
PEDOT-PSS CLEVIOS PH510 (solid content concentration: 1.89%, manufactured by HC Starck) is formed on the fine metal wire by using an extrusion method, and the slit gap of the extrusion head is adjusted to a dry film thickness of 150 nm. And applied. Next, heating and drying were performed at 110 ° C. for 5 minutes to form a transparent conductive layer composed of a conductive polymer and a water-soluble polymer P-1 (poly (2-hydroxyethyl acrylate)).

<Preparation of organic EL elements 128 to 131>
Organic EL devices 128 to 131 were produced in the same manner as in the production of the organic EL device 121 except that the thickness of the transparent conductive layer was set to the value shown in Table 1.

<Preparation of organic EL element 132>
In the production of the organic EL element 121, before forming a thin metal wire pattern, an organic layer was formed in the same manner as described above except that an underlayer (thiol-based) was formed on a transparent flexible substrate (gas barrier layer) as follows. An EL element 132 was manufactured.

(1) Formation of Underlayer On a transparent flexible base material (gas barrier layer), Karenz MTBD1 (manufactured by Showa Denko KK, Exemplified Compound SE-20) and 1 equivalent of A-TMM-3LM-N (pentane) Erythritol triacrylate (triester 57%), manufactured by Shin-Nakamura Chemical Co., Ltd.), and a polymerization initiator Irgacure 184 (manufactured by BASF) in an amount to give a solid content of 0.2% by mass. Thus, a diluent having a solid content of 3% by mass was prepared with methyl isobutyl ketone (MIBK). This was formed into a film at 2000 rpm using a spin coater, and then dried by the above-mentioned infrared irradiation device. Thereafter, the outer peripheral portion is wiped so that the base layer is contained in the sealing at the time of manufacturing the organic EL element, and cured with an excimer lamp (apparatus: excimer irradiation apparatus MODEL MECL-M-1-200 manufactured by M.D.COM Co., Ltd.). Irradiation wavelength: 172 nm, lamp filling gas: Xe, excimer lamp light intensity: 130 mW / cm ² (172 nm), distance between sample and light source: 2 mm, stage heating temperature: 70 ° C., oxygen concentration in irradiation device: 20. 0%, irradiation energy: 1 J / cm ² ) to form an underlayer having a thickness of 100 nm. The thickness of the underlayer is a value measured by a contact type surface profiler (DECTAK).

<Preparation of organic EL elements 133 and 134>
Instead of the thiol-based underlayer of the organic EL element 132, an organic ethyl element-based acrylic-based underlayer was used for the organic EL element 133, and an aminoethyl-based methacryl-based underlayer was used for the organic EL element 134.
In the production of the organic EL element 132, instead of Karenz MTBD1 added to the underlayer, the organic EL element 133 uses Polyment NK-350, and the organic EL element 134 uses Exemplified Compound PA-4 (weight average molecular weight (Mw) 56000). Organic EL elements 133 and 134 were produced in the same manner except for the above.

<Production of organic EL elements 135 and 136>
Organic EL elements 135 and 136 were produced in the same manner as in the production of the organic EL element 107, except that the inorganic protective layer was made into four layers, and the film density and the film thickness were set to the values shown in Table 1, respectively. When the number of inorganic protective layers is four, the second and third layers are intermediate layers, and the intermediate layer of “[thickness of intermediate layer / thickness of entire inorganic protective layer] × 100” in Table 1 is used. Is the thickness of the intermediate layer (second layer) having the lowest film density.

《Evaluation》
The following evaluation was performed about the produced organic EL elements 101-136.
Table 1 shows the evaluation results.

<Dark spot before storage (DS)>
Each of the prepared organic EL devices was lit under a constant current density condition of ^2.5 mA / cm ² , and the area of a non-light emitting point (dark spot (DS)) in a region to emit light was measured. Was evaluated. Out of the following evaluations, three or more were judged to be acceptable.

6: The area of DS in the region to emit light is less than 0.5% 5: The area of DS in the region to emit light is 0.5% or more and less than 1% 4: The area of DS in the region to emit light is 1 % To less than 5% 3: DS area in the region to emit light is 5% to less than 10% 2: DS area in the region to emit light is 10% to less than 15% 1: DS in the region to emit light Area is more than 15%

<Dark spot after storage (DS)>
Each of the produced organic EL elements was put into a thermostat at 85 ° C. (dry), taken out after 500 hours, turned on under the condition of a constant current density of ^2.5 mA / cm ² , and a point where no light was emitted in a region to emit light. The area of (dark spot (DS)) was measured and evaluated according to the following criteria. Out of the following evaluations, three or more were judged to be acceptable.

6: The area of DS in the region to emit light is less than 1% 5: The area of DS in the region to emit light is 1% or more and less than 2.5% 4: The area of DS in the region to emit light is 2.5 % To less than 5% 3: DS area in a region to emit light is 5% to less than 10% 2: DS area in a region to emit light is 10% to less than 30% 1: DS in a region to emit light Area is 30% or more

<Rectification characteristics>
For each of the produced organic EL elements, ten were produced by the same production procedure, the rectification ratio was measured, the average value was determined, and the rectification ratio was evaluated using the following index. Out of the following evaluations, three or more were judged to be acceptable.

Rectification ratio = current value when +4 V is applied / current value when −4 V is applied 6: Rectification ratio is 1.0 × 10 ⁵ or more 5: Rectification ratio is 1.0 × 10 ⁴ or more and less than 1.0 × 10 ⁵ 4: Rectification ratio is 1.0 × 10 ³ or more and less than 1.0 × 10 ⁴ 3: Rectification ratio is 1.0 × 10 ² or more and less than 1.0 × 10 ³ 2: Rectification ratio is 1.0 × 10 or more and 1.0 Less than × 10 ² 1: Rectification ratio less than 1.0 × 10

<Adhesion>
For each organic EL element, at the stage of forming up to the thin metal wire, the strength of the thin metal wire (adhesion between the substrate and the thin metal wire) was evaluated by a tape peeling method. Specifically, pressure bonding / peeling was repeated 10 times using a ST film (Panac 0.1 N / 25 mm) on the thin metal wire, and the metal thin wire pattern was visually observed for dropping. A sample having little peeling of the metal fine line pattern was rated as ○, and a sample having no peeling of the metal fine line pattern was rated as ◎.

<Summary>
As is clear from Tables 1 and 2, it was confirmed that the organic EL device of the present invention had an excellent rectification ratio and suppressed the occurrence of dark spots as compared with the organic EL device of the comparative example.
Further, in the organic EL elements 108 and 109 in which the arithmetic average roughness Ra of the thin metal wire is a preferable value, the generation of dark spots was suppressed as compared with the organic EL element 110.
In addition, the organic EL elements 106 and 107 in which the arithmetic average roughness Ra of the thin metal wire is a more preferable value have excellent rectification ratios and suppress generation of dark spots as compared with the organic EL elements 108 to 110. .
Further, in the organic EL elements 112 and 113 in which the thickness of the inorganic protective layer is a preferable value, the generation of dark spots was suppressed as compared with the organic EL elements 111 and 114.

Further, in the organic EL elements 117 and 118 in which the inorganic protective layer was formed from three layers having different film densities, generation of dark spots was suppressed as compared with the organic EL elements 111 to 116.
Further, among the three inorganic protective layers, the organic EL element 119 in which the intermediate layer has the lowest film density was superior in the rectification ratio as compared with the organic EL elements 117 and 118.
Further, the organic EL elements 120 to 122 in which the thickness of the intermediate layer is 20 to 50% of the total thickness of the inorganic protective layer are superior in rectification ratio and dark in comparison with the organic EL elements 119 and 123. The generation of spots was suppressed.

Further, in the organic EL element 121 in which the inorganic protective layer was silicon nitride, the generation of dark spots was suppressed as compared with the organic EL elements 124 and 125.
Further, in the organic EL element 121 in which the transparent conductive layer was an amorphous metal oxide, the generation of dark spots was suppressed as compared with the organic EL element 127.
In addition, the organic EL elements 129 and 130 having a preferable thickness of the transparent conductive layer had excellent rectification ratios and suppressed the occurrence of dark spots as compared with the organic EL elements 128 and 131.
Further, the organic EL elements 132 to 134 provided with the base layer were superior to the organic EL element 121 in the adhesion between the substrate and the fine metal wires.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Transparent flexible base material 3 First electrode 3a Thin metal wire 3b Transparent conductive layer 4 Organic functional layer 5 Second electrode 6 Inorganic protective layer 6a First inorganic protective layer 6b Second inorganic protective layer 6c Third inorganic protective layer 7 adhesive layer 8 sealing member (sealing layer)
9 Gas barrier layer 10 Underlayer

Claims (12)

  An organic electroluminescence element in which a first electrode including at least a thin metal wire and a transparent conductive layer, an organic functional layer, a second electrode, an inorganic protective layer, an adhesive layer, and a sealing member are sequentially laminated on a transparent flexible base material.   The organic electroluminescent element according to claim 1, wherein the arithmetic average roughness Ra of the thin metal wire is 1 to 20 nm.   The organic electroluminescent device according to claim 1, wherein an arithmetic average roughness Ra of the thin metal wire is 1 to 10 nm.   The organic electroluminescent device according to any one of claims 1 to 3, wherein the inorganic protective layer has a thickness of 500 to 1500 nm.   The organic electroluminescence device according to any one of claims 1 to 4, wherein the inorganic protective layer is formed from three layers having different film densities.   The organic electroluminescence device according to claim 5, wherein the intermediate layer has the lowest film density among the three inorganic protective layers.   The organic electroluminescence device according to claim 6, wherein the thickness of the intermediate layer is 20 to 50% of the total thickness of the inorganic protective layer.   The organic electroluminescence device according to any one of claims 1 to 7, wherein the inorganic protective layer is silicon nitride.   The organic electroluminescence device according to any one of claims 1 to 8, wherein the transparent conductive layer is an amorphous metal oxide.   The organic electroluminescence device according to any one of claims 1 to 9, wherein the transparent conductive layer has a thickness of 50 to 300 nm.   The organic electroluminescence device according to any one of claims 1 to 10, wherein a base layer is provided between the transparent flexible substrate and the first electrode.   The said underlayer contains at least 1 sort (s) selected from the compound which has a thiol group, the poly (meth) acrylate which has an aminoethyl group, and the poly (meth) acrylamide which has an aminoethyl group. Organic electroluminescent element.

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