WO2013031794A1 - Organic electroluminescence element, display device, and illumination device - Google Patents

Abstract

An organic electroluminescence element in which at least one organic layer containing a light-emitting layer is sandwiched between a positive electrode and a negative electrode, wherein at least one of the organic layers contains a phosphorescent light-emitting organic metal complex in which a ligand represented by general formula (1) is coordinated on a metal atom.

Description

Organic electroluminescence element, display device and lighting device

The present invention relates to an organic electroluminescence element, a display device, and a lighting device.

Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).
Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
On the other hand, an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. It is an element that emits light by using light emission (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability. For future practical use, it is desired to develop an organic EL element that emits light with high power and efficiency with low power consumption.

For example, Japanese Patent No. 3093796 discloses a technique for doping a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative with a trace amount of a phosphor to improve emission luminance and extend the lifetime of the device. It is disclosed.
Further, an element having an organic light-emitting layer in which 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped to the host compound (for example, Japanese Patent Laid-Open No. 63-264692), 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

As described above, when light emission from an excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of the luminescent excited species is 25%. Therefore, the limit of the external extraction quantum efficiency (η) is set to 5%.

However, since the University of Princeton reported on organic EL devices using phosphorescence emission from excited triplets (MA Baldo et al., Nature, 395, 151-154 (1998)), Research on materials exhibiting phosphorescence is being actively conducted. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so that in principle the luminous efficiency is four times that of excited singlets, and there is a possibility that almost the same performance as cold cathode tubes can be obtained. Therefore, it is attracting attention as a lighting application.
For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds are being studied focusing on heavy metal complexes such as iridium complexes.

Also, the above-mentioned M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), studies have been made using tris (2-phenylpyridine) iridium as a dopant.

In addition, M.M. E. Thompson et al. In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) used L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac), e 0 g, Tetsuo Tsutsui, etc., again The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), the dopant as tris (2-(p-tolyl) pyridine) iridium (Ir _{(ptpy) 3),} tris ( Investigations using benzo [h] quinoline) iridium (Ir (bzq) ₃ ) or the like are being conducted (note that these metal complexes are generally called orthometalated iridium complexes).
In addition, the S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) and Japanese Patent Application Laid-Open No. 2001-247859, etc., attempts have been made to form devices using various iridium complexes.

Although these complexes are also shown below, they are called phosphorescent dopants because they are used after being dispersed and added in the light emitting layer together with the light emitting host material (or simply called the host).
Since the performance (emission efficiency, emission lifetime, emission color, etc.) of organic EL varies greatly depending not only on the dopant but also on the host, the development of both has been energetically performed.
For example, in The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), in order to obtain high luminous efficiency, Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

Also, ortho-metalated complexes in which the central metal of the iridium complex is platinum are attracting attention. With respect to this type of complex, many examples are known in which ligands are characterized.

In any case, the light emission luminance and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. Has a problem that it is lower than the conventional fluorescent element. As described above, phosphorescent high-efficiency light-emitting materials are difficult to improve the light emission life of the device, and it is difficult to shorten the emission wavelength, and the performance that can withstand practical use cannot be sufficiently achieved. Currently.

Here, it is disclosed that a metal complex having phenylpyrazole as a ligand is a light-emitting material having a short emission wavelength (see, for example, Patent Document 1). Further, it is disclosed that a metal complex having phenylimidazole as a ligand is also a light emitting material having a short emission wavelength (see, for example, Patent Documents 2, 3, and 4). Furthermore, there is a disclosure of a metal complex that is a condensed aromatic heterocyclic ligand of an 18π electron system such as a phenanthridine skeleton (see, for example, Patent Documents 5 and 6).

International Publication No. 2004/085450 Pamphlet International Publication 2006/046980 Pamphlet US Patent Publication No. 2006/0251923 US Patent Publication 2011/0057559 Pamphlet International Publication No. 2007/095118 Pamphlet International Publication No. 2008/1568679 Pamphlet

By the way, in recent years, attention has been paid to the low power consumption of organic EL light-emitting elements, and as new applications, application as white backlights for outdoor display devices, illumination light sources for business use, or white light-emitting elements for large-scale lighting devices. It is being considered. In order to use for such applications, continuous light emission for a long time with higher brightness (over 2000 cd / m ² ) than before is required, and further improvement in light emission efficiency and light emission lifetime are problems. It has become.
Conventionally, attention has been focused on improvement of light emission efficiency at relatively medium to low luminance (1000 cd / m ² or less), and improvement of the light emission lifetime has been studied as long as it is. However, when it is assumed that light is emitted at high luminance, it has become clear that the conventional light emitting device cannot obtain sufficient light emission efficiency and the light emission life is greatly deteriorated.

This also applies to the technique described in the above-mentioned prior art document. When a metal complex having phenylpyrazole or a metal complex having phenylimidazole is used as a blue light emitting dopant, high luminance light emission (2000 cd / m ^2). If a high current is applied for the purpose of (super), the light emission efficiency in the high-luminance light emission region is lowered with the conventional element structure, and at the same time, the light emission life is greatly reduced.

The reason why the luminous efficiency in the high-luminance emission region decreases in the conventional device configuration is that the doping amount of the phosphorescent dopant in the light emitting layer is insufficient with respect to the current, and the doping amount of the dopant is increased. Although the luminous efficiency can be improved, this method cannot simultaneously improve the luminous lifetime.

Accordingly, a main object of the present invention is to provide an organic EL element, an illumination device, and a display device using an organic EL element material that exhibits high light emission efficiency in a high luminance light emission region (over 2000 cd / m ² ) and has a long light emission lifetime. Is to provide. Furthermore, another object of the present invention is to provide an organic EL element material that exhibits high luminous efficiency, has a low driving voltage, and has a long emission lifetime in white light emission, and productivity of such an organic EL element material. Is to provide a high wet process.

In order to solve the above problems, according to the present invention,
In an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode,
Organic electroluminescence characterized in that at least one layer of the organic layer contains a phosphorescent organometallic complex in which a ligand represented by the general formula (1) is coordinated to a metal atom. An element is provided.

In general formula (1), ring A, ring B and ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N. Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle. R1 and R2 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group, a silyl group, An arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. Ra, Rb and Rc are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group Represents an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb represents 1 to 3 Represents an integer. R is a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group Represents a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and n0 represents an integer of 1 to 5. Ra, Rb, Rc and R may be the same or different from each other.

According to the present invention, it is possible to provide an organic EL element that exhibits high light emission efficiency in a high-luminance light emission region (over 2000 cd / m ² ), has a low driving voltage, and has a long light emission lifetime.
Further, as a result of the study by the inventors, the present invention can greatly reduce the initial deterioration at the start of element driving, and further reduce the occurrence of dark spots in the light emitting element during element driving. Successful and useful organic EL devices can be provided.
In addition, it is possible to provide a highly efficient white light-emitting illumination device and a white light-emitting light source for a display device using the element.
Furthermore, an organic EL element material useful for an organic EL element using a highly productive wet process can be obtained.

It is the schematic perspective view which showed an example of the structure of the display apparatus of this invention. It is the schematic perspective view which showed an example of the structure of the display part A shown in FIG. It is a schematic perspective view which shows an example of the illuminating device using the organic EL element of this invention. It is a schematic sectional drawing which shows an example of the illuminating device using the organic EL element of this invention.

Hereinafter, preferred embodiments of the present invention will be described.
<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode

In the organic EL device of the present invention, the blue light emitting layer preferably has an emission maximum wavelength of 430 nm to 480 nm, the green light emitting layer has an emission maximum wavelength of 510 nm to 550 nm, and the red light emitting layer has an emission maximum wavelength of 600 nm to 640 nm. A monochromatic light emitting layer in the range is preferable, and the display device of the present invention is preferably configured using such an organic EL element. The organic EL element may be a white light emitting layer formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and the lighting device of the present invention is preferably configured using these.

Each layer constituting the organic EL element of the present invention will be described.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferably adjusted to a range of 2 nm to 5 μm, more preferably adjusted to a range of 2 nm to 200 nm, and particularly preferably adjusted to a range of 10 nm to 20 nm.

For the formation of the light emitting layer, a light emitting dopant or a host compound, which will be described later, is formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. it can.

The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant).

(1) Host compound (also referred to as light-emitting host)
The host compound used in the present invention will be described.
In the present invention, the host compound has a mass ratio of 20% or more among the compounds contained in the light emitting layer, and has a phosphorescence quantum yield of phosphorescence of 0 at room temperature (25 ° C.). Defined as less than 1 compound. The phosphorescence quantum yield is preferably less than 0.01.

As the host compound, one kind of known host compound may be used alone, or a plurality of kinds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic EL element can be further increased. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

The light emitting host used in the present invention may be a low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). Alternatively, one or a plurality of such compounds may be used.

Specific examples of host compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

As the known host compound that can be used in combination, a compound having a hole transporting ability and an electron transporting ability, that prevents the emission of light from becoming longer in wavelength, and has a high Tg (glass transition temperature) is preferable.

Other specific examples of known host compounds include compounds described in the following documents.
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(2) Luminescent dopant The luminescent dopant which concerns on this invention is demonstrated.

As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with high luminous efficiency, the light emitting dopant used in the light emitting layer or the light emitting unit of the organic EL device of the present invention (sometimes simply referred to as a light emitting material) contains the above host compound. At the same time, it is preferable to contain a phosphorescent dopant.

(2.1) Phosphorescent dopant The phosphorescent dopant according to the present invention will be described.
The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

There are two types of light emission of phosphorescent dopants in principle. 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 dopant. The energy transfer type that obtains light emission from the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. Although it is a trap type, in any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

The phosphorescent dopant according to the present invention 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, or a platinum compound (platinum complex compound), Rare earth complexes, most preferably iridium compounds.

Specifically, as the phosphorescent dopant in the embodiment of the present invention, an organic compound having a ligand (also referred to as a ligand compound) represented by the following general formula (1) or general formula (1-1): Metal complexes and organometallic complexes represented by general formula (2), general formula (2-1), or general formula (3) are used.
Hereinafter, details of the organometallic complex according to the present invention will be sequentially described.

(2.1.1) Organometallic complex (also called metal complex compound)
The organometallic complex according to the present invention will be described.
The present inventors paid attention to the organic EL element material used for the light emitting layer of the organic EL element, and examined various organometallic complexes used as a light emitting dopant.

By introducing a specific substituent into the basic skeleton of the organometallic complex, the present inventors suppress the interaction of excitons of the luminescent dopant that causes a decrease in luminous efficiency, and excess electrons or Various complexes were studied under the focus of improving the lifetime degradation due to hole injection.

As a result of study, excitons are generated by recombination of charges on an organometallic complex while suppressing the injection of excessive electrons or holes into the light-emitting dopant by introducing the specific substituent disclosed in the present invention. Further, by suppressing the interaction of excitons of the light emitting dopant, the light emission efficiency was improved, and at the same time, the light emission lifetime of the light emitting element could be extended.

Furthermore, as an unexpected effect, the initial deterioration at the start of element driving can be greatly reduced, and further, the dark spot of the light emitting element has been greatly reduced, and a useful organic EL element is provided. I was able to.

The transition metal complex compound represented by general formula (2), general formula (2-1), or general formula (3) according to the present invention has a plurality of arrangements depending on the valence of the transition metal element represented by M. Although the ligand can have a ligand, all of the ligands may be the same or may have ligands having different structures.

(2.1.2) Conventionally Known Ligands In the present invention, a ligand represented by the general formula (1) or the general formula (1-1) and a conventionally known ligand are defined by those skilled in the art. Can be used together as necessary.

From the viewpoint of preferably obtaining the effects described in the present invention, one organometallic complex is preferably composed of 1 to 2 types of ligands, more preferably 1 type of ligand.

Conventionally known ligands include various known ligands. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag, Inc. Yersin published in 1987, “Organometallic Chemistry-Fundamentals and Applications-”, Lihuabosha, Yamamoto Akio, published in 1982, etc. (including halogen ligands (preferably chlorine ligands), etc. Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).

(2.1.3) Group 8-10 transition metal element of periodic table of elements Phosphorescence emission represented by general formula (2), general formula (2-1) or general formula (3) according to the present invention As a metal used for forming a functional organometallic complex (also referred to as a metal complex or a metal complex compound), a transition metal element belonging to Group 8 to 10 in the periodic table of elements (also simply referred to as a transition metal, specifically Ru, Rh) , Pd, Os, Ir, and Pt.), And iridium is a preferred transition metal element.

(2.1.4) Organometallic Complex Content Layer According to the Present Invention The organometallic complex represented by the general formula (2), general formula (2-1) or general formula (3) according to the present invention emits light. Although described as being contained in the layer, it may be contained in the layer that transports charges (charge transport layer), and may be contained in the hole transport layer or the electron blocking layer.

In addition, when the organometallic complex according to the present invention is contained in the light emitting layer, the efficiency of external extraction quantum efficiency of the organic EL device of the present invention is increased (higher brightness) by using it as a light emitting dopant in the light emitting layer. In addition, it is possible to achieve a longer light emission lifetime.

(2.1.5) Ligand Compound Represented by General Formula (1) First, the ligand compound represented by General Formula (1) according to the present invention will be described.

In the ligand compound having a partial structure represented by the general formula (1), ring A, ring B and ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH. Or represents N.
Benzene ring as 6-membered aromatic hydrocarbon ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, imidazole ring, thiazole ring, etc. as 6-membered aromatic heterocyclic ring, pyridine as 6-membered aromatic heterocyclic ring Ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring and the like.

Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle.
The 6-membered aromatic hydrocarbon ring is a benzene ring, the 5-membered aromatic heterocycle is an oxazole ring, thiazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole ring, thiatriazole ring, 6-membered aromatic heterocycles such as isothiazole ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, etc. Examples of the 5-membered non-aromatic hydrocarbon ring include cyclopentane ring and cyclopentene ring, and examples of the 6-membered non-aromatic hydrocarbon ring include cyclohexane ring, cyclohexene ring, 1,2,3,4-tetrahydronaphthalene ring, 9,9 , 10,10-Tetramethyl-9,10-dihydroanthra 5-membered non-aromatic heterocycle such as pyrrolidine ring, imidazolidine ring, oxazolidine ring, etc., 6-membered non-aromatic heterocycle such as piperidine ring, piperazine ring, morpholyl ring, thiomorpholine ring, tetrahydrofuran ring, And 10H-phenoxazine ring, phenoxathiin ring, chroman-2-one ring, 2,3,4,9-tetrahydro-1H-carbazole ring, and the like.

R1 and R2 are each independently a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group) , An octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, or the like, or a hydrogen atom of these alkyl groups substituted, a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group ( For example, vinyl group, allyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, Dodecyloxy group, etc.), cycloalkyloxy group (for example, Lopentyloxy group, cyclohexyloxy 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.), silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), arylalkyl group (benzyl group, phenethyl group, diphenylmethyl group, 1, 1-diphenylethyl group, 1,2-diphenylethyl group, etc.), aryl group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, Fluorenyl group, phena Tolyl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl 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-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 Quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is nitrogen (Represented by atoms replaced) Noxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), aryloxy group (for example, phenoxy group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyloxy group, anthryloxy group, Azulenyloxy group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyloxy group, pyrenyloxy group, biphenylyloxy group, etc., heteroaryloxy group (for example, pyridyloxy group, pyrimidinyloxy group) , Furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group, triazolyloxy group (for example, 1,2,4-triazol-1-yloxy group, 1, , 3-triazol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, thiazolyloxy group, isoxazolyloxy group, isothiazolyloxy group, furazanyloxy group, thienyloxy group, quinolyloxy group Benzofuryloxy group, dibenzofuryloxy group, benzothienyloxy group, dibenzothienyloxy group, indolyloxy group, carbazolyloxy group, carbolinyloxy group, etc.), non-aromatic hydrocarbon ring group (for example, 1 , 2,3,4-tetrahydronaphthalen-5-yl group, 9,9,10,10-tetramethyl-9,10-dihydroanthracen-2-yl group, biphenylene-1-yl group, etc.), or non-aromatic Group heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, oxazolidyl group, morpholyl group, Omorpholinyl group, tetrahydrofuran-2-yl group, 10H-phenoxazin-3-yl group, phenoxathiin-3-yl group, chroman-2-one-6-yl group, 2,3,4,9-tetrahydro- 1H-carbazol-7-yl group and the like.

Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, A hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group or the like, or a hydrogen atom of these alkyl groups substituted, a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl Group (for example, vinyl group, allyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group) Group, dodecyloxy group, etc.), cycloalkyloxy group (for example, , Cyclopentyloxy group, cyclohexyloxy 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.), silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), arylalkyl group (benzyl group, phenethyl group, diphenylmethyl group, 1, 1-diphenylethyl group, 1,2-diphenylethyl group, etc.), aryl group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, A fluorenyl group, Entanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl 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-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 Quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is nitrogen Shows what is replaced by an atom ), Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), aryloxy group (for example, phenoxy group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyloxy group, anthryloxy group) Group, azulenyloxy group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyloxy group, pyrenyloxy group, biphenylyloxy group, etc.), heteroaryloxy group (for example, pyridyloxy group, for example) Group, pyrimidinyloxy group, furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzoimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group, triazolyloxy group (for example, 1,2,4-triazol-1-yl) Oxy group, 1,2,3-triazol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, thiazolyloxy group, isoxazolyloxy group, isothiazolyloxy group, furazanyloxy group, Thienyloxy, quinolyloxy, benzofuryloxy, dibenzofuryloxy, benzothienyloxy, dibenzothienyloxy, indolyloxy, carbazolyloxy, carbolinyloxy, etc.), non-aromatic Hydrocarbon ring group (for example, 1,2,3,4-tetrahydronaphthalen-5-yl group, 9,9,10,10-tetramethyl-9,10-dihydroanthracen-2-yl group, biphenylene-1-yl Group), or non-aromatic heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, oxazolid group) Group, morpholyl group, thiomorpholinyl group, tetrahydrofuran-2-yl group, 10H-phenoxazin-3-yl group, phenoxathiin-3-yl group, chroman-2-one-6-yl group, 2,3,4 , 9-tetrahydro-1H-carbazol-7-yl group, etc.).

Na and nc represent 1 or 2, and nb represents an integer of 1 to 3.

R represents a halogen atom, a cyano group, or an optionally substituted alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group) , Tetradecyl group, pentadecyl group, etc., or those in which hydrogen atoms of these alkyl groups are substituted), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.) Alkynyl group (eg, ethynyl group, propargyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy 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., silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethyl) Silyl group, etc.), arylalkyl groups (eg benzyl group, phenethyl group, diphenylmethyl group, 1,1-diphenylethyl group, 1,2-diphenylethyl group etc.), aryl groups (eg phenyl group, p-chlorophenyl) Group, mesityl group, tolyl group, xylyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl group (for example, pyridyl group, pyrimidinyl group) Group 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, benzoxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, carbolinyl , A diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a quinoxalinyl group, a pyridazinyl group, a triazinyl group, a quinazolinyl group, a phthalazinyl group, etc.), aryl Oxy groups (eg pheno Xyl group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyloxy group, anthryloxy group, azulenyloxy group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyl Oxy group, pyrenyloxy group, biphenylyloxy group, etc.), heteroaryloxy group (for example, pyridyloxy group, pyrimidinyloxy group, furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzoimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group) Triazolyloxy group (for example, 1,2,4-triazol-1-yloxy group, 1,2,3-triazol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, Thiazolyloki Group, isoxazolyloxy group, isothiazolyloxy group, furazanyloxy group, thienyloxy group, quinolyloxy group, benzofuryloxy group, dibenzofuryloxy group, benzothienyloxy group, dibenzothienyloxy group, indolyloxy group, A carbazolyloxy group, a carbolinyloxy group, etc.), a non-aromatic hydrocarbon ring group, or a non-aromatic heterocyclic group, and n0 represents an integer of 1 to 5.
Ra, Rb, Rc and R may be the same or different from each other.
Further, any two of Ra, Rb, Rc and R may be bonded to form a cyclic structure.

(2.1.6) Ligand Compound Represented by General Formula (1-1) The ligand compound represented by the general formula (1-1) according to the present invention will be described.
Among the ligand compounds represented by the general formula (1) according to the present invention, the ligand compound represented by the general formula (1-1) is preferable.

In the ligand compound represented by the general formula (1-1), ring A, ring B and ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N Represents.
The 6-membered aromatic hydrocarbon ring is a benzene ring, the 5-membered aromatic heterocycle is a 6-membered aromatic heterocycle such as a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, an imidazole ring, an oxazole ring, or a thiazole ring. Examples thereof include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring.

Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle.
The 6-membered aromatic hydrocarbon ring is a benzene ring, the 5-membered aromatic heterocycle is an oxazole ring, thiazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole ring, thiatriazole ring, 6-membered aromatic heterocycles such as isothiazole ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, etc. Examples of the 5-membered non-aromatic hydrocarbon ring include cyclopentane ring and cyclopentene ring, and examples of the 6-membered non-aromatic hydrocarbon ring include cyclohexane ring, cyclohexene ring, 1,2,3,4-tetrahydronaphthalene ring, 9,9 , 10,10-Tetramethyl-9,10-dihydroanthra 5-membered non-aromatic heterocycle such as pyrrolidine ring, imidazolidine ring, oxazolidine ring, etc., 6-membered non-aromatic heterocycle such as piperidine ring, piperazine ring, morpholyl ring, thiomorpholine ring, tetrahydrofuran ring, And 10H-phenoxazine ring, phenoxathiin ring, chroman-2-one ring, 2,3,4,9-tetrahydro-1H-carbazole ring, and the like.

R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, A pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, etc., or a hydrogen atom of these alkyl groups substituted, a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, etc.) ), Alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group) Octyloxy group, dodecyloxy group, etc.), cycloalkyl Xyl group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group) Group, naphthylamino group, 2-pyridylamino group, etc.), silyl group (eg, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), arylalkyl group (eg, benzyl group, phenethyl group, Diphenylmethyl group, 1,1-diphenylethyl group, 1,2-diphenylethyl group, etc.), aryl group (eg, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, Azulenyl group, acenaphthenyl , Fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl 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, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (carbon atoms constituting the carboline ring of the carbolinyl group) One of them is a nitrogen atom Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), aryloxy group (for example, phenoxy group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyl) Oxy group, anthryloxy group, azulenyloxy group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyloxy group, pyrenyloxy group, biphenylyloxy group, etc.), heteroaryloxy group (for example, , Pyridyloxy group, pyrimidinyloxy group, furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzoimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group, triazolyloxy group (for example, 1,2,4-triazol group) -1-yloxy group, 1,2,3-triazol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, thiazolyloxy group, isoxazolyloxy group, isothiazolyloxy group, Frazanyloxy group, thienyloxy group, quinolyloxy group, benzofuryloxy group, dibenzofuryloxy group, benzothienyloxy group, dibenzothienyloxy group, indolyloxy group, carbazolyloxy group, carbolinyloxy group, etc.), non Aromatic hydrocarbon ring groups (for example, 1,2,3,4-tetrahydronaphthalen-5-yl group, 9,9,10,10-tetramethyl-9,10-dihydroanthracen-2-yl group, biphenylene- 1-yl group, etc.), or non-aromatic heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, Sazolidyl group, morpholyl group, thiomorpholinyl group, tetrahydrofuran-2-yl group, 10H-phenoxazin-3-yl group, phenoxathiin-3-yl group, chroman-2-one-6-yl group, 2,3, 4,9-tetrahydro-1H-carbazol-7-yl group, etc.).

At least one of R3 and R4 is a halogen atom, a cyano group, or an optionally substituted alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group) , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc., or those in which hydrogen atoms of these alkyl groups are substituted, cycloalkyl groups (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl groups (for example, vinyl) Group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) ), A cycloalkyloxy group (for example, cyclopenty Oxy group, cyclohexyloxy 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.), silyl groups (eg, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), arylalkyl groups (benzyl group, phenethyl group, diphenylmethyl group, 1,1- Diphenylethyl group, 1,2-diphenylethyl group, etc.), aryl group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group) , Phenanthryl group, Ndenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl 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, quinolyl group , Benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl) Group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), aryloxy group (for example, phenoxy group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyloxy group, anthryloxy group, azulenyloxy group) Group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyloxy group, pyrenyloxy group, biphenylyloxy group, etc., heteroaryloxy group (for example, pyridyloxy group, pyrimidinyloxy group, Furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group, triazolyloxy group (for example, 1,2,4-triazol-1-yloxy group, 1,2,3-tri Sol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, thiazolyloxy group, isoxazolyloxy group, isothiazolyloxy group, furazanyloxy group, thienyloxy group, quinolyloxy group, benzofuryl Oxy group, dibenzofuryloxy group, benzothienyloxy group, dibenzothienyloxy group, indolyloxy group, carbazolyloxy group, carbolinyloxy group, diazacarbazolyloxy group, quinoxalinyloxy group, Pyridazinyloxy group, triazinyloxy group, quinazolinyloxy group, phthalazinyloxy group, etc.), non-aromatic hydrocarbon ring group (for example, 1,2,3,4-tetrahydronaphthalene-5 Yl group, 9,9,10,10-tetramethyl-9,10-dihydroanthracene-2-y Group, biphenylene-1-yl group, etc.) or non-aromatic heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, oxazolidyl group, morpholyl group, thiomorpholinyl group, tetrahydrofuran-2-yl group, 10H-phenoxazine-3- Yl group, phenoxathiin-3-yl group, chroman-2-one-6-yl group, 2,3,4,9-tetrahydro-1H-carbazol-7-yl group and the like.
R3 and R4 may be the same or different.

Ra, Rb, Rc and Rd are each independently a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group (eg, 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., or those in which hydrogen atoms of these alkyl groups are substituted, cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.) An alkenyl group (for example, vinyl group, allyl group, etc.), an alkynyl group (for example, ethynyl group, propargyl group, etc.), an alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, Octyloxy group, dodecyloxy group, etc.), cycloalkyloxy group For example, cyclopentyloxy group, cyclohexyloxy group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthyl group) Amino group, 2-pyridylamino group, etc.), silyl group (eg, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), arylalkyl group (benzyl group, phenethyl group, diphenylmethyl group, 1 , 1-diphenylethyl group, 1,2-diphenylethyl group, etc.), aryl group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group) , Fluoreni Group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl 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-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, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group) With one replaced by a nitrogen atom Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), aryloxy group (for example, phenoxy group, p-chlorophenoxy group, mesityloxy group, tolyloxy group, xylyloxy group, naphthyloxy group, anthracene group) Tolyloxy group, azulenyloxy group, acenaphthenyloxy group, fluorenyloxy group, phenanthryloxy group, indenyloxy group, pyrenyloxy group, biphenylyloxy group, etc.), heteroaryloxy group (for example, pyridyloxy group) , Pyrimidinyloxy group, furyloxy group, pyrrolyloxy group, imidazolyloxy group, benzoimidazolyloxy group, pyrazolyloxy group, pyrazinyloxy group, triazolyloxy group (for example, 1,2,4-triazol-1-ylo Si group, 1,2,3-triazol-1-yloxy group, etc.), oxazolyloxy group, benzoxazolyloxy group, thiazolyloxy group, isoxazolyloxy group, isothiazolyloxy group, furazanyloxy group, Thienyloxy, quinolyloxy, benzofuryloxy, dibenzofuryloxy, benzothienyloxy, dibenzothienyloxy, indolyloxy, carbazolyloxy, carbolinyloxy, etc.), non-aromatic carbonization Hydrogen ring groups (for example, 1,2,3,4-tetrahydronaphthalen-5-yl group, 9,9,10,10-tetramethyl-9,10-dihydroanthracen-2-yl group, biphenylene-1-yl Group), or non-aromatic heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, oxazolidyl group) Morpholyl group, thiomorpholinyl group, tetrahydrofuran-2-yl group, 10H-phenoxazin-3-yl group, phenoxathiin-3-yl group, chroman-2-one-6-yl group, 2,3,4,9 -Tetrahydro-1H-carbazol-7-yl group and the like.

na and nc represent 1 or 2, and nb and nd represent an integer of 1 to 3.
Ra, Rb, Rc and Rd may be the same or different from each other.
Arbitrary two of Ra, Rb, Rc and Rd may be bonded to form a cyclic structure.

(2.1.7) Compound Represented by General Formula (2) The phosphorescent organometallic complex represented by the general formula (2) according to the present invention will be described.
The phosphorescent organometallic complex having the compound represented by the general formula (1) as a ligand of the present invention is a compound represented by the general formula (2).

Ring A, ring B and ring C represent a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N.
Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or a cyano group Or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryloxy group, It represents a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl. Represents a group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb represents an integer of 1 to 3.
R is a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group Represents a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and n0 represents an integer of 1 to 5.
Ra, Rb, Rc and R may be the same or different from each other.

Detailed description of ring A, ring B, ring C, R1, R2, Ra, Rb, Rc, R, and Cy is the same as that in the description of general formulas (1) and (1-1).

L is one or more of monoanionic bidentate ligands coordinated to M.
Examples of monoanionic bidentate ligands are shown below, but the present invention is not limited thereto.

M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table.
Specific metal atoms include Ru, Rh, Pd, Os, Ir, and Pt.

M represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n.

(2.1.8) Compound Represented by General Formula (2-1) The phosphorescent organometallic complex represented by the general formula (2-1) according to the present invention will be described.
As the phosphorescent organometallic complex represented by the general formula (2) of the present invention, a compound represented by the general formula (2-1) is preferable.

Ring A, ring B and ring C represent a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N.
Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle.
R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group , A silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and at least one of R3 and R4 is a halogen atom Atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryl Oxy group, heteroaryloxy group, non-aromatic hydrocarbon ring group or non- It represents an aromatic heterocyclic group. R3 and R4 may be the same or different.
Ra, Rb, Rc and Rd are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, aryl An alkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group, or a non-aromatic heterocyclic group is represented, na and nc represent 1 or 2, and nb and nd represent an integer of 1 to 3.
Ra, Rb, Rc and Rd may be the same as or different from each other.
L is one or more of monoanionic bidentate ligands coordinated to M.
M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table.
m represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n.

Ring A, ring B, ring C, R1, R2, R3, R4, Ra, Rb, Rc, Rd, L, M, m, n, and Cy are described in detail in formulas (1) and (1-1). , (2) in the description.

(2.1.9) Compound Represented by General Formula (3) The phosphorescent organometallic complex represented by the general formula (3) according to the present invention will be described.
As the phosphorescent organometallic complex represented by the general formula (2) of the present invention, a compound represented by the general formula (3) is more preferable.

Ring A and Ring C represent a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, or non-aromatic hydrocarbon Represents a ring or a non-aromatic heterocyclic ring.
R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group , A silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and at least one of R3 and R4 is a halogen atom Atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryl Oxy group, heteroaryloxy group, non-aromatic hydrocarbon ring group or non- It represents an aromatic heterocyclic group. R3 and R4 may be the same or different.
Ra, Rb, Rc and Rd are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, aryl Represents an alkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb and nd represent an integer of 1 to 3.
Ra, Rb, Rc and Rd may be the same as or different from each other.
L is one or more of monoanionic bidentate ligands coordinated to M.
M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table.
m represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n.

A detailed description of ring A, ring C, R1, R2, R3, R4, Ra, Rb, Rc, Rd, L, M, m, n, and Cy is given by general formulas (1), (1-1), (2 ).

(2.1.10) Specific Examples Hereinafter, specific examples of the organometallic complex represented by the general formula (2), (2-1) or (3) according to the present invention will be shown. It is not limited.

These metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), Organic Letter, vol8, No. 3, pp. 415 to 418 (2006), and further by applying methods such as references described in these documents.

Hereinafter, synthesis examples of the metal complex according to the present invention will be shown, but the present invention is not limited thereto.

(2.1.11) Synthesis Example of Compound (Evaluation Compound 1) Represented by General Formula (2-1) The following shows synthesis examples of typical compounds.

<Step 1: Synthesis of 3,5-diisopropyl- [1,1'-biphenyl] -4-amine>

In a 500 ml four-headed flask, 44.3 g (250 mmol) of 2,6-diisopropylaniline and 100 ml of DMF were placed, and a thermometer was attached. To this, 44.5 g (250 mmol) of N-bromosuccinimide was added with stirring, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, 300 ml of ethyl acetate and 100 ml of water were added to the reaction solution and dispersed at room temperature for 10 minutes. After separating the aqueous layer, the ethyl acetate layer was washed twice with water. It was dehydrated and dried over magnesium sulfate and concentrated under reduced pressure to obtain 60 g of 4-bromo-2,6-diisopropylaniline (yield 94%).

Under a nitrogen atmosphere, a 500 ml four-headed flask was charged with 60 g (234 mmol) of 4-bromo-2,6-diisopropylaniline, 61 g (500 mmol) of phenylboronic acid, 200 ml of toluene, and 50 ml of ethanol, and a condenser tube was attached. To this, 110 g (800 mmol) of potassium carbonate was added, and nitrogen gas was blown in for about 1 hour to substitute with nitrogen. Next, 10.4 g (9 mmol) of tetrakistriphenylphosphine palladium (0) complex was added, and the reaction was carried out under heating and reflux for 10 hours. The reaction solution was cooled to room temperature, insolubles were removed by filtration, washed with brine to neutrality, and concentrated under reduced pressure.
The crude product obtained after concentration was purified by silica gel column chromatography (hexane: ethyl acetate = 90: 10 to 70:30), and 3,5-diisopropyl- [1,1′-biphenyl] -4-amine 44 0.4 g (yield 75%) was obtained.

<Step 2: Synthesis of 3-bromo-N- (3,5-diisopropyl- [1,1'-biphenyl] -4-yl) benzamide>

Into a 500 ml four-headed flask, 44.4 g (175 mmol) of 3,5-diisopropyl- [1,1′-biphenyl] -4-amine, 30.3 g (300 mmol) of triethylamine and 200 ml of toluene were placed, and a thermometer was attached. To this, 39.5 g (180 mmol) of 3-bromobenzoyl chloride was added with stirring, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, 200 ml of water was added, stirred at room temperature for 1 hour, filtered and washed with water. The obtained crystals were dried by heating at 70 ° C. overnight, and 64.9 g (yield 85%) of 3-bromo-N- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) benzamide was obtained. Obtained.

<Step 3: Synthesis of 2- (3-bromophenyl) -1- (3,5-diisopropyl- [1,1'-biphenyl] -4-yl) -1H-imidazole>

Into a 300 ml four-headed flask was placed 64.9 g (149 mmol) of 3-bromo-N- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) benzamide and 71 g (600 mmol) of phosphoryl chloride. A tube and a thermometer were attached. This was heated gradually and reacted at reflux temperature for 6 hours. After completion of the reaction, the volatile component was distilled off under reduced pressure, and a soot-like material mainly composed of 3-bromo-N- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) benzimidoyl chloride was obtained. Obtained.
To this, 100 ml of dehydrated tetrahydrofuran was added, and then a mixture of 60 g (450 mmol) of aminoacetal and 45.5 g (450 mmol) of triethylamine was added dropwise at room temperature over 1 hour. After completion of the addition, the mixture was reacted at room temperature for 2 hours. After completion of the reaction, 200 ml of ethyl acetate and 100 ml of water were added to the reaction solution and dispersed at room temperature for 1 hour. After separating the aqueous layer, the ethyl acetate layer was washed with water three times. Dehydrated and dried over magnesium sulfate and concentrated under reduced pressure to give 3-bromo-N ′-(2,2-diethoxyethyl) -N- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) benzimidamide 82 g (100% yield) of crude product was obtained.
In a 500 ml four-headed flask, 82 g of the benzimidamide crude product and 300 ml of toluene were placed and dissolved. Next, 38 g (388 mmol) of phosphoric acid and 50 ml of water were added and gradually heated. When the reflux temperature was reached, the reaction was continued at the reflux temperature for 2 hours. Thereafter, the produced ethanol and water were distilled off azeotropically and reacted at the reflux temperature for another 2 hours. Again, the produced ethanol and water were distilled off azeotropically, and the reaction was further terminated at the reflux temperature for 2 hours. An 80 ml aqueous solution of 56 g (1.0 mol) of potassium hydroxide was added to the reaction solution to make it alkaline. It was dispersed for about 1 hour and filtered with a filter paper covered with diatomaceous earth. The aqueous layer was separated, washed three times with water, then dehydrated and dried over magnesium sulfate, and concentrated under reduced pressure to obtain 67 g of a crude product (yield 98%).
The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 90: 10 to 70:30) to give 2- (3-bromophenyl) -1- (3,5-diisopropyl- [1,1 49.3 g (yield 72%) of '-biphenyl] -4-yl) -1H-imidazole was obtained.

<Step 4: 1- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) -2- (2 ′, 6′-dimethyl- [1,1′-biphenyl] -3-yl) Synthesis of -1H-imidazole>

In a 100 ml three-headed flask under a nitrogen atmosphere, 4.59 g (10 mmol) of 2- (3-bromophenyl) -1- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) -1H-imidazole ), 1.65 g (11 mmol) of phenylboronic acid, 0.29 g (0.5 mmol) of bis (dibenzylideneacetone) palladium (0), 0.91 g (1.0 mmol) of S-Phos, and 40 ml of toluene, Attached. To this, 4.3 g (20 mmol) of potassium phosphate and 5 ml of water were added, and nitrogen gas was blown in for about 1 hour to substitute nitrogen. Subsequently, it reacted under heating reflux for 15 hours. The reaction solution was cooled to room temperature, insolubles were removed by filtration, washed with brine to neutrality, and concentrated under reduced pressure. The composition obtained after concentration was purified by silica gel column chromatography (hexane: ethyl acetate = 90: 10 to 70:30) to give 1- (3,5-diisopropyl- [1,1′-biphenyl] -4. There was obtained 3.97 g (82% yield) of -yl) -2- (2 ′, 6′-dimethyl- [1,1′-biphenyl] -3-yl) -1H-imidazole.

<Step 5: Synthesis of Complex A>

1- (3,5-Diisopropyl- [1,1′-biphenyl] -4-yl) -2- (2 ′, 6′-dimethyl- [1,1′-biphenyl] -3-yl under nitrogen atmosphere ) To a solution of 1.21 g (2.5 mmol) of -1H-imidazole in 12 ml of 2-ethoxyethanol, iridium chloride trihydrate, 350 mg (1.0 mmol) and 4 ml of water were added, and 6% under nitrogen atmosphere. Reflux for hours. The reaction solution was cooled, 15 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol and dried to obtain 1.04 g (yield 87%) of complex A.

<Step 6: Synthesis of Complex B>

In a nitrogen atmosphere, 956 mg (0.40 mmol) of complex A and 2.0 g of sodium carbonate were suspended in 30 ml of 2-ethoxyethanol. To this suspension, 0.5 g (5.0 mmol) of acetylacetone was added and refluxed for 5 hours under a nitrogen atmosphere. After cooling the reaction solution, a solid substance was collected by filtration under reduced pressure. Subsequently, when sodium carbonate and inorganic salt were removed by washing with water, complex B was obtained as lemon yellow crystals. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and after drying, 705 mg (yield 70%) of Complex B was obtained.

<Step 7: Synthesis of Evaluation Compound 1>

Complex B, 700 mg (0.55 mmol) and 1- (3,5-diisopropyl- [1,1′-biphenyl] -4-yl) -2- (2 ′, 6′-dimethyl- [1] under nitrogen atmosphere , 1′-biphenyl] -3-yl) -1H-imidazole (824 mg, 1.7 mmol) was suspended in 30 ml of ethylene glycol. The reaction was carried out in a nitrogen atmosphere at a reaction temperature of 180 to 190 ° C. for 2 hours, and when the disappearance of complex B was confirmed, the reaction was completed. The reaction solution was cooled, 30 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and after drying, a yield of 770 mg (yield 85%) was obtained. This crude product was dissolved in a small amount of hexane-tetrahydrofuran = 1: 1 and purified by silica gel column chromatography (hexane-tetrahydrofuran = 1: 1) to obtain 720 mg (yield 80%) of the evaluation compound 1.

It was confirmed by MASS and 1H-NMR that the purified compound was the target product.
1H-NMR (400 MHz, deuterated tetrahydrofuran)
(Chemical shift δ, peak shape, proton number)
: Δ = 0.98 (d, 9H, CH3-),
1.03 (d, 9H, CH3-),
1.11 (d, 9H, CH3-),
1.29 (d, 9H, CH3-),
1.81 (s, 9H, CH3-),
1.90 (s, 9H, CH3-),
2.50 (m, 3H,> CH-),
2.93 (m, 3H,> CH-),
6.00 (d, 3H,> CH of imidazole ring)
6.31 (d, 3H,> CH of benzene ring),
6.80 (m, 6H,> CH of benzene ring),
6.86 (m, 3H,> CH of benzene ring),
6.92 (m, 3H,> CH of benzene ring),
6.95 (d, 3H,> CH of imidazole ring)
7.08 (s, 3H,> CH of benzene ring),
7.30 (m, 3H,> CH of benzene ring),
7.35-7.45 (m, 18H, benzene group> CH)

The PL emission maximum wavelength in the solution of the exemplary compound measured using Hitachi F-4500 was 465 nm (T = 77 K, in 2-methyltetrahydrofuran) and 473 nm (room temperature, in methylene chloride).

Other compounds of the present invention can also be synthesized with good yield by using the same synthesis method as in the above synthesis examples and using appropriate raw materials.

(2.1.12) Combined use with conventionally known phosphorescent dopant In the present invention, the above-described phosphorescent dopant and a conventionally known phosphorescent dopant may be used in combination. The following compounds are mentioned.

(2.2) Fluorescent dopant (also called fluorescent compound)
Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, or rare earth complex phosphors.

Next, an injection layer, a blocking layer, an electron transport layer and the like used as a constituent layer of the organic EL element of the present invention will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists 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. May be.

An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Representative phthalocyanine buffer layer, oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polymer buffer layer using conductive polymer such as polyaniline (emeraldine) or polythiophene, tris (2-phenylpyridine) ) Orthometalated complex layers represented by iridium complexes and the like. Similarly, azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole injection material.

The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm, although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.

The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.

Moreover, the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.

The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

The hole blocking layer contains the carbazole derivative, carboline derivative, or diazacarbazole derivative (shown in which any one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced by a nitrogen atom). It is preferable to contain.

In the present invention, when the organic EL element has a plurality of light emitting layers having different emission colors, it is preferable that the light emitting layer whose emission maximum wavelength is the shortest is the closest to the anode among all the light emitting layers. In such a case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the layer. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.

(1) A keyword using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), which is molecular orbital calculation software manufactured by Gaussian, USA. The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

(2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.

Moreover, the structure of the hole transport layer described later can be used as an electron blocking layer as necessary. The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

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

The hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. Similarly, azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole transport material.

The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary 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 ′ Di (4-methoxyphenyl) -4,4′-diaminobiphenyl; N, N, N ′, N′-tetraphenyl-4,4′-diaminodiphenyl ether; 4,4′-bis (diphenylamino) quadriphenyl N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino -(2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two 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-4-308 No. 88, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units are linked in a starburst type (MTDATA).

Further, 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 addition, cyclometalated complexes and orthometalated complexes such as copper phthalocyanine and tris (2-phenylpyridine) iridium complex can also be used as the hole transport material.

Also, JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. The thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 nm to 200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

It is also possible to use a hole transport layer having a high p property doped with impurities. Examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. Appl. Phys. 95, 5773 (2004), and the like.

In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

Hereinafter, specific examples of compounds preferably used for forming the hole injection layer and the hole transport layer of the organic EL device of the present invention will be given, but the present invention is not limited to these.

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

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 light emitting layer on the cathode side is injected from the cathode. Any material may be used as long as it has a function of transferring electrons to the light-emitting layer, and any material known in the art can be selected and used alone or in combination. For example, nitro-substituted fluorene Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.

Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. 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.

Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as an electron transport material.

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 transporting material. In addition, the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. The thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 nm to 200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

It is also possible to use an electron transport layer having a high n property doped with impurities. 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.

In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be produced.

Hereinafter, specific examples of conventionally known compounds (electron transport materials) preferably used for forming the electron transport layer of the white organic EL device of the present invention will be given, but the present invention is not limited thereto.

"anode"
As the anode in the organic EL element, 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 pattern having a desired shape 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.

Alternatively, when a material that can be applied such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method can 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 selected in the range of 10 nm to 1000 nm, preferably 10 nm 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 nm to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

In addition, a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 nm to 20 nm. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
As a 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, there is no particular limitation on the type of glass, plastic, etc., and it 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. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and 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, polysulfone , Polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, cyclone resins such as Arton (trade name JSR) or Appel (trade name Mitsui Chemicals) Etc.

On the surface of the resin film, an inorganic film, an organic film or a hybrid film of both may be formed. 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 further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

The material for forming the barrier 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 can be used. 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 | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

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

The external extraction efficiency at room temperature of light emission of the organic EL element of the present invention 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.

Also, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

The sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. 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 ml / (m ² · 24 h · atm) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 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 photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. 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 adhesively cured from room temperature to 80 ° C. is preferable. A desiccant may be dispersed in the adhesive.

Application of the adhesive to the sealing portion may be performed using a commercially available dispenser or may be printed like screen printing.

In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be a material having 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 method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. 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.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the 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, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light undergoes total reflection between the light and the light, and the light is guided through the transparent electrode or the light emitting layer.

As a method of improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

In the present invention, by combining these means, it is possible to obtain an element having higher brightness or durability.

When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the efficiency of taking out the light from the transparent electrode to the outside increases as the refractive index of the medium decreases.

Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

Also, the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

It is desirable that the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

However, by making the refractive index distribution a two-dimensional distribution, the light traveling in all directions is diffracted, and the light extraction efficiency is increased.

As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

The arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.

As an example of a microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

As the condensing sheet, it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

Further, in order to control the light emission angle from the light emitting element, a light diffusion plate / film may be used in combination with the light collecting sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Method for Manufacturing Organic EL Element >>
As an example of the method for producing the 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 / hole blocking layer / electron transport 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 method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm.

Next, organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.

As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above. In view of the above, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

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 DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

After forming these layers, 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.

It is also possible to reverse the production order and produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.

In the organic EL device of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary. 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.

The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<Display device>
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention. Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here.

In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like. In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.
The configuration of the organic EL element included in the display device is selected from the organic EL elements of the present invention as necessary. Moreover, the manufacturing method of an organic EL element is as having shown in the one aspect | mode of the manufacturing method of the organic EL element of the above-mentioned this invention.
When a DC voltage is applied to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the anode as + and the cathode as-polarity. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. When an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

The multicolor display device can be used as a display device, a display, and various light emission sources. In display devices and displays, full-color display is possible by using three types of organic EL elements of red, green, and blue light emission.
Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
Light emitting sources include household 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, light sources for optical sensors, etc. The present invention is not limited to these examples.

Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic perspective view showing an example of the configuration of a display device composed of the organic EL element of the present invention, which displays image information by light emission of the organic EL element, for example, a display such as a mobile phone FIG.
As shown in FIG. 1, the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
The control unit B is electrically connected to the display unit A.
The control unit B sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. As a result, each pixel sequentially emits light according to the image data signal for each scanning line by the scanning signal, and the image information is displayed on the display unit A.

FIG. 2 is a schematic diagram of the display unit A shown in FIG.
The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
The main members of the display unit A will be described below.
FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material. The scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are not shown).
When a scanning signal is transmitted from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region in the same substrate on the same substrate.

《Lighting device》
The lighting device of the present invention will be described. The lighting device of the present invention has the organic EL element of the present invention.

The organic EL element of the present invention may be used as an organic EL element having a resonator structure, and the purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However It is not limited to these.
Moreover, you may use for the said use by making a laser oscillation. Furthermore, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).
The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. By using two or more kinds of the organic EL elements of the present invention having different emission colors, a full-color display device can be produced.

The organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green and blue, or two using the complementary colors such as blue and yellow, blue green and orange. The thing containing the light emission maximum wavelength may be used.
In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.

It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, an electrode film or the like can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is improved.
According to this method, unlike the white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.
There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known light emitting materials may be selected and combined to be whitened.

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.
The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material around LC0629B) is applied, and this is overlaid on the cathode to be in close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and as shown in FIG. 3 and FIG. Can be formed.
FIG. 3 shows a schematic diagram of the illumination device.
As shown in FIG. 3, the organic EL element 101 is covered with a glass cover 102. The sealing operation with the glass cover 102 is performed in a glove box (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere.
FIG. 4 shows a cross-sectional view of the lighting device.
As shown in FIG. 4, the cathode 105 and the organic EL layer 106 are formed on a glass substrate 107 with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Moreover, the structure of the compound used in an Example is shown below.

<< Production of Blue Light-Emitting Organic EL Element 1-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, 200 mg of OC-6 as a host compound is put into another molybdenum resistance heating boat, 100 mg of Comparative Compound 1 as a dopant compound is put into another molybdenum resistance heating boat, and 200 mg of the electron transport material 1 is put into another molybdenum resistance heating boat. Further, 200 mg of the electron transport material 2 was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the hole injection material 1 is heated and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection layer having a thickness of 20 nm was provided.

Further, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the hole transport material 1 is energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second. Then, a hole transport layer having a thickness of 20 nm was provided.

Further, the hole transport layer was heated by energizing the heating boat containing OC-6 as a host compound and Comparative Compound 1 as a dopant compound, respectively, at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. A 40 nm-thick luminescent layer was provided by co-evaporation. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Furthermore, the heating boat containing the electron transport material 1 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

Further, the heating boat containing the electron transporting material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transporting layer having a thickness of 20 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Subsequently, lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 1-1 was produced.

<< Production of Blue Light-Emitting Organic EL Elements 1-2 to 1-28 >>
In the production of the organic EL element 1-1, various materials were changed to the compounds shown in Table 1.
Otherwise, the organic EL elements 1-2 to 1-28 were produced in the same manner.

<< Evaluation of Organic EL Elements 1-1 to 1-28 >>
When evaluating the obtained organic EL elements 1-1 to 1-28, the non-light-emitting surface of each organic EL element after fabrication was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. In addition, an epoxy photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material to the periphery, and this is stacked on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed to form an illumination device as shown in FIGS. 3 and 4, and the illumination device was evaluated as a sample.
Each sample thus formed was evaluated as follows. The evaluation results are shown in Table 2.

(1) taking out at room temperature the quantum efficiency organic EL elements (about 23 ~ 25 ° C.), and a constant current drive with a current giving an initial brightness ^{2000cd / m 2, 4000cd / m} 2, immediately after the start of light emission drive current [mA The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance.
The external extraction quantum yield was expressed as a relative value with the light emission luminance of the organic EL element 1-1 as 100.

(2) driving voltages room temperature the organic EL element (about 23 ~ 25 ° C.), and a constant current drive with a current giving an initial brightness ^{2000cd / m 2, 4000cd / m} 2, the light emission immediately after the start of the driving current [mA] The drive voltage was measured by measuring. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance.
The drive voltage was expressed as a relative value where the drive voltage of the organic EL element 1-1 was 100.
Drive voltage = (drive voltage of each element / drive voltage of the organic EL element 1-1) × 100
A smaller drive voltage value indicates a lower drive voltage.

(3) Luminescence half-life The luminescence half-life was evaluated according to the measurement method shown below.
It is necessary for each organic EL element to be driven at a constant current at room temperature (about 23 to 25 ° C.) and with a current that gives an initial luminance of 2000 cd / m ² so that the emission luminance becomes 1/2 of the initial luminance (1000 cd / m ² ). Time (half-life) was determined and used as a measure of the luminescence half-life.
The light emission half-life was expressed as a relative value where the half-life of the organic EL device 1-1 was 100.

(4) Initial degradation Initial degradation was evaluated according to the measurement method shown below.
At the time of measuring the light emission half-life, the time required for the light emission luminance of each organic EL element to reach 90% (1800 cd / m ² ) of the initial luminance was measured, and this was used as a measure of initial deterioration. The initial deterioration value was calculated based on the following formula.
Initial degradation value = (luminance 90% arrival time / hr of organic EL element 1-1) / (luminance 90% arrival time / hr of each organic EL element) × 100
That is, the smaller the initial deterioration value, the smaller the initial deterioration.

(5) Dark Spot The light emitting surface when each organic EL element was continuously lit by driving at constant current with a current giving an initial luminance of 2000 cd / m ² at room temperature was visually evaluated. In the visual evaluation, 10 observers were randomly selected, and the number of people who confirmed dark spots in each element after 10 hours of continuous lighting time was used as an evaluation index. “X” when the number of confirmed dark spots is 5 or more, “△” when the number of confirmed dark spots is 1 to 4, and “○” when the number of confirmed dark spots is 0 It was.

(6) Summary As shown in Table 2, the organic EL elements 1-9 to 1-28 of the present invention have higher external extraction quantum efficiency than the organic EL elements 1-1 to 1-8 of the comparative example, It can be seen that the initial luminance degradation is small and the lifetime is accordingly increased. Further, it can be seen that in the organic EL elements 1-9 to 1-28 of the present invention, the generation of dark spots is also suppressed.

<< Preparation of Blue Light-Emitting Organic EL Element 2-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under conditions of 30 seconds and then dried at 200 ° C. for 1 hour to form a first hole transport layer having a thickness of 30 nm.

The substrate was transferred to a nitrogen atmosphere, and a thin film was formed on the first hole transport layer by spin coating using a solution of 50 mg of hole transport material 3 dissolved in 10 ml of toluene at 1000 rpm for 30 seconds. Formed. Further, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to form a second hole transport layer.

On this second hole transport layer, a solution obtained by dissolving 100 mg of the host material 1 as a host compound and 15 mg of the comparative compound 1 as a dopant compound in 10 ml of butyl acetate is spinned at 600 rpm for 30 seconds. A thin film was formed by a coating method. Further, ultraviolet light was irradiated for 15 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to obtain a light emitting layer having a thickness of about 70 nm.

Next, a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution in which 50 mg of the electron transport material 3 was dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 30 nm.

Subsequently, this substrate was fixed to a substrate holder of a vacuum evaporation apparatus, and after the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride was evaporated to form a cathode buffer layer, and further, aluminum 110 nm. The organic EL element 2-1 was produced by forming a cathode by vapor deposition.

<< Production of Blue Light-Emitting Organic EL Elements 2-2 to 2-28 >>
In the production of the organic EL element 1-1, various materials were changed to the compounds shown in Table 3.
Otherwise, the organic EL elements 2-2 to 2-28 were produced in the same manner.

<< Evaluation of organic EL elements 2-1 to 2-28 >>
When evaluating the obtained organic EL elements 2-1 to 2-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, emission half-life, initial degradation and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL element 2-1 was evaluated. It was expressed as a relative value with a value of 100. The evaluation results are shown in Table 4.

As shown in Table 4, the organic EL elements 2-9 to 2-28 of the present invention have a higher external extraction quantum efficiency and an initial luminance deterioration as compared with the organic EL elements 2-1 to 2-8 of the comparative example. It can be seen that is small and has a long life. Furthermore, it can be seen that in the organic EL elements 2-9 to 2-28 of the present invention, the generation of dark spots is also suppressed.

<< Production of White Light-Emitting Organic EL Element 3-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of OC-6 as a host compound was placed, and in another molybdenum resistance heating boat, 100 mg of Comparative Compound 1 as the first dopant compound was placed. 100 mg of Ir-9 was added as a dopant compound, 200 mg of the electron transport material 1 was placed in another molybdenum resistance heating boat, and 200 mg of the electron transport material 2 was placed in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the hole injection material 1 is heated and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection layer having a thickness of 20 nm was provided.

Further, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the hole transport material 1 is energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second. Then, a hole transport layer having a thickness of 20 nm was provided.

Further, the heating boat containing OC-6 as a host compound, Comparative compound 1 as a first dopant compound and Ir-9 as a second dopant compound was heated by energization, and the deposition rate was 0.2 nm, respectively. A light emitting layer having a thickness of 40 nm was provided by co-evaporation on the hole transport layer at a rate of 0.020 nm / second, 0.020 nm / second, and 0.0010 nm / second. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Furthermore, the heating boat containing the electron transport material 1 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

Further, the heating boat containing the electron transporting material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transporting layer having a thickness of 20 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Subsequently, lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 3-1 was produced.

<< Preparation of white light-emitting organic EL elements 3-2 to 3-28 >>
In the production of the organic EL element 3-1, various materials were changed to the compounds shown in Table 5.
Otherwise, the organic EL elements 3-2 to 3-28 were produced in the same manner.

<< Evaluation of organic EL elements 3-1 to 3-28 >>
When evaluating the obtained organic EL elements 3-1 to 3-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, light emission half-life, initial deterioration and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL element 3-1 was evaluated. It was expressed as a relative value with a value of 100. The evaluation results are shown in Table 6.

As shown in Table 6, the organic EL elements 3-9 to 3-28 of the present invention have a higher external extraction quantum efficiency than the organic EL elements 3-1 to 3-8 of the comparative example, and the initial luminance degradation. It can be seen that is small and has a long life. Furthermore, it can be seen that in the organic EL elements 3-9 to 3-28 of the present invention, the generation of dark spots is also suppressed.

<< Preparation of white light-emitting organic EL element 4-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of OC-1 as a host compound was placed, and in another molybdenum resistance heating boat, 100 mg of Comparative Compound 1 as a first dopant compound was placed. 100 mg of Ir-9 as a dopant compound, 100 mg of Ir-2 as a third dopant compound in another molybdenum resistance heating boat, 200 mg of the electron transport material 1 in another resistance heating boat made of molybdenum, 200 mg of electron transport material 2 is put into a resistance heating boat made of molybdenum and vacuum steamed. It was attached to the device.

Next, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the hole injection material 1 was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The hole injection layer was provided.

Further, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the hole transport material 1 is energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second. Then, a hole transport layer having a thickness of 20 nm was provided.

Further, the heating boat containing OC-1 as a host compound and comparative compound 1 as a first dopant compound was heated by energization, and the positive rate was increased at a deposition rate of 0.2 nm / second and 0.020 nm / second, respectively. A blue light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Further, the heating boat containing OC-1 as the host compound, Ir-9 as the second dopant compound, and Ir-2 as the third dopant compound was heated by energization, and the deposition rate was 0.2 nm, respectively. / Yellow, 0.0010 nm / second, and 0.010 nm / second were co-evaporated on the blue light emitting layer to provide a yellow light emitting layer having a thickness of 20 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Furthermore, the heating boat containing the electron transport material 1 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

In addition, the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 20 nm. Provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Subsequently, lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 3-1 was produced.

<< Preparation of white light-emitting organic EL elements 4-2 to 4-28 >>
In the production of the organic EL element 4-1, various materials were changed to the compounds shown in Table 7.
Other than that, organic EL elements 4-2 to 4-28 were produced in the same manner.

<< Evaluation of organic EL elements 4-1 to 4-28 >>
When evaluating the obtained organic EL elements 4-1 to 4-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, light emission half-life, initial degradation and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL element 4-1 was evaluated. It was expressed as a relative value with a value of 100. The evaluation results are shown in Table 8.

As shown in Table 8, the organic EL elements 4-9 to 4-28 of the present invention have higher external extraction quantum efficiency and initial luminance degradation as compared with the organic EL elements 4-1 to 4-8 of the comparative examples. It can be seen that is small and has a long life. Furthermore, it can be seen that in the organic EL elements 4-9 to 4-28 of the present invention, the formation of dark spots is also suppressed.

<< Preparation of white light-emitting organic EL element 5-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, Another molybdenum resistance heating boat is charged with 200 mg of OC-1 as the first host compound, and another molybdenum resistance heating boat is charged with 200 mg of OC-6 as the second host compound 2, and another molybdenum resistance heating boat. 100 mg of Comparative Compound 1 as a first dopant compound, 100 mg of Ir-9 as a second dopant compound in another molybdenum resistance heating boat, and Ir as a third dopant compound in another molybdenum resistance heating boat -2 is put in 100mg, and the electron transport material 1 is put on another molybdenum resistance heating boat. It placed 200 mg, further an electron transporting material 2 placed 200mg in a third resistive heating molybdenum boat, mounted in a vacuum deposition apparatus.

Next, the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the hole injection material 1 is heated and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection layer having a thickness of 20 nm was provided.

Further, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the hole transport material 1 is energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second. Then, a hole transport layer having a thickness of 20 nm was provided.

Further, the heating boat containing OC-1 as a host compound and comparative compound 1 as a first dopant compound was heated by energization, and the positive rate was increased at a deposition rate of 0.2 nm / second and 0.020 nm / second, respectively. A blue light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Further, the heating boat containing OC-6) as the host compound, Ir-9 as the second dopant compound, and Ir-2 as the third dopant compound was heated while being energized. A 20 nm-thick yellow light emitting layer was provided by co-evaporation on the blue light emitting layer at 2 nm / second, 0.0010 nm / second, and 0.010 nm / second. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Furthermore, the heating boat containing the electron transport material 1 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

Further, the heating boat containing the electron transporting material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transporting layer having a thickness of 20 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Subsequently, lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 3-1 was produced.

<< Preparation of white light-emitting organic EL elements 5-2 to 5-28 >>
In the production of the organic EL element 5-1, various materials were changed to the compounds shown in Table 9.
Other than that, organic EL elements 5-2 to 5-28 were produced in the same manner.

<< Evaluation of organic EL elements 5-1 to 5-28 >>
When evaluating the obtained organic EL elements 5-1 to 5-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, emission half-life, initial degradation and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL element 5-1 was evaluated. It was expressed as a relative value with a value of 100. Table 10 shows the evaluation results.

As shown in Table 10, the organic EL elements 5-9 to 5-28 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the organic EL elements 5-1 to 5-8 of the comparative examples. It can be seen that is small and has a long life. Further, it can be seen that in the organic EL elements 5-9 to 5-28 of the present invention, the generation of dark spots is suppressed.

<< Preparation of white light-emitting organic EL element 6-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) as an anode on a glass substrate of 100 mm × 100 mm × 1.1 mm, this ITO transparent electrode is provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under conditions of 30 seconds and then dried at 200 ° C. for 1 hour to form a first hole transport layer having a thickness of 30 nm.

The substrate was transferred to a nitrogen atmosphere, and a thin film was formed on the first hole transport layer by spin coating using a solution of 50 mg of hole transport material 3 dissolved in 10 ml of toluene at 1000 rpm for 30 seconds. Formed. Further, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to form a second hole transport layer.

On this second hole transport layer, 100 mg of OC-1 as a host compound, 10 mg of comparative compound 1 as a first dopant compound, 1 mg of Ir-2 as a second dopant compound, and a third dopant A thin film was formed by spin coating under conditions of 1000 rpm and 30 seconds using a solution of 0.5 mg Ir-9 as a compound dissolved in 10 ml of toluene. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 70 nm.

Next, a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution in which 50 mg of the electron transport material 3 was dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 30 nm.

Subsequently, this substrate was fixed to a substrate holder of a vacuum evaporation apparatus, and after the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride was evaporated to form a cathode buffer layer, and further, aluminum 110 nm. The organic EL element 6-1 was produced by forming a cathode by vapor deposition.

In addition, the substrate temperature at the time of vapor deposition was room temperature.

<< Production of White Light-Emitting Organic EL Elements 6-2 to 6-28 >>
In the production of the organic EL element 6-1, various materials were changed to the compounds shown in Table 11.
Otherwise, the organic EL elements 6-2 to 6-28 were produced in the same manner.

<< Evaluation of Organic EL Elements 6-1 to 6-28 >>
When evaluating the obtained organic EL elements 6-1 to 6-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, emission half-life, initial degradation and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL element 6-1 was evaluated. It was expressed as a relative value with a value of 100. The evaluation results are shown in Table 12.

As shown in Table 12, the organic EL elements 6-9 to 6-28 of the present invention have higher external extraction quantum efficiency and initial luminance degradation than the organic EL elements 6-1 to 6-8 of the comparative example. It can be seen that is small and has a long life. Furthermore, it can be seen that in the organic EL elements 6-9 to 6-28 of the present invention, the formation of dark spots is also suppressed.

<< Production of White Light-Emitting Organic EL Element 7-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) as an anode on a glass substrate of 100 mm × 100 mm × 1.1 mm, this ITO transparent electrode is provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under conditions of 30 seconds and then dried at 200 ° C. for 1 hour to form a first hole transport layer having a thickness of 30 nm.

The substrate was transferred to a nitrogen atmosphere, and a thin film was formed on the first hole transport layer by spin coating using a solution of 50 mg of hole transport material 3 dissolved in 10 ml of toluene at 1000 rpm for 30 seconds. Formed. Further, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to form a second hole transport layer.

On this second hole transport layer, 100 mg of host material 1 as a host compound, 10 mg of comparative compound 1 as a first dopant compound, 1 mg of Ir-2 as a second dopant compound, and a third dopant Using a solution of 0.5 mg Ir-21 as a compound dissolved in 10 ml butyl acetate, a thin film was formed by spin coating under conditions of 1000 rpm and 30 seconds. Further, ultraviolet light was irradiated for 15 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to obtain a light emitting layer having a thickness of about 70 nm.

Next, a thin film was formed on the light emitting layer by spin coating under a condition of 1000 rpm for 30 seconds using a solution of 50 mg of the electron transport material 4 dissolved in 10 ml of methanol. Further, ultraviolet light was irradiated for 60 seconds to perform photopolymerization / crosslinking, and then vacuum-dried at 60 ° C. for 1 hour to obtain an electron transport layer having a film thickness of about 30 nm.

Subsequently, this substrate was fixed to a substrate holder of a vacuum evaporation apparatus, and after the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride was evaporated to form a cathode buffer layer, and further, aluminum 110 nm. The organic EL element 7-1 was produced by forming a cathode by vapor deposition.

In addition, the substrate temperature at the time of vapor deposition was room temperature.

<< Preparation of white light-emitting organic EL elements 7-2 to 7-28 >>
In the production of the organic EL device 7-1, various materials were changed to the compounds shown in Table 13.
Other than that, organic EL elements 7-2 to 7-28 were produced in the same manner.

<< Evaluation of organic EL elements 7-1 to 7-28 >>
When evaluating the obtained organic EL elements 7-1 to 7-28, these organic EL elements were sealed in the same manner as the organic EL element of Example 1, and an illumination device as shown in FIGS. Formed and evaluated.
For each sample thus formed, the external extraction quantum efficiency, drive voltage, light emission half-life, initial deterioration and dark spot were evaluated in the same manner as in Example 1, and each characteristic of the organic EL device 7-1 was evaluated. It was expressed as a relative value with a value of 100. The evaluation results are shown in Table 14.

As shown in Table 14, the organic EL elements 7-9 to 7-28 of the present invention have higher external extraction quantum efficiency and initial luminance degradation as compared with the organic EL elements 7-1 to 7-8 of the comparative example. It can be seen that is small and has a long life. Furthermore, it can be seen that in the organic EL elements 7-9 to 7-28 of the present invention, the formation of dark spots is also suppressed.

As described above, the present invention provides an organic EL element, an illuminating device, and a display device using an organic EL element material that exhibits high light emission efficiency in a high luminance light emission region (over 2000 cd / m ² ) and has a long light emission lifetime. Suitable for doing. Furthermore, the present invention provides an organic EL element material that exhibits high luminous efficiency, has a low driving voltage, and has a long emission lifetime in white light emission, and a wet process with high productivity of such an organic EL element material. Suitable for providing in.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 101 Organic EL element 102 Glass cover 105 Cathode 106 Organic EL layer 107 Glass substrate 108 with a transparent electrode Nitrogen gas 109 Water catching agent A Display part B Control part

Claims (24)

In an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode,
Organic electroluminescence characterized in that at least one layer of the organic layer contains a phosphorescent organometallic complex in which a ligand represented by the general formula (1) is coordinated to a metal atom. element.

[In General Formula (1), Ring A, Ring B and Ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N. Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle. R1 and R2 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group, a silyl group, An arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. Ra, Rb and Rc are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group Represents an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb represents 1 to 3 Represents an integer. R is a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group Represents a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and n0 represents an integer of 1 to 5. Ra, Rb, Rc and R may be the same as or different from each other. ] In an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode,
An organic layer characterized in that at least one of the organic layers contains a phosphorescent organometallic complex in which a ligand represented by the general formula (1-1) is coordinated to a metal atom. Electroluminescence element.

[In the general formula (1-1), ring A, ring B and ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N. Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle. R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group , A silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and at least one of R3 and R4 is a halogen atom Atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryl Oxy group, heteroaryloxy group, non-aromatic hydrocarbon ring group or non- It represents an aromatic heterocyclic group. R3 and R4 may be the same or different. Ra, Rb, Rc and Rd are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, aryl Represents an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb and nd represent Represents an integer of 1 to 3. Ra, Rb, Rc and Rd may be the same as or different from each other. ] In the organic electroluminescent element according to claim 1 or 2,
In the general formula (1) or (1-1), at least one of R1 and R2 is an alkyl group. In the organic electroluminescent element according to claim 1 or 2,
In the general formula (1) or (1-1), at least one of R1 and R2 is an alkyl group having 2 or more carbon atoms. In the organic electroluminescent element according to claim 1 or 2,
In the general formula (1) or (1-1), R1 and R2 are both alkyl groups. In the organic electroluminescent element according to claim 1 or 2,
In the general formula (1) or (1-1), R1 and R2 are both alkyl groups having 2 or more carbon atoms. The organic electroluminescence device according to any one of claims 1 to 6,
An organic electroluminescence device characterized in that in formula (1) or (1-1), ring B is a benzene ring. The organic electroluminescence device according to any one of claims 1 to 7,
In general formula (1) or (1-1), Cy is a benzene ring, The organic electroluminescent element characterized by the above-mentioned. In an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode,
An organic electroluminescence element, wherein an organic metal complex represented by the general formula (2) is contained in at least one of the organic layers.

[In General Formula (2), Ring A, Ring B and Ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N. Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle. R1 and R2 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group, a silyl group, An arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group. Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group. Represents an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb represents 1 to 3 Represents an integer. R is a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group Represents a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and n0 represents an integer of 1 to 5. Ra, Rb, Rc and R may be the same as or different from each other. L is one or more of monoanionic bidentate ligands coordinated to M, M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table, and m is Represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n. ] In an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode,
An organic electroluminescence device, wherein at least one of the organic layers contains an organometallic complex represented by the general formula (2-1).

[In General Formula (2-1), Ring A, Ring B, and Ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Z represents CH or N. Cy represents a 5- or 6-membered aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic hydrocarbon ring or non-aromatic heterocycle. R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group , A silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and at least one of R3 and R4 is a halogen atom Atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryl Oxy group, heteroaryloxy group, non-aromatic hydrocarbon ring group or non- It represents an aromatic heterocyclic group. R3 and R4 may be the same or different. Ra, Rb, Rc and Rd are each independently a hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, aryl Represents an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, and nb and nd represent Represents an integer of 1 to 3; Ra, Rb, Rc and Rd may be the same as or different from each other. L is one or more of monoanionic bidentate ligands coordinated to M, M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table, and m is Represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n. ] In the organic electroluminescent element according to claim 9 or 10,
In the general formula (2) or (2-1), at least one of R1 and R2 is an alkyl group. In the organic electroluminescent element according to claim 9 or 10,
In the general formula (2) or (2-1), at least one of R1 and R2 is an alkyl group having 2 or more carbon atoms. In the organic electroluminescent element according to claim 9 or 10,
In the general formula (2) or (2-1), R1 and R2 are both alkyl groups. In the organic electroluminescent element according to claim 9 or 10,
In the general formula (2) or (2-1), R1 and R2 are both alkyl groups having 2 or more carbon atoms. The organic electroluminescence device according to any one of claims 9 to 14,
An organic electroluminescence device characterized in that in formula (2) or (2-1), ring B is a benzene ring. The organic electroluminescence device according to any one of claims 9 to 15,
In general formula (2) or (2-1), Cy is a benzene ring, The organic electroluminescent element characterized by the above-mentioned. The organic electroluminescence device according to any one of claims 10 to 16,
An organic electroluminescence device, wherein the general formula (2-1) is represented by the general formula (3).

[In general formula (3), ring A and ring C represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Cy represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle. Represents a ring, a non-aromatic hydrocarbon ring or a non-aromatic heterocyclic ring. R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an amino group , A silyl group, an arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and at least one of R3 and R4 is a halogen atom Atom, cyano group, optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyloxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, aryl Oxy group, heteroaryloxy group, non-aromatic hydrocarbon ring group or non- It represents an aromatic heterocyclic group. R3 and R4 may be the same or different. Ra, Rb, Rc and Rd are each independently a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, An arylalkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, na and nc represent 1 or 2, nb and nd Represents an integer of 1 to 3. Ra, Rb, Rc and Rd may be the same as or different from each other. L is one or more of monoanionic bidentate ligands coordinated to M, M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table, and m is Represents 2 or 3, and n represents an integer of 1 to 3. However, m ≧ n. ] The organic electroluminescence device according to any one of claims 9 to 17,
An organic electroluminescence device wherein M is iridium in the general formula (2), (2-1) or (3). The organic electroluminescence device according to any one of claims 9 to 18,
The light emitting layer contains at least one type of host compound and at least one type of guest compound, and the compound represented by the general formula (2), (2-1) or (3) as the guest compound, 10% by weight or more based on the whole light emitting layer, The organic electroluminescence element characterized by the above-mentioned. The organic electroluminescence device according to any one of claims 9 to 19,
An organic layer comprising an organic layer containing at least one compound represented by the general formula (2), (2-1) or (3), wherein the organic layer is formed using a wet process Electroluminescence element. In the organic electroluminescence device according to any one of claims 1 to 20,
The light emitting layer contains a derivative in which at least one of carbon atoms of a hydrocarbon ring of a fluorene derivative, a dibenzofuran derivative, a dibenzothiophene derivative, a carbazole derivative, or a condensed compound derivative thereof is substituted with a nitrogen atom. An organic electroluminescence device characterized. The organic electroluminescence device according to any one of claims 1 to 21,
An organic electroluminescence device characterized in that the emission color is white. A display device comprising the organic electroluminescence element according to any one of claims 1 to 22. An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 22.

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