JP5790536B2 - Organic electroluminescence device and method for manufacturing the same - Google Patents

Description

The present invention relates to an organic electroluminescent device excellent in luminous efficiency, luminous lifetime and thermal stability, and a method for producing the same .

  In recent years, organic electroluminescence devices using organic substances (hereinafter also referred to as organic EL devices) are promising for use as solid light-emitting, inexpensive large-area full-color display devices and writing light source arrays, and are actively researched. Development is underway.

  The organic EL element is composed of an organic functional layer (single layer portion or multilayer portion) having a thickness of only about 0.1 μm containing an organic light emitting material between a pair of anode and cathode formed on a film. It is a thin film type all solid state device.

  In such an organic EL element, when a relatively low voltage of about 2 to 20 V is applied, electrons are injected from the cathode and holes are injected from the anode into the organic functional layer. It is known that when electrons and holes recombine in the light-emitting layer that constitutes the organic functional layer, and the generated excitons return from the excited state to the ground state, light is emitted as light and light can be obtained. This technology is expected as the next generation flat display and lighting.

  In recent years, organic EL devices using phosphorescence emission have a light emission efficiency of about 4 times that of organic EL devices using fluorescence emission in the past. Researches on the layer structure and electrode structure of light-emitting elements are widely performed all over the world.

  In particular, as one of the measures to prevent global warming, application to lighting fixtures, which account for a high proportion of human energy consumption, has begun to be studied, and research has been conducted toward the practical application of white light-emitting panels that can replace conventional lighting fixtures. Has been actively conducted.

  In the white light emitting panel for illumination, in order to spread the organic electroluminescence device in the market in response to the rapid light emission efficiency, life improvement and price reduction of recent LEDs, further light emission efficiency and device life Improvement and price reduction are required. In particular, the vapor deposition method that has been widely used for the production of organic EL elements in the past increases the manufacturing cost, so it is required to improve the performance of the organic EL element produced by a method that can reduce the cost. ing. As a method with high possibility that cost can be reduced, the manufacturing method of the organic EL element by a wet coating method is mentioned, for example.

  A general organic EL element has a thin film formed of tin-doped indium oxide (Indium Tin Oxide; hereinafter abbreviated as ITO) as an anode and a water-based solvent as a hole injection layer, and an alkali metal such as LiF or an alkali. It is composed of an electron injection layer containing an earth metal and a cathode made of a metal thin film such as Al.

  When the organic EL device having such a configuration has an organic layer produced by a coating method, Li atoms or ions that are chemically unstable from the peripheral layer of the light emitting layer, impurities contained in the material, and further a coating process The residual solvent used in the above process diffuses into the light emitting layer, and this causes a decrease in luminous efficiency and a deterioration in lifetime. In addition, the film formed by the coating process has a problem that the formed film is not uniform and luminance unevenness is likely to occur compared to a conventional organic EL layer formed by using a vapor deposition process.

  The reason for this is considered that the film formed using the coating process is a rough film compared to the film formed using the vapor deposition process, so that it is likely to be affected by the diffusion material from the peripheral layer. In addition, in the film formation, it is extremely difficult to stably form a uniform film with a large area in particular due to the physical properties of the coating liquid and the influence of the coating process or the drying process. .

  As a method of increasing the density of the formed thin film with respect to these problems, for example, by compressing the entire organic EL element with a laminate material, the formed film is uniformly pressed to increase the film density and formed by a coating method. A method for enhancing the rough film to the film quality level formed by the vapor deposition method is disclosed. (For example, refer to Patent Document 1). In the method disclosed in Patent Document 1, a load is applied to the film after being formed by coating and drying, which is likely to cause leakage, and has an effect on the remaining solvent. small.

  Moreover, the method of apply | coating the non-aqueous dispersion liquid which has the molecular weight in the range of 1,000-20,000, and forming an organic electroluminescent element structural layer is disclosed (for example, refer patent document 2). According to the method described in Patent Document 2, an organic EL device excellent in luminous efficiency and luminous lifetime can be obtained, and a high-density state not containing a solvent can be realized inside the dispersed particles. However, since no dispersant or binder is used as the composition of the non-aqueous dispersion, the dispersion medium easily aggregates and settles with the passage of time. However, the crystal state of the film is likely to change, and the characteristics vary greatly.

  In addition, a method of containing a nonionic dispersion stabilizer in a nonaqueous dispersion liquid of an organic electroluminescence element forming material is disclosed (for example, see Patent Document 3). According to the method described in Patent Document 3, although the temporal stability of the non-aqueous dispersion can be improved, the presence of the dispersion stabilizer inhibits the carrier movement of the dispersed grain boundary. It has a problem of inducing a problem and being unable to drive at a low voltage.

JP 2007-128799 A JP 2007-80657 A JP 2007-165231 A

The present invention has been made in view of the above problems, and the problem to be solved is that even in the formation of an organic functional layer by wet film formation, it has high light emission efficiency and long light emission lifetime, and is driven in a high temperature environment. An organic electroluminescence device having excellent stability and a method for producing the same.

  In the process of studying the solution of the above problems from various viewpoints, the present inventors have prepared a dispersion containing various constituent materials used for formation in the formation of an organic functional layer using wet film formation in the form of particles. It was discovered that solvation with respect to the solute of the substance had an unexpected effect on the density and stability of the formed layer, and a method for reducing or eliminating the influence of the solvation was found, leading to the present invention. It depends on you.

  The above-described problems of the present invention are solved by the following means.

1. An organic electroluminescent device having an organic functional layer between the two electrodes and at least one layer, at least one layer of the organic functional layer is a light emitting layer, the light-emitting layer, the particles and the following general formula containing a luminescent material It has a partial structure represented by (1) in the main chain, contains a carrier transportable binder having a weight average molecular weight in the range of 2,000 to 100,000, and has a thickness in the range of 5 to 100 nm. An organic electroluminescence element characterized by the above.
[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. ]

2 . The carrier transporting binder, with the partial structure represented by the general formula (1), an organic electroluminescence device according to paragraph 1 characterized by having a partial structure represented by the following structural formula (A) .

3 . The average particle diameter (nm) of the particles containing the light emitting material is in the range of 0.1 to 1.2 times the film thickness (nm) of the organic functional layer containing the particles. Item 3. The organic electroluminescence device according to Item 1 or Item 2 .
4). The weight average molecular weight of the carrier transportable binder is in the range of 3,000 to 80,000, and the organic electroluminescent element according to any one of the first to third aspects.
5. It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element as described in any one of Claim 1 to 4,
A luminescent material solution in which a luminescent material is dissolved in a good solvent and a partial structure represented by the following general formula (1) dissolved in a poor solvent of the luminescent material in the main chain, and a weight average molecular weight of 2,000 to 100 The carrier transportable binder solution in the range of 1,000 is associated by a liquid phase growth method to prepare a dispersion containing particles containing the light emitting material, and the coating liquid containing the dispersion is applied to emit light. A method for producing an organic electroluminescent element, comprising forming a layer .
[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. ]

  It is presumed that the above-mentioned means of the present invention can solve the above problem for the following reason.

  For example, in the formation of the organic functional layer by the conventional coating method, the solute (the constituent material of each organic functional layer) is applied by dissolving in a molecular state using a solvent or the like. Is presumed to be a state in which many solvents are solvated around one molecule of the constituent material. In order to volatilize this solvent during coating and drying, solvent molecules solvated with dissolved molecules are volatilized after the polymer film is formed. Is considered to be a low-density film.

  On the other hand, when the organic functional layer is formed using a dispersion containing particles composed of the organic functional material defined in the present invention, the number of solvent molecules solvated with respect to one particle is overwhelmingly small. It can be expected that a high-density film can be obtained. In order to allow particles composed of an organic functional material to stably exist in the dispersion without agglomeration, it is considered preferable to protect the particles with an additive. In general, the additive is a steric hindrance caused by adsorbing a surfactant on the particle surface and stabilizing the particle using the repulsive force of the charge, or adsorbing a polymer binder on the particle surface. A method of stabilizing the particles by using the above can be considered.

  However, the additive for maintaining the dispersed state of the particles by these methods remains in the formed film even after the organic functional layer is formed, thereby inhibiting the carrier transport and quenching the excitation energy of the luminescent material. In many cases, various problems such as obstruction occur. As a result of intensive studies, the inventors have found that the use of the specific polymer binder defined in the present invention can achieve both stabilization of the dispersion and enhancement of the functionality as the organic functional layer. It is up to you.

  By the above means of the present invention, an organic electroluminescent device having high luminous efficiency and long luminous lifetime and excellent driving stability in a high temperature environment can be provided even in the formation of an organic functional layer by wet film formation.

Sectional drawing which shows an example of a schematic structure of an organic electroluminescent element. The schematic block diagram of the micro mixer apparatus which is an example of the dispersion apparatus used for preparation of the dispersion liquid containing the particle | grains based on this invention.

The organic electroluminescence device of the present invention is an organic electroluminescence element having an organic functional layer between two electrodes at least one layer, at least one layer of the organic functional layer is a light emitting layer, the light-emitting layer, the light emitting A carrier- containing binder having a particle containing the material and a partial structure represented by the following general formula (1) in the main chain and having a weight average molecular weight in the range of 2,000 to 100,000; The film thickness is in the range of 5 to 100 nm. This feature is a technical feature common to the inventions according to claims 1 to 5 .

As an embodiment of the present invention, the carrier transportable binder includes the partial structure represented by the general formula (1) and the structural formula (A) from the viewpoint that the object effect of the present invention can be further expressed. It is preferable that it has the partial structure represented by these. Moreover, it is preferable that the average particle diameter (nm) of the particles is in the range of 0.1 to 1.2 times the film thickness (nm) of the organic functional layer containing the particles. Moreover, it is a preferable aspect that the weight average molecular weight of the said carrier transportable binder exists in the range of 3,000-80,000 .

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

<< Preparation Method of Particles Used for Formation of Organic Functional Layer >>
In the organic EL element of the present invention, at least one layer of the organic functional layer contains particles and a binder having a weight average molecular weight in the range of 2,000 to 100,000, and the film thickness is in the range of 5 to 100 nm. It is a layer.

  The particles according to the present invention preferably contain a light emitting material (hereinafter also referred to as a light emitting dopant), and particularly preferably contain a phosphorescent light emitting material (hereinafter also referred to as a phosphorescent light emitting dopant) described later as the light emitting material. Particles.

  First, the method for preparing particles according to the present invention will be described.

  As a method for preparing the particles according to the present invention, any of a dry pulverization method, a wet pulverization top-down method, a bottom-up method such as a liquid phase growth method and a vapor phase growth method may be used. From the viewpoint of reducing the thickness, the bottom-up method is preferable.

  The liquid phase growth method, for example, can use a reprecipitation method using a micromixer that precipitates fine particles by dissolving a solute in a good solvent and adding a poor solvent thereto. This method can be suitably used when it is desired to achieve this. As an apparatus for preparing particles that can be suitably used in the present invention, for example, an apparatus as described in the 42nd Academic Lecture Summary 5-23 of the Nihon University College of Production Engineering can be used.

  In addition, a synthesis reaction method in a supercritical state medium as described in JP-A-2008-12453 can also be applied, and particles prepared by these methods are dispersed in a medium to obtain a dispersion liquid. May be prepared and used. As the medium in the supercritical state, for example, water, carbon dioxide, methane, ethane, propane, ethylene, propylene, methanol, ethanol, and acetone can be used, but not limited thereto.

The solubility of the solute, which is a constituent material of the organic functional layer, can be measured for each solvent, and one with a low solubility can be used. For example, the difference in solubility parameter (SP value) between the solute and the poor solvent can be used. Can be used as an index of solubility. At this time, if the SP value is too close, the solute dissolves, so that large particles cannot be formed. However, if the SP value difference is extremely large, a poor solvent is added to the supercritical medium containing the solute. Since many crystal nuclei are generated at the moment, the crystal becomes small. If the difference in the SP value is 2 to 10 (MPa ^1/2 ), preferably 3 to 6 (MPa ^1/2 ), an appropriate amount of crystal nuclei is generated when a poor solvent is added. By adjusting the temperature of the growing reaction field and the reaction time, particles having a particle size of several tens of nm can be prepared. Further, any number of solutes may be used as constituent materials of the dissolved organic functional layer. In this case, the particle size of the particles may have a wide distribution.

  In the present invention, the smaller the difference in SP value between the good solvent and the poor solvent, the smaller the average particle diameter can be prepared. Here, in order to prepare particles having an average particle diameter in the range of 10 to 50 nm, a combination of a good solvent and a poor solvent having a difference in SP value of 2 to 8 can be suitably used. 6. When toluene having an SP value of 8.8 is used as a good solvent, the poor solvent is not limited to the following. For example, alcohol such as n-butanol, n-propanol, ethanol, methanol, or phenol may be used. it can. On the other hand, in order to prepare particles having a particle diameter in the range of 3 to 10 nm defined by the minimum maximum value B, a combination of a good solvent and a poor solvent having a SP value difference of 8 to 20 can be suitably used. More preferably, it is 12-18. When toluene is used as the good solvent, for example, water can be used as the poor solvent.

  A dispersion containing two types of particles having different average particle diameters can also be used. Here, the two types of particles may be of the same type or different types. For example, as a light emitting material used for the light emitting layer, for example, a liquid containing particles having an average particle diameter of 30 nm composed of a host compound and a blue dopant compound and particles having an average particle diameter of 9 nm composed of a host compound and green or red dopant is used. Also good.

  Moreover, you may use the liquid containing the particle | grains prepared by said method as a poor solvent added to the good solvent which melt | dissolved the solute. At this time, there are two types of processes: a process in which newly generated nuclei grow to form another particle, and a process in which the originally contained particles are further grown. Is expressed. The primary particulate material contained in the poor solvent to be added may or may not be the same as the solute dissolved in the good solvent.

  The shape of the particles to be generated varies depending on the material, but in the particles according to the present invention, the average value of the ratio of the minor axis to the major axis (major axis / minor axis) is 1.0 or more and 2.0. It is preferable that it is less than the range. For example, in the case of a rugby ball type particle, it corresponds to the ratio of the length of the major axis to the minor axis, and is preferably closer to a sphere. The shape of the particles can be obtained, for example, by observing a particle image taken with a transmission electron microscope (TEM), and the longest distance (long axis) and the shortest distance (short axis) of 300 particles are measured. The average is defined as the average (major axis / minor axis) ratio used in the present invention. Here, the major axis is the diameter of a circle in contact with two points on the outer periphery of the particle, and the minor axis is the diameter of a circle inscribed in the particle at two points.

  The particle size distribution of the particles according to the present invention can be determined by the following method.

  About the produced organic EL element, the cross section of the organic functional layer containing the particles according to the present invention was observed at a magnification of 250,000 times using a transmission electron microscope, and the particle size of about 300 particles was measured. A particle diameter distribution profile is created by plotting the particle diameter (nm) on the horizontal axis and the number of particles on the vertical axis. The particle size used in the particle size distribution is an average value of the major axis and the minor axis of the particle.

  Further, the film thickness of the organic functional layer containing particles is the average value of the layer thicknesses that can be obtained by TEM observation of the cross section of the organic EL element. A 1 μm visual field is observed at a magnification of 250,000 times, the average of the layer thicknesses is obtained, and this is defined as the thickness of the organic functional layer.

  Next, an apparatus for preparing a dispersion containing particles according to the present invention will be described.

  FIG. 2 is a schematic configuration diagram of a micromixer device (also referred to as a microreactor device) which is an example of a dispersion device used for preparing a dispersion liquid containing particles according to the present invention.

  As shown in FIG. 2, the micromixer device 31 has a poor solvent tank 33 with a stirrer 32 on the left side and a solute / good solvent tank 40 with a stirrer 39 on the opposite side. .

  A solute here is a material that constitutes particles, and specifically, a constituent material of each organic functional layer, for example, a hole transport material, an electron transport material, and a light emission that forms a light emitting layer, which will be described in detail later. A material (dopant compound), a host compound, etc. can be mentioned.

  Moreover, the good solvent said by this invention is a solvent which has high solubility with respect to the constituent material of these organic functional layers, and a poor solvent is a solvent with low solubility with respect to a solute. Therefore, in this invention, a good solvent or a poor solvent cannot be determined uniquely, but it classifies by the solubility with respect to the solute to be used.

  In the method for preparing particles according to the present invention, the solute solution dissolved in the good solvent is associated with a large amount of poor solvent to form fine particles containing a solute. At this time, when the particles are precipitated, since the interaction between the solvent molecules and the solute molecules is low, the poor solvent is not taken into the formed particles, and the solvent molecules oriented on the particle surface are also very Since the particles are attached with a weak interaction, they can be dried and evaporated with low energy after forming the organic functional film. The amount of the solvent remaining in the film can be measured by, for example, temperature programmed desorption gas analysis (TDS).

  In FIG. 2, the poor solvent stored in the poor solvent tank 33 is guided to the flow path a of the T-type micromixer 35 via the pump 34. On the other hand, the solute solution dissolved in the good solvent stored in the solute / good solvent tank 40 is guided to the flow path b of the T-type micromixer 35 via the pump 38. Then, while controlling the liquid feeding conditions of the pumps 34 and 38, the two liquids are associated with each other at the center of the flow path, the particles formed from the solute are precipitated, and the dispersion liquid containing the particles is discharged from the flow path c. The particles are stored in a particle storage tank 36.

  The particle diameter of each particle can be controlled by controlling the solute concentration, the good solvent, the kind of the poor solvent, the association ratio between the poor solvent and the solute solution dissolved in the good solvent, the association speed, the association time, and the like.

  In the present invention, the association ratio between the poor solvent and the solute solution dissolved in the good solvent (poor solvent: solute solution dissolved in the good solvent, volume ratio) is in the range of 5: 1 to 50: 1. The range of 5: 1 to 25: 1 is more preferable, and the range of 8: 1 to 15: 1 is still more preferable.

  The dispersion containing the particles according to the present invention prepared as described above can be adjusted to a concentration suitable for coating by diluting or concentrating. When such an operation is performed or before coating, it is also preferable to perform a treatment for solving secondary aggregation by ultrasonic dispersion or the like. Moreover, you may melt | dissolve the organic low molecular weight compound used as the binder melt | dissolved in this dispersion liquid. When dissolved, it is a single molecule and is not a particle subject to the present invention unless it is crystallized into particles. The particles referred to in the present invention are particles having a size of 0.5 nm or more.

<< Binder used to form organic functional layer >>
In the organic electroluminescence device of the present invention, at least one layer of the organic functional layer contains a binder having a weight average molecular weight in the range of 2,000 to 100,000 together with the particles described above.

  The weight average molecular weight defined in the present invention is a value measured by GPC (gel permeation chromatography) for molecular weight measurement using THF (tetrahydrofuran) as a column solvent.

  An example of a specific method for measuring the weight average molecular weight of a polymer material using gel permeation chromatography is shown below.

Solvent: Tetrahydrofuran Column: Shodex K806, K805, K803G (used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 2,800,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

The binder according to the present invention preferably has a carrier (hole or electron) transport property so that the organic functional layer comprising the particles according to the present invention functions as an organic semiconductor. The carrier mobility is preferably 1 × 10 ⁻⁸ cm ² / Vs or higher. In addition, the binder according to the present invention preferably has a high triplet excitation energy in order to obtain high luminous efficiency, and specifically has a triplet excitation energy of 2.8 eV or more.

  Moreover, it is preferable that the binder which concerns on this invention has the partial structure represented by following General formula (1).

  In the general formula (1), R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group.

  Examples of the alkyl group represented by R include 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, a tridecyl group, a tetradecyl group, and a pentadecyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aromatic hydrocarbon ring group, an aromatic carbocyclic group, and an aryl group. , Phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc. Examples of the heterocyclic group include a pyridyl group, a pyrazinyl group, and a pyrimid group. Nyl group, triazinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazole- 1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl Group, carbazolyl group, azacarbazolyl group (in which one or more carbon atoms constituting the carbazole ring of the carbazolyl group are replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group Etc. Can.

  The binder according to the present invention preferably has a partial structure represented by the following structural formula (A) together with the partial structure represented by the general formula (1).

  Below, the example compound 1-1a of the high molecular compound in which the weight average molecular weight which can be preferably used as a binder which comprises the organic functional layer of the organic electroluminescent element of this invention exists in the range of 2,000-100,000- Although 2-8c is shown, this invention is not limited to these.

  The binder according to the present invention can be obtained by synthesis according to a conventionally known synthesis method.

  The exemplified compounds 1-1a to 2-8c exemplified above all have carrier transport properties and triplet excitation energy is 2.8 eV or more.

<< Structure of organic electroluminescence element >>
FIG. 1 is a cross-sectional view showing an example of a schematic configuration of an organic electroluminescence element of the present invention.

  As shown in FIG. 1, an organic electroluminescent element 100 of the present invention (hereinafter abbreviated as “organic EL element 100”) has a flexible support substrate 1. An anode 2 is formed on the flexible support substrate 1, an organic functional layer 20 is formed on the anode 2, and a cathode 8 is formed on the organic functional layer 20.

  The organic functional layer 20 refers to each layer provided between the anode 2 and the cathode 8. Specifically, the organic functional layer 20 includes a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7, in addition to the hole block layer and the electron block layer. Layers and the like may be included.

  The anode 2, the organic functional layer 20, and the cathode 8 on the flexible support substrate 1 are sealed with a flexible sealing member 10 through a sealing adhesive 9.

  In addition, these layer structures (refer FIG. 1) of the organic EL element 100 show an example of a preferable structure, and this invention is not limited to these. That is, the organic EL element 100 of the present invention may have the following layer structures (i) to (viii).

(I) Flexible support substrate / anode / light emitting layer / electron transport layer / cathode / thermal conductive layer / sealing adhesive / sealing member (ii) Flexible support substrate / anode / hole transport layer / light emission Layer / electron transport layer / cathode / thermal conductive layer / sealing adhesive / sealing member (iii) flexible support substrate / anode / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode / Thermal conductive layer / sealing adhesive / sealing member (iv) flexible support substrate / anode / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / cathode / heat conduction Layer / adhesive for sealing / sealing member (v) flexible support substrate / anode / anode buffer layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / cathode / heat Conductive layer / adhesive for sealing / sealing member (vi) glass support / anode / hole injection layer / light emitting layer / electron injection layer / cathode / sealing member (vii) glass Holder / anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode / sealing member (viii) glass support / anode / hole injection layer / hole transport layer / light emitting layer / electron Transport layer / electron injection layer / cathode / sealing member [organic functional layer of organic EL element]
The detail of the organic functional layer which comprises the organic EL element of this invention is demonstrated.

(1: Injection layer Hole injection layer, electron injection layer)
In the organic EL device of the present invention, the injection layer can be provided as necessary. As the injection layer, there are an electron injection layer and a hole injection layer. As described above, the injection layer may exist between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer.

  The injection layer referred to in the present invention is a layer provided between the electrode and the organic functional layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of “S. Co., Ltd.”, and includes a hole injection layer and an electron injection layer.

  Details of the hole injection layer are described in, for example, JP-A-9-45479, JP-A-9-260062, and JP-A-8-288069. Examples of the hole injection material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives. Derivatives, polymers containing silazane derivatives and the like, aniline copolymers, polyarylalkane derivatives, or conductive polymers may be mentioned, preferably polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, more preferably Is a re-thiophene derivatives.

  Details of the electron injection layer are described in, for example, JP-A-6-325871, JP-A-9-17574, and JP-A-10-74586, and specifically, strontium, aluminum and the like are representative. A metal buffer layer, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and an oxide buffer layer typified by aluminum oxide. In the present invention, the buffer layer (injection layer) is desirably a very thin film, and potassium fluoride and sodium fluoride are preferable. The film thickness is about 0.1 nm to 5 μm, preferably 0.1 to 100 nm, more preferably 0.5 to 10 nm, and most preferably 0.5 to 4 nm.

(2: Hole transport layer)
As the hole transport material constituting the hole transport layer according to the present invention, the same compounds as those applied in the hole injection layer can be used, and further, porphyrin compounds, aromatic tertiary compounds can be used. It is preferable to use an amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-30 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 688 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. In the present invention, since the light emitting layer is applied on the upper layer of the hole transport layer, these polymer materials can be suitably used.

  JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004), JP-A-11-251067, J. MoI. Huang et. al. It is also possible to use a hole transport material that has a so-called p-type semiconducting property as described in the literature (Applied Physics Letters 80 (2002), p. 139), JP 2003-519432 A. it can.

  In the present invention, the hole transport layer uses a dispersion liquid containing particles containing a hole transport material, which is a technical feature of the present invention, in a dispersed state, and uses a wet coating method (for example, spin coating method, cast method, ink jet method). It can be formed by applying and drying using a printing method including a method. As another method for forming the hole transport layer, the hole transport material is formed by thinning it by a known method such as a vacuum vapor deposition method or a Langmuir-Blodgett method (LB method). be able to.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.

  Hereinafter, although the preferable compound example (Exemplary compound (1)-(60)) of the compound used for the hole transport material of the organic EL element of this invention is given, this invention is not limited to these.

  In addition, n described in the above exemplary compounds represents the degree of polymerization and represents an integer having a weight average molecular weight in the range of 50,000 to 200,000. The weight average molecular weight is more preferably in the range of 60,000 to 100,000. When it is desired to make the polymer into primary particles, it is preferable to use the higher molecular weight side than the above molecular weight range, and more preferably in the range of 200,000 to 1,000,000.

  These polymer compounds are described in, for example, Makromol. Chem. , Pages 193, 909 (1992) and the like.

(3: Electron transport layer)
The electron transport layer which is one of the organic functional layers according to the present invention is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer may be a single layer or a plurality of layers. For example, a combination of a hole block layer / electron transport layer can be used.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the cathode side with respect to the light emitting layer is injected from the cathode. As long as it has a function of transmitting electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, fluorene derivatives, carbazole derivatives, azacarbazole Examples thereof include metal complexes such as derivatives, oxadiazole derivatives, triazole derivatives, silole derivatives, pyridine derivatives, pyrimidine derivatives, and 8-quinolinol derivatives.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material.

  Among these, a carbazole derivative, an azacarbazole derivative, a pyridine derivative, and the like are preferable in the present invention, and an azacarbazole derivative is more preferable.

  In the present invention, the electron transport layer uses a dispersion containing particles containing the electron transport material, which is a technical feature of the present invention, in a dispersed state, and uses a wet coating method (for example, a spin coating method, a casting method, an ink jet method). For example, by using a printing method including a printing method). As another method for forming the electron transport layer, the electron transport material may be formed by thinning it by a known method such as a vacuum vapor deposition method or a Langmuir-Blodgett method (LB method). it can.

  Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  In the present invention, semiconductor nanoparticles may be used. For example, oxides such as zinc oxide, yttrium oxide, and titanium oxide can be used, but this is not restrictive.

  In addition to the semiconductor nanoparticles of the present invention, an electron transport layer having a high n property doped with impurities as a guest material can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  The electron transport layer in the present invention preferably contains an organic alkali metal salt. There are no particular restrictions on the type of organic substance, but formate, acetate, propionic acid, butyrate, valerate, caproate, enanthate, caprylate, oxalate, malonate, succinate Benzoate, phthalate, isophthalate, terephthalate, salicylate, pyruvate, lactate, malate, adipate, mesylate, tosylate, benzenesulfonate , Preferably formate, acetate, propionate, butyrate, valerate, caprate, enanthate, caprylate, oxalate, malonate, succinate, benzoate, more preferably Is preferably an alkali metal salt of an aliphatic carboxylic acid such as formate, acetate, propionate or butyrate, and the aliphatic carboxylic acid preferably has 4 or less carbon atoms. Most preferred is acetate.

  The type of alkali metal of the alkali metal salt of the organic substance is not particularly limited, and examples thereof include Na, K, and Cs, preferably K, Cs, and more preferably Cs. Examples of the alkali metal salt of the organic substance include a combination of the organic substance and the alkali metal, preferably, formic acid Li, formic acid K, formic acid Na, formic acid Cs, acetic acid Li, acetic acid K, Na acetate, acetic acid Cs, propionic acid Li, Propionic acid Na, propionic acid K, propionic acid Cs, oxalic acid Li, oxalic acid Na, oxalic acid K, oxalic acid Cs, malonic acid Li, malonic acid Na, malonic acid K, malonic acid Cs, succinic acid Li, succinic acid Na, succinic acid K, succinic acid Cs, benzoic acid Li, benzoic acid Na, benzoic acid K, benzoic acid Cs, more preferably Li acetate, K acetate, Na acetate, Cs acetate, most preferably Cs acetate.

  The content of these dope materials is preferably in the range of 1.5 to 35% by mass, more preferably in the range of 3 to 25% by mass, and most preferably 5 to 15% by mass with respect to the electron transport layer to be added. % Range.

(4: Light emitting layer)
Hereinafter, the light emitting layer which is one of the organic functional layers constituting the organic EL element will be described in detail.

  The light emitting layer constituting the organic EL element is a layer that emits light by recombination of electrons and holes injected from the electrode or the electron transport layer and the hole transport layer, and the light emitting portion is within the layer of the light emitting layer. It may be the interface between the light emitting layer and the adjacent layer.

  The organic EL device of the present invention is characterized in that at least one of the organic functional layers contains particles together with a binder having a weight average molecular weight in the range of 2,000 to 100,000. The organic functional layer containing the particles is a light emitting layer, the particles contain a light emitting material, and the light emitting material (also referred to as a light emitting dopant) is a phosphorescent light emitting material (also referred to as a phosphorescent light emitting dopant). Is a preferred embodiment.

  The film thickness of the light emitting layer according to the present invention is generally in the range of 5 to 500 nm, but when the organic functional layer containing the particles according to the present invention is a light emitting layer, the film thickness of the light emitting layer is 5 to 5 nm. The range is 100 nm.

  In the present invention, the light emitting layer uses a dispersion liquid containing particles containing a light emitting layer shown below, for example, a light emitting material (dopant compound), a host compound, etc. in a dispersed state. It can be formed by coating and drying by a coating method, a casting method, a printing method including an inkjet method, or the like. Further, if necessary, a film can be formed by other known light emitting layer forming methods such as a Langmuir-Blodgett method (LB method).

  The light emitting layer is mainly composed of a dopant compound and a host compound.

  Hereinafter, each of the host material and the dopant material will be described.

<4.1: Host compound>
As a host compound contained in the light emitting layer of the organic EL device of the present invention, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Further, the non-light emitting organic material may contain a host compound.

  As a host compound, it is possible to mix different luminescence by using a known host compound and a plurality of luminescent materials described later, thereby obtaining an arbitrary luminescent color.

  As the known host compound, a compound having a hole transporting ability and an electron transporting ability, preventing an increase in the wavelength of light emission, and having a high Tg (glass transition temperature) is preferable. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  Specific examples of known host compounds include compounds described in the following documents. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  The host compound used in the present invention is preferably a carbazole derivative.

  In the present invention, it is preferable to use a compound represented by the following general formula (2) as a host compound.

  In the above general formula (2), X represents NR ′, O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring. N represents an integer of 0 to 8.

  In X in the general formula (2), the substituents represented by R ′ and R ″ may be alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group). Group, octyl group, dodecyl group, 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 hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, Anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl , Biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole) -1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, Azinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl 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, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group) 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 (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylamino) Sulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethyl Nyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy) Group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propyl) Carbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, Silcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group) Octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentyl) Ureido group, cyclohexylureido group, octylureido group, dosylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc. ), Sulfinyl group (eg, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkyl A sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl) Group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyla) Group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg. , Fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group) Group, phenyldiethylsilyl group, etc.). These substituents may be further substituted with the above substituents. A plurality of these substituents may be bonded to each other to form a ring.

  Among them, X is preferably NR ′ or O, and R ′ is an aromatic hydrocarbon group (also referred to as aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, A tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group, or an aromatic heterocyclic group (for example, a furyl group, a thienyl group, a pyridyl group) Group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalazinyl group and the like are particularly preferable.

  The above aromatic hydrocarbon group and aromatic heterocyclic group each may have a substituent represented by R ′ or R ″ in X of the general formula (2).

  In the general formula (2), examples of the aromatic ring represented by Ar include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Further, the aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent represented by R ′ or R ″ in X of the general formula (2).

  In the general formula (2), the aromatic hydrocarbon ring represented by Ar includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a naphthacene ring, a triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, Examples include a pyranthrene ring and anthraanthrene ring. These rings may further have substituents each represented by R ′ and R ″ in X of the partial structure represented by the general formula (a).

  In the general formula (2), examples of the aromatic heterocycle represented by Ar include a furan ring, a dibenzofuran ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. , Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indazole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline Ring, isoquinoline ring, phthalazine ring, naphthyridine ring, carbazole ring, carboline ring, diazacarbazole ring (showing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc. Can be mentioned.

  These rings may further have substituents represented by R ′ and R ″ in the general formula (2).

  Among the above, in the general formula (2), the aromatic ring represented by Ar is preferably a carbazole ring, carboline ring, dibenzofuran ring, or benzene ring, and more preferably used is a carbazole ring, A carboline ring and a benzene ring, more preferably a benzene ring having a substituent, and particularly preferably a benzene ring having a carbazolyl group.

  In the general formula (2), each of the aromatic rings represented by Ar is preferably a condensed ring having three or more rings, and the aromatic hydrocarbon condensed ring in which three or more rings are condensed includes Specifically, naphthacene ring, anthracene ring, tetracene ring, pentacene ring, hexacene ring, phenanthrene ring, pyrene ring, benzopyrene ring, benzoazulene ring, chrysene ring, benzochrysene ring, acenaphthene ring, acenaphthylene ring, triphenylene ring, coronene ring, Benzocoronene ring, hexabenzocoronene ring, fluorene ring, benzofluorene ring, fluoranthene ring, perylene ring, naphthoperylene ring, pentabenzoperylene ring, benzoperylene ring, pentaphen ring, picene ring, pyrantrene ring, coronene ring, naphthocolonene ring, ovalen ring Anthracanthrene ring And the like. In addition, these rings may further have the above substituent.

  Specific examples of the aromatic heterocycle condensed with three or more rings include an acridine ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, Kindin ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring is a nitrogen atom Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, A Tiger thiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, such as thio fan Tren ring (naphthaldehyde thiophene ring), and the like. In addition, these rings may further have a substituent.

  Moreover, in General formula (2), although n represents the integer of 0-8, it is preferable that it is 0-2, and when X is O and S especially, it is preferable that it is 1 or 2.

  In the present invention, a host compound having both a dibenzofuran ring and a carbazole ring is particularly preferable.

  Specific examples (a-1 to a-41) of the host compound represented by the general formula (2) are shown below, but are not limited thereto.

<4.2: Light emitting material (light emitting dopant)>
In this invention, it is a preferable aspect that the particle | grains which concern on this invention contain the luminescent material (luminescent dopant).

  As the light-emitting material (light-emitting dopant) according to the present invention, a fluorescent compound or a phosphorescent light-emitting material (also referred to as a phosphorescent compound or a phosphorescent compound) can be used. A preferred embodiment is a particle containing a phosphorescent dopant).

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

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

  There are two types of light-emitting principles of phosphorescent materials. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent material. Energy transfer type to obtain light emission from the phosphorescent light emitting material, and another one is that the phosphorescent light emitting material becomes a carrier trap, and carrier recombination occurs on the phosphorescent light emitting material and light emission from the phosphorescent light emitting material is obtained. In any case, the condition is that the excited state energy of the phosphorescent material is lower than the excited state energy of the host compound.

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

  The phosphorescent dopant suitable for the present invention is described in detail below.

  As the phosphorescent dopant according to the present invention, a compound represented by the following general formula (3) is preferable.

In the general formula (3), R ₁ represents a substituent. Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring. n1 represents the integer of 0-5. B ₁ .about.B ₅ represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, at least one nitrogen atom. M ₁ represents a group 8 to group 10 metal in the periodic table. X ₁ and X ₂ represent a carbon atom, a nitrogen atom, or an oxygen atom, and L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . m1 represents an integer of 1, 2, or 3, m2 represents an integer of 0, 1, or 2, and m1 + m2 is 2 or 3.

  The phosphorescent compound represented by the general formula (3) has a highest occupied orbital (HOMO) energy level in the range of −5.15 to −3.50 eV, and the lowest unoccupied orbital (Lowest orbital (Lowest The energy level of Unoccupied Molecular Orbital (LUMO) is in the range of −1.25 to +1.00 eV, preferably the energy level of HOMO is in the range of −4.80 to −3.50 eV, and the LUMO energy level. Is in the range of -0.80 to +1.00 eV.

In the phosphorescent compound represented by the general formula (3), examples of the substituent represented by R ₁ 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). Group, hexyl group, octyl group, dodecyl group, 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 (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, Naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, inde Nyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1, 2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, A quinolyl group, a benzofuryl group, a dibenzofuryl group, a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is a nitrogen atom) ), Quinoxalinyl group, Dazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyl) Oxy 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, 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 (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl 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 group ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbo Ruamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexyl). Aminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl 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, naphthylureido group, 2-pyridy Aminoureido groups, etc.), sulfinyl groups (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Etc.), alkylsulfonyl groups (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl groups or heteroarylsulfonyl groups (for example, phenylsulfonyl) Group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group) , Cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, trimethyl group) Isopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.). Of these substituents, preferred are an alkyl group and an aryl group.

  Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring. Examples of the 5- to 7-membered ring formed by Z include a benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, and thiazole ring. Of these, a benzene ring is preferred.

B ₁ .about.B ₅ is a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, at least one nitrogen atom. The aromatic nitrogen-containing heterocycle formed by these five atoms is preferably a monocycle. Examples include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, oxadiazole ring, and thiadiazole ring. Among these, a pyrazole ring and an imidazole ring are preferable, and an imidazole ring in which B ₂ and B ₅ are nitrogen atoms is particularly preferable. These rings may be further substituted with the above substituents. Preferred as the substituent are an alkyl group and an aryl group, and more preferably an aryl group.

L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . Specific examples of the bidentate ligand represented by X ₁ -L ₁ -X ₂ include, for example, substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, picolinic acid And acetylacetone. These groups may be further substituted with the above substituents.

m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. Especially, the case where m2 is 0 is preferable. The metal represented by M _1, but 8-10 transition metal elements of the Periodic Table of the Elements (also referred to simply as a transition metal) is used, inter alia iridium, platinum are preferred, more preferably iridium.

  The particles containing the light-emitting material according to the present invention can be prepared from the above-described light-emitting materials according to the above-described particle preparation method, for example, using the micromixer apparatus shown in FIG.

  Specific examples of the phosphorescent compound (D-1 to D-133) represented by the general formula (3) are illustrated below, but the present invention is not limited to these.

〔anode〕
As the anode constituting the organic EL device, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a desired shape pattern may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually in the range of 10 to 1000 nm, preferably in the range of 10 to 200 nm.

〔cathode〕
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. 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 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the metal with a film thickness of 1 to 20 nm on the cathode, a transparent or semitransparent cathode can be produced by forming the conductive transparent material mentioned in the explanation of the anode on the cathode, By applying this, an organic EL element in which both the anode and the cathode are transmissive can be produced.

[Support substrate]
The support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. Since the effect of suppressing high-temperature storage stability and chromaticity variation appears greatly in a flexible substrate than a rigid substrate, a particularly preferable support substrate has flexibility that can give flexibility to an organic EL element. Resin film.

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

An inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and more preferably oxygen permeability measured by a method according to JIS K 7126-1987. It is preferable that the degree is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less and the water vapor permeability is 1 × 10 ⁻³ g / (m ² · 24 h) or less. More preferably, the water vapor permeability is 1 × 10 ⁻⁵ g / (m ² · 24 h) or less.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of factors that cause deterioration of the organic EL element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. Can do. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination order of an inorganic layer and an organic functional layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma. A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  In the organic EL device of the present invention, the external extraction efficiency of light emission at room temperature is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

[Sealing: sealing adhesive, sealing member]
Examples of the sealing means applicable to the organic EL element of the present invention include a method of bonding with a sealing member and an electrode, and a support substrate with an adhesive.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

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

In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned. Furthermore, the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, and conforms to JIS K 719-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the above method is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photo-curing and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. Can be mentioned. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned. In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. Further, a desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  It is also preferable that the electrode and the organic functional layer are coated on the outside of the electrode facing the support substrate with the organic functional layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. Can be. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. 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 organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, 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, or the like can be used.

  In order to form a gas phase and a liquid phase in the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, an inert gas such as fluorinated hydrocarbon or silicon oil is used. It is preferable to inject a liquid. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

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

  Sealing includes casing type sealing (can sealing) and close contact type sealing (solid sealing), but solid sealing is preferable from the viewpoint of thinning. Moreover, when producing a flexible organic EL element, since sealing is also required for the sealing member, solid sealing is preferable.

  Below, the preferable aspect in the case of performing solid sealing is demonstrated.

  As the sealing adhesive according to the present invention, a thermosetting adhesive, an ultraviolet curable resin, or the like can be used, but preferably a thermosetting adhesive such as an epoxy resin, an acrylic resin, or a silicon resin, more preferably moisture resistant. It is an epoxy thermosetting adhesive resin that is excellent in water resistance and water resistance and has little shrinkage during curing.

  The water content of the sealing adhesive according to the present invention is preferably 300 ppm or less, more preferably in the range of 0.01 to 200 ppm, and most preferably in the range of 0.01 to 100 ppm.

  The moisture content referred to in the present invention may be measured by any method. For example, a volumetric moisture meter (Karl Fischer), an infrared moisture meter, a microwave transmission moisture meter, a heat-dry weight method, GC / MS , IR, DSC (differential scanning calorimeter), TDS (temperature programmed desorption analysis). Further, using a precision moisture meter AVM-3000 (Omnitech) or the like, moisture can be measured from a pressure increase caused by evaporation of moisture, and moisture content of a film or a solid film can be measured.

  In the present invention, the moisture content of the sealing adhesive can be adjusted by, for example, placing it in a nitrogen atmosphere with a dew point temperature of −80 ° C. or lower and an oxygen concentration of 0.8 ppm, and changing the time. Further, it can be dried in a vacuum state of 100 Pa or less while changing the time. Further, the sealing adhesive can be dried only with an adhesive, but can also be placed in advance on the sealing member and dried.

  When close sealing (solid sealing) is performed, as the sealing member, for example, a 50 μm thick PET (polyethylene terephthalate) laminated with an aluminum foil (30 μm thick) is used. Using this as a sealing member, it is uniformly applied to the aluminum surface using a dispenser, a sealing adhesive is placed in advance, the resin substrate 1 and the sealing member 5 are aligned, and then both are crimped ( 0.1-3 MPa) and a temperature of 80-180 ° C. for tight adhesion / bonding (adhesion) for tight sealing (solid sealing).

  The heating or pressure bonding time varies depending on the type, amount, and area of the adhesive, but temporary bonding is performed at a pressure in the range of 0.1 to 3 MPa, and the heat curing time is 5 seconds at a temperature in the range of 80 to 180 ° C. You can select a range of 10 minutes.

  The use of a heated crimping roll is preferred because it allows simultaneous crimping (temporary bonding) and heating, and eliminates internal voids at the same time.

  As a method for forming the adhesive layer, a coating method such as roll coating, spin coating, screen printing, or spray coating, or a printing method can be used depending on the material.

As described above, solid sealing is a form in which there is no space between the sealing member and the organic EL element substrate and the resin is covered with a cured resin. Examples of the sealing member include metals such as stainless steel, aluminum, and magnesium alloys, polyethylene terephthalate, polycarbonate, polystyrene, nylon, plastics such as polyvinyl chloride, and composites thereof, glass, and the like. In the case of a resin film, a laminate of gas barrier layers such as aluminum, aluminum oxide, silicon oxide, and silicon nitride can be used as in the case of a resin substrate. The gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method. . Also in this case, the oxygen permeability is 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, and the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 ×. It is preferably 10 ⁻³ g / (m ² · 24 h) or less.

  The sealing member may be a film laminated with a metal foil such as aluminum. As a method for laminating the polymer film on one side of the metal foil, a generally used laminating machine can be used. As the adhesive, polyurethane-based, polyester-based, epoxy-based, acrylic-based adhesives and the like can be used. You may use a hardening | curing agent together as needed. A hot melt lamination method, an extrusion lamination method and a coextrusion lamination method can also be used, but a dry lamination method is preferred.

  In addition, when the metal foil is formed by sputtering or vapor deposition and is formed from a fluid electrode material such as a conductive paste, it may be produced by a method of forming a metal foil on a polymer film as a base material. Good.

[Protective film, protective plate]
In order to increase the mechanical strength of the organic EL element, a protective film or a protective plate may be provided outside the sealing film on the side facing the support substrate with the organic functional layer interposed therebetween or on the outer side of the sealing film. In particular, when sealing is performed with a sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

  In the present invention, it is preferable to have a light extraction member between the flexible support substrate and the anode or at any location on the light emission side from the flexible support substrate.

  Examples of the light extraction member include a prism sheet, a lens sheet, and a diffusion sheet. Moreover, the diffraction grating introduce | transduced in the interface which raise | generates total reflection, or any medium, a diffusion structure, etc. are mentioned.

  In general, in an organic electroluminescence element that emits light from a substrate, a part of the light emitted from the light emitting layer causes total reflection at the interface between the substrate and air, causing a problem of loss of light. In order to solve this problem, the prism surface, lens-like processing is applied to the surface of the substrate, or the prism sheet, the lens sheet and the diffusion sheet are attached to the surface of the substrate, thereby suppressing the total reflection and the light extraction efficiency. To improve.

  In order to increase the light extraction efficiency, a method of introducing a diffraction grating or a method of introducing a diffusion structure in an interface or any medium that causes total reflection is known.

<< Method for Manufacturing Organic EL Element >>
As an example of the method for producing an organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate by a thin film forming method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, An anode is produced.

Next, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic functional layer (organic compound thin film) of an electron injection layer, which are organic EL element materials, are formed thereon. In the present invention, At least one of the light emitting layers has a particle containing a light emitting material and a partial structure represented by the general formula (1) in the main chain, and the weight average molecular weight is in the range of 2,000 to 100,000. It is formed by using a coating liquid containing a carrier transporting binder.

  The step of forming the organic functional layer mainly includes a step of applying and laminating the coating liquid constituting the organic functional layer on the anode of the support substrate and a step of drying the coating liquid after coating and lamination. Composed. The step of applying and drying may be performed in the air, but the step of drying is preferably performed in an inert gas atmosphere such as nitrogen, and the step of applying is also preferably performed in an inert gas atmosphere. . Here, the inert gas atmosphere preferably contains 100 ppm or less of water or oxygen, more preferably 10 ppm or less, and even more preferably 1 ppm or less.

  As a forming method using the dispersion liquid containing particles according to the present invention, a wet process (for example, spin coating method, casting method, die coating method, blade coating method, roll coating method, ink jet method, printing method, spray coating method, curtain) Coating method, LB method (Langmuir Brodgett method, etc. can be used.) Among the wet processes in the present invention, spin coating method, casting method, die coating method, blade coating can be used. Film formation by a coating method such as a coating method, a roll coating method or an ink jet method is preferred.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) can be used. Moreover, as a dispersion method, it can disperse | distribute by addition to the poor solvent in dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  Moreover, it is preferable that the liquid preparation process which melt | dissolves or disperse | distributes the organic EL material which concerns on this invention is in inert gas atmosphere, and a solution is not exposed to an application atmosphere until it apply | coats on a base material by the above-mentioned wet process. It is preferable that it is a process.

  The coating / laminating and drying steps of these layers may be single wafer manufacturing or line manufacturing. Moreover, the atmosphere at the time of applying each layer may be common, but from the viewpoint of the influence of the solvent that volatilizes, it is preferable that the coating booth of each layer is surrounded by a partition wall and the circulation of the atmosphere is independent. Further, the drying process may be performed while being conveyed on the line, but from the viewpoint of productivity, it may be deposited or rolled in a non-contact manner in a roll form.

  After these layers are dried, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm. By providing, a desired organic EL element can be obtained.

  After the heat treatment, the organic EL element can be produced by adhering the close-sealing or sealing member to the electrode and the support substrate with an adhesive.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources.

  Examples of light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, and light sources for optical sensors. Furthermore, it can be used in a wide range of applications such as general household appliances that require a display device, but it can be used effectively as a backlight for a liquid crystal display device combined with a color filter, and as a light source for illumination. it can. In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

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

<< Production of organic EL element >>
[Production of Organic EL Element 1: Comparative Example]
(1: Production of flexible film)
As the flexible film, a polyethylene naphthalate film (a film manufactured by Teijin DuPont Co., Ltd., hereinafter abbreviated as PEN) was used. An inorganic gas barrier film made of SiO _{x is} continuously formed on the entire surface of the flexible film on the side on which the anode is formed, using an atmospheric pressure plasma discharge treatment apparatus having the structure described in JP-A-2004-68143. The oxygen permeability measured by the method according to JIS K 7126-1987 is 0.001 ml / m ² / day or less, the water vapor permeability (25 ± 0.5 ° C., A gas barrier flexible film having a relative humidity (90 ± 2)% RH) of 0.001 g / m ² / day or less was produced.

(2: Formation of anode layer)
An ITO (indium tin oxide) film having a thickness of 120 nm was formed on the produced gas barrier flexible film by sputtering, and patterned by photolithography to form an anode. The pattern was such that the light emission area was 50 mm square.

(3: Formation of hole injection layer)
The patterned ITO substrate was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. On this substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (abbreviated as PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. The film was formed by spin coating. Film formation was performed in an air atmosphere. Then, it dried at 200 degreeC for 1 hour, and provided the positive hole injection layer with a film thickness of 30 nm.

(4: Formation of hole transport layer)
This substrate was transferred to a nitrogen gas atmosphere, and a solution obtained by dissolving 0.5% of compound A (Mw = 80,000, see below) as a hole transport material in chlorobenzene was spin-coated at 1500 rpm for 30 seconds. A film was formed and dried at 130 ° C. for 30 minutes to form a hole transport layer having a thickness of 30 nm.

(5: Formation of light emitting layer)
Next, the light emitting layer composition 1 prepared by mixing and dissolving the following additives and the substrate are maintained at room temperature, and the light emitting layer is formed on the hole transport layer by spin coating at 1500 rpm for 30 seconds. The composition 1 was applied and dried at 120 ° C. for 30 minutes to form the light emitting layer 1. Separately, when the light emitting layer 1 was formed on a glass substrate by the same method, the film thickness was 40 nm.

<Preparation of the light emitting layer composition 1>
1) Non-luminescent organic material Compound B (see below) 11.600 parts by mass 2) Luminescent dopant Compound C (see below) 2.880 parts by weight Compound D (see below) 0.008 parts by mass Compound E (see below) ) 0.008 parts by mass 3) Solvent Toluene 2000 parts by mass (6: Formation of electron transport layer)
Subsequently, a solution of 20 mg of compound F (see below) dissolved in 4 ml of tetrafluoropropanol (TFPO) was formed into a film by spin coating at 1500 rpm for 30 seconds, and dried at 120 ° C. for 30 minutes. A 30 nm electron transport layer was formed.

(7: Formation of electron injection layer and cathode)
Subsequently, the substrate was attached to a vacuum deposition apparatus without being exposed to the atmosphere. A molybdenum resistance heating boat containing potassium fluoride is attached to a vacuum deposition apparatus, and the vacuum chamber is depressurized to 4 × 10 ⁻⁵ Pa, and then the boat is energized and heated to reduce potassium fluoride to 0. An electron injection layer having a thickness of 2 nm was formed on the electron transport layer at a rate of 0.02 nm / second. Subsequently, aluminum was deposited to a thickness of 100 nm to form a cathode.

(8: Sealing and production of organic EL element)
Then, the sealing member was adhere | attached using the commercially available roll laminating apparatus, and the organic EL element 1 was produced.

  In addition, as a sealing member, a polyethylene terephthalate (PET) film (12 μm thickness) is bonded to a flexible aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) with a thickness of 30 μm. (Urethane-based adhesive) and a laminate (adhesive layer thickness of 1.5 μm) were used.

  A thermosetting adhesive as a sealing adhesive was uniformly applied to the aluminum surface at a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser. This was dried under a vacuum of 100 Pa or less for 12 hours. Furthermore, it moved to nitrogen atmosphere with a dew point temperature of −80 ° C. or lower and an oxygen concentration of 0.8 ppm, dried for 12 hours or longer, and adjusted the moisture content of the sealing adhesive to 100 ppm or lower.

  As the thermosetting adhesive, an epoxy adhesive mixed with the following (A) to (C) was used.

(A) Bisphenol A
(B) Diglycidyl ether (DGEBA)
(C) Dicyandiamide (DICY) Epoxy Adduct Curing Accelerator As described above, take out the sealing substrate so as to be in the form shown in FIG. Then, the organic EL element 1 was produced by tightly sealing with a pressure bonding roll at a pressure bonding condition, a pressure roll temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min.

[Production of Organic EL Element 2]
In the production of the organic EL element 1, the organic EL element 2 was produced in the same manner except that the light emitting layer 1 was changed to the light emitting layer 2 formed by the following method.

(Formation of the light emitting layer 2)
<Preparation of the light emitting layer composition 2>
1) Nonluminous organic material Compound B (supra) 130.50 parts by mass 2) Luminescent dopant Compound C (supra) 14.30 parts by mass Compound D (supra) 0.08 parts by mass Compound E (supra) 0.08 parts by mass 3) Solvent Toluene 2000 parts by mass The luminescent layer composition 2 was prepared as a solute solution dissolved in a good solvent and introduced into the T-type micromixer 35 shown in FIG. Here, the length of the micromixer tube can be arbitrarily changed, and the reaction time after mixing the liquid can be freely changed. The pump 34 feeds tetrafluoropropanol as a poor solvent from the poor solvent tank 33, adjusts the rotational speed of each pump 34, 38, and forms a T-type micro of the luminescent layer composition 2 that is a solute solution dissolved in a good solvent. The liquid feed rate to the mixer 35 is 4 ml / min, the liquid feed rate of tetrafluoropropanol, which is a poor solvent, is 40 ml / min, and both liquids are formed at the center in the T-type micromixer 35 having a flow path inner diameter of 150 μm. Were dispersed at high speed to prepare a dispersion liquid (first liquid) of the light-emitting layer composition 2 containing particles on which the non-light-emitting organic material and the light-emitting dopant were deposited. At this time, the time required from when the two liquids were associated to when the liquid was discharged from the T-type micromixer 35 as a dispersion liquid containing particles was 1 second.

  The particles contained in the luminescent layer composition 2 dispersion (first liquid) prepared above were photographed at 250,000 times using an electron microscope, and the major axis / minor axis of the particles were measured. ) / 2 was measured for about 300 particles, and the average value was determined to be 31 nm.

  The prepared luminescent layer composition 2 dispersion (first liquid) was dropped onto the substrate coated up to the hole transport layer, formed into a film by spin coating at 1500 rpm for 30 seconds, and dried at 120 ° C. for 30 minutes, A light emitting layer 2 having a thickness of 40 nm was formed.

  The cross section of the organic EL element 2 produced above was photographed at 250,000 times using an electron microscope, and the (major axis / minor axis) ratio was measured as a result of measuring the (major axis / minor axis) ratio of 300 particles. Is 2.3, and a particle diameter distribution curve in which the particle diameter ((major axis + short axis) / 2) is plotted on the horizontal axis and the number of particles is plotted on the vertical axis is obtained. there were.

[Production of Organic EL Element 3]
In the production of the organic EL element 1, the organic EL element 3 was produced in the same manner except that the light emitting layer 1 was changed to the light emitting layer 3 formed by the following method.

(Formation of the light emitting layer 3)
<Preparation of the light emitting layer composition 3>
1) Nonluminous organic material Compound B (supra) 80.50 parts by mass 2) Luminescent dopant Compound C (supra) 14.30 parts by mass Compound D (supra) 0.08 parts by mass Compound E (supra) 0.08 parts by mass 3) Solvent Toluene 2000 parts by mass <Preparation of binder solution 3>
1) Binder Example Compound 2-8b 50 parts by mass 2) Solvent Tetrafluoropropanol 2000 parts by mass The light emitting layer composition 3 was prepared as a solute solution dissolved in a good solvent and introduced into the T-type micromixer 35 shown in FIG. . The pump 34 feeds tetrafluoropropanol as a poor solvent from the poor solvent tank 33, adjusts the rotational speed of each pump 34, 38, and forms a T-type micro of the luminescent layer composition 3 that is a solute solution dissolved in a good solvent. The liquid feed rate to the mixer 35 is 4 ml / min, the liquid feed rate of tetrafluoropropanol, which is a poor solvent, is 36 ml / min, and both liquids are placed in the center of the T-type micromixer 35 with a flow path inner diameter of 150 μm. A light-emitting layer composition 3 dispersion (first liquid) containing particles on which a non-light-emitting organic material and a light-emitting dopant were deposited was prepared by high-speed association. Furthermore, the binder solution 3 was mixed in-line at a feed rate of 4 ml / min from a branch pipe (in-line mixing section) formed in the discharge side flow path of the micromixer. At this time, the time required for discharging the two liquids from the T-type micromixer 35 as the light-emitting layer composition 3 dispersion (second liquid) containing particles was 1.2 seconds.

  The particles contained in the luminescent layer composition 3 dispersion (second liquid) prepared above were photographed at 250,000 times using an electron microscope, and the major axis / minor axis of the particles were measured. ) / 2 is the particle diameter of the particles, about 300 particles were measured, and the average value was determined to be 33 nm.

  The prepared light emitting layer composition 3 dispersion (second liquid) was dropped onto a substrate coated up to the hole transport layer, formed into a film by spin coating at 1500 rpm for 30 seconds, and dried at 120 ° C. for 30 minutes, The light emitting layer 3 was formed.

  The cross section of the organic EL element 3 produced above was photographed at 250,000 times using an electron microscope, and the (major axis / minor axis) ratio was measured as a result of measuring the (major axis / minor axis) ratio of 300 particles. 1.6, a particle diameter distribution curve in which the particle diameter ((long axis + short axis) / 2) is plotted on the horizontal axis and the number of particles is plotted on the vertical axis. As a result, there is one maximum peak at 33 nm. there were.

[Production of Organic EL Element 4]
In the production of the organic EL element 1, the organic EL element 4 was produced in the same manner except that the light emitting layer 1 was changed to the light emitting layer 4 formed by the following method.

(Formation of the light emitting layer 4)
<Preparation of the light emitting layer composition 4>
1) Non-luminescent organic material Compound B (supra) 80.50 parts by mass 2) Luminescent dopant Compound C (supra) 14.30 parts by mass Compound D (supra) 0.08 parts by mass Compound E (supra) ) 0.08 parts by mass 3) Solvent Toluene 2000 parts by mass <Preparation of binder solution 4>
1) Binder Exemplified compound 2-8b 500 parts by mass 2) Solvent Tetrafluoropropanol 20000 parts by mass The luminescent layer composition 4 is prepared as a solute solution dissolved in a good solvent and introduced into the T-type micromixer 35 shown in FIG. did. The light emitting layer composition which is a solute solution dissolved in a good solvent by feeding the binder solution 4 dissolved in tetrafluoropropanol as a poor solvent from the poor solvent tank 33 by the pump 34, adjusting the rotation speed of each pump 34, 38. The amount of the liquid 4 fed to the T-type micromixer 35 is 4 ml / min, the amount of the binder solution 4 dissolved in tetrafluoropropanol, which is a poor solvent, is 40 ml / min, and the inner diameter of the flow path is 150 μm. In the center part in the micromixer 35, both liquids were made to associate at high speed, and the light emitting layer composition 4 dispersion liquid (1st liquid) containing the non-light-emitting organic material, the particle | grains which precipitated the light emission dopant, and the binder was prepared. At this time, the time required for the two liquids to be discharged from the T-type micromixer 35 as a dispersion liquid containing particles was 1.2 seconds.

  The particles contained in the light-emitting layer composition 4 dispersion (first liquid) prepared above were photographed at 250,000 times using an electron microscope, and the major axis / minor axis of the particles were measured. ) / 2 is the particle diameter of the particles, about 300 particles were measured, and the average value was determined to be 33 nm.

  The prepared luminescent layer composition 4 dispersion (first liquid) was dropped onto the substrate coated up to the hole transport layer, formed by spin coating at 1500 rpm for 30 seconds, and dried at 120 ° C. for 30 minutes, The light emitting layer 4 was formed.

  The cross section of the organic EL device 4 produced above was photographed at 250,000 times using an electron microscope, and the (major axis / minor axis) ratio was measured as a result of measuring the (major axis / minor axis) ratio of 300 particles. 1.6, a particle diameter distribution curve in which the particle diameter ((long axis + short axis) / 2) is plotted on the horizontal axis and the number of particles is plotted on the vertical axis. As a result, there is one maximum peak at 33 nm. there were.

[Production of organic EL elements 5 to 16]
In the production of the organic EL element 4, the type of binder used for the production of the light emitting layer, the average particle diameter of the particles (control of the association conditions in the T-type micromixer), and the film thickness of the light emitting layer were changed as shown in Table 1. Organic EL elements 5 to 16 were produced in the same manner except that.

[Production of Organic EL Element 17]
In the production of the organic EL element 4, the type of the binder used for the production of the light emitting layer is the same as that shown in Example Compound 2-3a except that the weight average molecular weight is changed to the comparative binder 1 of 1,800. An organic EL element 17 was produced.

[Production of Organic EL Element 18]
In the production of the organic EL element 4, the kind of the binder used for the production of the light emitting layer was changed in the same manner except that it was changed to the comparative binder 2 having the structure shown in Exemplary Compound 2-8b and the weight average molecular weight of 110,000. An organic EL element 18 was produced.

[Production of Organic EL Element 19]
In the production of the organic EL element 1, an organic EL element 19 was produced in the same manner except that the film thickness of the light emitting layer was changed from 40 nm to 55 nm.

<< Evaluation of Luminescent Layer Composition Dispersion >>
The dispersion stability of each light emitting layer composition dispersion used for forming the light emitting layer of each organic EL device was evaluated according to the following method.

[Evaluation of dispersion stability]
After preparing the above light emitting layer composition dispersions 1 to 19, each light emitting layer composition dispersion was filled in a transparent sample bottle and sealed, and after 10 minutes in an untreated sample and a constant temperature bath at 40 ° C. About 1 hour later, about the sample preserve | saved for 10 hours, the dispersion liquid state was observed visually and dispersion stability was evaluated according to the following reference | standard.

  In addition, the light emitting layer composition dispersions 1 and 19 are in the same light emitting layer composition and are in a state where each additive is dissolved.

○: The light-emitting layer composition dispersion is almost clear. Δ: The light-emitting layer composition dispersion shows a slight turbidity or increased viscosity of the dispersion, but is at a practically acceptable level. Table 2 shows the results obtained for the composition dispersion, in which sedimentation of the dispersoid occurred or gelled at the bottom.

  As is clear from the results shown in Table 2, the luminescent layer composition dispersion used for the production of the organic EL device of the present invention is superior in dispersion stability of the dispersed particles to the comparative luminescent layer composition dispersion. I understand that The comparative light emitting layer compositions (dispersions) 1 and 19 have a structure in which the composition is completely dissolved and no particles are present.

<< Evaluation of organic EL elements >>
The following evaluation was performed about the produced said organic EL elements 1-19.

[Measurement of power efficiency]
The power efficiency (lm / W) when a constant current of ^2.5 mA / cm ² was applied to each of the produced organic EL elements was measured. In addition, the spectral radiance meter CS-2000 (made by Konica Minolta Sensing) was used for the measurement. The power efficiencies of the organic EL elements 1 to 19 were expressed as relative values with the measured value of the organic EL element 1 being 100. Higher values indicate higher power efficiency.

[Evaluation of heat resistance]
The produced organic EL elements 1 to 19 were stored in an environment of 85 ° C. for 100 hours, and then the power efficiency (lm / W) was measured by the same method as described above. The power efficiency after storage was displayed as a relative value with the power efficiency before storage as 100. The closer the value is to 100, the better the heat resistance of the organic EL element.

[Evaluation of element life]
While the produced organic EL elements 1 to 19 had a luminance at the start of driving of 4000 cd / m ² and were continuously driven at a constant current value, the luminance was measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta Sensing). The change was measured, and the time (LT50) until the measured luminance was halved was determined.

  A relative value was determined by setting the LT50 of the organic EL element 1 to 100, and this was taken as a measure of the element life (continuous drive stability). It shows that it is excellent in element lifetime, so that a numerical value is high.

  The results obtained as described above are shown in Table 3.

  As is apparent from the results shown in Table 3, it can be seen that the organic EL device having the configuration defined in the present invention is stable against heating, exhibits high power efficiency, and has an excellent device life.

DESCRIPTION OF SYMBOLS 1 Flexible support substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode 9 Sealing adhesive 10 Flexible sealing member 20 Organic functional layer 31 Micromixer Equipment 32, 39 Stirrer 33 Poor solvent tank 34, 38 Pump 35 T-type micromixer 36 Particle storage tank 37 Pressure gauge 40 Solute / good solvent tank 100 Organic electroluminescence elements a, b, c Channels

Claims (5)

An organic electroluminescent device having an organic functional layer between the two electrodes and at least one layer, at least one layer of the organic functional layer is a light emitting layer, the light-emitting layer, the particles and the following general formula containing a luminescent material It has a partial structure represented by (1) in the main chain, contains a carrier transportable binder having a weight average molecular weight in the range of 2,000 to 100,000, and has a thickness in the range of 5 to 100 nm. An organic electroluminescence element characterized by the above.
[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. ] The organic electroluminescent device according to claim 1, wherein the carrier transportable binder has a partial structure represented by the following structural formula (A) together with the partial structure represented by the general formula (1). .
The average particle size of particles containing luminescent material (nm), wherein the range der Rukoto of 0.1-1.2 times the thickness of the organic functional layer containing the particles (nm) The organic electroluminescent element according to claim 1 or 2. The weight average molecular weight of the said carrier transportable binder exists in the range of 3,000-80,000, The organic electroluminescent element as described in any one of Claim 1 to 3 characterized by the above-mentioned. It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element as described in any one of Claim 1 to 4, Comprising:
A luminescent material solution in which a luminescent material is dissolved in a good solvent and a partial structure represented by the following general formula (1) dissolved in a poor solvent of the luminescent material in the main chain, and a weight average molecular weight of 2,000 to 100 The carrier transportable binder solution in the range of 1,000 is associated by a liquid phase growth method to prepare a dispersion containing particles containing the light emitting material, and the coating liquid containing the dispersion is applied to emit light. A method for producing an organic electroluminescent element, comprising forming a layer .
[Wherein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. ]