JP2016081796A - Transparent electrode, electronic device, and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a transparent electrode that has an intermediate layer having a tolerance to a variety of organic solvents in addition to an excellent durability; an electronic device including said transparent electrode; and an organic electroluminescent element.SOLUTION: The inventive transparent electrode 1 is a transparent electrode including a conductive layer 1b, and an intermediate layer 1a provided adjacent to the conductive layer, and in which the conductive layer contains gold, silver or copper as a main component, and the intermediate layer is formed of a curable composition, and in which the curable composition contains an aromatic heterocyclic compound comprising a nitrogen atom having an unshared electron pair not involved in aromaticity.SELECTED DRAWING: Figure 1A

Description

  The present invention relates to a transparent electrode, an electronic device, and an organic electroluminescence element. More specifically, the present invention relates to a transparent electrode having both light transmittance and conductivity, and further excellent in durability, and an electronic device and an organic electroluminescence element including the transparent electrode.

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

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

As the transparent electrode, an oxide semiconductor material such as indium tin oxide (SnO ₂ -In ₂ O ₃ : Indium Tin Oxide: ITO) is generally used. Studies aiming at resistance have also been made (see, for example, Patent Documents 1 and 2). However, since ITO uses rare metal indium, the material cost is high, and it is necessary to anneal at about 300 ° C. after film formation in order to reduce resistance.

Therefore, by providing silver (Ag) having a high electrical conductivity as a conductive layer, and providing an intermediate layer made of a nitrogen-containing organic compound having a lone pair not involved in aromaticity under the conductive layer, Technologies that can produce a transparent electrode that has both excellent light transmittance and conductivity due to a strong interaction between the nitrogen-containing organic compound and silver have been proposed (see, for example, Patent Documents 3 to 6). .)
However, the main forming method of the conductive layer disclosed in Patent Documents 3 to 6 is a dry method. The dry method is advantageous in that it does not use a solvent, but has a problem that the film formation rate is slow.
On the other hand, when the conductive layer is formed by a wet method, the durability of rinsing the organic layer, which is the lower layer of the conductive layer, to the organic solvent is a key, and there is a problem that the usable organic solvent is extremely limited. It was.
In addition, the light transmittance change in the forced deterioration test under high temperature storage for confirming long-term durability was somewhat large, and there was concern about long-term durability.

JP 2002-015623 A Japanese Unexamined Patent Publication No. 2006-164961 International Publication No. 2013/105569 International Publication No. 2013/141097 International Publication No. 2013/161750 International Publication No. 2013/180020

  The present invention has been made in view of the above-mentioned problems and circumstances, and its solution is a transparent electrode having an intermediate layer having resistance to various organic solvents in addition to excellent durability, and an electron equipped with the transparent electrode. It is to provide a device and an organic electroluminescent element.

As a result of examining the cause of the above-mentioned problem in order to solve the above-mentioned problems, the present inventor is a transparent electrode comprising a conductive layer and an intermediate layer provided adjacent to the conductive layer, The conductive layer contains gold, silver or copper as a main component, the intermediate layer is formed of a curable composition, and the curable composition includes an unshared electron pair that does not participate in aromaticity. It has been found that by containing an aromatic heterocyclic compound containing a nitrogen atom, it has resistance to various organic solvents in addition to excellent durability, and has led to the present invention.
That is, the said subject concerning this invention is solved by the following means.

1. A transparent electrode comprising a conductive layer and an intermediate layer provided adjacent to the conductive layer,
The conductive layer contains gold, silver or copper as a main component,
The intermediate layer is formed of a curable composition;
The said curable composition contains the aromatic heterocyclic compound containing the nitrogen atom which has a lone pair which does not participate in aromaticity, The transparent electrode characterized by the above-mentioned.

  2. 2. The transparent electrode according to item 1, wherein the conductive layer contains silver as a main component.

  3. The transparent electrode according to item 1 or 2, wherein both the intermediate layer and the conductive layer are formed by a wet method.

  4). The transparent electrode according to any one of Items 1 to 3, wherein the curable composition is a thermosetting composition or a photocurable composition.

  5. The transparent electrode according to any one of items 1 to 4, wherein the curable composition is a polymerizable composition.

  6). 6. The transparent electrode according to item 5, wherein the polymerizable composition is a composition comprising one kind of monomer having a vinyl group.

  7). 6. The transparent electrode according to item 5, wherein the polymerizable composition is a copolymerizable composition comprising two or more types of monomers having a vinyl group.

  8). 6. The transparent electrode according to item 5, wherein the polymerizable composition is a copolymerizable composition of a monomer having a vinyl group and a monomer having a thiol group.

  9. The transparent electrode according to any one of Items 5 to 8, wherein the polymerizable composition is a composition containing a monomer having two or more vinyl groups in the molecule.

  10. The transparent electrode according to any one of Items 5 to 9, wherein the polymerizable composition is a composition polymerized using a radical polymerization initiator.

  11. An electronic device comprising the transparent electrode according to any one of items 1 to 10.

12 An organic electroluminescence device having at least a light emitting layer between an anode and a cathode,
The organic electroluminescent element, wherein the anode or the cathode has the transparent electrode according to any one of items 1 to 10.

  ADVANTAGE OF THE INVENTION According to this invention, in addition to outstanding durability, the transparent electrode which has an intermediate | middle layer which has tolerance with respect to various organic solvents, the electronic device provided with the said transparent electrode, and an organic electroluminescent element can be provided.

Although the expression mechanism and action mechanism of the effect of the present invention are not clarified, it is presumed as follows.
In the transparent electrode of the present invention, the conductive layer contains gold, silver or copper as a main component adjacent to the intermediate layer, and the intermediate layer is formed of a curable composition. Contains an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair not involved in aromaticity (hereinafter also referred to as a nitrogen-containing aromatic heterocyclic compound).
As a result, when the conductive layer is formed on the intermediate layer, when the metal atom constituting the conductive layer is a silver atom, the unshared electron pair not involved in the aromaticity contained in the intermediate layer is removed. It is presumed that the diffusion distance of silver atoms on the surface of the intermediate layer decreased by interacting with the nitrogen atoms possessed, and the aggregation of silver at specific locations could be suppressed. Moreover, it is thought that it works similarly when it contains gold and copper as main components in the conductive layer.

  As a specific mechanism, in the intermediate layer formed of the curable composition according to the present invention, a gold atom, a silver atom, or a copper atom, which the conductive layer contains as a main component, first has an affinity for these metal atoms. A layer-growth type (Frank-van der) in which a two-dimensional nucleus is formed on the surface of an intermediate layer formed of a curable composition having a curable atom and a two-dimensional single crystal layer is formed around the nucleus. (Merwe: FM type) film growth.

In general, metal atoms attached on the surface of the intermediate layer are combined while diffusing on the surface to form three-dimensional nuclei and grow into three-dimensional islands (Volume- It is considered that the film is easily formed into an island shape by the film growth using the Weber (VW type).
However, in the present invention, island-like growth is suppressed by the aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that does not participate in aromaticity, which is a silver affinity compound contained in the intermediate layer, It is assumed that layer growth is promoted.
In addition, by adding an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair not involved in aromaticity to the curable composition, the initial addition amount can be reduced without desorption even under forced deterioration conditions. Since it can be maintained, it is estimated that it contributes to the performance improvement of the transparent electrode and the effect of the present invention can be obtained.
For this reason, as a method for inclusion in the intermediate layer, it is more effective to contain an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair not involved in aromaticity as a partial substituent of the curable resin. It is estimated that.

Accordingly, it is possible to obtain a conductive layer having a uniform thickness even though the layer thickness is thin. As a result, it is presumed that the transparent electrode with the conductivity maintained while maintaining the light transmittance with a thinner layer thickness can be obtained.
Furthermore, by using the curable composition for the intermediate layer, a solvent that could not be used with conventional organic compounds composed of low molecules can be used, and the resistance to rinsing of the solvent can be improved. This is effective in that the range of manufacturing conditions is widened.

Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic sectional view showing a first example of an organic EL device using the transparent electrode of the present invention Schematic sectional view showing a second example of an organic EL device using the transparent electrode of the present invention Schematic sectional view showing a third example of an organic EL element using the transparent electrode of the present invention Schematic cross-sectional view of an illuminating device having a light-emitting surface enlarged using an organic EL element having a transparent electrode of the present invention Schematic cross-sectional view of a light-emitting panel equipped with an organic EL device produced in the examples

  The transparent electrode of the present invention is a transparent electrode comprising a conductive layer and an intermediate layer provided adjacent to the conductive layer, and the conductive layer contains gold, silver or copper as a main component. The intermediate layer is formed of a curable composition, and the curable composition contains an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that does not participate in aromaticity. Features. This feature is a technical feature common to the inventions according to claims 1 to 12.

  As an embodiment of the present invention, it is preferable to contain silver as a main component. Thereby, a strong interaction with the nitrogen atom of the aromatic heterocyclic compound contained in the intermediate layer can be formed.

  As an embodiment of the present invention, it is preferable that both the intermediate layer and the conductive layer are formed by a wet method. This makes it possible to increase the area of the transparent electrode and reduce the manufacturing cost.

  As an embodiment of the present invention, the curable composition is preferably a thermosetting composition or a photocurable composition. Thereby, an intermediate | middle layer can be formed by the simple method of a heating or light irradiation, and also the rinse durability with respect to the various organic solvent of an intermediate | middle layer can be improved.

  As an embodiment of the present invention, the curable composition is preferably a polymerizable composition from the viewpoint that an intermediate layer can be easily formed by a polymerization reaction.

  As an embodiment of the present invention, it is preferable that the polymerizable composition is a composition composed of one kind of monomer having a vinyl group in that a polymerization reaction can be easily caused.

  As an embodiment of the present invention, it is preferable that the polymerizable composition is a copolymerizable composition composed of two or more types of monomers having a vinyl group from the viewpoint of being easily obtained by organic synthesis and easily undergoing a copolymerization reaction. .

  As an embodiment of the present invention, it is preferable that the polymerizable composition is a copolymerizable composition of a monomer having a vinyl group and a monomer having a thiol group from the viewpoint of easy copolymerization reaction. In addition, by using a copolymerizable composition that takes into consideration the molecular structure, molecular shape, and characteristics, it is possible to improve the degree of freedom of the intermediate layer as a film state, or to fill a gap into a higher density film. This is preferable because a transparent electrode excellent in long-term storage stability under high temperature and high humidity can be produced.

  In an embodiment of the present invention, the polymerizable composition is a composition containing a monomer having two or more vinyl groups in the molecule, so that the polymerization reaction can be caused more reliably. preferable.

  As an embodiment of the present invention, the polymerizable composition is preferably a composition that is polymerized using a radical polymerization initiator. As a result, a polymerization reaction can be caused more reliably, an unevenness of the degree of polymerization due to a specific portion is small, and an intermediate layer excellent in rinse durability as a whole can be formed.

  The transparent electrode of the present invention can be suitably included in an electronic device from the viewpoint of manifesting the effects of the present invention.

  The organic EL device of the present invention is an organic EL device having at least a light emitting layer between an anode and a cathode, and the organic EL device of the present invention is used as the anode or the cathode from the viewpoint of the effect of the present invention. The transparent electrode of the invention is suitably provided.

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

<< 1. Transparent electrode >>
<Configuration of transparent electrode>
As shown in FIG. 1, the transparent electrode 1 includes a conductive layer 1b and an intermediate layer 1a provided adjacent to the conductive layer 1b. Specifically, the transparent electrode 1 has a two-layer structure in which an intermediate layer 1a and a conductive layer 1b are stacked on the intermediate layer 1a. The layers 1b are provided in this order. The intermediate layer 1a is a layer formed of a curable composition. The conductive layer 1b is a layer composed mainly of gold, silver or copper, and more preferably composed mainly of silver.

The main component of the conductive layer 1b is a component having the highest component ratio among the components constituting the conductive layer 1b. For example, when silver is the main component, the composition ratio of silver in the conductive layer 1b is preferably 60% by mass or more, more preferably 90% by mass or more, and 98% by mass or more. Is particularly preferred.
Moreover, the transparency of the transparent electrode 1 means that the light transmittance at a measurement light wavelength of 550 nm is 50% or more.
Further, the sheet resistance value as the transparent electrode 1 is preferably 20Ω / □ or less, and the film thickness is usually selected in the range of 5 to 20 nm, preferably 5 to 12 nm.
Next, the detailed configuration will be described in the order of the substrate 11 on which the transparent electrode 1 having such a laminated structure is provided, the intermediate layer 1a constituting the transparent electrode 1 and the conductive layer 1b.

(substrate)
Examples of the substrate 11 on which the transparent electrode 1 of the present invention is formed include, but are not limited to, glass and plastic. Further, the substrate 11 may be transparent or opaque. When the transparent electrode 1 of the present invention is used in an electronic device that extracts light from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a transparent resin film.

  Examples of the glass include silica glass, soda-lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoints of adhesion to the intermediate layer 1a, durability, and smoothness, the surface of these glass materials may be subjected to physical treatment such as polishing, if necessary, or from an inorganic or organic material. Or a hybrid film obtained by combining these films may be formed.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Film.

As described above, a film made of an inorganic material or an organic material, or a hybrid film combining these films may be formed on the surface of the resin film. Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2%) measured by a method according to JIS K 7129-1992 of 0.01 g / m ² · 24 h or less. It is preferably a barrier film (also referred to as a barrier film). Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / m ² · A high barrier film of 24 hours or less is preferable.

  The material for forming the barrier film as described above may be any material that has a function of suppressing intrusion of factors that cause deterioration of electronic devices such as moisture and oxygen and organic EL elements. For example, silicon oxide, Silicon, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of a layer made of these inorganic materials (inorganic layer) and a layer made of an organic material (organic layer). Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

The method for producing the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is particularly preferable.
On the other hand, when the substrate 11 is made of an opaque material, for example, a metal substrate such as aluminum or stainless steel, a film, an opaque resin substrate, a ceramic substrate, or the like can be used.

(Middle layer)
The intermediate layer according to the present invention is formed of a curable composition, and the curable composition contains an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that does not participate in aromaticity.
As a result, when forming a conductive layer adjacent to the intermediate layer, it is involved in the aromaticity that contains gold atoms, silver atoms, or copper atoms, which are the main components constituting the conductive layer, in the intermediate layer. Interacts with nitrogen atoms that have unshared electron pairs, reduces the diffusion distance of gold, silver or copper atoms on the surface of the intermediate layer, and suppresses the aggregation of these metal atoms at specific locations it can.

[Curable composition]
The intermediate layer according to the present invention is formed of a curable composition.
A curable composition is a composition containing the compound hardened | cured by performing the process to harden | cure. Therefore, at the stage where the curable composition is disposed on the substrate by a predetermined method, the fluidity is present.
The curable composition is preferably a thermosetting composition or a photocurable composition because the method of curing the curable composition by heating or light irradiation is simple.

Furthermore, the curable composition is preferably a polymerizable composition.
Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization.
Examples of a method for causing a polymerization reaction include a method of undergoing a heating step, a light irradiation step, and both steps, and the like. The method is appropriately selected according to the type of the curable composition used and the performance of the target intermediate layer. be able to.

The polymerizable composition according to the present invention is preferably a single monomer having a vinyl group from the viewpoint of easily causing a polymerization reaction and easy organic synthesis.
The vinyl group represented by —CH═CH ₂ causes a radical reaction that creates a new bond with another carbon atom by taking one π electron on the carbon atom at the 1-position.
In other words, since radicals serve as reaction initiators, heating or light irradiation is performed after the raw material solution is disposed on the substrate, or radical polymerization initiators are added before the intermediate layer is cured. Thus, if radicals can be generated, it can be easily polymerized and an intermediate layer can be expected to be formed.

The polymerizable composition according to the present invention is also preferably a copolymerizable composition comprising two or more types of monomers having a vinyl group. Even when the polymerizable composition is not a single monomer, the polymerization reaction proceeds in the same manner, and therefore, it is also preferably a copolymerizable composition.
The polymerizable composition according to the present invention may be a copolymerizable composition of a monomer having a vinyl group and a monomer having a thiol group. The reaction between the thiol group and the vinyl group is called a thiol-ene reaction and can be easily polymerized in the same manner as the polymerization of vinyl groups.

Although the copolymerizable composition of a monomer having a vinyl group and a monomer having a thiol group changes the content ratio of the monomer having a vinyl group or the monomer having a thiol group, the magnitude of the effect is also changed. It can be appropriately adjusted according to a desired purpose such as improvement of rinse durability and improvement of long-term storage stability under high temperature and high humidity resulting from the use of a copolymerizable composition.
In addition, the polymerizable composition according to the present invention is preferably a composition containing a monomer having two or more vinyl groups in the molecule from the viewpoint that the polymerization reaction can be caused more reliably.

It is also preferable that the raw material solution before curing of the intermediate layer according to the present invention contains a radical polymerization initiator.
Examples of radical polymerization initiators include azobisisobutyronitrile (AIBN), acetophenone, benzophenone, p-anisyl, diphenylethanedione, 2-benzoylbenzoic acid, 4,4'-dichlorobenzophenone, 2,4-diethyl. Examples include thioxanthen-9-one, 2-ethylanthraquinone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-isonitrosopropiophenone.
By containing these in the raw material solution of the intermediate layer before curing, the polymerization reaction is more likely to occur, the polymerization unevenness due to a specific portion is less, and an intermediate layer having excellent rinse durability as a whole can be formed. The above radical polymerization initiators and known radical polymerization initiators can be used according to the desired purpose.

In the present invention, the “nitrogen atom having an unshared electron pair not involved in aromaticity” is a nitrogen atom having an unshared electron pair, and the unshared electron pair becomes an aromatic property of the unsaturated cyclic compound. A nitrogen atom that is not directly involved as an essential element. That is, a non-localized π electron system on a conjugated unsaturated ring structure (aromatic ring) has a nitrogen atom in which a lone pair is not involved as an essential element for aromatic expression in the chemical structural formula Say.
Hereinafter, the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention will be described.

The nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs, so that the number of bonds of nitrogen atoms is usually three.
For example, an amino group (—NR ¹ R ² ), an amide group (—C (═O) NR ¹ R ² ), a nitro group (—NO ₂ ), a cyano group (—CN), a diazo group (—N ₂ ), An azide group (—N ₃ ), a urea bond (—NR ¹ C═ONR ² —), an isothiocyanate group (—N═C═S), a thioamide group (—C (═S) NR ¹ R ² ), and the like. These correspond to the “nitrogen atom having an unshared electron pair not involved in aromaticity” in the present invention. R ¹ and R ² each represent a substituent.
Among these, for example, the resonance formula of a nitro group (—NO ₂ ) can be expressed as follows. Strictly speaking, the unshared electron pair of the nitrogen atom in the nitro group is used for the resonance structure with the oxygen atom, but in the present invention, it is defined that the nitrogen atom of the nitro group also has an unshared electron pair. .

On the other hand, a nitrogen atom can also create a fourth bond by utilizing an unshared electron pair. For example, as shown below, tetrabutylammonium chloride (abbreviation: TBAC) is a quaternary ammonium salt in which a fourth butyl group is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion. . Tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) ₃ ) is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. Although these compounds have a nitrogen atom, the unshared electron pair is used for ionic bond and coordination bond, respectively. Therefore, in the present invention, the “nitrogen atom having an unshared electron pair not involved in aromaticity” Is not applicable.

That is, the present invention effectively uses a lone pair of nitrogen atoms that are not used for bonding.
Note that in the structural formulas shown below, the left side shows the structure of tetrabutylammonium chloride (abbreviation: TBAC), and the right side shows the structure of tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) ₃ ).

  Moreover, a nitrogen atom is general as a hetero atom which can comprise an aromatic ring, and can contribute to the expression of aromaticity. Examples of the “nitrogen-containing aromatic ring” include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like.

In the case of a pyridine ring, as shown below, in a conjugated (resonant) unsaturated ring structure arranged in a 6-membered ring, the number of delocalized π electrons is 6, so 4n + 2 (n = 0 or natural number) ) Satisfies the Hückel rule. Since the nitrogen atom in the 6-membered ring is substituted with —CH═, only one unpaired electron is mobilized to the 6π-electron system, and an unshared electron pair is essential for aromatic expression. Not involved as a thing.
Therefore, the nitrogen atom of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention. The molecular orbital of the pyridine ring is shown below.

  In the case of a pyrrole ring, as shown below, one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of π electrons is six and satisfies the Hückel rule. A nitrogen-containing aromatic ring. Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, an unshared electron pair is mobilized to the 6π electron system.

Therefore, although the nitrogen atom of the pyrrole ring has an unshared electron pair, it has been utilized as an essential element for the expression of aromaticity. Therefore, in the present invention, the “unshared electron pair not involved in aromaticity” Does not fall under “nitrogen atom having”.
The molecular orbital of the pyrrole ring is shown below.

On the other hand, as shown below, the imidazole ring is a nitrogen-containing aromatic ring having a structure in which two nitrogen atoms are substituted at the 1- and 3-positions in a 5-membered ring, and also has 6 π electrons. . The nitrogen atom N ¹ is a pyridine ring-type nitrogen atom in which only one unpaired electron is mobilized to the 6π-electron system, and the unshared electron pair is not used for aromaticity expression. On the other hand, the nitrogen atom N ² is a pyrrole-ring nitrogen atom that mobilizes an unshared electron pair to the 6π electron system.
Therefore, the nitrogen atom N ¹ of the imidazole ring corresponds to “a nitrogen atom having an unshared electron pair not involved in aromaticity” in the present invention. The molecular orbital of the imidazole ring is shown below.

The same applies to a condensed ring compound having a nitrogen-containing aromatic ring skeleton. For example, as shown below, δ-carboline is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order. The nitrogen atom N ³ of the pyridine ring mobilizes only one unpaired electron, and the nitrogen atom N ⁴ of the pyrrole ring mobilizes an unshared electron pair to the π-electron system, respectively, to form a ring. Together with 11 π electrons from the atoms, the total number of π electrons is 14 aromatic rings.

Therefore, among the two nitrogen atoms of δ-carboline, the nitrogen atom N ³ of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention, but the nitrogen of the pyrrole ring The atom N ⁴ does not fall under this.
Thus, even when the pyridine ring or pyrrole ring is incorporated in a condensed ring compound, its effect is not inhibited or suppressed, and there is no difference from when it is used as a single ring. Absent. The molecular orbital of δ-carboline is shown below.

As described above, the “nitrogen atom having an unshared electron pair that does not participate in aromaticity” defined in the present invention means that the unshared electron pair strongly interacts with gold, silver, or copper, which is the main component of the conductive layer. It is important for expressing the action. Such a nitrogen atom is preferably a nitrogen atom in a nitrogen-containing aromatic ring from the viewpoint of stability and durability.
The strength of the interaction between the nitrogen atom and gold, silver or copper can be inferred from the nucleophilic strength of the nitrogen atom. In other words, the stronger the nucleophilicity, the stronger the coordination power to these metal atoms and the stronger the interaction.

Furthermore, it is known that the strength of nucleophilicity is correlated with the strength of basicity. The basicity according to the definition of Bronsted Raleigh is the property of receiving protons. In other words, it can be said that the attack target is protons.
In order to quantitatively understand the basic strength, it is preferable to refer to the pKa value (acid dissociation constant) of the conjugate acid. The conjugate acid is a form in which protons are added to the base, and the pKa value indicates that the smaller the value, the stronger the acidity (proton releasing ability).
Therefore, the larger the pKa value of the conjugate acid, the stronger the basicity.

HA represents an acid, B represents a base, A ⁻ represents a conjugate base, and HB ⁺ represents a conjugate acid.
The present invention utilizes the interaction between the nitrogen-containing aromatic heterocyclic compound in the intermediate layer and the metal atom. Therefore, from the above viewpoint, the pKa value of the conjugate acid of the main nitrogen-containing aromatic heterocyclic compound was referred to. For the pKa value, the list at the end of the volume was used (see Table 1), Hiroshi Yamanaka, Satoshi Hino, Masako Nakagawa, Naoko Sakamoto, “New edition of heterocyclic compounds”, Kodansha Scientific, March 1, 2004. .

  From the above viewpoint, it is considered that a stronger interaction is expressed when the intermediate layer contains a compound having many structures derived from structures represented by an imidazole ring or a pyridine ring.

As a method for forming the intermediate layer, a coating method, an inkjet method, a coating method, a dipping method, etc. as a method using a wet method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method as a method using a dry method. Law. Although there is no restriction | limiting in particular as an organic solvent used with a wet method, From a viewpoint of high versatility and suppression of an environmental load, ethanol, n-propanol, 2-propanol, PGME (1-methoxy-2-propanol), methyl acetate , MEK (methyl ethyl ketone) and water are preferable.
In the intermediate layer according to the present invention, the raw material solution based on the aromatic heterocyclic compound contained in the curable composition is disposed on the substrate, and then the raw material solution on the substrate is heated or irradiated with light, etc. An intermediate layer is formed. Therefore, it is not preferable that an unintended reaction occurs in the stage before curing, and a method using a wet method capable of forming a film under milder conditions than a dry method such as a vapor deposition method in which a raw material solution is heated to a high temperature and vaporized to form a film is used. Is preferred.

  Specific examples of aromatic heterocyclic compounds containing nitrogen atoms having unshared electron pairs not involved in aromaticity, constituting the curable composition contained in the intermediate layer according to the present invention (monomer state) However, the present invention is not limited to this.

[Synthesis Example: Synthesis of P-70]
The organic compound according to the present invention can be easily synthesized according to a conventionally known synthesis method. As an example, a method for synthesizing P-70 is shown.

(1) Synthesis of Intermediate 1 In a 200 ml eggplant flask, δ-carboline (10 g, 0.059 mol), iodobenzene (1.5 eq.), K ₃ PO ₄ ( ₂ eq.), Cu ₂ O (0.2 eq. DMSO (100 ml) solution containing diphenylomethane (0.5 eq.) Was added and refluxed at 150 ° C. for 10 hours under nitrogen atmosphere.
Thereafter, the temperature was returned to room temperature, and the solution was transferred to a separating funnel for extraction. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid (11 g, yield 82%) of intermediate 1.

(2) Synthesis of Intermediate 2 In a 100 ml eggplant flask, add Intermediate 1 (10 g, 0.041 mol), NBS (N-bromosuccinimide) (1.2 eq.), And DMF (50 ml), and dissolve. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere.
After returning to room temperature, the solution was transferred to a separatory funnel and extracted. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 2 (10 g, yield 78%).

(3) Synthesis of Intermediate 3 In a 100 ml eggplant flask, Intermediate 2 (10 g, 0.032 mol), δ-carboline (1.2 eq.), K ₃ PO ₄ ( ₂ eq.), Cu ₂ O (0.2 eq) DMSO (50 ml) containing diphenylomethane (0.5 eq.) Was added, and the mixture was refluxed at 150 ° C. for 15 hours under a nitrogen atmosphere.
Thereafter, the temperature was returned to room temperature, and the solution was transferred to a separating funnel for extraction. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 3 (10 g, yield 80%).

(4) Synthesis of Intermediate 4 In a 100 ml eggplant flask, add Intermediate 3 (10 g, 0.024 mol), NBS (N-bromosuccinimide) (1.2 eq.), And DMF (50 ml), and dissolve. The mixture was heated and stirred at 80 ° C. for 10 hours in a nitrogen atmosphere.
After returning to room temperature, the solution was transferred to a separatory funnel and extracted. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 4 (10 g, yield 78%).

(5) Synthesis of P-70 In a 100 ml eggplant flask, intermediate 4 (10 g, 0.020 mol), vinyl boronic acid pinole ester (1.5 eq.), Pd (PPh ₃ ) ₄ (0.025 eq.), K A Dioxane (50 ml) solution containing ₂ CO ₃ (3 eq.) Was added, and the mixture was refluxed at 100 ° C. for 13 hours under a nitrogen atmosphere.
Thereafter, the temperature was returned to room temperature, and the solution was transferred to a separating funnel for extraction. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of P-70 (5.8 g, yield 65%).

(Conductive layer)
The conductive layer 1b according to the present invention contains gold, silver or copper as a main component. The conductive layer 1b is a layer formed on the intermediate layer 1a.
The conductive layer 1b may have a configuration in which a layer mainly composed of gold, silver, or copper is divided into a plurality of layers as necessary.

The conductive layer 1b preferably has a layer thickness in the range of 5 to 20 nm, and more preferably in the range of 5 to 12 nm.
A layer thickness of 20 nm or less is preferable because the absorption component or reflection component of the layer is reduced and the light transmittance of the transparent electrode 1 is improved. A layer thickness of 5 nm or more is preferable because the layer has sufficient conductivity.

  Note that, in the transparent electrode 1 having a laminated structure including the intermediate layer 1a as described above and the conductive layer 1b formed thereon, the upper part of the conductive layer 1b may be covered with a protective film. Another conductive layer may be laminated. In this case, it is preferable that the protective film and another conductive layer have light transmittance so that the light transmittance of the transparent electrode 1 is not impaired. Moreover, it is good also as a structure which provided the layer as needed also under the intermediate | middle layer 1a, ie, between the intermediate | middle layer 1a and the board | substrate 11. FIG.

  The conductive layer 1b may be composed of an alloy containing silver (Ag) as a main component. Examples of such an alloy include silver magnesium (AgMg), silver copper (AgCu), and silver palladium (AgPd). ), Silver palladium copper (AgPdCu), silver indium (AgIn), and the like.

  As a method for forming the conductive layer 1b, a coating method, an inkjet method, a coating method, a dipping method, etc. as a method using a wet method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, etc. as a method using a dry method. And CVD method. Since the conductive layer according to the present invention is provided with an intermediate layer having high rinsing durability against an organic solvent in the lower layer, it is preferable to use a wet method from the viewpoint of reducing manufacturing costs. A preferable organic solvent for rinsing the conductive layer formed by a wet method is the same as the organic solvent preferably used for rinsing the intermediate layer.

  When the conductive layer is formed using a wet method, it is preferable to use a conductive ink containing gold, silver, or copper as a main component. In the present configuration in which high light transmission is realized by reducing the thickness of the conductive layer, the conductive layer is made of a conductive ink composed of nanoparticles having a small particle diameter of about 10 nanometers or a complex. It is particularly preferable to use a conductive ink.

However, since many of the commercially available conductive inks are mainly used for the production of electric circuits and light reflection films, etc., they can be used in the usual way to produce thin films with excellent light transmittance. It is difficult to do. Therefore, it is necessary to devise a method of diluting the conductive ink with a solvent and optimizing thin film formation process conditions.
As the solvent to be diluted, a conventionally known solvent such as an organic solvent or an aqueous solvent can be used without particular limitation as long as the effect of the transparent electrode 1 of the present invention is not impaired.
Further, the conductive layer 1b is formed on the intermediate layer 1a, so that a high-temperature annealing treatment (for example, a heating process at 100 ° C. or higher) after the formation of the conductive layer is performed as necessary. Good.

<Effect of transparent electrode>
The transparent electrode 1 having the above-described configuration is formed on the intermediate layer 1a formed of a curable composition containing an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair not involved in aromaticity. The conductive layer 1b is composed mainly of silver or copper.
Thus, when the conductive layer is formed on the intermediate layer, the aromatic heterocycle in which the intermediate layer 1a contains gold atoms, silver atoms, or copper atoms contained as the main component in the conductive layer. The diffusion distance on the intermediate layer surface of gold atoms, silver atoms or copper atoms contained as a main component in the conductive layer by interacting with the compound is reduced, and aggregation is also suppressed.

Here, the case where silver is used as the main component of the conductive layer will be described as an example. In the formation of a conductive layer generally composed of silver as a main component, an island-like growth type (VW type) is used. Since the thin film grows, the silver particles are easily isolated in an island shape, and when the film thickness is thin, it is difficult to obtain conductivity, and the sheet resistance value becomes high.
Therefore, it is necessary to increase the film thickness in order to ensure conductivity. However, if the film thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.
However, according to the transparent electrode 1 of the configuration of the present invention, since aggregation of silver is suppressed on the intermediate layer 1a as described above, in the film formation of the conductive layer 1b composed mainly of silver, the layered A thin film is grown by the growth type (FM type).

  In addition, the transparency of the transparent electrode 1 of the present invention means that the light transmittance at a measurement light wavelength of 550 nm is 50% or more, but each of the above materials used as the intermediate layer 1a is mainly composed of silver. Compared with the conductive layer 1b, a film having sufficiently good light transmittance is formed. On the other hand, the conductivity of the transparent electrode 1 is ensured mainly by the conductive layer 1b. Therefore, as described above, the conductive layer 1b composed mainly of silver has a thinner layer to ensure conductivity, thereby improving the conductivity and light transmission of the transparent electrode 1. It is possible to achieve a balance with improvement in performance.

(Optical adjustment layer)
As shown in FIG. 1B, the transparent electrode 2 of the present invention preferably further includes an optical adjustment layer 2c on the substrate 12 in addition to the intermediate layer 2a and the conductive layer 2b. The optical adjustment layer 2c is a layer formed on the conductive layer 2b.
The optical adjustment layer may contain either an organic compound or an inorganic compound as a main component, and the layer constituting the optical adjustment layer may have a configuration in which a plurality of layers are laminated as necessary.

The optical adjustment layer is configured to sandwich the conductive layer together with the intermediate layer. In order to improve the light transmittance by reducing the reflection component of the conductive layer containing metal as a main component, such a configuration is preferable.
In order to produce an excellent transparent electrode with the maximum improvement in light transmittance, it is necessary to optimize it in consideration of the refractive index and film thickness of the compound contained in the intermediate layer and the optical adjustment layer. These can be estimated by optical simulation.

The optical adjustment layer is provided as appropriate for improving light transmittance, but in view of being an adjacent layer of the conductive layer, the main component of the conductive layer is gold, silver, or copper. It is preferable to contain a compound that interacts strongly from the viewpoints of adhesion, scratch resistance and long-term storage.
Therefore, it is particularly preferable to use an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair not involved in aromaticity.
In the following description, the transparent electrode 2 including the optical adjustment layer 2c can be used in the same manner even when the transparent electrode 1 including no optical adjustment layer is described.

≪2. Applications of transparent electrodes >>
The transparent electrode 1 having the above-described configuration can be used for various electronic devices. Examples of electronic devices include organic EL elements, LEDs (Light Emitting Diodes), liquid crystal elements, solar cells, touch panels, etc. As electrode members that require light transmission in these electronic devices, the above-mentioned transparent The electrode 1 can be used.
Below, embodiment of the organic EL element using the transparent electrode 1 of this invention is described as an example of a use.

≪3. First example of organic EL element >>
<Configuration of organic EL element>
FIG. 2 is a schematic cross-sectional view showing a first example of an organic EL element using the transparent electrode 1 described above as an example of the electronic device of the present invention.
Below, the structure of an organic EL element is demonstrated based on this figure.

  As shown in FIG. 2, the organic EL element 100 is provided on a transparent substrate (substrate) 13, and in order from the transparent substrate 13 side, an organic functional layer 3 configured using the transparent electrode 1, an organic material, and the like. The counter electrode 5a is laminated in this order. In the organic EL element 100, the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, the organic EL element 100 is configured to extract the generated light (hereinafter referred to as emission light h) from at least the transparent substrate 13 side.

  Further, the layer structure of the organic EL element 100 is not limited to the example described below, and may be a general layer structure. Here, the transparent electrode 1 functions as an anode (that is, an anode), and the counter electrode 5a functions as a cathode (that is, a cathode). In this case, for example, the organic functional layer 3 has a structure in which a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d / an electron injection layer 3e are stacked in this order from the transparent electrode 1 side which is an anode. Although illustrated, it is essential to have at least the light emitting layer 3c composed of an organic material. The hole injection layer 3a and the hole transport layer 3b may be provided as a hole transport injection layer. The electron transport layer 3d and the electron injection layer 3e may be provided as an electron transport injection layer. Of these organic functional layers 3, for example, the electron injection layer 3e may be made of an inorganic material.

In addition to these layers, the organic functional layer 3 may have a hole blocking layer, an electron blocking layer, or the like laminated as necessary. Furthermore, the light emitting layer 3c may have a structure in which each color light emitting layer that generates light emitted in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting auxiliary layer. The auxiliary layer may function as a hole blocking layer or an electron blocking layer. Furthermore, the counter electrode 5a as a cathode may also have a laminated structure as necessary. In such a configuration, only a portion where the organic functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5 a becomes a light emitting region in the organic EL element 100.
In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the conductive layer 1 b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1.

  The organic EL element 100 having the above configuration is sealed with a sealing material 17 described later on the transparent substrate 13 for the purpose of preventing deterioration of the organic functional layer 3 configured using an organic material or the like. ing. The sealing material 17 is fixed to the transparent substrate 13 side with an adhesive 19. However, it is assumed that the terminal portions of the transparent electrode 1 and the counter electrode 5a are provided on the transparent substrate 13 so as to be exposed from the sealing material 17 in a state of being insulated from each other by the organic functional layer 3.

  Hereinafter, the details of the main layers for constituting the organic EL element 100 described above will be described in terms of the transparent substrate 13, the transparent electrode 1, the counter electrode 5a, the light emitting layer 3c of the organic functional layer 3, the other layers of the organic functional layer 3, and the auxiliary. The electrode 15 and the sealing material 17 will be described in this order.

(Transparent substrate)
The transparent substrate 13 is the substrate 11 on which the transparent electrode 1 of the present invention described above is provided, and among the substrates 11 described above, the transparent substrate 11 having optical transparency is used.

(Transparent electrode (anode))
The transparent electrode 1 is the transparent electrode 1 of the present invention described above, and has a configuration in which an intermediate layer 1a and a conductive layer 1b are sequentially formed from the transparent substrate 13 side. Here, in particular, the transparent electrode 1 functions as an anode, and the conductive layer 1b is a substantial anode.

(Counter electrode (cathode))
The counter electrode 5a is an electrode film that functions as a cathode for supplying electrons to the organic functional layer 3, and is made of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specifically, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ , An oxide semiconductor such as SnO ₂ can be given.

The counter electrode 5a can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5a is preferably several hundred Ω / □ or less, and the film thickness is usually selected within a range of 5 nm to 5 μm, preferably 5 to 200 nm.
In addition, when this organic EL element 100 takes out the emitted light h also from the counter electrode 5a side, the counter electrode is made of a conductive material having a good light transmission property selected from the above-described conductive materials. 5a should just be comprised.

(Light emitting layer)
The light emitting layer 3c contains a light emitting material, and among them, it is preferable that a phosphorescent dopant (phosphorescent material, phosphorescent compound, phosphorescent compound) is contained as the light emitting material.
The light emitting layer 3c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 3d and holes injected from the hole transport layer 3b, and the light emitting portion is the light emitting layer 3c. Even within the layer, it may be the interface between the light emitting layer 3c and the adjacent layer.
There is no restriction | limiting in particular in the structure as such a light emitting layer 3c, if the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting auxiliary layer (not shown) between the light emitting layers 3c.

The total thickness of the light emitting layer 3c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the layer thickness of the light emitting layer 3c is a layer thickness also including the said auxiliary layer, when a nonluminous auxiliary layer exists between the light emitting layers 3c.
In the case of the light emitting layer 3c having a configuration in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

The light emitting layer 3c configured as described above is formed by using a known thin film forming method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, or an ink jet method, for example, by using a light emitting material or a host compound described later. Can be formed.
The light emitting layer 3c may be configured by mixing a plurality of light emitting materials, and a phosphorescent light emitting dopant (phosphorescent compound) and a fluorescent dopant (fluorescent light emitting material, fluorescent compound) are mixed. It may be configured.
The light emitting layer 3c contains a host compound (light emitting host) and a light emitting material (light emitting dopant), and it is preferable that the light emitting material emits more light.

(Host compound)
As the host compound contained in the light emitting layer 3c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in the light emitting layer 3c.
As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .
As the known host compound, a compound having a hole transporting ability and an electron transporting ability while preventing the emission of light from being increased in wavelength and having a high Tg (glass transition temperature) is preferable.
The glass transition temperature here is a value obtained by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).

  As specific examples of known host compounds, compounds described in the following documents may be used. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, No. 2003/0175553, No. 2006/0280965. US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Application Publication No. 2005/0238919 ,Country Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. Examples include 2012/023947, JP 2008-074939 A, JP 2007-254297 A, and European Patent No. 2034538.

(Luminescent material)
(1) Phosphorescence emission dopant As a luminescent material which can be used by this invention, a phosphorescence emission dopant is mentioned.
A phosphorescent dopant is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.). Although defined as being a compound of 01 or more, a preferable phosphorescence quantum yield is 0.1 or more.
The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in a solution can be measured using various solvents, but when using a phosphorescent dopant in the present invention, the above phosphorescence quantum yield (0.01 or more) is achieved in any solvent. It only has to be done.

There are two types of light emission principles of the phosphorescent dopant.
One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. It is an energy transfer type.
The other is a carrier trap type in which the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant to emit light from the phosphorescent dopant. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

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

In the present invention, at least one light emitting layer 3c may contain two or more phosphorescent light emitting dopants, and the concentration ratio of the phosphorescent light emitting dopant in the light emitting layer 3c varies in the thickness direction of the light emitting layer 3c. It may be.
The phosphorescent dopant is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 3c.

Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
Nature, 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. , 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. , 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem. , 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. , 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. , 34, 592 (2005), Chem. Commun. , 2906 (2005), Inorg. Chem. , 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. United States Patent Application Publication No. 2009/0108737, United States Patent Application Publication No. 2009/0039776, United States Patent No. 6921915, United States Patent No. 6,687,266, United States Patent Application Publication No. 2007/0190359. No., US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Patent No. 7396598 Writing, U.S. Patent Application Publication No. 2006/0263635, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. , 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics, 23, 3745 (2004), Appl. Phys. Lett. , 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication. No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. No. 7, U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Application Publication No. 2007/0190359, U.S. Patent Application Publication No. 2008/0297033, U.S. Pat. No. 7,338,722. Letter, United States Published Patent Application No. 2002/0134984, U.S. Pat. No. 7,279,704, U.S. Patent Application Publication No. 2006/098120, U.S. Patent Application Publication No. 2006/103874, International Publication No. 2005/076380. International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, US Patent Application Publication No. 2012/228583 , Rice Japanese Patent Application Publication No. 2012/212126, Japanese Patent Application Laid-Open No. 2012-069737, Japanese Patent Application Laid-Open No. 2011-181303, Japanese Patent Application Laid-Open No. 2009-114086, Japanese Patent Application Laid-Open No. 2003-81988, Japanese Patent Application Laid-Open No. 2002-302671. Japanese Patent Laid-Open No. 2002-363552.
Among these, a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

(2) Fluorescent dopant The fluorescent luminescent dopant (henceforth "fluorescent dopant") which concerns on this invention is demonstrated.
The fluorescent dopant according to the present invention is a compound that can emit light from an excited singlet, and is not particularly limited as long as light emission from the excited singlet is observed.
Examples of the fluorescent dopant according to the present invention include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, and perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
In recent years, light emitting dopants utilizing delayed fluorescence have been developed, and these may be used.
Specific examples of the luminescent dopant using delayed fluorescence include, for example, the compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Is not limited to these.

(Injection layer: hole injection layer, electron injection layer)
The injection layer is a layer provided between the electrode and the light emitting layer 3c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (November 30, 1998 2) Chapter 2 “Electrode Material” (pages 123 to 166) of “S.
The injection layer can be provided as necessary. The hole injection layer 3a may be present between the anode and the light emitting layer 3c or the hole transport layer 3b, and the electron injection layer 3e may be present between the cathode and the light emitting layer 3c or the electron transport layer 3d. Good.

  The details of the hole injection layer 3a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 3e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically represented by strontium, aluminum and the like. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 3e is preferably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 μm, although it depends on the material.

(Hole transport layer)
The hole transport layer 3b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 3a and the electron blocking layer are also included in the hole transport layer 3b. The hole transport layer 3b can be provided as a single layer or a plurality of layers.

The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and also two fused aromatic rings described in US Pat. No. 5,061,569 In the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in the publication are linked in a starburst type Etc.

Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer 3b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. be able to. Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 3b, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The hole transport layer 3b may have a single layer structure composed of one or more of the above materials.

Also, the p-type can be enhanced by doping impurities into the material of the hole transport layer 3b. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
Thus, it is preferable to increase the p property of the hole transport layer 3b because an element with lower power consumption can be manufactured.

(Electron transport layer)
The electron transport layer 3d is made of a material having a function of transporting electrons, and in a broad sense, the electron injection layer 3e and the hole blocking layer are also included in the electron transport layer 3d. The electron transport layer 3d can be provided as a single layer structure or a multilayer structure of a plurality of layers.

  From the cathode, an electron transport material for the electron transport layer 3d having a single layer structure and an electron transport material (also serving as a hole blocking material) constituting the layer portion adjacent to the light emitting layer 3c in the electron transport layer 3d having a multilayer structure. What is necessary is just to have the function to transmit the inject | poured electron to the light emitting layer 3c. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group are also used as the material for the electron transport layer 3d. Can do. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced by Cu, Ca, Sn, Ga, or Pb can also be used as the material for the electron transport layer 3d.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 3d. Further, a distyrylpyrazine derivative that is also used as the material of the light emitting layer 3c can be used as the material of the electron transport layer 3d, and n-type-Si, n-type as in the case of the hole injection layer 3a and the hole transport layer 3b. An inorganic semiconductor such as -SiC can also be used as the material of the electron transport layer 3d.

  The electron transport layer 3d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the layer thickness of 3 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer 3d may have a single-layer structure made of one or more of the above materials.

  In addition, the electron transport layer 3d can be doped with impurities to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, it is preferable that the electron transport layer 3d contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 3d is increased, an element with lower power consumption can be manufactured.

  Further, as the material (electron transporting compound) of the electron transport layer 3d, the same material as that constituting the intermediate layer 1a described above may be used. The same applies to the electron transport layer 3d also serving as the electron injection layer 3e.

(Blocking layer: hole blocking layer, electron blocking layer)
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic functional layer 3 described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has the function of the electron transport layer 3d in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of said electron carrying layer 3d can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 3c.

On the other hand, the electron blocking layer has the function of the hole transport layer 3b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. Moreover, the structure of said positive hole transport layer 3b can be used as an electron blocking layer as needed.
The thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

(Auxiliary electrode)
The auxiliary electrode 15 is provided for the purpose of reducing the resistance of the transparent electrode 1, and is provided in contact with the conductive layer 1 b of the transparent electrode 1. The material for forming the auxiliary electrode 15 is preferably a metal with low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface 13a. Examples of a method for producing such an auxiliary electrode 15 include a vapor deposition method, a sputtering method, a printing method, an ink jet method, an aerosol jet method, and the like. The line width of the auxiliary electrode 15 is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode 15 is preferably 1 μm or more from the viewpoint of conductivity.

(Encapsulant)
The sealing material 17 covers the organic EL element 100 and may be a plate-like (film-like) sealing member that is fixed to the transparent substrate 13 side by the adhesive 19. It may be a stop film. Such a sealing material 17 is provided in a state of covering at least the organic functional layer 3 in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. In addition, an electrode may be provided on the sealing material 17 so that the transparent electrode 1 and the terminal portion of the counter electrode 5a of the organic EL element 100 are electrically connected to this electrode.

  Specific examples of the plate-like (film-like) sealing material 17 include a glass substrate, a polymer substrate, a metal substrate, and the like. These substrate materials may be used in the form of a thin 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.

Among them, since the element can be thinned, a thin film-like polymer substrate or metal substrate can be preferably used as the sealing material.
Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%) measured by a compliant method is preferably 1 × 10 ⁻³ g / m ² · 24 h or less.

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing material 17. In this case, the above-described substrate material is subjected to processing such as sandblasting and chemical etching to form a concave shape.

The adhesive 19 for fixing the plate-shaped sealing material 17 to the transparent substrate 13 side seals the organic EL element 100 sandwiched between the sealing material 17 and the transparent substrate 13. It is used as a sealing agent. Specifically, such an adhesive 19 is a photocuring and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer, a methacrylic acid-based oligomer, a moisture-curing type such as 2-cyanoacrylic acid ester, or the like. Can be mentioned.
In addition, epoxy-based heat and chemical curing type (two-component mixing), hot-melt type polyamide, polyester, polyolefin, and cationic curing type UV-curable epoxy resin adhesive can also be exemplified.

In addition, the organic material which comprises the organic EL element 100 may deteriorate with heat processing. For this reason, the adhesive 19 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 19.
Application | coating of the adhesive agent 19 to the adhesion part of the sealing material 17 and the transparent substrate 13 may use a commercially available dispenser, and may print like screen printing.

  In addition, when a gap is formed between the plate-shaped sealing material 17, the transparent substrate 13, and the adhesive 19, in this gap, in the gas phase and the liquid phase, an inert gas such as nitrogen or argon or a fluorine is used. It is preferable to inject an inert liquid such as activated hydrocarbon or silicon oil. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

On the other hand, when a sealing film is used as the sealing material 17, the organic functional layer 3 in the organic EL element 100 is completely covered and the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. A sealing film is provided on the transparent substrate 13.
Such a sealing film is configured using an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing entry of a substance that causes deterioration of the organic functional layer 3 in the organic EL element 100 such as moisture and oxygen. As such a material, for example, inorganic materials such as silicon oxide, silicon dioxide, and silicon nitride are used. Furthermore, in order to improve the brittleness of the sealing film, a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.

  The method for producing these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, 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.

(Protective film, protective plate)
A protective film or a protective plate may be provided so as to sandwich the organic EL element 100 and the sealing material 17 together with the transparent substrate 13. This protective film or protective plate is for mechanically protecting the organic EL element 100, and in particular when the sealing material 17 is a sealing film, sufficient mechanical protection is provided for the organic EL element 100. Therefore, it is preferable to provide such a protective film or protective plate.
As the protective film or protective plate as described above, 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. In particular, it is preferable to use a polymer film because it is lightweight and thin.

<Method for producing organic EL element>
Here, as an example, a method for manufacturing the organic EL element 100 shown in FIG. 2 will be described.
First, the intermediate layer 1a is formed on the transparent substrate 13 by an appropriate method such as a wet method so as to have a layer thickness of 1 μm or less, preferably 10 to 100 nm, using a curable composition. Next, an appropriate method such as a wet method is used so that the conductive layer 1b mainly composed of silver (or an alloy containing silver) has a layer thickness within a range of 5 to 20 nm, preferably within a range of 8 to 12 nm. A transparent electrode 1 which is formed on the intermediate layer 1a by the method and serves as an anode is produced.

Next, a hole injection layer 3a, a hole transport layer 3b, a light emitting layer 3c, an electron transport layer 3d, and an electron injection layer 3e are formed in this order on this, and the organic functional layer 3 is formed. The film formation of each of these layers includes spin coating, casting, ink jet, vapor deposition, and printing, but vacuum vapor deposition is easy because a homogeneous film is easily obtained and pinholes are difficult to generate. The method or spin coating method is particularly preferred. Further, different film formation methods may be applied for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 × 10 ⁻⁶ to 1 × 10 ^−2. It is desirable to appropriately select each condition within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and layer thickness of 0.1 to 5 μm.

  After the organic functional layer 3 is formed as described above, the counter electrode 5a serving as a cathode is formed thereon by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the counter electrode 5 a is patterned in a shape in which a terminal portion is drawn from the upper side of the organic functional layer 3 to the periphery of the transparent substrate 13 while being kept insulated from the transparent electrode 1 by the organic functional layer 3. Thereby, the organic EL element 100 is obtained. Thereafter, the sealing material 17 that covers at least the organic functional layer 3 is provided in a state where the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed.

As described above, a desired organic EL element is obtained on the transparent substrate 13. In the production of such an organic EL element 100, it is preferable that the organic functional layer 3 to the counter electrode 5a are consistently produced by a single evacuation. A film method may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
When a DC voltage is applied to the organic EL element 100 thus obtained, the transparent electrode 1 as an anode has a positive polarity, the counter electrode 5a as a cathode has a negative polarity, and a voltage of about 2 to 40V. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Effect of organic EL element>
The organic EL element 100 described above has a configuration in which the transparent electrode 1 having both light transmittance and conductivity according to the present invention is used as an anode, and an organic functional layer 3 and a counter electrode 5a serving as a cathode are provided thereon. is there. For this reason, the extraction efficiency of the emitted light h from the transparent electrode 1 side is improved while applying a sufficient voltage between the transparent electrode 1 and the counter electrode 5a to realize high luminance light emission in the organic EL element 100. Therefore, it is possible to increase the luminance. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

<< 4. Second example of organic EL element >>
<Configuration of organic EL element>
FIG. 3 is a schematic cross-sectional view showing a second example of an organic EL element using the transparent electrode 1 described above as an example of the electronic device of the present invention. The organic EL element 200 of the second example shown in FIG. 3 is different from the organic EL element 100 of the first example shown in FIG. 2 in that the transparent electrode 1 is used as a cathode.
Hereinafter, a detailed description of the same components as those in the first example will be omitted, and a characteristic configuration of the organic EL element 200 in the second example will be described.

  As shown in FIG. 3, the organic EL element 200 is provided on the transparent substrate 13, and the transparent electrode 1 of the present invention described above is used as the transparent electrode 1 on the transparent substrate 13 as in the first example. ing. For this reason, the organic EL element 200 is configured to extract the emitted light h from at least the transparent substrate 13 side. However, the transparent electrode 1 is used as a cathode (cathode). For this reason, the counter electrode 5b is used as an anode.

The layer structure of the organic EL element 200 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example.
As an example of the second example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a are laminated in this order on the transparent electrode 1 functioning as a cathode. The configuration is exemplified. However, it is essential to have at least the light emitting layer 3c made of an organic material.

In addition to these layers, the organic functional layer 3 employs various configurations as necessary, as described in the first example. In such a configuration, only the portion where the organic functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5 b becomes the light emitting region in the organic EL element 200 as in the first example.
In the layer structure as described above, the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. The same as in the example.

Here, the counter electrode 5b used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO ₂ , and SnO ₂ .

The counter electrode 5b configured as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5b is preferably several hundred Ω / □ or less, and the film thickness is usually selected within a range of 5 nm to 5 μm, preferably 5 to 200 nm.
In addition, when this organic EL element 200 is comprised so that emitted light h can be taken out also from the counter electrode 5b side, as a material which comprises the counter electrode 5b, favorable light transmittance is mentioned among the electrically conductive materials mentioned above. A suitable conductive material is selected and used.

The organic EL element 200 having the above configuration is sealed with the sealing material 17 in the same manner as in the first example for the purpose of preventing the deterioration of the organic functional layer 3.
Of the main layers constituting the organic EL element 200 described above, the detailed structure of the constituent elements other than the counter electrode 5b used as the anode and the method for manufacturing the organic EL element 200 are the same as in the first example. For this reason, detailed description is omitted.

<Effect of organic EL element>
The organic EL element 200 described above has a configuration in which the transparent electrode 1 having both light transmittance and conductivity according to the present invention is used as a cathode, and an organic functional layer 3 and a counter electrode 5b serving as an anode are provided thereon. is there. For this reason, as in the first example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5b to realize high-luminance light emission in the organic EL element 200, and light emitted from the transparent electrode 1 side. It is possible to increase the luminance by improving the extraction efficiency of h. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

≪5. Third example of organic EL element >>
<Configuration of organic EL element>
FIG. 4 is a schematic cross-sectional view showing a third example of the organic EL element using the transparent electrode 1 described above as an example of the electronic device of the present invention. The organic EL element 300 of the third example shown in FIG. 4 is different from the organic EL element 100 of the first example shown in FIG. 2 in that the counter electrode 5c is provided on the substrate 131 side, and the organic functional layer 3 and It is in the place which laminated | stacked the transparent electrode 1 in this order.
Hereinafter, the detailed description of the same components as those in the first example will be omitted, and the characteristic configuration of the organic EL element 300 in the third example will be described.

The organic EL element 300 shown in FIG. 4 is provided on a substrate 131, and the counter electrode 5c serving as an anode, the organic functional layer 3, and the transparent electrode 1 serving as a cathode are laminated in this order from the substrate 131 side. . Among these, the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, the organic EL element 300 is configured to extract the emitted light h from at least the transparent electrode 1 side opposite to the substrate 131.
The layer structure of the organic EL element 300 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example.

  An example of the case of the third example is a configuration in which a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d are stacked in this order on the counter electrode 5c functioning as an anode. The However, it is essential to have at least the light emitting layer 3c configured using an organic material. The electron transport layer 3d also serves as the electron injection layer 3e, and is provided as an electron transport layer 3d having electron injection properties.

  In particular, the characteristic structure of the organic EL element 300 of the third example is that an electron transport layer 3 d having electron injection properties is provided as the intermediate layer 1 a in the transparent electrode 1. That is, in the third example, the transparent electrode 1 used as a cathode is composed of an intermediate layer 1a also serving as an electron transport layer 3d having electron injection properties, and a conductive layer 1b provided on the intermediate layer 1a. It is.

Such an electron transport layer 3d is configured by using the material constituting the intermediate layer 1a of the transparent electrode 1 described above.
In addition to these layers, the organic functional layer 3 adopts various configurations as necessary, as described in the first example. However, the electron transport also serving as the intermediate layer 1a of the transparent electrode 1 is used. No electron injection layer or hole blocking layer is provided between the layer 3d and the conductive layer 1b of the transparent electrode 1. In the above configuration, only the portion where the organic functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5c becomes the light emitting region in the organic EL element 300, as in the first example.

In the layer structure as described above, the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. The same as in the example.
Furthermore, the counter electrode 5c used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specific examples include metals such as silver (Ag) and gold (Au), and oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO ₂ and SnO ₂ .

The counter electrode 5c configured as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5c is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In addition, when this organic EL element 300 is comprised so that the emitted light h can be taken out also from the counter electrode 5c side, as a material which comprises the counter electrode 5c, light transmittance is favorable among the electrically conductive materials mentioned above. A suitable conductive material is selected and used. In this case, the substrate 131 is the same as the transparent substrate 13 described in the first example, and the surface facing the outside of the substrate 131 is the light extraction surface 131a.

<Effect of organic EL element>
In the organic EL element 300 described above, the electron transport layer 3d having the electron injecting property constituting the uppermost part of the organic functional layer 3 is used as the intermediate layer 1a, and the conductive layer 1b is provided on the intermediate layer 1a. The transparent electrode 1 composed of the conductive layer 1b is provided as a cathode.
Therefore, similarly to the first example and the second example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5c to realize high-luminance light emission in the organic EL element 300, while the transparent electrode 1 side. It is possible to increase the luminance by improving the extraction efficiency of the emitted light h from the light source.
Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance. Further, when the counter electrode 5c is light transmissive, the emitted light h can be extracted from the counter electrode 5c.

  In the third example described above, the intermediate layer 1a of the transparent electrode 1 has been described as also serving as the electron transport layer 3d having electron injection properties. However, the present example is not limited to this, and the intermediate layer 1a may also serve as an electron transport layer 3d that does not have electron injection properties, or the intermediate layer 1a may serve as an electron injection layer instead of an electron transport layer. In addition, the intermediate layer 1a may be formed as an extremely thin film that does not affect the light emitting function of the organic EL element. In this case, the intermediate layer 1a has electron transport properties and electron injection properties. Not.

  Further, when the intermediate layer 1a of the transparent electrode 1 is formed as an extremely thin film that does not affect the light emitting function of the organic EL element, the counter electrode 5c on the substrate 131 side is used as a cathode, The transparent electrode 1 may be an anode. In this case, the organic functional layer 3 is, for example, in order from the counter electrode (cathode) 5c side on the substrate 131, for example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a. Are stacked. And the transparent electrode 1 which consists of a laminated structure of the ultra-thin intermediate | middle layer 1a and the electroconductive layer 1b is provided in this upper part as an anode.

≪6. Applications of organic EL elements >>
Since the organic EL elements having the above-described configurations are surface light emitters as described above, they can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. In particular, it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display). In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic EL elements are joined together in a plane.

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

  Hereinafter, a lighting device will be described as an example of the application, and then a lighting device in which the light emitting surface is enlarged by tiling will be described.

≪7. Lighting device-1 >>
The organic EL element of the present invention can be used for a lighting device.
The organic EL element of the present invention may be designed such that each organic EL element having the above-described configuration has a resonator structure. The purpose of use of the organic EL element configured to have a resonator structure includes a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, etc. It is not limited to. Moreover, you may use for the said use by making a laser oscillation.

  In addition, the material used for the organic EL element of this invention is applicable to the organic EL element (white organic EL element) which produces substantially white light emission. For example, a plurality of luminescent colors can be simultaneously emitted by a plurality of luminescent materials, and white light emission can be obtained by mixing colors. As a combination of a plurality of emission colors, those containing the three emission maximum wavelengths of the three primary colors of red, green and blue may be used, or two emission using the complementary colors such as blue and yellow, blue green and orange, etc. It may contain a maximum wavelength.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and excitation of light from the light emitting materials. Any combination with a pigment material that emits light as light may be used, but in a white organic EL element, a combination of a plurality of light-emitting dopants may be used.

  Such a white organic EL element is different from a configuration in which organic EL elements each emitting light are individually arranged in parallel in an array to obtain white light emission, and the organic EL element itself emits white light. For this reason, a mask is not required for film formation of most layers constituting the element, and deposition can be performed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is also improved. To do.

Moreover, there is no restriction | limiting in particular as a light emitting material used for the light emitting layer of such a white organic EL element, For example, if it is a backlight in a liquid crystal display element, it will fit in the wavelength range corresponding to CF (color filter) characteristic. As described above, any one of the above-described metal complexes and known light-emitting materials may be selected and combined to be whitened.
If the white organic EL element demonstrated above is used, it is possible to produce the illuminating device which produces substantially white light emission.

≪8. Lighting device-2 >>
FIG. 5 is a schematic cross-sectional view of an illuminating device having a large light emitting surface using a plurality of organic EL elements having the above-described configurations.
As shown in FIG. 5, the lighting device 21 has a large light emitting surface by arranging a plurality of light emitting panels 22 including the organic EL elements 100 on the transparent substrate 13 on the support substrate 23 (tiling). This is the configuration. The support substrate 23 may also serve as the sealing material 17, and each light-emitting panel 22 is tied with the organic EL element 100 sandwiched between the support substrate 23 and the transparent substrate 13 of the light-emitting panel 22. Ring. An adhesive 19 may be filled between the support substrate 23 and the transparent substrate 13, thereby sealing the organic EL element 100. In addition, the edge part of the transparent electrode 1 which is an anode, and the counter electrode 5a which is a cathode are exposed around the light emission panel 22. FIG. However, only the exposed part of the counter electrode 5a is shown in FIG.
In FIG. 5, as the organic functional layer 3 constituting the organic EL element 100, the hole injection layer 3a / the hole transport layer 3b / the light emitting layer 3c / the electron transport layer 3d / the electron injection layer 3e are formed on the transparent electrode 1. A configuration in which the layers are sequentially stacked is shown as an example.

  In the lighting device 21 having such a configuration, the center of each light emitting panel 22 is a light emitting area A, and a non-light emitting area B is generated between the light emitting panels 22. For this reason, a light extraction member for increasing the light extraction amount from the non-light-emitting region B may be provided in the non-light-emitting region B of the light extraction surface 13a. As the light extraction member, a light collecting sheet or a light diffusion sheet can be used.

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

[Example 1]
<< Preparation of transparent electrode >>
As described below, the transparent electrodes 101 to 117 were fabricated so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 101 to 117 were produced as transparent electrodes having a laminated structure of an intermediate layer and a conductive layer.

(1) Production of Transparent Electrode 101 A thin film was formed on a non-alkali glass substrate using a PGME (1-methoxy-2-propanol) solution of Comparative Compound 1 by a spin coating method. A polymerization reaction was carried out by heating and drying at 130 ° C. for 1 hour to provide an intermediate layer containing a polymer formed from Comparative Compound 1 having a layer thickness of 30 nm.

  On this intermediate layer, 1.0 ml of inkjet ink (TEC-IJ-010, manufactured by Ink Tec Co., Ltd.) made of complex silver as a conductive layer material was diluted 10 times with ethanol. After applying and patterning 0.1 ml of this diluted solution by spin coating, baking is performed at 120 ° C. for 30 minutes to form a conductive layer made of silver having a thickness of 10 nm, and a laminated structure of an intermediate layer and a conductive layer A transparent electrode 101 made of

(2) Production of transparent electrode 102 Transparent electrode 102 was produced in the same manner as production of transparent electrode 101 except that the thickness of the conductive layer was changed to 15 nm.

(3) Production of Transparent Electrode 103 An intermediate layer was provided by the same production procedure as that for the transparent electrode 101.
The substrate formed up to the intermediate layer was transferred to a vacuum chamber, and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing a heating boat containing silver, with a deposition rate of 0.1 to 0.2 nm / Within a range of seconds, a conductive layer made of silver having a thickness of 10 nm was formed on the intermediate layer, and a transparent electrode 103 having a laminated structure of the intermediate layer and the conductive layer was produced.

(4) Production of Transparent Electrode 104 A thin film was formed on a non-alkali glass base material by a spin coating method using a P-1 PGME solution. An intermediate layer containing a polymer formed from P-1 having a layer thickness of 30 nm was provided by heating and drying at 130 ° C. for 30 minutes.

  On this intermediate layer, 1.0 ml of conductive ink composed of gold nanoparticles as a conductive layer material (manufactured by Sigma Aldrich Japan G.K., product number: 741949, diameter 5 nm) was diluted 10 times with ethanol. After applying and patterning 0.1 ml of this diluted solution by spin coating, baking is performed at 120 ° C. for 30 minutes to form a conductive layer made of gold having a thickness of 10 nm, and a laminated structure of an intermediate layer and a conductive layer A transparent electrode 104 made of

(5) Production of transparent electrode 105 Transparent electrode 105 was produced in the same manner as in production of transparent electrode 104 except that the thickness of the conductive layer was changed to 15 nm.

(6) Production of transparent electrode 106 Transparent electrode 106 was produced in the same manner as in production of transparent electrode 104, except that the constituent material of the conductive layer was changed to the inkjet ink described in Table 2.

(7) Production of transparent electrode 107 Transparent electrode 107 was produced in the same manner as in production of transparent electrode 103 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 2.

(8) Production of transparent electrodes 108 to 111 Transparent electrodes 108 to 111 were produced in the same manner as the production of the transparent electrode 101 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 2.

(9) Production of transparent electrode 112 Properties that are cured by applying and patterning by spin coating using a PGME solution containing P-15 and acetophenone in a molar ratio of 100: 1 on a non-alkali glass substrate. The layer which consists of a composition which has was formed. Then, it moved on the hotplate, and it dried and superposition | polymerization reaction by heating for 30 minutes at 130 degreeC, and provided the intermediate | middle layer containing the polymer formed from P-15 with a layer thickness of 30 nm.
On the intermediate layer, a conductive layer was formed in the same manner as the conductive layer manufacturing procedure of the transparent electrode 101, and a transparent electrode 112 having a laminated structure of the intermediate layer and the conductive layer was manufactured.

(10) Production of transparent electrode 113 A thin film was formed by spin coating on a non-alkali glass substrate using a PGME solution containing P-17 and P-36 at a molar ratio of 1: 100. An intermediate layer containing a copolymer formed from P-17 and P-36 having a layer thickness of 30 nm was provided by heating and drying at 130 ° C. for 30 minutes.
On this intermediate layer, a conductive layer was formed in the same manner as the conductive layer manufacturing procedure of the transparent electrode 101, and a transparent electrode 113 having a laminated structure of the intermediate layer and the conductive layer was manufactured.

(11) Production of transparent electrode 114 Transparent electrode 114 was produced in the same manner as production of transparent electrode 113 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 2.

(12) Fabrication of transparent electrode 115 Coating and patterning by spin coating using a toluene solution containing P-16, P-47 and AIBN in a molar ratio of 100: 10000: 1 on a non-alkali glass substrate. Thus, a layer made of a composition having a curing property was formed. Then, it is moved onto a hot plate and heated at 130 ° C. for 30 minutes to carry out drying and polymerization reaction, and heated and dried at 130 ° C. for 30 minutes to form a co-form formed from P-16 and P-47 having a layer thickness of 30 nm. An intermediate layer containing a polymer was provided.

  On the intermediate layer, a conductive layer was formed in the same manner as the conductive layer manufacturing procedure of the transparent electrode 101, and a transparent electrode 115 having a laminated structure of the intermediate layer and the conductive layer was manufactured.

(13) Production of transparent electrodes 116 and 117 In production of the transparent electrodes 111 and 115, except that the base material was changed to PET (Teijin DuPont Films Co., Ltd., Teijin (registered trademark) Tetron (registered trademark) film K). Similarly, transparent electrodes 116 and 117 were produced.

<< Evaluation of transparent electrode >>
About the produced transparent electrodes 101-117, according to the following method, the light transmittance, sheet resistance value, and the sheet resistance value change (durability) under high temperature storage were measured.

(1) Measurement of light transmittance About each produced transparent electrode, using a spectrophotometer (U-3300 by Hitachi High-Technologies), the light transmittance (%) at a measurement light wavelength of 550 nm with reference to the substrate of each transparent electrode. Was measured.
The measurement results are shown in Table 2.

(2) Measurement of sheet resistance value For each of the produced transparent electrodes, a sheet resistance value (Ω / □) was measured by a 4-probe method constant current application method using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.). did.
The measurement results are shown in Table 2.

(3) Measurement of change in sheet resistance value under high temperature storage Each of the produced transparent electrodes was stored in an atmosphere at a temperature of 80 ° C / 90% relative humidity, and the change in sheet resistance value was measured. Specifically, the sheet resistance values before the start of the test and after the lapse of 120 hours were compared, the change was evaluated, and the results are shown in Table 2. The sheet resistance value was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and the sheet resistance value (Ω / □) was measured by a four-point probe constant current application method, and the change in resistance value from the initial sheet Was calculated. The sheet resistance value change under high temperature storage of each transparent electrode is shown as a relative value with the sheet resistance value change of the transparent electrode 108 being 100, indicating that the smaller the value, the less the change, and the better the durability. Yes.

(4) Summary With respect to the transparent electrode numbers 101 to 104 of the comparative example, neither the sheet resistance value nor the sheet resistance value under high temperature storage can be measured. This is because when the conductive layer is formed by a wet method, the intermediate layer is eluted in the PGME solvent, the layer is disturbed, and the function as the transparent electrode is lost.
Further, as is clear from Table 2, the transparent electrodes 104 to 117 of the present invention in which the conductive layer is provided on the intermediate layer formed of the curable composition according to the present invention have a light transmittance of 53%. The sheet resistance value is suppressed to 16.9Ω / □ or less. On the other hand, the transparent electrodes 101 to 103 of the comparative example had a light transmittance of less than 53%, and the sheet resistance value could not be measured.

Further, in terms of durability (change in sheet resistance value under high temperature storage), the transparent electrodes 101 to 103 of the comparative example cannot be measured, whereas the transparent electrodes 104 to 117 of the present invention are small and excellent. I understood that.
Moreover, also when the resin film like PET was used for the base material, it was confirmed that the effect was exhibited regardless of the substrate because the evaluation result equivalent to that of the alkali-free glass was obtained.

  From the above, it was confirmed that the transparent electrode of the present invention has high light transmittance and conductivity, and is further excellent in durability.

[Example 2]
<< Preparation of transparent electrode >>
As described below, the transparent electrodes 201 to 218 were prepared so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 201 to 218 were produced as transparent electrodes having a laminated structure of an intermediate layer, a conductive layer, and an optical adjustment layer.

(1) Production of transparent electrode 201 A thin film was formed on a non-alkali glass base material by spin coating using a MEK solution of Comparative Compound 2. An intermediate layer containing a polymer formed from Comparative Compound 2 having a layer thickness of 60 nm was provided by heating and drying at 110 ° C. for 1 hour.

  On this intermediate layer, 1.0 ml of inkjet ink (TEC-IJ-010, manufactured by Ink Tec Co., Ltd.) made of complex silver as a conductive layer material was diluted 10 times with ethanol. After 0.1 ml of this diluted solution was applied and patterned by spin coating, it was baked at 120 ° C. for 30 minutes to form a conductive layer made of silver having a layer thickness of 10 nm.

  A thin film was formed on the conductive layer by spin coating using a K-1 MEK solution. Heat-dried at 150 ° C. for 1 hour, an optical adjustment layer containing K-1 having a layer thickness of 50 nm was provided, and a transparent electrode 201 having a laminated structure of an intermediate layer, a conductive layer, and an optical adjustment layer was produced.

(2) Production of transparent electrode 202 Transparent electrode 202 was produced in the same manner as in production of transparent electrode 201 except that the thickness of the conductive layer was changed to 15 nm.

(3) Production of transparent electrode 203 An intermediate layer was provided by the same production procedure as the transparent electrode 201.
The substrate formed up to the intermediate layer was transferred to a vacuum chamber, and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing a heating boat containing silver, with a deposition rate of 0.1 to 0.2 nm / Within a range of seconds, a conductive layer made of silver having a layer thickness of 10 nm was formed on the intermediate layer.

  On this conductive layer, an optical adjustment layer is formed in the same manner as the optical adjustment layer of the transparent electrode 201 under the atmosphere, and the transparent electrode 203 having a laminated structure of the intermediate layer, the conductive layer, and the optical adjustment layer is formed. Produced.

(4) Production of transparent electrode 204 A thin film was formed on a non-alkali glass base material by spin coating using a P-4 MEK solution. An intermediate layer containing a polymer formed from P-4 having a layer thickness of 60 nm was provided by heating and drying at 110 ° C. for 1 hour.

  On this intermediate layer, 1.0 ml of conductive ink composed of gold nanoparticles as a conductive layer material (manufactured by Sigma Aldrich Japan GK, product number: 741949, diameter 5 nm) was diluted 10-fold with 2-propanol. After 0.1 ml of this diluted solution was applied and patterned by a spin coating method, it was baked at 120 ° C. for 30 minutes to form a conductive layer made of gold having a layer thickness of 10 nm.

  On this conductive layer, an optical adjustment layer was formed in the same manner as the optical adjustment layer preparation procedure of the transparent electrode 201, and a transparent electrode 204 having a laminated structure of an intermediate layer, a conductive layer, and an optical adjustment layer was prepared.

(5) Production of transparent electrode 205 Transparent electrode 205 was produced in the same manner as in production of transparent electrode 204 except that the thickness of the conductive layer was changed to 15 nm.

(6) Production of transparent electrode 206 Transparent electrode 206 was produced in the same manner as in production of transparent electrode 204 except that the constituent material of the conductive layer was changed to the inkjet ink shown in Table 3.

(7) Production of transparent electrode 207 Transparent electrode 207 was produced in the same manner as in production of transparent electrode 203 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 3.

(8) Production of transparent electrode 208 In production of the transparent electrode 201, the transparent electrode 208 was produced in the same manner except that the constituent material of the intermediate layer was changed to the compounds shown in Table 3 and no optical adjustment layer was provided. .

(9) Production of transparent electrode 209 Transparent electrode 209 was produced in the same manner as in production of transparent electrode 201 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 3.

(10) Production of transparent electrodes 210 and 211 Transparent electrodes 210 and 211 were produced in the same manner except that the constituent materials of the intermediate layer and the optical adjustment layer were changed to the compounds shown in Table 3 in the production of the transparent electrode 201. .

(11) Fabrication of transparent electrode 212 Transparent electrode 212 was fabricated in the same manner as in fabrication of transparent electrode 209 except that the layer thickness of the optical adjustment layer was changed to 25 nm.

(12) Fabrication of transparent electrode 213 A property of curing by applying and patterning by spin coating using a toluene solution containing P-14 and benzophenone in a molar ratio of 200: 1 on a non-alkali glass substrate. The layer which consists of a composition which has was formed. Then, it moved on the hotplate and heated at 110 degreeC for 1 hour, drying and the polymerization reaction were performed, and the intermediate layer containing the polymer formed from P-14 with a layer thickness of 60 nm was provided.

  On this intermediate layer, the conductive layer and the optical adjustment layer are formed in the same manner as the procedure for producing the conductive layer and the optical adjustment layer of the transparent electrode 211, and has a laminated structure of the intermediate layer, the conductive layer, and the optical adjustment layer. A transparent electrode 213 was produced.

(13) Production of transparent electrode 214 A thin film was formed by spin coating on a non-alkali glass substrate using a toluene solution containing P-77 and P-20 in a molar ratio of 2: 1. An intermediate layer containing a copolymer formed from P-77 and P-20 having a layer thickness of 60 nm was provided by heating and drying at 110 ° C. for 1 hour.

  On this intermediate layer, a conductive layer was formed in the same manner as the procedure for manufacturing the conductive layer of the transparent electrode 201. Moreover, the transparent electrode 214 was produced in the same manner as the production procedure of the optical adjustment layer of the transparent electrode 201 except that the constituent material of the optical adjustment layer was changed to the compounds shown in Table 3.

(14) Production of transparent electrode 215 Transparent electrode 215 was produced in the same manner as production of transparent electrode 214 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 3.

(15) Production of transparent electrode 216 On a non-alkali glass base material, a toluene solution containing P-71, P-60 and AIBN in a molar ratio of 100: 100: 1 is applied and patterned by a spin coating method. Thus, a layer made of a composition having a curing property was formed. Then, it is moved on a hot plate and heated at 110 ° C. for 1 hour to dry and polymerize, and an intermediate layer containing a copolymer formed from P-71 and P-60 with a layer thickness of 60 nm is provided. It was.

  On this intermediate layer, a conductive layer and an optical adjustment layer are formed in the same manner as the procedure for producing the conductive layer and the optical adjustment layer of the transparent electrode 214, and has a laminated structure of the intermediate layer, the conductive layer, and the optical adjustment layer. A transparent electrode 216 was produced.

(16) Preparation of transparent electrodes 217 and 218 In the preparation of transparent electrodes 211 and 216, except that the base material was changed to PET (manufactured by Teijin DuPont Films, Teijin (registered trademark) Tetron (registered trademark) film K). Similarly, transparent electrodes 217 and 218 were produced.

<< Evaluation of transparent electrode >>
About the produced transparent electrodes 201-218, according to the following method, the light transmittance, sheet resistance value, and the light transmittance change (durability) under high temperature storage were measured. (1) Measurement of light transmittance and (2) measurement of sheet resistance were carried out in the same manner as in Example 1.

(3) Measurement of light transmittance change under high temperature storage Each of the produced transparent electrodes was stored in a 60 ° C./90% relative humidity atmosphere, and the light transmittance change was measured. Specifically, the change in light transmittance after 120 hours was evaluated as compared with before the start of the test, and the results are shown in Table 3. The light transmittance was measured using a spectrophotometer (U-3300 manufactured by Hitachi High-Technologies), and the light transmittance (%) at a measurement light wavelength of 550 nm was measured using the substrate of each transparent electrode as a reference. The light transmittance change of each transparent electrode under high-temperature storage is shown as a relative value with the light transmittance change of the transparent electrode 209 as 100.

(4) Summary With respect to the transparent electrode numbers 201 to 203 of the comparative example, neither the sheet resistance value nor the sheet resistance value under high temperature storage can be measured. This is because when the conductive layer is formed by a wet method, the intermediate layer is eluted in the MEK solvent, the layer is disturbed, and the function as the transparent electrode is lost.
As is apparent from Table 3, the transparent electrodes 204 to 218 of the present invention in which the conductive layer is provided on the intermediate layer formed from the curable composition according to the present invention have a light transmittance of 62% or more. Yes, the sheet resistance value is suppressed to 16.5Ω / □ or less. On the other hand, the transparent electrodes 201 to 203 of the comparative example had a light transmittance of less than 62%, and the sheet resistance value could not be measured.

Further, in terms of durability (change in light transmittance under high temperature storage), the transparent electrodes 201 to 203 of the comparative example cannot be measured, whereas the transparent electrodes 204 to 218 of the present invention are small and excellent. I understand that.
Moreover, also when the resin film like PET was used for the base material, it was confirmed that the effect was exhibited regardless of the substrate because the evaluation result equivalent to that of the alkali-free glass was obtained.
From the above, it was confirmed that the transparent electrode of the present invention has high light transmittance and conductivity, and is further excellent in durability.

[Example 3]
<Production of light emitting panel>
Double-sided light emitting panels 401 to 417 using a transparent electrode as an anode were manufactured. Hereinafter, the manufacturing procedure will be described with reference to FIG.

(1) Production of Light-Emitting Panel 401 A thin film was formed on a non-alkali glass base material by spin coating using a methyl acetate solution of Comparative Compound 3. An intermediate layer containing a polymer formed from Comparative Compound 3 having a layer thickness of 20 nm was provided by heating and drying at 110 ° C. for 1 hour.

  On this intermediate layer, 1.0 ml of inkjet ink (TEC-IJ-010, manufactured by Ink Tec Co., Ltd.) made of complex silver as a conductive layer material was diluted 10 times with ethanol. After applying and patterning 0.1 ml of this diluted solution by spin coating, baking is performed at 120 ° C. for 30 minutes to form a conductive layer made of silver having a thickness of 10 nm, and a laminated structure of an intermediate layer and a conductive layer A transparent electrode 1 comprising:

Next, the transparent substrate on which the transparent electrode 1 was formed was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, and a vapor deposition mask was disposed facing the formation surface side of the transparent electrode 1. Moreover, each material which comprises the organic functional layer 3 was filled in each heating boat in a vacuum evaporation apparatus in the optimal quantity for film-forming of each layer. In addition, what was produced with the resistance heating material made from tungsten was used for the heating boat.
Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.

  First, a heating boat containing α-NPD (4,4′-Bis [phenyl (1-naphthyl) amino] -1,1′-biphenyl) as a hole transport injection material is energized and heated, and α-NPD A hole transport injection layer 31 serving as both a hole injection layer and a hole transport layer was formed on the conductive layer 1 b constituting the transparent electrode 1. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 20 nm.

  Next, the heating boat containing the host material H4 and the heating boat containing the phosphorescent dopant Ir-4 are energized independently, and the light emitting layer 3c containing the host material H4 and the phosphorescent dopant Ir-4. Was formed on the hole transport injection layer 31. At this time, the energization of the heating boat was adjusted so that the deposition rate was host material H4: phosphorescent dopant Ir-4 = 100: 6. The layer thickness was 30 nm.

  Next, the hole blocking layer 33 made of BAlq is heated by energizing a heating boat containing BAlq ([Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum]) as a hole blocking material. A film was formed on the light emitting layer 3c. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 10 nm.

Thereafter, a heating boat containing ET-6 shown below as an electron transporting material and a heating boat containing potassium fluoride were energized independently, and an electron transporting layer 3d containing ET-6 and potassium fluoride. Was formed on the hole blocking layer 33. At this time, the energization of the heating boat was adjusted so that the deposition rate was ET-6: potassium fluoride = 75: 25. The layer thickness was 30 nm.
Next, a heating boat containing potassium fluoride as an electron injection material was energized and heated to form an electron injection layer 3e made of potassium fluoride on the electron transport layer 3d. At this time, the deposition rate was 0.01 to 0.02 nm / second, and the layer thickness was 1 nm.

  Thereafter, the transparent substrate 13 formed up to the electron injection layer 3e was transferred from the vapor deposition chamber of the vacuum vapor deposition apparatus to the processing chamber of the sputtering apparatus to which an ITO target as a counter electrode material was attached while maintaining the vacuum state. Next, in the processing chamber, a film was formed at a film forming rate of 0.3 to 0.5 nm / second, and a light-transmitting counter electrode 5a made of ITO having a film thickness of 150 nm was formed as a cathode. As described above, the organic EL element 400 was formed on the transparent substrate 13.

  Thereafter, the organic EL element 400 is covered with a sealing material 17 made of a glass substrate having a thickness of 300 μm, and the adhesive 19 (sealing material) is interposed between the sealing material 17 and the transparent substrate 13 so as to surround the organic EL element 400. ). As the adhesive 19, an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used. The adhesive 19 filled between the sealing material 17 and the transparent substrate 13 is irradiated with UV light from the glass substrate (sealing material 17) side to cure the adhesive 19 and seal the organic EL element 400. Stopped.

  In forming the organic EL element 400, an evaporation mask is used for forming each layer, and the central 4.5 cm × 4.5 cm of the 5 cm × 5 cm transparent substrate 13 is defined as the light emitting region A, and the entire circumference of the light emitting region A is formed. A non-light emitting region B having a width of 0.25 cm was provided. Further, the transparent electrode 1 serving as the anode and the counter electrode 5a serving as the cathode are insulated by the organic functional layer 3 from the hole transport injection layer 31 to the electron injection layer 3e, and a terminal portion is provided on the periphery of the transparent substrate 13. Was formed in a drawn shape.

As described above, the light emitting panel 401 in which the organic EL element 400 was provided on the transparent substrate 13 and sealed with the sealing material 17 and the adhesive 19 was manufactured.
In the light emitting panel 401, the emitted light h of each color generated in the light emitting layer 3c is extracted from both the transparent electrode 1 side, that is, the transparent substrate 13 side, and the counter electrode 5a side, that is, the sealing material 17 side.

(2) Production of Light-Emitting Panel 402 A light-emitting panel 402 was produced in the same manner as the light-emitting panel 401 except that the thickness of the conductive layer 1b was changed to 15 nm.

(3) Production of Light-Emitting Panel 403 A light-emitting panel 403 was produced in the same manner as in the production of the light-emitting panel 401 except that the conductive layer 1b was formed by vapor deposition. The production by the vapor deposition method is the same as that of the transparent electrode 103 of Example 1.

(4) Production of light-emitting panel 404 In production of the light-emitting panel 401, an intermediate layer was formed by the same formation method except that the constituent material of the intermediate layer was changed to P-3.
On this intermediate layer, 1.0 ml of conductive ink composed of gold nanoparticles as a conductive layer material (manufactured by Sigma Aldrich Japan GK, product number: 741949, diameter 5 nm) was diluted 10-fold with n-propanol. After applying and patterning 0.1 ml of this diluted solution by spin coating, baking is performed at 120 ° C. for 30 minutes to form a conductive layer made of gold having a thickness of 10 nm, and a laminated structure of an intermediate layer and a conductive layer A transparent electrode comprising:
In the production of the light emitting panel 401, a light emitting panel 404 was produced in the same manner except that the transparent electrode produced as described above was used with P-3 as the constituent material of the intermediate layer.

(5) Production of Light-Emitting Panel 405 A light-emitting panel 405 was produced in the same manner as in the production of the light-emitting panel 404 except that the thickness of the conductive layer was changed to 15 nm.

(6) Production of Light-Emitting Panel 406 A light-emitting panel 406 was produced in the same manner as in the production of the light-emitting panel 404, except that the constituent material of the conductive layer was changed to the inkjet ink shown in Table 4.

(7) Production of Light-Emitting Panel 407 A light-emitting panel 407 was produced in the same manner as in the production of the light-emitting panel 403 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 4.

(8) Production of light-emitting panels 408 to 411 Light-emitting panels 408 to 411 were produced in the same manner as the light-emitting panel 401 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 4.

(9) Production of light-emitting panel 412 On a non-alkali glass substrate, a methyl acetate solution containing P-67 and acetophenone in a molar ratio of 150: 1 is applied and patterned by spin coating to be cured. A layer made of a composition having properties was formed. Then, it moved on the hotplate and heated at 100 degreeC for 1 hour, drying and the polymerization reaction were performed, and the intermediate layer containing the polymer formed from P-67 with a layer thickness of 20 nm was provided.
In the production of the light emitting panel 401, a light emitting panel 412 was produced in the same manner except that the constituent material of the intermediate layer was P-67 and the produced transparent electrode was used with acetophenone as a radical polymerization initiator.

(10) Production of Light-Emitting Panel 413 A thin film was formed by spin coating on a non-alkali glass base material using a methyl acetate solution containing P-74 and P-35 at a molar ratio of 5: 1. An intermediate layer containing a copolymer formed from P-74 and P-35 having a layer thickness of 20 nm was provided by heating and drying at 100 ° C. for 1 hour.
In the manufacture of the light-emitting panel 401, the light-emitting panel 413 was manufactured in the same manner except that the above-prepared transparent electrode was used with P-74 and P-35 as the constituent materials of the intermediate layer.

(11) Production of Light-Emitting Panel 414 A light-emitting panel 414 was produced in the same manner as in the production of the light-emitting panel 413 except that the constituent material of the intermediate layer was changed to the compounds shown in Table 4.

(12) Production of light-emitting panel 415 Coating and patterning by spin coating using a methyl acetate solution containing P-79, P-58 and AIBN in a molar ratio of 200: 200: 1 on a non-alkali glass substrate. Thus, a layer made of a composition having a curing property was formed. Then, it is moved on a hot plate and heated at 100 ° C. for 1 hour to dry and polymerize, and an intermediate layer containing a copolymer formed of P-79 and P-58 with a layer thickness of 20 nm is provided. It was.
A light-emitting panel 415 was manufactured in the same manner as in the manufacture of the light-emitting panel 401 except that the constituent material of the intermediate layer was P-79 and P-58 and the transparent electrode prepared above was used.

(13) Production of transparent electrodes 416 and 417 In production of the light-emitting panels 411 and 415, except that the base material was changed to PET (manufactured by Teijin DuPont Films, Teijin (registered trademark) Tetron (registered trademark) film K). Similarly, light-emitting panels 416 and 417 were manufactured.

<Evaluation of luminous panel>
About the produced light emission panels 401-417, according to the following method, the measurement of the external transmittance | permeability (durability) under light transmittance, a drive voltage, and high temperature storage was performed.

(1) Measurement of light transmittance About each produced light emission panel, using the spectrophotometer (U-3300 by Hitachi High-Technologies Corporation), the substrate of the transparent electrode of each light emission panel was used as a reference at a measurement light wavelength of 550 nm. The light transmittance (%) was measured.

(2) Measurement of driving voltage The front luminance on both sides of the transparent electrode 1 side (that is, the transparent substrate 13 side) and the counter electrode 5a side (that is, the sealing material 17 side) of each of the produced light emitting panels is measured. The voltage when the sum was 1000 cd / m ² was measured as the drive voltage (V). For the measurement of luminance, a spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used. It represents that it is so preferable that the numerical value of the obtained drive voltage is small.

(3) Measurement of external quantum efficiency (EQE) change under high-temperature storage Each organic EL element contained in the produced light-emitting panel was allowed to emit light at 75 ° C. under a constant current condition of ^2.5 mA / cm ² . The emission luminance immediately after the start of light emission and the emission luminance after 200 hours from the start were measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta).
Relative light emission luminance after 200 hours from the light emission luminance immediately after the start of light emission was obtained, and this was used as a measure of external quantum efficiency (EQE). The smaller the value, the smaller the change in emission luminance and the better the external quantum efficiency.

(4) Summary In the light emitting panels 401 to 403 of the comparative example, neither the drive voltage nor the EQE change under high temperature storage could be measured. This is because when the conductive layer is formed by the wet method, the intermediate layer is eluted in the methyl acetate solvent, the layer is disturbed, and the function as the transparent electrode is lost.
As is clear from Table 4, the light-emitting panels 406 to 417 have the light transmittance of 65% or more and the driving voltage is suppressed to 5.6 V or less with the transparent electrode of the present invention as the anode of the organic EL element. Yes. On the other hand, the light-emitting panels 401 to 403 using the transparent electrode of the comparative example as the anode of the organic EL element had a light transmittance of less than 65%, and the drive voltage could not be measured.

Further, in terms of durability (change in external quantum efficiency under high temperature storage), it was found that the light emitting panels 404 to 417 were excellent while the light emitting panels 401 to 403 of the comparative example could not be measured.
From the above, it was confirmed that the light-emitting panel using the organic EL element of the present invention has both high light transmittance and conductivity and is further excellent in durability.
In addition, as shown in Examples 1 to 3, by forming an intermediate layer using the curable composition according to the present invention, the intermediate layer has resistance to various solvents, so that a desired effect is obtained. A transparent electrode having a layer structure suitable for development and a light-emitting panel including the transparent electrode could be produced.

1, 2 Transparent electrodes 1a, 2a Intermediate layer 1b, 2b Conductive layer 2c Optical adjustment layer 3 Organic functional layer 3a Hole injection layer 3b Hole transport layer 3c Light emitting layer 3d Electron transport layer 3e Electron injection layer 31 Hole transport injection Layer 33 Hole blocking layer 5a, 5b, 5c Counter electrode 11, 12 Substrate 13, 131 Transparent substrate (substrate)
13a, 131a Light extraction surface 15 Auxiliary electrode 17 Sealing material 19 Adhesive 21 Illumination device 22 Light emitting panel 23 Support substrate 100, 200, 300, 400 Organic EL element A Light emitting region B Non-light emitting region h Light emitting light

Claims (12)

A transparent electrode comprising a conductive layer and an intermediate layer provided adjacent to the conductive layer,
The conductive layer contains gold, silver or copper as a main component,
The intermediate layer is formed of a curable composition;
The said curable composition contains the aromatic heterocyclic compound containing the nitrogen atom which has a lone pair which does not participate in aromaticity, The transparent electrode characterized by the above-mentioned.   The transparent electrode according to claim 1, wherein the conductive layer contains silver as a main component.   The transparent electrode according to claim 1, wherein both the intermediate layer and the conductive layer are formed by a wet method.   The said curable composition is a thermosetting composition or a photocurable composition, The transparent electrode as described in any one of Claim 1- Claim 3 characterized by the above-mentioned.   The said curable composition is a polymeric composition, The transparent electrode as described in any one of Claim 1- Claim 4 characterized by the above-mentioned.   The transparent electrode according to claim 5, wherein the polymerizable composition is a composition comprising one kind of monomer having a vinyl group.   The transparent electrode according to claim 5, wherein the polymerizable composition is a copolymerizable composition comprising two or more types of monomers having a vinyl group.   The transparent electrode according to claim 5, wherein the polymerizable composition is a copolymerizable composition of a monomer having a vinyl group and a monomer having a thiol group.   The transparent electrode according to any one of claims 5 to 8, wherein the polymerizable composition is a composition containing a monomer having two or more vinyl groups in a molecule.   The transparent electrode according to any one of claims 5 to 9, wherein the polymerizable composition is a composition polymerized using a radical polymerization initiator.   An electronic device comprising the transparent electrode according to any one of claims 1 to 10. An organic electroluminescence device having at least a light emitting layer between an anode and a cathode,
The said anode or cathode has a transparent electrode as described in any one of Claim 1-10, The organic electroluminescent element characterized by the above-mentioned.

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