JP6774425B2 - Organic electroluminescence device and its manufacturing method - Google Patents

Description

The present invention relates to an organic electroluminescence device and a method for manufacturing the same, and more specifically, to an organic electroluminescence device having excellent current efficiency and a method for manufacturing the same.

In recent years, large-area organic electroluminescence (EL) devices have been required for lighting applications. In a large-area organic EL device, a low-resistance electrode is required to obtain stable light emission.

As a low resistance electrode, one having an auxiliary wiring provided on the light emitting surface is known. However, since the auxiliary wiring is opaque, the light emission from the light emitting layer of the organic EL element is blocked, and as a result, it is a factor of lowering the current efficiency.

As a solution to this, it is conceivable that the area overlapping the auxiliary wiring is not emitted in the first place.
For example, in Patent Document 1, a plurality of electrode films are arranged at intervals from each other, an auxiliary electrode film is formed between the electrode films, and an insulating film is formed so as to cover the auxiliary electrode film. Is disclosed. According to this configuration, electricity does not flow from the auxiliary electrode film to the organic light emitting part (organic functional layer) even when the electrode is energized, that is, the organic light emitting part overlapping with the auxiliary electrode film can not emit light. Therefore, the decrease in current efficiency can be suppressed.
However, providing an insulating layer only on the auxiliary electrode film in addition to the electrode film and the auxiliary electrode film complicates the manufacturing process and leads to an increase in cost.

International Publication No. 2012/090903

The present invention has been made in view of the above problems and situations, and the problem of solving the present invention is to provide an organic electroluminescence device having excellent current efficiency and a method for manufacturing the same by using a simpler method.

In the process of examining the cause of the above problem in order to solve the above problem, the present inventor presents at least a part of the region where at least one of the auxiliary wiring and the organic functional layer overlaps when viewed in a plan view. We have found that it is possible to provide an organic electroluminescence element having excellent current efficiency and a method for producing the same by modulating the light emitting function of the above, and have arrived at the present invention.

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

1. 1. An organic electroluminescence device in which a lower electrode, an organic functional layer including at least a light emitting layer, and an upper electrode are sequentially laminated on a support substrate.
The lower electrodes is constituted by a transparent conductive layer, an opaque auxiliary wiring,
A resin layer is provided between the support substrate and the auxiliary wiring.
An organic electroluminescence device characterized in that, when viewed in a plan view, the light emitting function of at least a part of a region where the auxiliary wiring and at least one layer of the organic functional layer overlap is modulated.
2. As the light emitting layer, at least one layer of a fluorescent light emitting layer containing the following compounds BD-1 and H-1 or a phosphorescent light emitting layer containing the following compounds GD-1, RD-1 and H-2 is provided. The organic electroluminescence element according to the first item.

3 . On a supporting substrate, a lower electrode, an organic functional layer including at least a light emitting layer, and an upper electrode are sequentially stacked, the lower electrodes includes a transparent conductive layer, an opaque auxiliary wiring and the organic electro that consists It is a manufacturing method of luminescence element.
at least,
A step of forming the lower electrode composed of the transparent conductive layer and the auxiliary wiring, and
The step of forming the organic functional layer and
A step of forming a resin layer between the support substrate and the auxiliary wiring,
And also
When viewed in a plan view, at least a step of modulating the light emitting function of a part of the region where the auxiliary wiring and at least one of the organic functional layers overlap.
A method for manufacturing an organic electroluminescence device, which comprises.
4. As a step of forming the light emitting layer, at least one of a fluorescent light emitting layer containing the following compounds BD-1 and H-1 or a phosphorescent light emitting layer containing the following compounds GD-1, RD-1 and H-2. The method for producing an organic electroluminescence element according to claim 3, further comprising a step of forming a layer.

5 . The method for producing an organic electroluminescence device according to item 3 or 4 , wherein in the step of modulating the light emitting function, at least a part of the overlapping region is modulated by ultraviolet irradiation.

6 . The method for manufacturing an organic electroluminescence device according to item 3 or 4 , wherein in the step of modulating the light emitting function, at least a part of the overlapping region is modulated by laser irradiation.

By the above means of the present invention, it is possible to provide an organic electroluminescence device having excellent current efficiency and a method for manufacturing the same.

Although the mechanism of expression and mechanism of action of the effects of the present invention have not been clarified, it is inferred as follows.

As described above, when the auxiliary wiring is provided as the low resistance electrode, the opaque auxiliary wiring blocks the light emission from the light emitting layer of the organic EL element, which causes a decrease in current efficiency.
FIG. 6 shows an organic EL element in which the light emitting function of the organic functional layer is not modulated.
In the organic EL element 100, the emitted light from the organic functional layer (light emitting layer) 106 is from the organic functional layer (light emitting layer) 106 that does not overlap the emitted light L1 on the auxiliary wiring 104b and the auxiliary wiring 104b. There is emission light L2. As shown in FIG. 6, the light emitting light L2 can be taken out to the outside without being blocked by the auxiliary wiring 104b, but the light emitting light L1 can be taken out by the auxiliary wiring 104b because the auxiliary wiring 104b is opaque. Most of them are reflected and difficult to take out.

Therefore, in the present invention, by modulating the light emitting function of a part of the region where at least one of the auxiliary wiring and the organic functional layer overlaps, the light emitting intensity from the light emitting layer overlapping with the auxiliary electrode is lowered. Therefore, it is considered that an organic EL element having excellent current efficiency can be provided.

Sectional drawing which shows the schematic structure as an example of the organic EL element of this invention. Sectional drawing which shows the schematic structure as another example of the organic EL element of this invention. Sectional drawing which shows the schematic structure as another example of the organic EL element of this invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Schematic diagram of a plan showing the pattern shape of the auxiliary wiring according to the present invention. Front view showing the outline of the vacuum ultraviolet irradiation device Schematic cross-sectional view of an organic EL element whose light emitting function is not modulated

The organic EL device of the present invention comprises a support substrate, a lower electrode, and at least a light emitting layer containing an organic functional layer are sequentially laminated and the upper electrode, the lower electrodes includes a opaque auxiliary wiring, and a transparent conductive layer A resin layer is provided between the support substrate and the auxiliary wiring, and when viewed in plan view, at least a part of the region where at least one of the auxiliary wiring and the organic functional layer overlaps is emitted. The function is characterized in that it is modulated.
This feature is a technical feature common to or corresponding to each of the following embodiments .

Further, the present invention comprises a support substrate, a lower electrode, is an organic functional layer, and the upper electrode are sequentially stacked, including at least a light emitting layer, composed of the lower electrodes includes a opaque auxiliary wiring, a transparent conductive layer This is a method for manufacturing an organic EL element, which includes, at least, a step of forming a lower electrode composed of an auxiliary wiring and a transparent conductive layer, a step of forming an organic functional layer, and a support substrate and an auxiliary wiring. A step of forming a resin layer between them , and further, a step of modulating the light emitting function of a part of a region where at least one of the auxiliary wiring and the organic functional layer overlaps when viewed in a plan view. A method for manufacturing an organic EL element having the above can be provided.

As an embodiment of the present invention, since the light emitting function can be modulated with high positional accuracy, the light emitting layer can be modulated without peeling, and the light emitting layer can be modulated even in a vacuum, at least overlapping regions can be obtained by ultraviolet irradiation or laser irradiation. It is preferable to modulate the light emitting function of a part.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

<< Configuration of organic EL element >>
The organic EL element of the present invention is configured by sequentially laminating a lower electrode, an organic functional layer including at least a light emitting layer, and an upper electrode on a support substrate.
Hereinafter, the details will be described with reference to the drawings.

As shown in FIG. 1, the organic EL element 1 of the present invention is configured by sequentially laminating a lower electrode 4, an organic functional layer 6 including at least a light emitting layer, and an upper electrode 8 on a support substrate 2. ..
The lower electrode 4 is composed of a transparent conductive layer 4a and an auxiliary wiring 4b.
The organic functional layer 6 is configured to include at least a light emitting layer, and may also have various organic layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.

In the organic EL element 1 of the present invention, when viewed in a plan view, at least a part of the light emitting function of a region where the auxiliary wiring 4b and at least one layer of the organic functional layer 6 overlap is modulated. It is a feature. Here, the partial portion is not particularly limited in its position and area as long as it is within the region where the auxiliary wiring 4b and the organic functional layer 6 overlap.
It is a preferred embodiment that the light emitting function of the organic functional layer 6 is modulated in all the regions where the auxiliary wiring 4b and at least one layer of the organic functional layer 6 overlap. FIG. 1 shows a case where the entire region where the auxiliary wiring 4b and at least one of the organic functional layers 6 overlap is modulated. That is, in the overlapping region T, the light emitting function of the organic functional layer 6 is modulated.
Here, the modulated light emitting function means a state in which the function of the hole transport material or the like constituting the organic functional layer 6 is changed. Specifically, it is compared with the unmodulated organic layer. This means that the charge transport capacity (mobility) and the quantum yield of the light emitting material are reduced. In the present invention, it is preferable that the charge transport capacity of the overlapping region T and the like are completely lost, and that the quantum efficiency of the light emitting material is almost nonexistent.
The charge transport capability (mobility) can be measured by a TOF (time of flight) method or impedance spectroscopy.
Further, if there is a modulated portion in the same light emitting surface, the modulated portion can be identified by thermography.
When the quantum efficiency of the luminescent material is low, there is a lot of heat deactivation, a lot of heat generation, and the temperature of that part rises. On the other hand, when the mobility is low, it becomes difficult for current to flow through that portion, heat generation is reduced, and the temperature rise is reduced.

Further, as shown in FIG. 2, the organic EL element of the present invention is placed between the support substrate 2 and the auxiliary wiring 4b (lower electrode 4) for the purpose of improving the adhesion between the support substrate 2 and the auxiliary wiring 4b. The resin layer 10 may be provided.
Further, an absorption layer containing a material that absorbs the irradiation light when modulating the light emitting function of the organic functional layer may be provided. For example, as shown in FIG. 3, an absorption layer 12 containing an infrared absorber may be provided on the surface of the support substrate 2 opposite to the organic functional layer 6.

In the above description, the bottom emission type organic EL element has been described as an example, but a top emission type organic EL element, that is, an element in which the upper electrode is composed of a transparent conductive layer and auxiliary wiring may be used.

Hereinafter, each member constituting the organic EL element of the present invention shown in FIG. 1 will be described.

<Support substrate (2)>
The support substrate according to the present invention has a total light transmittance of 80% or more in the visible light wavelength region measured by a method based on JIS K 7361-1: 1997 (test method for total light transmittance of plastic-transparent material). The transparent resin substrate of is preferably used. In addition, "transparency" means that the total light transmittance in the visible light wavelength region measured by a method conforming to the JIS standard is 50% or more.

The support substrate is preferably made of a material having excellent flexibility, a sufficiently small dielectric loss coefficient, and a smaller absorption of microwaves than the auxiliary wiring. As the support substrate, for example, it is preferable to use a transparent resin film from the viewpoint of productivity and performance such as light weight and flexibility.

The transparent resin film that can be preferably used is not particularly limited, and the material, shape, structure, thickness, and the like thereof can be appropriately selected from known ones. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) or modified polyester, polyolefins such as polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film or cyclic olefin resin. Resin film, vinyl-based resin film such as polyvinyl chloride or polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysalphon (PSF) resin film, polyether salphon (PES) resin film, polycarbonate (PC) resin film , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film and the like.

A resin film having a total light transmittance of 80% or more can be preferably used as a support substrate. In particular, a polyester resin film is preferable, and a biaxially stretched polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film are more preferable from the viewpoints of transparency, infrared absorption characteristics, ease of handling, strength and cost.

Further, the support substrate may be provided with a surface treatment or an easy-adhesion layer (base layer) in order to ensure the wettability and adhesiveness of the coating liquid. Conventionally known techniques can be used for the surface treatment and the easy-adhesion layer. For example, examples of the surface treatment include surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
Examples of the easy-adhesion layer include polyester, polyamide, polyurethane, vinyl-based copolymer, butadiene-based copolymer, acrylic-based copolymer, vinylidene-based copolymer, and epoxy-based copolymer. The easy-adhesion layer may be a single layer, but may be composed of two or more layers in order to improve the adhesiveness.
It is preferable to form a gas barrier layer made of a coating of an inorganic substance or an organic substance or a gas barrier layer made of a hybrid coating of an inorganic substance and an organic substance on the front surface or the back surface of the support substrate.

<Lower electrode (4)>
The lower electrode according to the present invention is composed of a transparent conductive layer and an opaque auxiliary wiring.

(Transparent conductive layer (4a))
The lower electrode according to the present invention is provided with a transparent conductive layer so as to cover the auxiliary wiring.
The transparent conductive layer is formed so as to cover the unevenness of the auxiliary wiring so that the surface becomes smooth or flat.

The transparent conductive layer is composed of a material having at least conductivity (conductive material). Examples of the conductive material include a conductive transparent material, a conductive polymer, and carbon nanotubes. In addition, "conductivity" in the transparent conductive layer and the conductive material refers to a state in which electricity flows, and is a method based on JIS K 7194-1994 "resistivity test method by 4-probe method of conductive electric plastic". The sheet resistance measured in 1 × 10 ⁶ Ω / sq. It means lower.

The electric resistance value of the transparent conductive layer is 10000 Ω / sq. It is preferably 2000Ω / sq. More preferably:
The dry layer thickness of the transparent conductive layer is preferably in the range of 30 to 2000 nm. From the viewpoint of conductivity, it is more preferably 100 nm or more, and from the viewpoint of surface smoothness of the electrode, it is further preferably 200 nm or more. Further, from the viewpoint of transparency, it is more preferably 1000 nm or less.

As the conductive transparent material, a transparent conductive metal oxide is preferable, and for example, a conductive oxide such as indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO ₂ ), IGZO, and zinc oxide. Examples thereof include an amorphous transparent conductive film such as (IZO).

When the transparent conductive layer is formed of a conductive polymer, it is preferable to include a non-conductive polymer together with the conductive polymer. Further, the transparent conductive layer contains a conductive polymer and a non-conductive polymer, and the non-conductive polymer contains a self-dispersing polymer and / or a hydroxy group-containing polymer, so that the conductivity of the transparent conductive layer can be improved. The required amount of the conductive polymer can be reduced without loss. As a result, a transparent electrode having both high conductivity and transparency can be obtained.

(1) Conductive polymer The conductive polymer contains a π-conjugated conductive polymer and a polyanion. The conductive polymer can be easily produced by chemically oxidizing and polymerizing a precursor monomer for forming a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst and a polyanion described later.

(2) π-conjugated conductive polymer The π-conjugated conductive polymer is not particularly limited, and polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines. , Polyacetylenes, Polyfurans, Polyparaphenylene Vinylenes, Polyazulenes, Polyparaphenylenes, Polyparaphenylene sulfides, Polyisothianaftens, Polythiazyl and other chain conductive polymers can be used. Among them, polythiophenes and polyanilines are preferable from the viewpoint of conductivity, transparency, stability and the like, and polyethylenedioxythiophene is most preferable.

(3) Polyanions Polyanions used in conductive polymers include substituted or unsubstituted polyalkylenes, substituted or unsubstituted polyalkenylenes, substituted or unsubstituted polyimides, substituted or unsubstituted polyamides, substituted or unsubstituted polyesters, and the like. In addition, these copolymers are composed of a structural unit having an anionic group and a structural unit having no anionic group.
This polyanion is a polymer that solubilizes or disperses a π-conjugated conductive polymer in a solvent. Further, the anionic group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

The anionic group of the polyanion may be a functional group capable of chemically oxidizing a π-conjugated conductive polymer, but from the viewpoint of ease of production and stability, a monosubstituted sulfate group is used. A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Further, a sulfo group, a monosubstituted sulfate group and a carboxy group are more preferable from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer.

Specific examples of the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, ethyl acrylate poly acrylate, butyl sulfonic acid poly acrylate, poly-2-acrylamide-2-methyl propane sulfonic acid, and polyisoprene sulfone. Examples thereof include acids, polyvinylcarboxylic acids, polystyrene carboxylic acids, polyallylcarboxylic acids, polyacrylic carboxylic acids, polymethacrylcarboxylic acids, poly-2-acrylamide-2-methylpropanecarboxylic acids, polyisoprenecarboxylic acids, and polyacrylic acids. .. Further, these homopolymers may be used, or two or more kinds of copolymers may be used.
Further, it may be a polyanion having a fluorine atom in the compound. Specific examples thereof include Nafion (manufactured by DuPont) containing a perfluorosulfonic acid group, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like. Further, these fluorinated polyanions can be integrally formed with a transparent electrode having a hole injection function when used in combination with a non-fluorinated polyanion, which is desirable from the viewpoint of device efficiency and productivity.
The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

As such a conductive polymer, a commercially available material can also be preferably used. For example, a conductive polymer (abbreviated as PEDOT / PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is available from Heraeus as the Clevios series and from Aldrich as PEDOT-PSS 483095 and 560596. It is commercially available as a Denatron series from Nagase Polymer. In addition, polyaniline is commercially available from Nissan Chemical Industries, Ltd. as the ORMECON series.

(Auxiliary wiring (4b))
The auxiliary wiring is mainly composed of a metal and is formed with a metal content ratio to the extent that conductivity can be obtained. The ratio of the metal in the auxiliary wiring is preferably 50% by mass or more.

The auxiliary wiring is formed in a pattern so as to have an opening on the support substrate. The opening is a portion having no auxiliary wiring when a transparent support substrate is used, and is a translucent portion of the auxiliary wiring.
When a transparent support substrate is used, the ratio occupied by the openings, that is, the aperture ratio is preferably 80% or more from the viewpoint of transparency. For example, the aperture ratio of a striped pattern having a line width of 100 μm and a line spacing of 1 mm is about 90%.

There is no particular limitation on the pattern shape of the auxiliary wiring. The pattern shape of the auxiliary wiring includes, for example, a striped pattern (see FIGS. 4A and 4B), a grid pattern (see FIGS. 4C and D), a hexagonal honeycomb pattern (see FIG. 4E), and the like. , Random mesh shape (see FIG. 4F) and the like. In particular, a grid pattern, a honeycomb pattern, or a random mesh pattern is preferable, and a grid pattern is most preferable, from the viewpoint that even if a defect (disconnection) occurs in the auxiliary wiring, the influence as an electrode is small.

The line width of the auxiliary wiring is preferably in the range of 10 to 200 μm, and more preferably in the range of 10 to 100 μm. When the line width of the auxiliary wiring is 10 μm or more, the desired conductivity can be obtained, and when it is 200 μm or less, the transparency of the electrode is improved.
In the striped or grid pattern, the interval between the auxiliary wirings is preferably in the range of 0.5 to 4 mm.

The height (thickness) of the auxiliary wiring is preferably in the range of 0.1 to 5.0 μm, and more preferably in the range of 0.1 to 2.0 μm. When the height of the auxiliary wiring is 0.1 μm or more, the desired conductivity can be obtained, and when the height is 5.0 μm or less, when the resin layer is formed on the support substrate, the difference in unevenness is the layer of the functional layer. The effect on the thickness distribution can be reduced.

For the auxiliary wiring, a coating liquid for forming an auxiliary wiring containing a metal or a metal forming material is prepared, and after applying the coating liquid, post-treatment such as drying treatment and firing treatment is appropriately selected to perform auxiliary wiring. Can be formed.

The metal (elemental metal or alloy) to be blended in the coating liquid for forming auxiliary wiring is preferably particulate or fibrous (tube-shaped, wire-shaped, etc.), and more preferably metal nanoparticles. Further, it is preferably formed from a metal forming material which has a metal atom (element) and produces a metal by a structural change such as decomposition. The metal and the metal forming material in the coating liquid for forming the auxiliary wiring may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio can be arbitrarily adjusted.

Examples of the metal used for the metal nanoparticles include metals such as gold, silver, copper and platinum, and alloys containing these as main components. Among these, gold and silver are preferable from the viewpoint of having excellent light reflectance and further improving the efficiency of the obtained organic EL element. As these metals or alloys, any one type may be used alone or two or more types may be used in combination as appropriate.

The coating liquid for forming auxiliary wiring is preferably a metal colloid or a metal nanoparticle dispersion liquid having a structure in which the surface of metal nanoparticles is coated with a protective agent and stably and independently dispersed in a solvent.

As the average particle size of the metal nanoparticles in the coating liquid for forming auxiliary wiring, those having an atomic scale of 1000 nm or less can be preferably applied. In particular, as the metal nanoparticles, those having an average particle size in the range of 3 to 300 nm are preferable, and those having an average particle size in the range of 5 to 100 nm are more preferably used. In particular, silver nanoparticles having an average particle size in the range of 3 to 100 nm are preferable. Further, as the metal nanowire, a silver wire having a width of 1 nm or more and less than 1000 nm, preferably in the range of 1 to 100 nm is preferable.

Here, the average particle size of the metal nanoparticles and the metal colloid and the width of the metal nanowires are determined by using a transmission electron microscope (TEM) to determine the particle size of the metal nanoparticles and the width of the metal nanowires in the dispersion. Can be measured and obtained. For example, among the particles observed in the TEM image, the particle diameter of 300 independent metal nanoparticles that do not overlap can be measured to calculate the average particle diameter.

In the metal colloid, the organic π-bonded ligand is preferable as the protective agent for coating the surface of the metal nanoparticles. Conductivity is imparted to the metal colloid by π-bonding the organic π-conjugated ligand to the metal nanoparticles.

As the organic π-bonded ligand, one or more compounds selected from the group consisting of phthalocyanine derivatives, naphthalocyanine derivatives and porphyrin derivatives are preferable.
Further, as the organic π-bonded ligand, an amino group, an alkylamino group, a mercapto group, a hydroxyl group, etc. At least one selected from a carboxyl group, a phosphine group, a phosphonic acid group, a sulfonic acid group, a halogen group, a selenol group, a sulfide group, a selenoether group, an amide group, an imide group, a cyano group, a nitro group, and salts thereof. It is preferable to have a substituent of.

Further, as the organic π-bonded ligand, the organic π-conjugated ligand described in International Publication No. 2011/114713 pamphlet can be used.

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

OTAN: 2,3,11,12,20,21,29,30-octakis [(2-N, N-dimethylaminoethyl) thio] naphthalocyanine OTAP: 2,3,9,10,16,17,23 , 24-octakis [(2-N, N-dimethylaminoethyl) thio] phthalocyanine OCAN: 2,3,11,12,20,21,29,30-naphthalocyanine octacarboxylic acid

As a method for preparing a metal nanoparticle dispersion liquid containing an organic π-bonded ligand, a liquid phase reduction method can be mentioned. Further, the production of the organic π-bonded ligand and the preparation of the metal nanoparticle dispersion liquid containing the organic π-bonded ligand are described in the methods described in paragraphs [0039] to [0060] of International Publication No. 2011/114713. It can be done according to the same procedure.

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

In the metal nanoparticle dispersion liquid, as the protective agent for coating the surface of the metal nanoparticles, it is preferable to use a protective agent whose ligand is released at a low temperature of 200 ° C. or lower. As a result, the protective agent is peeled off due to low temperature or low energy, metal nanoparticles are fused, and conductivity can be imparted.
Specific examples thereof include the metal nanoparticle dispersions described in JP2013-142173, JP2012-162767, JP2014-139343, and Patent No. 5606439.

Examples of the metal forming material include metal salts, metal complexes, organometallic compounds (compounds having a metal-carbon bond), and the like. The metal salt and the metal complex may be either a metal compound having an organic group or a metal compound having no organic group. By using a metal-forming material for the coating liquid for forming auxiliary wiring, metal is generated from the material, and auxiliary wiring containing this metal is formed.

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

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

Examples of the ammonium carbamate compound include ammonium carbamate, ethyl ammonium ethyl carbamate, isopropylammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t-butyl carbamate, and 2-ethylhexyl ammonium 2. -Ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutylammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl decyl carbamate, hexamethylene Examples thereof include iminium hexamethyleneimine carbamate, morphorium morpholin carbamate, pyridinium ethylhexyl carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzyl carbamate, triethoxysilylpropylammonium triethoxysilylpropyl carbamate and the like. Among the above ammonium carbamate compounds, the alkylammonium alkyl carbamate substituted with the primary amine is preferable because it is superior to the secondary or tertiary amine in terms of reactivity and stability.

The organic silver complex compound can be produced by the method described in JP-A-2011-48795. For example, one or more of the silver compounds and one or more of the ammonium carbamate compounds can be directly reacted under normal pressure or pressure in a nitrogen atmosphere without using a solvent. Also, alcohols such as methanol, ethanol, isopropanol and butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate and carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Methyl ethyl ketone, ketones such as acetone, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, and solvents such as halogen-substituted solvents such as chloroform, methylene chloride and carbon tetrachloride. Can be reacted.

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

The organic silver complex compound is well soluble in various solvents including solvents for producing organic silver complex compounds, such as alcohols such as methanol, esters such as ethyl acetate, and ether solvents such as tetrahydrofuran. Therefore, the organic silver complex compound can be easily applied to the coating and printing steps as a coating liquid for forming auxiliary wiring.

Further, as a material for forming metallic silver, silver carboxylate having a group represented by the formula "-COOAg" can be exemplified. The silver carboxylate is not particularly limited as long as it has a group represented by the formula "-COOAg". For example, the number of groups represented by the formula "-COOAg" may be only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

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

When the coating liquid for forming auxiliary wiring contains the above silver carboxylate as a metal forming material, the amine compound having 25 or less carbon atoms, the quaternary ammonium salt, ammonia, and the amine compound or ammonia are acids together with silver carboxylate. It is preferable that one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting with the above are blended.

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

<Organic functional layer (6)>
Typical configurations of the organic functional layer according to the present invention include, but are not limited to, the following configurations.

(I) (Lower electrode) / Light emitting layer / (Upper electrode)
(Ii) (Lower electrode) / Light emitting layer / Electron transport layer / (Upper electrode)
(Iii) (Lower electrode) / Hole transport layer / Light emitting layer / (Upper electrode)
(Iv) (Lower electrode) / Hole transport layer / Light emitting layer / Electron transport layer / (Upper electrode)
(V) (Lower electrode) / Hole transport layer / Light emitting layer / Electron transport layer / Electron injection layer / (Upper electrode)
(Vi) (Lower electrode) / Hole injection layer / Hole transport layer / Light emitting layer / Electron transport layer / (Upper electrode)
(Vii) (lower electrode) / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / (upper electrode)

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

The light emitting layer according to the present invention may be composed of a plurality of layers, and in this case, a non-light emitting intermediate layer may be provided between the light emitting layers.

Any known material can be used for each of the above layers.

(Light emitting layer)
The light emitting layer according to the present invention is a layer in which electrons and holes injected from an electrode or an electron transport layer and a hole transport layer are recombined to emit light.
The total thickness of the light emitting layer is not particularly limited, but from the viewpoint of film homogeneity, prevention of application of an unnecessary high voltage during light emission, and improvement of emission color stability with respect to drive current. It is preferably adjusted in the range of 2 nm to 5 μm, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 5 to 100 nm.
The thickness of each light emitting layer is preferably adjusted within the range of 2 nm to 1 μm, more preferably adjusted within the range of 2 to 200 nm, and further preferably adjusted within the range of 3 to 150 nm. To.

The light emitting layer preferably contains a light emitting dopant (a light emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light emitting host compound, also simply referred to as a host).

Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
For example, Nature 395, 151 (1998), Apple. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19,739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/10991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 / 020194, US Patent Application Publication No. 2007/0087321, US 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, Apple. Phys. Lett. 86,153505 (2005), Chem. Lett. 34,592 (2005), Chem. Common. 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, US Patent No. 7332232 , US Patent Application Publication No. 2009/01087737, US Patent Application Publication No. 2009/00397776, US Patent Application Publication No. 6921915, US Patent No. 6687266, US Patent Application Publication No. 2007/0190359 Specification, US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Patent No. 7250226, US Patent No. 7396598, US Patent Application Publication No. 2006/0263635, US Patent Application Publication No. 2003/0138657, US Patent Application Publication No. 2003/0152802, US Patent No. 70090928, Angew .. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18,5119 (2006), Inorg. Chem. 46,4308 (2007), Organometallics 23,3745 (2004), Apple. Phys. Lett. 74,1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/090024, International Publication No. 2006/056418, International Publication No. 2005/019373, 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. 2005/02060441, US Patent No. 73935999, US Patent No. 75334505 Specification, US Patent Application Publication No. 7445855, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2008/0297033, US Patent No. 7338722, US Patent Application Publication No. 2002 / 0134984, US Patent No. 7279704, US Patent Application Publication No. 2006/098120, US 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. 2009/113666 No., International Publication No. 2012/20327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, US Patent Application Publication No. 2012/228583, US Patent Application Publication 2012/212126, Japanese Patent Application Laid-Open No. 2012-069737, Japanese Patent Application Laid-Open No. 2012-195554, Japanese Patent Application Laid-Open No. 2009-114086, Japanese Patent Application Laid-Open No. 2003-81988, Japanese Patent Application Laid-Open No. 2002-302671 2002-363552, Japanese Patent Application Laid-Open No. 2009-231516, International Publication No. 2012/112853, Japanese Patent Application Laid-Open No. 51294242, Japanese Patent Application Laid-Open No. 4784600, Japanese Patent Application Laid-Open No. 2010-47764, and the like.

Specific examples of known host compounds used in the organic EL device of the present invention include, but are not limited to, the compounds described in the following documents.
Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860, 2002-334787A, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002. 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003 No. 3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183, No. 2002-299060, No. 2002- 302516, 2002-305083, 2002-305084, 2002-308837, US Patent Application Publication No. 2003/0175553, US Patent Application Publication No. 2006/0280965, USA 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, International 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. 2007/0637996, 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. 2012/0293947 , JP-A-2008-074939, JP-A-2007-254297, European Patent No. 2034538 and the like.

(Hole transport layer)
The hole transport layer in the present invention may be made of a material having a function of transporting holes and may have a function of transmitting holes injected from the anode to the light emitting layer.
The total thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 μm, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm.

The material used for the hole transport layer (hereinafter referred to as the hole transport material) may have any of hole injectability, transportability, and electron barrier property, and is among conventionally known compounds. Any one can be selected and used from.
For example, porphyrin derivative, phthalocyanine derivative, oxazole derivative, oxadiazole derivative, triazole derivative, imidazole derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, hydrazone derivative, stilben derivative, polyarylalkane derivative, triarylamine derivative, carbazole derivative. , Indolocarbazole derivative, isoindole derivative, acene derivative such as anthracene and naphthalene, fluorene derivative, fluorenone derivative, polyvinylcarbazole, polymer material or oligomer in which aromatic amine is introduced into the main chain or side chain, polysilane, conductivity Examples thereof include sex polymers or oligomers (eg, PEDOT: PSS, aniline-based copolymers, polyaniline, polythiophene, etc.).
Examples of the triarylamine derivative include a benzidine type represented by α-NPD, a starburst type represented by MTDATA, and a compound having fluorene or anthracene in the triarylamine connecting core portion.
Hexaazatriphenylene derivatives as described in JP-A-2003-591432 and JP-A-2006-135145 can also be used as the hole transport material in the same manner.
Further, a hole transport layer having a high p property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. Apple. Phys. , 95, 5773 (2004) and the like.
In addition, JP-A-11-251667, J. Am. Hung et. al. So-called p-type hole transporting materials and inorganic compounds such as p-type-Si and p-type-SiC, as described in the authored literature (Applied Physics Letters 80 (2002), p.139), can also be used. Further, an orthometalated organometallic complex having Ir or Pt in the central metal as represented by Ir (ppy) 3 is also preferably used.
As the hole transport material, the above-mentioned materials can be used, but a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organic metal complex, and an aromatic amine are introduced into the main chain or the side chain. High molecular weight materials or oligomers are preferably used.

Specific examples of known and preferable hole transporting materials used in the organic EL device of the present invention include the compounds described in the following documents in addition to the above-mentioned documents, but the present invention is limited thereto. Not done.
For example, Apple. Phys. Lett. 69,2160 (1996), J. Mol. Lumin. 72-74,985 (1997), Apple. Phys. Lett. 78,673 (2001), Apple. Phys. Lett. 90,183503 (2007), Apple. Phys. Lett. 90,183503 (2007), Apple. Phys. Lett. 51,913 (1987), Synth. Met. 87,171 (1997), Synth. Met. 91,209 (1997), Synth. Met. 111,421 (2000), SID Symposium Digital, 37,923 (2006), J. Mol. Mater. Chem. 3,319 (1993), Adv. Mater. 6,677 (1994), Chem. Mater. 15, 3148 (2003), US Patent Application Publication No. 2003/0162053, US Patent Application Publication No. 2002/0158242, US Patent Application Publication No. 2006/0240279, US Patent Application Publication No. 2008 / 0220265, US Patent No. 5061569, International Publication No. 2007/002683, International Publication No. 2009/01809, European Patent No. 650955, US Patent Application Publication No. 2008/01245772, USA Japanese Patent Application Publication No. 2007/0278938, US Patent Application Publication No. 2008/0106190, US Patent Application Publication No. 2008/0018221, International Publication No. 2012/115034, Japanese Patent Application Laid-Open No. 2003-591432 , Japanese Patent Application Laid-Open No. 2006-135145, US Patent Application Publication No. 2013/0049576, etc.

The hole transporting material may be used alone, or a plurality of types may be used in combination.

(Electronic blocking layer)
The electron blocking layer is a layer having a function of a hole transporting layer in a broad sense, and is preferably made of a material having a function of transporting holes and a small ability to transport electrons, while transporting holes. By blocking the electrons, the recombination probability of the electrons and holes can be improved.
In addition, the structure of the hole transport layer described above can be used as an electron blocking layer, if necessary.
The electron blocking layer is preferably provided adjacent to the anode side of the light emitting layer.
The thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
As the material used for the electron blocking layer, the material used for the hole transporting layer described above is preferably used, and the material used as the host compound described above is also preferably used for the electron blocking layer.

(Hole injection layer)
The hole injection layer (also referred to as an anode buffer layer) is a layer provided between the anode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness. It is described in detail in Volume 2, Chapter 2, "Electrode Materials" (pages 123-166) of "November 30, 1998, published by NTS Co., Ltd.).
In the present invention, the hole injection layer may be provided as needed and may be present between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
The details of the hole injection layer are also described in JP-A-9-45479, 9-2660062, 8-288609, etc., and examples of the material used for the hole injection layer include. Examples thereof include materials used for the hole transport layer described above.
Among them, phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives as described in JP-A-2003-591432 and JP-A-2006-135145, metal oxides typified by vanadium oxide, and amorphous Conductive polymers such as carbon, polyaniline (emeraldine) and polythiophene, orthometallated complexes typified by tris (2-phenylpyridine) iridium complexes, triarylamine derivatives and the like are preferable.
The material used for the hole injection layer described above may be used alone, or a plurality of types may be used in combination.

(Electronic transport layer)
In the present invention, the electron transport layer may be made of a material having a function of transporting electrons and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
The total thickness of the electron transport layer of the present invention is not particularly limited, but is usually in the range of 2 nm to 5 μm, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm. is there.
On the other hand, if the thickness of the electron transport layer is increased, the voltage tends to increase. Therefore, especially when the thickness is large, the electron mobility of the electron transport layer should be 1 × ^10-5 cm ² / Vs or more. Is preferable.

The material used for the electron transport layer (hereinafter referred to as an electron transport material) may have any of electron injectability, transportability, and hole barrier property, and is among conventionally known compounds. Any one can be selected and used.
For example, nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more of the carbon atoms constituting the carbazole ring substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivative, quinoline derivative, quinoxalin derivative, phenanthroline derivative, azatriphenylene derivative, oxazole derivative, thiazole derivative, oxadiazole derivative, thiadiazol derivative, triazole derivative, benzimidazole derivative, benzoxazole derivative, benzthiazole derivative, etc.), dibenzofuran derivative, Examples thereof include dibenzothiophene derivatives, silol derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene, etc.).
Further, metal complexes having a quinolinol skeleton or a dibenzoquinolinol skeleton as ligands, for example, 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 metal complexes thereof. A metal complex in which the central metal of the above is replaced with In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as an electron transport material.

In the electron transport layer, the electron transport layer may be doped with a doping material as a guest material to form an electron transport layer having a high n property (electron rich). Examples of the doping material include n-type dopants such as metal compounds and metal compounds such as metal halides. Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-2970776, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Mol. Apple. Phys. , 95, 5773 (2004) and the like.
Further, it is preferable that the metal fluoride is doped from the viewpoint of lowering the driving voltage.

Specific examples of known and preferable electron transporting materials used in the organic EL device of the present invention include, but are not limited to, the compounds described in the following documents.
US Patent No. 6528187, US Patent No. 7230107, US Patent Application Publication No. 2005/0025993, US Patent Application Publication No. 2004/0036077, US Patent Application Publication No. 2009/0115316. Books, US Patent Application Publication No. 2009/0101870, US Patent Application Publication No. 2009/0179554, International Publication No. 2003/060956, International Publication No. 2008/132805, Appl. Phys. Lett. 75, 4 (1999), Apple. Phys. Lett. 79,449 (2001), Apple. Phys. Lett. 81, 162 (2002), Apple. Phys. Lett. 81, 162 (2002), Apple. Phys. Lett. 79,156 (2001), US Patent No. 7964293, US Patent Application Publication No. 2009/030202, International Publication No. 2004/080975, International Publication No. 2004/063159, International Publication No. 2005/085387 , International Publication No. 2006/067931, International Publication No. 2007/0865552, International Publication No. 2008/114690, International Publication No. 2009/0694242, International Publication No. 2009/066797, International Publication No. 2009/054253, International Publication No. 2011/086935, International Publication No. 2010/150593, International Publication No. 2010/047707, European Patent No. 2311826, JP-A-2010-251675, JP-A-2009-209133, JP-A-2009. -124114, 2008-277810, 2006-156445, 2005-340122, 2003-45662, 2003-31367, 2003-282270. No., International Publication No. 2012/11034, etc.

More preferable electron transporting materials include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives and benzimidazole derivatives.

The electron transport material may be used alone, or a plurality of types may be used in combination.

(Hole blocking layer)
The hole blocking layer is a layer having a function of an electron transporting layer in a broad sense, and is preferably made of a material having a function of transporting electrons and a small ability to transport holes, and is positive while transporting electrons. By blocking the holes, the recombination probability of electrons and holes can be improved.
In addition, the above-mentioned structure of the electron transport layer can be used as a hole blocking layer, if necessary.
The hole blocking layer is preferably provided adjacent to the cathode side of the light emitting layer.
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.

As the material used for the hole blocking layer, the material used for the electron transporting layer described above is preferably used, and the material used as the host compound described above is also preferably used for the hole blocking layer.

(Electron injection layer)
The electron injection layer (also referred to as a cathode buffer layer) is a layer provided between the cathode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness, and is "organic EL element and its forefront of industrialization (1998). It is described in detail in Volume 2, Chapter 2, "Electrode Materials" (pages 123-166) of "November 30, 2014, published by NTS".
In the present invention, the electron injection layer may be provided as needed and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
The electron injection layer is preferably a very thin film, and its thickness is preferably in the range of 0.1 to 5 nm, although it depends on the material. Further, it may be a non-uniform film in which the constituent material is intermittently present.

The details of the electron-injected layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specific examples of materials preferably used for the electron-injected layer include , Metals such as strontium and aluminum, alkali metal compounds such as lithium fluoride, sodium fluoride and potassium fluoride, alkaline earth metal compounds such as magnesium fluoride and calcium fluoride, oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by lithium 8-hydroxyquinolate (Liq) and the like. It is also possible to use the above-mentioned electron transport material.

The material used for the above-mentioned electron injection layer may be used alone, or a plurality of types may be used in combination.

<Upper electrode (8)>
As the upper electrode, a metal having a small work function (4 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O). ₃ ) Examples thereof include a mixture, indium, a lithium / aluminum mixture, aluminum, and a rare earth metal. Among these, from the viewpoint of electron injectability and durability against oxidation and the like, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture. Magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture, aluminum and the like are suitable.

The upper electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance of the upper electrode is preferably several hundred Ω / □ or less. The thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.
Further, a transparent or translucent upper electrode is produced by producing the above metal on the upper electrode to a thickness of 1 to 20 nm and then producing the conductive transparent material mentioned in the description of the lower electrode on the metal. By applying this, it is possible to manufacture an element in which both the lower electrode and the upper electrode are transparent.

<Resin layer (10)>
In the organic EL element of the present invention, a resin layer may be provided between the support substrate and the auxiliary wiring. By providing the resin layer, the adhesion between the support substrate and the auxiliary wiring can be improved, the resistance of the lower electrode can be lowered, and the storage stability can be improved.
The resin layer may contain at least a curable resin, and as such a curable resin, a general resin such as an acrylic resin, an epoxy resin, or a urethane resin can be used.

Here, the curable resin is a resin containing a compound that is cured by performing a curing treatment. Therefore, when the curable resin is provided on the support substrate by a predetermined method, it is in a fluid state.
The curable resin is preferably a thermosetting resin or a photocurable resin because the method of curing the curable resin by heating or light irradiation is simple.

Further, the curable resin is preferably a polymerizable resin.
Examples of the polymerization reaction include radical polymerization, cationic polymerization, anionic polymerization and the like.
Examples of the method for causing the polymerization reaction include a method of undergoing a heating step, a light irradiation step, or both steps, and an appropriate selection should be made according to the type of curable resin used and the performance of the target resin layer. Can be done.

The polymerizable resin is preferably one type of monomer having a vinyl group from the viewpoint of easily causing a polymerization reaction and easily synthesizing organically.
The polymerizable resin is also preferably a copolymerizable resin composed of two or more types of monomers having a vinyl group. Even if the polymerizable resin is not one type of monomer, the polymerization reaction proceeds in the same manner, so that the polymerizable resin is preferably a copolymerizable resin.
Further, the polymerizable resin may be a copolymerization resin of a monomer having a vinyl group and a monomer having a thiol group.

The copolymerization resin of the monomer having a vinyl group and the monomer having a thiol group changes the magnitude of the effect brought about by changing the content ratio of the monomer having a vinyl group or the monomer having a thiol group, but the rinse It can be appropriately adjusted according to a desired purpose such as improvement of durability and improvement of long-term storage under high temperature and high humidity brought about by using a copolymer resin.
Further, the polymerizable resin is preferably a resin containing a monomer having two or more vinyl groups in the molecule, in that the polymerization reaction can be more reliably caused.

Further, it is preferable that the resin layer contains a nitrogen-containing compound or a sulfur-containing compound described later.

When forming the resin layer, it is also preferable that the coating liquid for forming the resin layer contains a radical polymerization initiator. By containing the radical polymerization initiator in the coating liquid, it is desirable that the polymerization reaction is more likely to occur, there is less uneven polymerization at specific locations, and a resin layer having excellent rinse durability as a whole can be formed. A known radical polymerization initiator can be used depending on the purpose of.

The resin layer may be provided only on a part of the surface of the support substrate on which the auxiliary wiring or the like is formed. For example, the resin layer may be provided only between the support substrate and the auxiliary wiring. In particular, from the viewpoint of reducing the amount of the resin layer material used and the light transmittance, it is preferable to provide the resin layer material only between the support substrate and the auxiliary wiring.

The thickness of the resin layer is appropriately set according to the material contained in the resin layer, but is preferably in the range of, for example, 10 nm to 5 μm, and more preferably in the range of 20 nm to 1 μm. It is preferably in the range of 30 to 500 nm, and particularly preferably in the range of 30 to 500 nm.

The method for forming the resin layer is appropriately selected according to the material contained in the resin layer, but when the resin layer is formed only between the support substrate and the auxiliary wiring, the inkjet method is preferable from the viewpoint of forming accuracy.

(Nitrogen-containing compound)
The resin layer preferably contains a compound containing a nitrogen atom (nitrogen-containing compound).
Examples of the nitrogen-containing compound include hexanediamine, isocyanate, polyamide, polyurethane, an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that does not participate in aromaticity, a low molecular weight organic compound containing a nitrogen atom, and nitrogen. Examples include a polymer containing an atom. Of these, aromatic heterocyclic compounds containing a nitrogen atom having an unshared electron pair that does not participate in aromaticity are preferable.

(1) Aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that is not involved in aromaticity The resin layer is formed by using a curable resin, and the curable resin is aromatic as a nitrogen-containing compound. It is preferable to contain an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that does not participate in.
As a result, when the auxiliary wiring is formed adjacent to the resin layer, the metal atom, which is the main component of the auxiliary wiring, is contained in the resin layer with a nitrogen atom having an unshared electron pair that does not participate in the aromaticity. It can interact and improve the adhesion to the auxiliary wiring.

In the present invention, the "nitrogen atom having an unshared electron pair that does not participate in aromaticity" is a nitrogen atom having an unshared electron pair, and the unshared electron pair has the aromaticity of an unsaturated cyclic compound. A nitrogen atom that is not directly involved as an essential element. That is, the unshared electron pair is not involved in the delocalized π-electron system on the conjugated unsaturated ring structure (aromatic ring) as essential for the expression of aromaticity in the chemical structural formula. To say.

The "nitrogen atom having an unshared electron pair that does not participate in aromaticity" defined in the present invention is important for exhibiting a strong interaction between the unshared electron pair and the metal atom that is the main component of the auxiliary wiring. .. As such a nitrogen atom, it is preferable that it is 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 the metal atom can be inferred from the strength of the nucleophilicity of the nitrogen atom. That is, the stronger the nucleophilicity, the stronger the coordinating force to these metal atoms and the stronger the interaction.

As a method for forming a resin layer using a curable resin containing an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair that is not involved in aromaticity, a coating method or an inkjet method is used as a method using a wet method. , Coating method, dip method and the like, and as a method using the dry method, a vapor deposition method (resistive heating, EB method, etc.), a sputtering method, a CVD (Chemical Vapor Deposition) method and the like can be mentioned. The organic solvent used in the wet method is not particularly limited, but from the viewpoint of high versatility and suppression of environmental load, ethanol, n-propanol, 2-propanol, PGME (1-methoxy-2-propanol), methyl acetate , MEK (methyl ethyl ketone) and water are preferable.

The resin layer is formed by applying a coating liquid containing a curable resin onto a support substrate, and then heating or irradiating the coating liquid on the support substrate with light or the like. Therefore, it is not preferable that an unintended reaction occurs in the stage before curing, and a wet method capable of forming a film under mild conditions is used rather than a dry method such as a thin film method in which a coating liquid is heated to a high temperature and vaporized to form a film. Is preferable.

Specific examples (monomer state) of an aromatic heterocyclic compound containing a nitrogen atom having an unshared electron pair contained in the resin layer, which is not involved in aromaticity, are shown below, but the present invention is not limited thereto. ..

(2) Low-molecular-weight organic compound containing a nitrogen atom As the low-molecular-weight organic compound containing a nitrogen atom, a compound having a melting point of 80 ° C. or higher and a molecular weight M in the range of 150 to 1200 is preferable. Further, the low molecular weight organic compound containing a nitrogen atom preferably has a large interaction with silver or the like, and examples thereof include a nitrogen-containing heterocyclic compound and a phenyl group-substituted amine compound.

When the number n of [effective unshared electron pairs] with respect to the molecular weight M of an organic compound containing a nitrogen atom is defined as the effective unshared electron pair content [n / M], what is a low molecular weight organic compound containing a nitrogen atom? , This [n / M] is a compound selected so that 2.0 × 10 ^-3 ≦ [n / M], and 3.9 × 10 ^-3 ≦ [n / M]. More preferred.

The [effective unshared electron pair] here is an unshared electron pair possessed by a nitrogen atom contained in a compound, which is not involved in aromaticity and is not coordinated with a metal. Suppose there is.

Aromaticity here refers to an unsaturated cyclic structure in which atoms with π electrons are arranged in a ring, and is aromaticity according to the so-called "Huckel's law", and is an electron contained in the π-electron system on the ring. The condition is that the number is "4n + 2" (n = 0, or a natural number).

The above [effective unshared electron pair] is the unshared electron pair possessed by the nitrogen atom regardless of whether the nitrogen atom itself having the unshared electron pair is a heteroatom constituting the aromatic ring. Is selected depending on whether or not is associated with aromaticity. For example, even if a certain nitrogen atom is a heteroatom constituting an aromatic ring, if the nitrogen atom has an unshared electron pair that does not participate in aromaticity, the unshared electron pair is [effective unshared electron]. It is counted as one of [pair].

On the other hand, even if a certain nitrogen atom is not a hetero atom constituting an aromatic ring, if all of the unshared electron pairs of the nitrogen atom are involved in aromaticity, the nitrogen atom is not shared. Lewis pairs are not counted as valid and unshared electron pairs.

In each compound, the number n of the above-mentioned [effective unshared electron pair] corresponds to the number of nitrogen atoms having [effective unshared electron pair].

When an organic compound having a nitrogen atom is composed of a plurality of compounds, for example, the molecular weight M of the mixed compound obtained by mixing these compounds is determined based on the mixing ratio of the compounds, and the molecular weight M with respect to the molecular weight M is obtained. The total number n of [effective and unshared electron pairs] is determined as the average value of the effective and unshared electron pair content [n / M], and this value is preferably in the above-mentioned predetermined range.

Below, as low molecular weight organic compounds containing nitrogen atoms constituting the resin layer, the above-mentioned effective unshared electron pair content [n / M] satisfies 2.0 × 10 ^-3 ≦ [n / M]. As the following example compound No. 1-No. 43 is shown.

In addition, the example compound No. In the copper phthalocyanine of 31, among the unshared electron pairs of the nitrogen atom, the unshared electron pair not coordinated with copper is counted as [effective unshared electron pair].

The above-mentioned compound No. 1-No. Table 1 shows the number (n), molecular weight (M), and effective unshared electron pair content (n / M) of [effective unshared electron pairs] for 43.

As a low molecular weight organic compound containing a nitrogen atom, the above-mentioned compound No. 1-No. In addition to 43, the following compound No. 44 and No. 45 can be mentioned.

(3) Nitrogen Atom-Containing Polymer In the present invention, a polymer can be used as the nitrogen atom-containing organic compound applied to the resin layer.

The polymer containing a nitrogen atom applicable to the present invention is preferably a polymer having a weight average molecular weight in the range of 1000 to 1000000.

The polymer according to the present invention is not particularly limited, but preferably contains a polymer having a partial structure represented by the following general formula (P1) or a partial structure represented by the following general formula (P2).

In the above general formula (P1), A ¹ represents a divalent nitrogen atom-containing group, and Y ¹ represents a divalent organic group or a single bond. n1 is the number of repetitions in which the weight average molecular weight is in the range of 1000 to 1000000.

In the above general formula (P2), A ² represents a monovalent nitrogen atom-containing group. n2 represents an integer of 1 or more. n2 is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of ease of synthesis. If n2 is 2 or more, to each of a plurality of A ² may be the same or different. Also, if it contains a plurality of A ² in the polymer, may be A ² are each the same or different.

In the general formula (P2), ^{A 3} and ^{A 4} represents a bivalent nitrogen-containing group. A ³ and A ⁴ may be the same or different. n3 and n4 represent 0 or 1, respectively.

In the above general formula (P2), Y ² represents an organic group having a (n2 + 2) valence.

As a nitrogen-containing polymer, a polymer having a partial structure represented by the general formula (P1) or (P2) has a single weight composed of only a single structural unit derived from the general formula (P1) or (P2). It may be a coalescence (homopolymer), or it may be a copolymer composed of two or more kinds of structural units derived from the above general formula (P1) or (P2).

Further, in addition to the structural unit represented by the general formula (P1) or (P2), another structural unit having no nitrogen-containing substituent (hereinafter, also simply referred to as “other structural unit”) is further provided. , Copolymers may be formed.

When the polymer containing nitrogen atoms applied to the present invention has other structural units that do not have nitrogen atoms, the content of the other structural units is particularly high as long as the effect of the polymer having nitrogen atoms is not impaired. The content of the monomer derived from other structural units is not limited, but is in the range of 10 to 75 mol%, preferably in the range of 20 to 50 mol%, in the monomer derived from all the structural units.

The end of the polymer having a partial structure represented by the general formula (P1) or (P2) is not particularly limited and is appropriately defined depending on the type of raw material (monomer) used, but usually a hydrogen atom Is.

In the above general formula (P2), the monovalent nitrogen atom-containing group represented by A ² is not particularly limited as long as it is an organic group containing a nitrogen atom. For example, amino group, dithiocarbamate group, thioamide group, cyano group (-CN), isonitrile group (-N ⁺ ≡C-), isocyanate group (-N = C = O), thioisocyanate group (-N =). Examples thereof include C = S), or a group containing a substituted or unsubstituted nitrogen-containing aromatic ring.

Specific examples of the polymer composed of the following monomer units containing a nitrogen atom will be shown below, but the present invention is not limited to these exemplified monomers. The polymer containing a nitrogen atom according to the present invention is composed of the following monomer units in a repeating number in the range of 1000 to 1000000 by weight average molecular weight.

(Sulfur-containing compound)
The resin layer preferably contains a compound containing a sulfur atom (sulfur-containing compound).

(1) Organic compound containing a sulfur atom The organic compound containing a sulfur atom has a sulfide bond (also referred to as a thioether bond), a disulfide bond, a mercapto group, a sulfone group, a thiocarbonyl bond and the like in the molecule. In particular, it may be a sulfide bond or a mercapto group.

Specifically, sulfur-containing compounds represented by the following general formulas (1) to (4) can be mentioned.

In the above general formula (1), R ₁ and R ₂ each independently represent a substituent.

The substituents represented by R ₁ and R ₂ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group and a tridecyl group. , Tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic Group hydrocarbon groups (also referred to as aromatic carbocyclic groups, aryl groups, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xsilyl group, naphthyl group, anthryl group, azulenyl group, acenaftenyl group, fluorenyl group. , Phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (eg, frill group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, etc. Thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating one of any carbon atoms constituting the carbolin ring of the carbolinyl group replaced with a nitrogen atom), phthalazinyl group, etc.), Heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholic group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, etc.) , Hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl) Group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl) Group, methylaminosulfonyl group, dime Thylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (For example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), Acyloxy groups (eg, acetyloxy groups, ethylcarbonyloxy groups, butylcarbonyloxy groups, octylcarbonyloxy groups, dodecylcarbonyloxy groups, phenylcarbonyloxy groups, etc.), amide groups (eg, methylcarbonylamino groups, ethylcarbonylamino groups, etc.) , Sulfonylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), Carbamoyl groups (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group , Sulfonylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido Group naphthylureid group, 2-pyridylaminoureid group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group Group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexy) Lusulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group) , Ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group), 2, 2,6,6-tetramethylpiperidinyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoro) Ethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester Examples include a group (for example, a dihexylphosphoryl group, etc.), a phosphite ester group (for example, a diphenylphosphinyl group, etc.), a phosphono group, and the like.

In the above general formula (2), R ₃ and R ₄ represent a substituent.
Examples of the substituent represented by R ₃ and R ₄ include the same substituents as R ₁ and R ₂ .

In the above general formula (3), R ₅ represents a substituent.
Examples of the substituent represented by R ₅ include the same substituents as R ₁ and R ₂ .

In the above general formula (4), R ₆ represents a substituent.
Examples of the substituent represented by R ₆ include the same substituents as R ₁ and R ₂ .

Specific examples of the sulfur atom-containing organic compound applicable to the resin layer are given below.

(2) Sulfur Atom-Containing Polymer In the resin layer, a sulfur atom-containing polymer can be used. The weight average molecular weight of the polymer containing a sulfur atom is preferably in the range of 1000 to 1000000.

The polymer containing a sulfur atom applicable to the present invention is not particularly limited, and examples thereof include a polymer composed of the following monomer units. The numerical values not shown in parentheses represent the composition ratio (molar ratio) of each monomer unit.

Table 2 shows the weight average molecular weight of the above-mentioned polymer containing a sulfur atom.

The weight average molecular weight of the polymer containing a nitrogen atom or the polymer containing a sulfur atom is a value measured in a room temperature environment according to the following measurement conditions.

(Measurement condition)
Equipment: Tosoh High-speed GPC equipment HLC-8220GPC
Column: TOSOH TSKgel Super HM-M
Detector: RI and / or UV
Eluent flow rate: 0.6 ml / min Temperature: 30 ° C
Sample concentration: 0.1% by mass
Sample amount: 100 μl
Calibration curve: Made of standard polystyrene: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) A calibration curve (also called a calibration curve) is created using 13 samples from Mw = 1000000 to 500, and the molecular weight is calculated. used. Here, the 13 samples were arranged at substantially equal intervals.

<Absorption layer (12)>
In the organic EL device of the present invention, a material that absorbs irradiation light when modulating the light emitting function of the organic functional layer, particularly an absorbing layer containing an infrared absorber may be provided. As a result, the infrared absorber can promote heat generation and accelerate the modulation of the light emitting function of the organic functional layer. The absorption layer may be provided only in a portion overlapping the auxiliary wiring when viewed in a plan view.
Further, in the present invention, an infrared absorber may be mixed with an opaque auxiliary wiring material and irradiated with infrared rays to modulate the light emitting function of the organic functional layer.

As the infrared absorber, various known infrared absorbers can be used, for example, cyanine compounds, merocyanine compounds, benzenethiol-based metal complexes, mercaptophenol-based metal complexes, aromatic diamine-based metal complexes, diimonium compounds, and aminium. Compounds, nickel complex compounds, phthalocyanine compounds, anthraquinone compounds, naphthalocyanine compounds and the like can be used.
Specifically, metal complex-based infrared absorbers (manufactured by Mitsui Chemicals, SIR-130, SIR132), bis (dithiobenzyl) nickel (manufactured by Midori Chemicals: MIR-101), bis [1,2-bis (p). −methoxyphenyl) -1,2-ethylene dithiolate] Nickel (Midori Chemical Co., Ltd .: MIR-102), tetra-n-butylammonium bis (cis-1,2-diphenyl-1,2-ethylenedithiolate) nickel (Midori Chemical Co., Ltd .: MIR-1011), Tetra-n-butylammonium bis [1,2-bis (p-methoxyphenyl) -1,2-ethylenedithiolate] nickel (Midori Chemical Co., Ltd .: MIR-1021) , Bis (4-tert-1,2-butyl-1,2-dithiophenorate) Nickel-tetra-n-butylammonium (manufactured by Sumitomo Seika Co., Ltd .: BBDT-NI), cyanine-based infrared absorber (Fuji Photo Film) Manufacturers: IRF-106, IRF-107), inorganic salt-based infrared absorbers (Teikoku Kagaku Sangyo Co., Ltd .: NIR-AM1), imonium compounds (Nippon Carlit Co., Ltd .: CIR-1080, CIR-1081), aminium compounds (manufactured by Nippon Carlit) Nippon Carlit Co., Ltd .: CIR-960, CIR-961), anthraquinone compounds (Nippon Kayaku Co., Ltd .: IR-750), Aminium compounds (Nippon Kayaku Co., Ltd .: IRG-002, IRG-003, Nagase ChemteX) Company: IR-AM1), Polymethine compound (manufactured by Nippon Kayaku Co., Ltd .: IR-820B), Diimonium compound (manufactured by Nippon Kayaku Co., Ltd .: IRG-022, IRG-023, Nagase ChemteX Co., Ltd .: NIR-IM1), Dianine compounds (manufactured by Nippon Kayaku Co., Ltd .: CY-2, CY-4, CY-9), soluble phthalocyanine (manufactured by Nippon Catalyst Co., Ltd .: TX-305A) and the like can be used.

<Antistatic layer>
The organic EL device of the present invention may have an antistatic layer on one surface of the support substrate. The antistatic layer is composed of an antistatic agent and a binder resin for holding the antistatic agent.

The antistatic layer preferably contains an organic antistatic agent as an antistatic agent.
The organic antistatic agent preferably contains one or more selected from a conjugated polymer and an ionic polymer. Further, the antistatic layer may be composed of other conductive polymers or antistatic agents.

It is preferable that the antistatic layer does not contain metal oxide particles that are easily desorbed during lamination as an antistatic agent. Therefore, the content of the metal oxide particles with respect to the total mass of the antistatic layer is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably no metal oxide particles. Metal oxide particles that are preferably not contained in the antistatic layer include, for example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₂ , V ₂ O _{5, and the} like, or Examples of these composite oxides can be mentioned. However, SiO ₂ is excluded from the regulation of metal oxide particles which are preferably not contained in the antistatic layer.

(Organic antistatic agent)
The organic antistatic agent is basically composed of an organic material having an antistatic ability. When the organic antistatic agent forms the antistatic layer, the sheet resistance value on the back surface side of the antistatic layer is set to 1 × 10 ¹¹ Ω / sq. Hereinafter, preferably 1 × 10 ¹⁰ Ω / sq. Hereinafter, more preferably, 1 × 10 ⁹ Ω / sq. It is a material that can be as follows.
Examples of the organic antistatic agent include conventionally known surfactant-type antistatic agents, silicone-based antistatic agents, organic boric acid-based antistatic agents, polymer-based antistatic agents, antistatic polymer materials, and the like. In particular, it is preferable to use an ionic conductive substance or the like as the organic antistatic agent from the viewpoint of antistatic of the antistatic layer. The ionic conductive substance is a substance containing ions exhibiting electrical conductivity. Examples of the ionic conductive substance include a conjugated polymer and an ionic polymer.

(Conjugated polymer)
Examples of the conjugated polymer include a π-electron conductive polymer composite of a polymer having the following (1) to (8) in a side chain via a connecting group.
(1) aliphatic conjugated system: A carbon-carbon conjugated system such as polyacetylene, which is a polymer that is alternately long and continuous. For example, polyacetylene, poly (1,6-heptadiene), etc. (2) Aromatic conjugated system: poly A polymer with developed conjugation to which aromatic hydrocarbons are long-bonded, such as (paraphenylene). For example, polyparaphenylene, polynaphthalene, polyanthracene, etc. (3) Heterocyclic conjugated system: complex such as polypyrrole and polythiophene A polymer in which a cyclic compound is bonded to develop a conjugated system, for example, polypyrrole and its derivative, polyfuran and its derivative, polythiophene and its derivative, polyisothionaphthene and its derivative, polyselenophen and its derivative, etc. (4) Heteroatom-containing conjugated system: A polymer in which an aliphatic or aromatic conjugated system such as polyaniline is bonded with a hetero atom, such as polyaniline and its derivatives, poly (paraphenylene sulfide) and its derivatives, and poly (paraphenylene oxide). Its derivatives, poly (paraphenylene serenide) and its derivatives, and in aliphatic systems, poly (vinylene sulfide), poly (vinylene oxide), poly (vinylene serenide), etc. (5) Mixed conjugated system: poly (phenylene vinylene) ), Which is a conjugated polymer having a structure in which the constituent units of the conjugated system are alternately bonded, for example, poly (paraphenylene vinylene) and its derivative, poly (pyrrole vinylene) and its derivative, and poly (thiophenine vinylene). Derivatives, poly (franbinylene) and its derivatives, poly (2,2'-thienylpyrrole) and its derivatives, etc. (6) Double-chain conjugated system: A conjugated system with multiple conjugated chains in the molecule, aromatic A polymer having a structure close to that of a conjugated system, for example, polyperinaphthalene, etc. (7) Metal phthalocyanine system: Metal phthalocyanines or a polymer in which these molecules are bonded by a hetero atom or a conjugated system, for example, metal phthalocyanine. Etc. (8) Conductive composite: A polymer obtained by graft-copolymerizing the conjugated polymer chain to a saturated polymer and a composite obtained by polymerizing the conjugated polymer in the saturated polymer, for example, polythiophene (3). Derivatives included), polypyrrole (including derivatives), 4) polyaniline (including derivatives), etc., and 5) poly (paraphenylene vinylene) (including its derivatives), poly (thiophenebinylene). ) (Including its derivatives.) Etc.

(Ionic polymer)
Examples of the ionic polymer include the following (1) to (3).
(1) Anionic polymer compounds as found in Japanese Patent Publication No. 49-23828, Japanese Patent Publication No. 49-23827, Japanese Patent Publication No. 47-288937, etc. (2) Japanese Patent Publication No. 55-734, Japanese Patent Application Laid-Open No. Dissociation in the main chain as seen in Japanese Patent Publication No. 50-54672, Japanese Patent Publication No. 59-14735, Japanese Patent Publication No. 57-18175, Japanese Patent Publication No. 57-18176, Japanese Patent Publication No. 57-56059, etc. Ionen-type polymer having a group (3) Japanese Patent Publication No. 53-13223, Japanese Patent Publication No. 57-15376, Japanese Patent Publication No. 53-45231, Japanese Patent Publication No. 55-145783, Japanese Patent Publication No. 55-65950, Special Publication No. See Kosho 55-67746, Tokusho 57-11342, Tokusho 57-19735, Tokusho 58-56858, Japanese Patent Application Laid-Open No. 61-27853, Tokusho 62-9346, etc. Cationic pendant polymer with a cationic dissociation group in the side chain, such as

(Conductive polymer)
Examples of the conductive polymer constituting the antistatic layer include an ionen conductive polymer described in JP-A-9-203810, a quaternary ammonium cationic conductive polymer having an intermolecular crosslink, and the like.

(Other antistatic agents)
Examples of other antistatic agents constituting the antistatic layer include antistatic hard coat agents described in JP-A-2006-265271, JP-A-2007-70456, and JP-A-2009-62406. Can be used. Further, for example, an antistatic agent manufactured by Aica Kogyo Co., Ltd., which is also available as a commercially available product, can be appropriately selected and used.

(Binder resin)
Examples of the binder resin for holding the antistatic agent in the antistatic layer include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose nitrate, polyvinyl acetate, and polystyrene. Polyesters such as polycarbonate, polybutylene terephthalate, or copolybutylene / tele / isophthalate, polyvinyl alcohols, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl benzal and other polyvinyl alcohol derivatives, norbornene polymers containing norbornene compounds, polymethylmethacrylate. , Polyethyl methacrylate, polypropyltyl methacrylate, polybutyl methacrylate, polymethyl acrylate and other acrylic resins, and copolymers of acrylic resins and other resins can be used. In particular, cellulose derivatives and acrylic resins are preferable, and acrylic resins are most preferably used.

As the binder resin used for the antistatic layer, a thermoplastic resin having a weight average molecular weight of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. is preferable. The glass transition temperature can be determined by the method described in JIS K 7121. The binder resin used here is 60% by mass or more, more preferably 80% by mass or more, based on the total mass of the resin constituting the antistatic agent layer, and an active ray-curable resin or a thermosetting resin is applied as necessary. You can also do it.

<Underground layer>
The support substrate according to the present invention may be subjected to surface treatment or provided with a base layer in order to ensure the wettability and adhesiveness of the coating liquid. Conventionally known techniques can be used for the surface treatment and the base layer. For example, examples of the surface treatment include surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
Examples of the base layer include polyester, polyamide, polyurethane, vinyl-based copolymer, butadiene-based copolymer, acrylic-based copolymer, vinylidene-based copolymer, epoxy-based copolymer, and the like. The base layer may be a single layer, but may be composed of two or more layers in order to improve the adhesiveness.

<Gas barrier layer>
Since the performance of an organic EL device easily deteriorates when a small amount of water or oxygen is present inside the device, it is preferable to provide a gas barrier layer having a high shielding ability against water or oxygen.

The support substrate on which the gas barrier layer is formed has a water vapor permeability of 1 × 10 ^-3 g / at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% measured by a method in accordance with JIS K 7129-1992. preferably ^(m 2 · 24h) or less, and further, the oxygen permeability measured in compliance with the method provided in JIS K 7126-1987 ^{is, 1 × 10 -3 ml / (} m 2 · 24h · atm) ( Here, 1 atm is 1.01325 × 10 ⁵ Pa) or less, and the water vapor permeability at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% is 1 × 10 ^-3 g / (m). and more preferably ² · 24h) or less.

The composition and structure of the gas barrier layer and the method for forming the gas barrier layer are not particularly limited, and a layer made of an inorganic compound such as silica can be formed by vacuum deposition or a CVD method. For example, a conventionally known silicon-containing polymer-modified layer or silicon compound layer can be used alone or in combination to form a gas barrier layer.

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

<< Manufacturing method of organic EL element >>
The method for manufacturing an organic EL element of the present invention includes at least a step of forming an electrode composed of a transparent conductive layer and an auxiliary wiring, and a step of forming an organic functional layer, and further, when viewed in a plan view. It is characterized by having at least a step of modulating the light emitting function of a part of the region where the auxiliary wiring and at least one of the organic functional layers overlap.
Hereinafter, each step of the method for manufacturing an organic EL device of the present invention will be described.

<Step of forming electrodes>
In the step of forming the electrode according to the present invention, after forming the auxiliary wiring on the support substrate, a transparent conductive layer is formed so as to cover the auxiliary wiring.

(Process of applying coating liquid for forming auxiliary wiring)
The auxiliary wiring is formed by applying a coating liquid for forming an auxiliary wiring containing a metal or a material for forming a metal onto a support substrate. The method for forming the auxiliary wiring is not particularly limited, and a conventionally known method can be used. As a method for forming the auxiliary wiring, for example, a method applying a photolithography method, a coating method, a printing method, or the like can be used.

The coating liquid for forming auxiliary wiring contains metal nanoparticles and a solvent, which will be described later, and may contain additives such as a dispersant, a viscosity modifier, and a binder. The solvent contained in the coating liquid for forming auxiliary wiring is not particularly limited, but is preferably a compound having an OH group in that the solvent can be efficiently volatilized by irradiation with mid-infrared rays, and water, alcohol, or glycol ether. Is preferable.

As the solvent used for the coating liquid for forming auxiliary wiring, water, methanol, ethanol, propanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, hexane Diol, heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalol, geraniol, nerol, heptadienol, tetradecenol, hexadeceneol, phytol, oleyl alcohol, dedecenol, decenol, undecylenel alcohol , Citronerol, octenol, heptenol, methylcyclohexanol, menthol, dimethylcyclohexanol, methylcyclohexenol, terpineol, dihydrocarbeol, isopregol, cresol, trimethylcyclohexenol, glycerin, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, butanediol, pentanediol, heptanediol, propanediol, hexanediol, octanediol, ethylene glycol monoethyl ether, ethylene glycol Examples include monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. Be done.

When forming the auxiliary wiring by the printing method, the method generally used for forming the electrode pattern can be applied. As a specific example, regarding the gravure printing method, the methods described in JP-A-2009-295980, JP-A-2009-259826, JP-A-2009-96189, JP-A-2009-90662, and the like are used for flexographic printing. Regarding the method, the methods described in JP-A-2004-268319 and JP-A-2003-168560 are used. For the screen printing method, JP-A-2010-34161, JP-A-2010-10245, and JP-A-2009-302345 are used. Examples of the method described in Japanese Patent Application Laid-Open No. 11-180562, 2000-127410, and 8-238774 are examples of the inkjet printing method.

When the auxiliary wiring is formed by the photolithography method, specifically, the coating liquid for forming the auxiliary wiring is applied to the entire surface of the support substrate by printing or coating, and the drying treatment and the firing treatment described later are performed. After that, it is processed into a desired pattern by etching using a known photolithography method.

(Step of drying the coating liquid for forming auxiliary wiring)
After applying the coating liquid for forming auxiliary wiring, it is preferable to dry the coating liquid for forming auxiliary wiring.
The drying treatment can be carried out using a known drying method. Examples of the drying method include air cooling drying, convection heat transfer drying using warm air, radiant electric heat drying using infrared rays, conduction heat transfer drying using a hot plate, vacuum drying, and internal use of microwaves. Heat-generating drying, IPA steam drying, marangoni drying, rotagoni drying, freeze drying and the like can be used.

The heat drying is preferably performed within a temperature range of 50 to 200 ° C. at a temperature at which the support substrate is not deformed. It is more preferable to heat the support substrate under the condition that the surface temperature is in the range of 50 to 150 ° C. When a polyethylene terephthalate (PET) support substrate is used as the support substrate, it is particularly preferable to heat it at 100 ° C. or lower.
The drying time is preferably in the range of 10 seconds to 30 minutes, and is in the range of 10 seconds to 15 minutes from the viewpoint of productivity, although it depends on the temperature and the size of the metal nanoparticles used. Is more preferable, and it is particularly preferable that it is in the range of 10 seconds to 5 minutes.

In the drying treatment, it is preferable to perform the drying treatment by infrared irradiation. In particular, it is preferable to selectively irradiate a specific wavelength region with a wavelength-controlled infrared heater or the like. By selectively using a specific wavelength region, it is possible to cut the absorption region of the support substrate and selectively irradiate a specific wavelength effective for the solvent of the coating liquid for forming auxiliary wiring. In particular, it is preferable to use an infrared heater in which the filament temperature of the light source is in the range of 1600 to 3000 ° C.

(Auxiliary wiring firing process)
Next, the auxiliary wiring is fired.
Depending on the type of metal composition contained in the coating liquid for forming auxiliary wiring (for example, silver colloid having an organic π-bonding ligand described later), sufficient conductivity can be exhibited by performing a drying treatment. Therefore, it is not necessary to perform the firing step.

(Baking by irradiation with flash light)
It is preferable that the auxiliary wiring is fired by irradiating pulsed light using a flash lamp (flash firing) in order to improve the conductivity of the electrode. As the discharge tube of the flash lamp used in the flash firing, a discharge tube of xenon, helium, neon, argon or the like can be used, but it is preferable to use a xenon lamp.

The preferred spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. Within this range, there is little damage such as thermal deformation of the support substrate due to flash firing.

Light irradiation conditions of the flash lamp is arbitrary, it is preferable that total irradiation energy in the range of 0.1~50J / cm ^2, in a range of 0.5~10J / cm ² More preferred. The light irradiation time is preferably in the range of 10 μs to 100 msec, more preferably in the range of 100 μs to 10 msec. The number of times of light irradiation may be once or a plurality of times, and is preferably performed within the range of 1 to 50 times. By irradiating the flash light within these preferable condition ranges, the auxiliary wiring can be fired without damaging the support substrate.

It is preferable that the flash lamp irradiation to the support substrate is performed from the side where the auxiliary wiring of the support substrate is formed. When the support substrate is transparent, it may be irradiated from the side opposite to the side where the auxiliary wiring of the support substrate is formed, or may be irradiated from both sides of the support substrate.

The surface temperature of the support substrate during flash firing is the heat resistant temperature of the support substrate, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the coating liquid for forming auxiliary wiring, the type and pressure of atmospheric gas, and the formation of fine metal wire patterns. It may be determined in consideration of the dispersibility of the coating liquid for use, thermal behavior such as oxidizing property, and the like, and it is preferably performed in the range of room temperature (25 ° C.) to 200 ° C.

The light irradiation device of the flash lamp may be any one that satisfies the above irradiation energy and irradiation time. The flash firing may be performed in the atmosphere, but if necessary, it may be performed in an atmosphere of an inert gas such as nitrogen, argon, or helium.

<Process of forming an organic functional layer>
The method for forming the organic functional layer is not particularly limited, and conventionally known methods such as a vacuum vapor deposition method and a wet method (also referred to as a wet process) can be used.
The wet method includes a spin coating method, a casting method, an inkjet method, a printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, an LB method (Langmuir-Blogget method), and the like. From the viewpoint of easy obtaining a homogeneous thin film and high productivity, a method having high suitability for the roll-to-roll method such as a die coating method, a roll coating method, an inkjet method, and a spray coating method is preferable.

Examples of the liquid medium for dissolving or dispersing the organic functional layer material include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesityrene and cyclohexylbenzene. Aromatic hydrocarbons such as, cyclohexane, decalin, aliphatic hydrocarbons such as dodecane, and organic solvents such as DMF and DMSO can be used.

Further, as a dispersion method, dispersion can be performed by a dispersion method such as ultrasonic waves, high shear force dispersion, or media dispersion.

When a thin-film deposition method is used for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally, the boat heating temperature is 50 to 450 ° C., the degree of vacuum is 1 × 10 ^-6 to 1 × 10 ^-2 Pa, and the deposition rate is high. It is desirable to appropriately select within the range of 0.01 to 50 nm / sec, the support substrate temperature of -50 to 300 ° C., and the thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm.

The organic functional layer is preferably formed from the hole injection layer to the cathode by one vacuuming, but it may be taken out in the middle and a different film forming method may be applied. In that case, it is preferable to carry out the work in a dry inert gas atmosphere.

<Process of modulating the light emission function>
Examples of the method of modulating the light emitting function of a part of the region where the auxiliary wiring and at least one of the organic functional layers overlap include ultraviolet rays, microwaves, infrared irradiation, laser irradiation, application of high frequency current, and the like. Above all, it is preferable to modulate the light emitting function by ultraviolet irradiation or laser irradiation.

FIG. 5 shows an example of a vacuum ultraviolet irradiation device.
As shown in FIG. 5, the vacuum ultraviolet irradiation device 20 carries the support substrate 2 on which the auxiliary wiring is formed on the stage 24 and conveys the inside of the chamber 22. Water vapor is removed from the chamber 22 by exhaust gas, and the oxygen concentration is constantly adjusted by introducing an inert gas. The stage 24 has a built-in heater and can heat the support substrate 2.
The inside of the chamber 22 is divided into three zones along the transport direction V of the support substrate 2 by the shielding plate 26, and a plurality of Xe excimer lamps 28 are installed in the central zone.
The Xe excimer lamp 28 is supported by a holder 30 having a built-in power supply and is lit and controlled. Vacuum ultraviolet rays can be irradiated by passing the support substrate 2 through the zone in which the Xe excimer lamp 28 is installed.

A laser is a coherent (interfering) light (electromagnetic wave) generated by amplifying light using an oscillator. Lasers are monochromatic (half width of wavelength is small) and have excellent directivity. Since it has strong monochromaticity and directivity, it has advantages such as easy concentration of energy in a small area.

Lasers are classified into gas lasers, solid-state lasers, semiconductor lasers, and the like, depending on the medium (substance that causes stimulated emission).
Gas lasers have good monochromaticity, directivity, and high output. Examples of the gas laser include a CO2 laser (wavelength 10600 nm), a He-Ne laser (632 nm), and an Ar laser (488 nm, 514 nm).
The solid-state laser has the advantage that the device can be made small and has a large transmission output. Examples of the solid-state laser include an Er: YAG laser (2960 nm) and an Nd: YAG laser (1064 nm), as well as a second high frequency (530 nm) of the Nd: YAG laser and a third high frequency (350 nm) of the Nd: YAG laser. It is used.
Semiconductor lasers are characterized in that they can be made even smaller and can be manufactured at a relatively low cost. Light is emitted by injecting holes and electrons into the pn junction of a semiconductor. Examples of the semiconductor laser include a laser of an AlGaAs semiconductor, and there are lasers having various emission wavelengths.

The laser used in the present invention is not particularly limited to the above-mentioned gas laser, solid-state laser, semiconductor laser, etc., but a solid-state laser or semiconductor laser is preferable because it is easy to use in a vacuum.
Further, the laser output may be appropriately set to an output sufficient to modulate the light emitting function without peeling off the electrodes and the light emitting layer.

Modulation of the light emitting function by light irradiation may be performed after the organic functional layer is formed or after the upper electrode is formed. However, since the upper electrode has reflectivity, after the organic functional layer is formed. , It is preferable to carry out before forming the upper electrode.
Further, in the case of a top emission type organic EL element (when the upper electrode is composed of a transparent conductive layer and auxiliary wiring), since the upper electrode has light transmission, the upper electrode is formed after the organic functional layer is formed. Light irradiation may be performed before the formation, or light irradiation may be performed after the upper electrode is formed.

<Sealing>
Examples of the sealing means used for sealing the organic EL element of the present invention include a method of adhering the sealing substrate, the electrode, and the supporting substrate with an adhesive. The sealing substrate may be arranged so as to cover the display area of the organic EL element, and may be intaglio-shaped or flat-plate-shaped. Further, the electrical insulation is not particularly limited.
Specifically, as the sealing substrate, the same material as that used for the above-mentioned support substrate can be used.
As with the support substrate, the sealing substrate is preferably provided with a gas barrier layer. Further, the sealing substrate may be provided with an antistatic layer.

In the present invention, a polymer film can be preferably used because the organic EL element can be thinned. In addition, the polymer film JIS oxygen permeability measured by the method conforming to K 7126-1987 is ^{1 × 10 -3 ml / (m} 2 · 24h · atm) or less, a method in accordance with JIS K 7129-1992 the measured water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%) is preferably that of ^{1 × 10 -3 g / (m} 2 · 24h) or less.

Specific examples of the adhesive include a photocurable and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer, a moisture-curable adhesive such as 2-cyanoacrylic acid ester, and the like. be able to. In addition, heat and chemical curing type (two-component mixture) such as epoxy type can be mentioned. Further, hot melt type polyamide, polyester and polyolefin can be mentioned. In addition, a cation-curable type ultraviolet-curable epoxy resin adhesive can be mentioned.
Since the organic EL element may be deteriorated by heat treatment, it is preferable that the organic EL element can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Further, the desiccant may be dispersed in the adhesive. A commercially available dispenser may be used for applying the adhesive to the sealing substrate, or printing may be performed as in screen printing.

It is also preferable to coat the electrode and the organic functional layer on the outside of the electrode on the side facing the support substrate with the organic functional layer sandwiched between them, and form an inorganic or organic layer in contact with the support substrate to form a sealing film. Can be done. In this case, the material for forming the film may be any material having a function of suppressing infiltration of a material that causes deterioration of the element such as moisture and oxygen, and for example, silicon oxide, silicon dioxide, silicon nitride or the like may be used. it can.
The difference in refractive index between the sealing film and the adhesive is preferably small from the viewpoint of increasing the transmittance.

Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of an organic material. The method for forming these films is not particularly limited, and for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight. Legal, plasma CVD method, laser CVD method, thermal CVD method, coating method and the like can be used.

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

[Example 1]
<< Fabrication of organic EL element >>
<Manufacturing of organic EL element 101>
(1) Preparation of Support Substrate On one side of a 100 μm-thick polyethylene terephthalate (PET) film (Toray Industries, Inc. Lumirror (registered trademark) U48) whose both sides have been surface-activated, organic antistatic is prevented by the following method. An antistatic layer containing the agent was formed.

(1.1) Formation of Antistatic Layer (Organic Antistatic Agent) A colloidal silica-containing monomer (A) is prepared according to the following method, and the colloidal silica-containing monomer (A) is used for organic charging. An antistatic hard coat agent (A), which is an inhibitor, was prepared. Then, an antistatic layer was formed using this organic antistatic agent.

(Preparation of colloidal silica-containing monomer (A))
2-Methylloyloxyethyl isocyanate (MOI) (molecular weight 155, molecular weight 155, in 130 parts by mass of colloidal silica (SiO ₂ component 30% by mass, average particle size 20 nm, manufactured by Nissan Chemical Co., Ltd.) dispersed using ethyl acetate as a solvent. 30 parts by mass of Showa Denko Co., Ltd. and 0.1 parts by mass of di-n-butyltin dilaurate (DBTDL) as a catalyst were added, and the mixture was stirred at room temperature (25 ° C.) for 24 hours. The reaction of the isocyanate group was confirmed by infrared spectroscopy, and ethyl acetate as a solvent was removed by an evaporator to obtain a colloidal silica-containing monomer (A).

(Preparation of antistatic hard coat agent (A))
Li ⁺ / CF ₃ SO ₃ ⁻ methyl ethyl ketone solution (nonvolatile content: 50% by mass, Sanko Chemical Industry Co., Ltd.) in 100 parts by mass of the colloidal silica-containing monomer (A) (nonvolatile content: 36% by mass) produced above. 5 parts by mass of (manufactured by Co., Ltd.) was mixed and stirred. As an initiator, 1 part by mass of Irgacure907 (manufactured by BASF Japan Ltd.) was added to prepare an antistatic hard coat agent (A) which is an organic antistatic agent.

(Formation of antistatic layer)
Next, the prepared antistatic hard coat agent (A), which is an organic antistatic agent, was applied and dried on the support substrate under the condition that the thickness after curing was 10 μm. After that, an ultraviolet irradiation treatment was carried out under the condition of 300 mJ using an 80 W / cm mercury lamp to form an antistatic layer made of an organic antistatic agent.

(1.2) Formation of Underlayer Next, an underlayer having a thickness of 2 μm was formed on the other surface of the PET film. Specifically, UV curable resin Opster (registered trademark) Z7527 (manufactured by JSR Corporation) was applied so that the thickness after drying was 2 μm. After the coating film was dried at 80 ° C., it was subjected to a curing treatment in which it was irradiated with ultraviolet rays having an irradiation energy amount of 0.5 J / cm ² using a high-pressure mercury lamp in the atmosphere.

(1.3) Formation of Gas Barrier Layer The PET film on which the base layer was formed was cut out in a size of 120 mm × 100 mm, and a silicon-containing polymer modified layer was formed on the base layer as follows.

20% by mass dibutyl ether solution of uncatalyzed perhydropolysilazane (Aquamica NN120-20, manufactured by AZ Electronic Materials) and amine catalyst (N, N, N', N'-tetramethyl-1,6-diaminohexane) ) Was mixed with a 20% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by mass of the solid content at a ratio of 4: 1 to further adjust the thickness. Therefore, a coating solution was prepared by appropriately diluting with dibutyl ether.

The coating liquid prepared on the base layer was applied with a die coater so that the thickness after drying was 100 nm, and dried at 80 ° C. for 2 minutes. A Xe excimer lamp having a wavelength of 172 nm was used in the vacuum ultraviolet irradiation device shown in FIG. 5, and the dried coating film was subjected to a modification treatment of irradiating the dried coating film with vacuum ultraviolet rays of 2.5 mJ / cm ^2. A silicon-containing polymer modified layer was formed. When irradiated with vacuum ultraviolet rays, substitution with nitrogen was performed so that the atmosphere had an oxygen concentration of 0.1% by volume. Further, the temperature of the stage on which the PET film was installed was set to 80 ° C., and the transport speed of the stage was set to 0.5 m / min.

Subsequently, silicon compound layers having a thickness of 300 nm were each formed by a plasma CVD method to obtain a support substrate with a gas barrier layer.
The film forming conditions of the silicon compound layer are as follows.

Supply amount of raw material gas (hexamethyldisiloxane: HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas (O ₂ ) supply: 500 sccm
Vacuum degree in vacuum chamber: 3Pa
Power applied from the plasma generation power supply: 1.2 kW
Frequency of power supply for plasma generation: 80kHz
Film transport speed: 0.5 m / min

Further, the silicon-containing polymer modified layer was applied in the same manner as above so as to have a film thickness of 300 nm, and was cured by ultraviolet rays.

(2) Formation of resin layer (2.1) Application of coating liquid for resin layer formation The substrate formed up to the gas barrier layer is cut into 70 mm × 70 mm, and Hitachi Chemical's Hitaroid 7975D is applied as an acrylic resin with a spin coater. did. The film thickness was adjusted so that the thickness after drying was 1 μm. Unnecessary parts were wiped off and removed.
Subsequently, it was dried on a hot plate at 70 ° C. for 3 minutes, and further, radiant heat transfer drying using an infrared (IR) heater was performed for 5 minutes.

(2.2) Curing of coating liquid for forming a resin layer Next, a Xe excimer lamp having a wavelength of 172 nm was used in the vacuum ultraviolet irradiation device shown in FIG. 5, and the vacuum ultraviolet irradiation device was used to apply the vacuum ultraviolet irradiation device to the coating film after drying. It was polymerized by irradiating with vacuum ultraviolet rays of 5 mJ / cm ² .

(3) Formation of lower electrode (anode) (3.1) Formation of opaque auxiliary wiring pattern Silver nano ink (Harima Kasei NPS) is used on the support substrate (resin layer side) formed up to the resin layer using an inkjet device. -JL) was formed with an auxiliary wiring having a stripe pattern having a width of 90 mm × 50 μm and a pitch of 1 mm. At this time, recoating was performed three times so that a sufficient height could be obtained.
The inkjet device was controlled by an inkjet evaluation device EB150 (manufactured by Konica Minolta Co., Ltd.) using a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an inkjet head KM512SHX manufactured by Konica Minolta Co., Ltd.
Subsequently, it was dried on a hot plate at 70 ° C. for 3 minutes, and further, radiant heat transfer drying using an infrared (IR) heater was performed for 5 minutes.
The stripe pattern of the auxiliary wiring was formed so that the light emitting area was 50 mm × 50 mm.

(3.2) Firing of Opaque Auxiliary Wiring The support substrate on which the auxiliary wiring was drawn was irradiated with xenon light using PulseForge 1300 manufactured by Novacentrix and fired.
The xenon light was pulsed at 250 μs in a cycle of 500 μs, adjusted so that energy of 1500 mJ / cm ² was given, and irradiated.

(3.3) Formation of transparent conductive layer A target of In ₂ O ₃ : ZnO (90% by mass: 10% by mass) is attached to a commercially available sputtering device, and the transparent material is made of IZO having a thickness of 250 nm under the following conditions. A conductive layer was formed.

Total pressure: 0.4 MPa
Argon flow rate: 99 sccm
Oxygen flow rate: 1 sccm
Output: 5W / cm ²

(4) Formation of Organic Functional Layers Various organic layers were formed on the prepared lower electrode as follows.

Each of the melting crucibles in the vacuum vapor deposition apparatus was filled with the constituent materials of each layer in the optimum amount for manufacturing the device. As the crucible for vapor deposition, a crucible made of molybdenum or tungsten made of a resistance heating material was used.

After reducing the vacuum to 1 × 10 ^-4 Pa, the crucible for vapor deposition containing the following compound M-4 is energized and heated, and the film is deposited on the lower electrode at a vapor deposition rate of 0.1 nm / sec to a thickness of 15 nm. A hole injection layer was formed.

Next, a crucible for vapor deposition containing the following compound M-2 was energized and heated, and vapor deposition was carried out on the anode at a vapor deposition rate of 0.1 nm / sec to form a hole transport layer having a thickness of 50 m.

Next, the following compound BD-1 and the following compound H-1 are co-deposited at a vapor deposition rate of 0.1 nm / sec so that the compound BD-1 has a concentration of 5% by mass, and fluorescence exhibiting blue emission with a thickness of 15 nm is exhibited. A light emitting layer was formed.

Next, the following compound GD-1, the following compound RD-1 and the following compound H-2 were deposited at a concentration of 17% by mass for the compound GD-1 and 0.8% by mass for the compound RD-1. Co-deposited at 1 nm / sec, a phosphorescent layer having a thickness of 15 nm and exhibiting yellow color was formed.

Then, the following compound ET-1 was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to form an electron transport layer having a thickness of 30 nm.

Further, an electron injection layer was formed with LiF having a thickness of 1.5 nm.

(5) Formation of Upper Electrode (Cathode) Subsequently, 100 nm of aluminum was vapor-deposited to obtain an upper electrode.

(6) Formation of Sealing Film A silicon nitride film was formed by a depot-up type plasma CVD film forming apparatus under the following conditions to form a sealing film. The film thickness of the silicon nitride film was set to 300 nm.

The silicon nitride film includes an electrode provided so as to face the base material, a high-frequency power source that supplies plasma excitation power to the electrode, and a bias power supply that supplies bias power to a holding member that holds the base material. The film was formed by a plasma CVD film forming apparatus provided with a gas supply means for supplying a carrier gas and a raw material gas toward the electrodes.
As the film-forming gas, silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ) and hydrogen gas (H ₂ ) were used. The supply amounts of these gases were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas.
The film forming pressure was 50 Pa.
A plasma excitation power of 3000 W was supplied to the electrodes at a frequency of 13.5 MHz from a high-frequency power source. Further, a bias power of 500 W was supplied to the holding member from the bias power supply.

(7) Encapsulation (7.1) Preparation of adhesive composition 100 parts by mass of "Opanol B50 (manufactured by BASF, Mw: 340,000)" as the polyisobutylene resin (A) and "Nippon Oil" as the polybutene resin (B) Polybutene grade HV-1900 (manufactured by Nippon Oil Co., Ltd., Mw: 1900) "30 parts by mass," TINUVIN765 (manufactured by BASF Japan, having a tertiary hindered amine group) "0.5 as a hindered amine-based light stabilizer (C) By mass, 0.5 parts by mass of "IRGANOX1010 (manufactured by BASF Japan, both β-positions of hindered phenol groups have tertiary butyl groups)" as a hindered phenolic antioxidant (D), and cyclic olefin. As the system polymer (E), 50 parts by mass of "Eastotac H-100L Resin (manufactured by Eastman Chemical Co., Inc.)" was dissolved in toluene to prepare an adhesive composition having a solid content concentration of about 25% by mass.

(7.2) Preparation of Encapsulating Substrate The supporting substrate with the gas barrier layer prepared above was prepared and used as it is as the encapsulating substrate. Next, the prepared solution of the adhesive composition is applied to the surface of the sealing substrate (on the upper electrode side) on the gas barrier layer side so that the thickness of the adhesive layer formed after drying is 20 μm. , 120 ° C. for 2 minutes to form an adhesive layer. Next, a peeling-treated surface of a polyethylene terephthalate film having a thickness of 38 μm and being peeled was attached to the formed adhesive layer surface as a peeling sheet to prepare a sealed substrate.

The sealed substrate prepared by the above method was left to stand in a nitrogen atmosphere for 24 hours or more.
After being left to stand, the release sheet was removed and laminated with a vacuum laminator heated to 80 ° C. so as to cover the upper electrode of the organic EL element. Further, it was heated at 120 ° C. for 30 minutes and sealed to prepare an organic EL element 101.

(Confirmation of UV irradiation effect)
The effect of ultraviolet irradiation was confirmed.
Specifically, in the production of the organic EL element 101, an ultraviolet absorbing filter (manufactured by Gosuzu Seiko Glass Co., Ltd.) is placed in a vacuum on the entire surface of the element formed up to the electron injection layer (LiF), and a UV tester is used. (SUV-W 151: 100 mW / cm ² manufactured by Iwasaki Electric Co., Ltd.) was used to irradiate ultraviolet rays from the film-forming surface side for 30 minutes.
As the ultraviolet absorption filter, a filter having a light transmittance of 50% or less (cut wavelength: 320 nm) of a wavelength component of 320 nm or less was used.
After the irradiation with ultraviolet rays, the upper electrode was formed into a film, and the film was sealed and sealed in the same manner as in the production of the organic EL element 101.
Similarly, an element irradiated with ultraviolet rays for 60 minutes and 120 minutes was prepared.
When a current of 50 A / m ² was passed through each of them and the current-voltage characteristics were evaluated, the voltage increased as shown in Table 3.

From Table 3, it was confirmed that the function of the charge transport layer was partially lost by the irradiation with ultraviolet rays.

<Manufacturing of organic EL element 102>
In the production of the organic EL element 101, a pattern mask and an ultraviolet absorbing filter (manufactured by Gosuzu Seiko Glass Co., Ltd.) are placed in a vacuum on the entire surface of the element formed up to the electron injection layer (LiF), and a UV tester (Iwasaki) is provided. An organic EL element 102 was produced in the same manner using SUV-W151: 100 mW / cm ² ) manufactured by Denki Co., Ltd., except that ultraviolet rays were irradiated from the film-forming surface side for 30 minutes.

The pattern mask is a mask that exposes only the opaque auxiliary wiring to ultraviolet rays.
As the ultraviolet absorption filter, a filter having a light transmittance of 50% or less (cut wavelength: 320 nm) of a wavelength component of 320 nm or less was used.

<Manufacturing of organic EL element 103>
In the production of the organic EL element 102, the organic EL element 103 was produced in the same manner except that the ultraviolet irradiation time was set to 60 minutes.

<Manufacturing of organic EL element 104>
In the production of the organic EL element 102, the organic EL element 104 was produced in the same manner except that the ultraviolet irradiation time was 120 minutes.

<Manufacturing of organic EL element 105>
In the production of the organic EL element 101, a pattern mask and an ultraviolet absorbing filter (manufactured by Gosuzu Seiko Glass Co., Ltd.) are placed in a vacuum on the entire surface of the element formed up to the electron injection layer (LiF), and a UV tester (Iwasaki) is provided. An organic EL element 105 was produced in the same manner using SUV-W 151: 100 mW / cm ² ) manufactured by Denki Co., Ltd., except that ultraviolet rays were irradiated from the film-forming surface side for 30 minutes.

The pattern mask was a mask in which ultraviolet rays were applied only to the opaque auxiliary wiring and its surrounding 30 μm.
As the ultraviolet absorption filter, a filter having a light transmittance of 50% or less (cut wavelength: 320 nm) of a wavelength component of 320 nm or less was used.

《Evaluation》
<Measurement of current efficiency>
A current of 50 A / m ² was passed through the produced organic EL elements 101 to 104, and the brightness of the entire light emitting surface was measured with a two-dimensional color luminance meter (CA-2000) manufactured by Konica Minolta. The current efficiency (cd / A) was determined from the measured luminance.
Here, the value of the applied current density is the area including the opaque auxiliary wiring portion. In this example, since the light emitting area is 50 mm × 50 mm, a current of 0.125 A was passed through the organic EL elements 101 to 104 for measurement.
The evaluation results are shown in Table 4. The current efficiency is shown as a relative value with the current efficiency of the organic EL element 101 as 100.

Further, when the light emission image of the organic EL element 105 was magnified and observed with a commercially available CCD microscope, almost no light emission of 30 μm around the opaque auxiliary wiring was observed.
Furthermore, when observation was performed while applying a pulse voltage to the element using a lock-in thermal system manufactured by DCG Systems GK, the temperature of the opaque auxiliary wiring and its surroundings of 30 μm was compared with the temperature of its surroundings. It was low.
From this, it was found that the function of the light emitting layer was modulated in the light-irradiated portion.

Similarly, when the organic EL elements 102 to 104 were observed by the lock-in thermal system, the temperature of the opaque auxiliary wiring was lower than the temperature of the surroundings.
From this, it was found that the function of the light emitting layer was modulated in the light-irradiated portion.

As is clear from Table 4, it was confirmed that the organic EL device of the present invention is superior in current efficiency as compared with the organic EL device of the comparative example.
From the above, when viewed in a plan view, at least a part of the light emitting function of the region where the auxiliary wiring and at least one of the organic functional layers overlap is modulated, which makes the organic EL element excellent in current efficiency. It turns out to be useful in providing.

[Example 2]
<< Fabrication of organic EL element >>
<Manufacturing of organic EL element 201>
In the production of the organic EL element 101 of Example 1, the organic EL element 201 is produced in the same manner except that the patterns are formed so that the light emitting areas of the lower electrode (anode) and the upper electrode (cathode) are 2 mm × 2 mm. did.

(Confirmation of laser irradiation effect)
The effect of laser irradiation was confirmed.
Specifically, in the production of the organic EL device 201, a laser having a wavelength of 532 nm and an output of 10 mW is squeezed to a diameter of 100 μm on the front surface of the device formed up to the electron injection layer (LiF), and the light emitting surface is scanned at a scanning speed of 0.50 mm / sec. Scanned with, so that the entire surface was exposed to light.
After the laser irradiation, the upper electrode was formed into a film, and the film was sealed and sealed in the same manner as in the production of the organic EL element 201.
Similarly, elements having scanning speeds of 0.25 mm / sec and 0.17 mm / sec were prepared.
When the change in the drive voltage was confirmed for each element whose scanning speed was changed, the voltage increased as shown in Table 5.

From Table 5, it was confirmed that the function of the charge transport layer was partially lost by the laser irradiation.

<Manufacturing of organic EL element 202>
In the production of the organic EL element 102 of Example 1, the organic EL element 202 was produced in the same manner except that the auxiliary wiring was irradiated with the laser used in the above confirmation experiment instead of the ultraviolet irradiation. The scanning speed was 0.50 mm / sec.

<Manufacturing of organic EL element 203>
In the production of the organic EL element 202, the organic EL element 203 was produced in the same manner except that the scanning speed of the laser was set to 0.25 mm / sec.

<Manufacturing of organic EL element 204>
In the production of the organic EL element 202, the organic EL element 204 was produced in the same manner except that the scanning speed of the laser was 0.17 mm / sec.

《Evaluation》
The current efficiency of each of the produced elements was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 6. The current efficiency is shown as a relative value with the current efficiency of the organic EL element 201 as 100.

Further, as in Example 1, when the organic EL elements 201 to 204 were observed by the lock-in thermal system, the temperature of the opaque auxiliary wiring was lower than the temperature of the surroundings.
From this, it was found that the function of the light emitting layer was modulated in the light-irradiated portion.

As is clear from Table 6, the organic EL element of the present invention is superior in current efficiency as compared with the organic EL element of the comparative example even when laser irradiation is performed instead of ultraviolet irradiation. confirmed.

[Example 3]
<< Fabrication of organic EL element >>
<Manufacturing of elements for confirming infrared irradiation effect>
In the production of the organic EL element 101 of Example 1, an element for confirming the infrared irradiation effect was produced in the same manner except that the following was used as the support substrate.

(1) Preparation of Support Substrate (1.1) Formation of Base Layer One side of 100 μm-thick polyethylene terephthalate (PET) film (Toray Industries, Inc. Lumirror (registered trademark) U48) with both sides surface activated. A base layer having a thickness of 2 μm was formed on the surface. Specifically, UV curable resin Opster (registered trademark) Z7527 (manufactured by JSR Corporation) was applied so that the thickness after drying was 2 μm. After the coating film was dried at 80 ° C., it was subjected to a curing treatment in which it was irradiated with ultraviolet rays having an irradiation energy amount of 0.5 J / cm ² using a high-pressure mercury lamp in the atmosphere.

(1.2) Formation of Gas Barrier Layer The PET film on which the base layer was formed was cut out in a size of 120 mm × 100 mm, and a silicon-containing polymer modified layer was formed on the base layer as follows.

20% by mass dibutyl ether solution of uncatalyzed perhydropolysilazane (Aquamica NN120-20, manufactured by AZ Electronic Materials) and amine catalyst (N, N, N', N'-tetramethyl-1,6-diaminohexane) ) Was mixed with a 20% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by mass of the solid content at a ratio of 4: 1 to further adjust the thickness. Therefore, a coating solution was prepared by appropriately diluting with dibutyl ether.

The coating liquid prepared on the base layer was applied with a die coater so that the thickness after drying was 100 nm, and dried at 80 ° C. for 2 minutes. A Xe excimer lamp having a wavelength of 172 nm was used in the vacuum ultraviolet irradiation device shown in FIG. 5, and the dried coating film was subjected to a modification treatment of irradiating the dried coating film with vacuum ultraviolet rays of 2.5 mJ / cm ^2. A silicon-containing polymer modified layer was formed. When irradiated with vacuum ultraviolet rays, substitution with nitrogen was performed so that the atmosphere had an oxygen concentration of 0.1% by volume. Further, the temperature of the stage on which the PET film was installed was set to 80 ° C., and the transport speed of the stage was set to 0.5 m / min.

Subsequently, silicon compound layers having a thickness of 300 nm were each formed by a plasma CVD method to obtain a support substrate with a gas barrier layer.
The film forming conditions of the silicon compound layer are as follows.

Supply amount of raw material gas (hexamethyldisiloxane: HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas (O ₂ ) supply: 500 sccm
Vacuum degree in vacuum chamber: 3Pa
Power applied from the plasma generation power supply: 1.2 kW
Frequency of power supply for plasma generation: 80kHz
Film transport speed: 0.5 m / min

Further, the silicon-containing polymer modified layer was applied in the same manner as above so as to have a film thickness of 300 nm, and was cured by ultraviolet rays.

(1.3) Formation of Infrared Absorption Layer NIR-AM1 manufactured by Nagase ChemteX Corporation was used as an aminium salt type infrared absorber on the other surface of the support substrate, and NIR-AM1 was dissolved with the following composition. , Infrared absorber was applied by an inkjet device (applied to the entire surface).

NIR-AM1 10 parts by mass Diacetone alcohol 45 parts by mass Ethylene glycol monobutyl ether 45 parts by mass

As the inkjet device, the same device as that used for forming the lower electrode of the organic EL element 101 was used, but the inkjet head was KM512MHX manufactured by Konica Minolta Co., Ltd.

Subsequently, it was dried on a hot plate at 70 ° C. for 3 minutes, and further, radiant heat transfer drying using an infrared (IR) heater was performed for 5 minutes.

(1.4) Formation of Resin Layer The substrate formed up to the infrared absorbing layer was cut into 70 mm × 70 mm, and Hitachi Kasei Hitaroid 7975D was applied as an acrylic resin on the gas barrier layer with a spin coater. The film thickness was adjusted so that the thickness after drying was 1 μm. Unnecessary parts were wiped off and removed.
Subsequently, it was dried on a hot plate at 70 ° C. for 3 minutes, and further, radiant heat transfer drying using an infrared (IR) heater was performed for 5 minutes.

Next, a Xe excimer lamp having a wavelength of 172 nm was used in the vacuum ultraviolet irradiation device shown in FIG. 5, and the dried coating film was irradiated with vacuum ultraviolet rays of 2.5 mJ / cm ² and polymerized by the vacuum ultraviolet irradiation device. ..

(Confirmation of infrared irradiation effect)
The effect of infrared irradiation was confirmed.
Specifically, the confirmation element was irradiated with infrared rays for 10 minutes using a near-infrared lamp ZKB600 / 80G manufactured by Heraeus Co., Ltd.
Similarly, an element irradiated with infrared rays for 20 minutes and 40 minutes was prepared.
When a current of 50 A / m ² was passed through each of them and the current-voltage characteristics were evaluated, the voltage increased as shown in Table 7.

From Table 7, it was confirmed that the function of the charge transport layer was partially lost by infrared irradiation.

<Manufacturing of organic EL element 301>
In the production of the confirmation element, the organic EL element 301 was produced in the same manner except that the infrared absorbing layer was provided only on the overlapping portion so as to face the auxiliary wiring, the pattern mask was overlapped, and the infrared ray was irradiated for 10 minutes.

<Manufacturing of organic EL element 302>
In the production of the organic EL element 301, the organic EL element 302 was produced in the same manner except that it was irradiated with infrared rays for 20 minutes.

<Manufacturing of organic EL element 303>
In the production of the organic EL element 301, the organic EL element 303 was produced in the same manner except that it was irradiated with infrared rays for 40 minutes.

《Evaluation》
The current efficiency of each of the produced elements was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 8. The current efficiency is shown as a relative value with the current efficiency of the organic EL element 101 as 100.

Further, as in Example 1, when the organic EL elements 301 to 303 were observed by the lock-in thermal system, the temperature of the opaque auxiliary wiring was lower than the temperature of the surroundings.
From this, it was found that the function of the light emitting layer was modulated in the light-irradiated portion.

As is clear from Table 8, it was confirmed that the organic EL device of the present invention is superior in current efficiency as compared with the organic EL device of the comparative example.
From the above, it can be seen that even when the infrared absorbing layer is provided, the light emitting function of the organic functional layer is modulated, and an organic EL element having excellent current efficiency can be provided.

The present invention can be particularly suitably used for providing an organic EL device having excellent current efficiency and a method for manufacturing the same.

1 Organic EL element 2 Support substrate 4 Lower electrode 4a Transparent conductive layer 4b Auxiliary wiring 6 Organic functional layer 8 Upper electrode 10 Resin layer 12 Absorption layer 20 Vacuum ultraviolet irradiation device 22 Chamber 24 Stage 26 Shielding plate 28 Xe Exima lamp 30 Holder 100 Organic EL element 102 Support substrate 104 Lower electrode 104a Transparent conductive layer 104b Auxiliary wiring 106 Organic functional layer 108 Upper electrode L1, L2 Emission light T Overlapping region V Conveyance direction

Claims (6)

An organic electroluminescence device in which a lower electrode, an organic functional layer including at least a light emitting layer, and an upper electrode are sequentially laminated on a support substrate.
The lower electrodes is constituted by a transparent conductive layer, an opaque auxiliary wiring,
A resin layer is provided between the support substrate and the auxiliary wiring.
An organic electroluminescence device characterized in that, when viewed in a plan view, the light emitting function of at least a part of a region where the auxiliary wiring and at least one layer of the organic functional layer overlap is modulated. The light emitting layer includes at least one of a fluorescent light emitting layer containing the following compounds BD-1 and H-1 or a phosphorescent light emitting layer containing the following compounds GD-1, RD-1 and H-2. The organic electroluminescence element according to claim 1.

On a supporting substrate, a lower electrode, an organic functional layer including at least a light emitting layer, and an upper electrode are sequentially stacked, the lower electrodes includes a transparent conductive layer, an opaque auxiliary wiring and the organic electro that consists It is a manufacturing method of luminescence element.
at least,
A step of forming the lower electrode composed of the transparent conductive layer and the auxiliary wiring, and
The step of forming the organic functional layer and
A step of forming a resin layer between the support substrate and the auxiliary wiring,
And also
When viewed in a plan view, at least a step of modulating the light emitting function of a part of the region where the auxiliary wiring and at least one of the organic functional layers overlap.
A method for manufacturing an organic electroluminescence device, which comprises. As a step of forming the light emitting layer, at least one of a fluorescent light emitting layer containing the following compounds BD-1 and H-1 or a phosphorescent light emitting layer containing the following compounds GD-1, RD-1 and H-2. The organic electrollate according to claim 3, further comprising a step of forming a layer.
Manufacturing method of luminescence element.

The method for manufacturing an organic electroluminescence device according to claim 3 or 4 , wherein in the step of modulating the light emitting function, at least a part of the overlapping region is modulated by ultraviolet irradiation. The method for manufacturing an organic electroluminescence device according to claim 3 or 4 , wherein in the step of modulating the light emitting function, at least a part of the overlapping region is modulated by laser irradiation.

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