JP4752220B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Description

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

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. As a constituent element of ELD, an inorganic electroluminescence element and an organic electroluminescence element (also referred to as an organic EL element) can be given. 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 electroluminescence device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer and recombines them to exciton (exciton). ) And emits light using the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several V to several tens of V. Since it is a self-luminous type, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it has attracted attention from the viewpoints of space saving and portability.

  As the development of organic electroluminescence elements for practical use in the future, organic electroluminescence elements that emit light efficiently and with high brightness and have a long lifetime are desired (for example, Patent Documents 1, 2, 3, 4, See 5 and 6.).

  In recent years, as an organic electroluminescence device having high luminous efficiency, phosphorous having an oligophenylene moiety having a substituent is improved from the viewpoint of improving luminous efficiency by suppressing concentration quenching caused by the proximity of luminescent substances. Examples of light dopants have been reported (for example, see Non-Patent Document 3). Thus, it is considered that the introduction of a bulky substituent into the phosphorescent dopant prevents the phosphorescent dopants from approaching each other and suppresses the concentration quenching that occurs when the phosphorescent compound approaches.

  In recent years, for the purpose of suppressing concentration quenching, luminescent compounds having a so-called dendrimer structure in which substituents are branched in multiples to form a dendritic structure have been proposed (for example, Non-Patent Documents 1, 2, and 3). reference.).

  In addition, an organic light-emitting device using a fluorescent color conversion film having an immobilized organic fluorescent dye in which an organic fluorescent dye is included in a cyclodextrin derivative (see, for example, Patent Document 8), or an encapsulation of an organic compound and a cyclodextrin An organic electroluminescence element containing a contact complex (for example, see Patent Document 7) is disclosed.

However, the inclusion of the organic fluorescent dye with the light-emitting compound having the above dendrimer structure or the cyclodextrin derivative has some effects on the suppression of exciplex formation or the reduction of concentration quenching. However, the effects of improving the external extraction quantum efficiency and emission lifetime of organic EL devices that use phosphorescent compounds (emission dopants) and reducing the driving voltage have not yet reached the practical level and have been improved. Is required.
JP 2001-181616 A JP 2001-247859 A Japanese Patent Laid-Open No. 2002-83684 JP 2002-175484 A JP 2002-338588 A JP 2003-7469 A JP 2003-243175 A Japanese Patent No. 3463867 Applied Physics Letters, 80, 2645 (2002). IDW02 Proceedings (1124 pages) Proceedings of the 50th Applied Physics Lecture

  An object of the present invention is to design a useful organic EL element material, and by using the organic EL element material, it exhibits a high external extraction quantum efficiency, a long emission lifetime, and a low driving voltage, An illumination device and a display device are provided.

The above object of the present invention has been achieved by the following constitutions 1 to 5 .

1. A crown ether derivative having a light emitting layer between a cathode and an anode, wherein at least one of the light emitting layers has a hole transporting group or an electron transporting group having a partial structure represented by the following general formula (1A) Alternatively, an organic electroluminescence device comprising at least one kind of a complex in which an organometallic complex exhibiting phosphorescence is included in a calixarene derivative.

[Wherein, R _{1 to} R ₅ each represents a hydrogen atom or a substituent, and Q represents a 5-membered to 6-membered aromatic hydrocarbon ring or a 5-membered to 6-membered structure containing at least one nitrogen atom as a constituent atom. It represents an atomic group necessary for forming a member aromatic heterocycle. ]

2. 2. The organic electroluminescence device as described in 1 above, which emits white light.

3. A display device comprising the organic electroluminescence element as described in 1 or 2 above.

4). 3. An illuminating device comprising the organic electroluminescence element as described in 1 or 2 above.

5. 5. A display device comprising the illumination device according to 4 and a liquid crystal element as display means.

  According to the present invention, a useful organic EL element material is designed, and by using the organic EL element material, a high external extraction quantum efficiency is exhibited, the light emission lifetime is long, and the driving voltage is low. And a display device could be provided.

  In the composite of the present invention, a useful organic EL element material can be designed by having the structure according to any one of claims 1 to 7, and the composite is further manufactured using the composite. In addition, it was found that the organic EL device has a high external extraction quantum efficiency, a long light emission lifetime, and a low driving voltage for driving the device. In addition, by using the organic EL element, the present inventors have succeeded in obtaining a high-luminance display device and a lighting device.

  Hereinafter, details of each component according to the present invention will be sequentially described.

《Composite》
The composite of the present invention will be described.

As described in claim 1, the complex of the present invention exists in a state in which an clathrate compound is clathrated with an organometallic complex exhibiting phosphorescence emission (also referred to as a light-emitting dopant, which will be described later). It is characterized by that.

  As described in claim 2, the inclusion compound according to the present invention preferably has at least a hole transporting group or an electron transporting group. The hole transporting group and the electron transporting group will be described in the case of an inclusion compound.

  Furthermore, the clathrate compound according to the present invention can be used in the form of a polymer having a partial structure having a clathrate function as a repeating unit.

  The inventors of the present invention achieved the above problems by improving the external extraction quantum efficiency and emission lifetime of the element, reducing the driving voltage, etc. by the organic EL element produced using the composite of the present invention. The background is shown below.

  Conventionally known organic light-emitting devices using fluorescent color conversion films having a light-emitting compound having a dendrimer structure, an immobilized organic fluorescent dye in which an organic fluorescent dye is included in a cyclodextrin derivative, and organic compounds and cyclodextrins In an organic electroluminescence device characterized by containing an inclusion complex, an inclusion effect (also called a wrinkle effect, which is a three-dimensional effect) due to the inclusion of each luminescent compound in the internal space of the inclusion compound. Although it has succeeded in obtaining concentration quenching by preventing the proximity of dopants due to factors, preventing deterioration of materials, improving device stability, etc., it is indispensable for light emission of organic EL devices. The efficiency of hole-electron recombination is reduced, or the phosphorescent compound (existence is determined from the excited triplet state of the host compound generated by hole-electron recombination). Smooth energy transfer to the metal complex) can be suppressed, decrease in luminous efficiency, unfavorable phenomena such as increase of driving voltage tended such that incurred.

  As a result of various studies, the present inventors consider that the adjustment of the balance between the inclusion effect and the charge injection is the key to solving the above-mentioned problem, and as a means for adjusting the balance, the molecules between the inclusion compound and the organometallic complex are intermolecular. Focusing on the action (here, the intermolecular interaction indicates the degree of inclusion of the organometallic complex by the inclusion compound).

  And, as a parameter representing the strength of the intermolecular interaction, the degree of inhibition of concentration quenching of each of the organometallic complex and the complex (in the present invention, the concentration indicating concentration quenching is calculated from the fluorescence intensity measurement. It is possible to estimate the state of balance between the clathrate effect and the charge injection by measuring the clathrate compound, which will be described in detail below.

  In addition to the various display devices and displays, the composite of the present invention is a kind of lamp forming material such as household lighting, interior lighting, and exposure light source used as a material for forming various light sources and lighting devices. It is also useful as a forming material for a display device such as a backlight of a liquid crystal display device. Among them, it is preferably used as a material for forming an organic EL element used in the above display device and lighting device. In particular, as a material for forming a light emitting layer (details of the light emitting layer will be described later) which are constituent layers of the organic EL element. Preferably used.

  Further, in the synthesis of the complex of the present invention, the clathrate compound is clathrated with an organometallic complex that exhibits phosphorescence, and a conventionally known clathrate (the clathrate compound includes a guest molecule as a clathrate compound). The synthesis of the complex of the present invention can be carried out by referring to the synthesis methods (in the state of being incorporated in the internal space of the above) (these synthesis methods are well known to those skilled in the art).

<< inclusion compound >>
The clathrate compound according to the present invention will be described.

  The inclusion compound according to the present invention is a compound having an inclusion function as shown below.

(Inclusion)
The inclusion according to the present invention is an ion binding force, ion-dipole interaction, hydrogen bond, charge transfer interaction, coordination bond, van der Waals force, π-π interaction (π stack), etc. Thus, the phenomenon of surrounding the compound in which the inclusion compound is included (in the present invention, the compound in which the organometallic complex exhibiting phosphorescence emission is included) to form the complex of the present invention is shown.

  In the present invention, the state in which the inclusion compound surrounds the guest molecule is a state in which the guest compound is completely or partially taken into the internal space of the inclusion compound. Including a case where a molecular assembly is formed by the intermolecular interaction, and a state where the guest compound is not completely taken into the internal space of the inclusion compound is included. In the present invention, the effect described in the present invention (improvement of external extraction quantum efficiency) can be more preferably obtained when the guest compound molecules are not completely taken into the internal space of the clathrate compound.

(Method of confirming inclusion)
As a method for confirming whether the organometallic complex exhibiting phosphorescence emission according to the present invention has been clathrated with an inclusion compound to form a complex or is present in an uninclusion body state, a conventionally known inclusion complex can be used. A general method for checking the contact can be used.

  For example, by performing inclusion in a solvent system in which the clathrate compound dissolves but the organometallic complex does not dissolve, the formation of the clathrate can be confirmed with the disappearance of the organometallic complex in the solution.

As a more quantitative confirmation means, by using ¹ H-NMR (nuclear magnetic resonance analysis) or ¹³ C-NMR (nuclear magnetic resonance analysis), etc. It can be quantitatively confirmed whether or not a complex is formed with the compound.

  The balance between the inclusion effect and the charge injection, that is, the magnitude of the intermolecular interaction between the inclusion compound and the organometallic complex is calculated by calculating the degree of inhibition of concentration quenching, which will be described in detail below. (Also called the degree of concentration quenching suppression) can be confirmed.

  Hereinafter, the degree of inclusion will be described.

<< Calculation method of degree of inclusion (inhibition of concentration quenching) >>
As a method of calculating the degree of inclusion, the concentration of concentration quenching is measured from the fluorescence intensity measurement of the complex of the present invention and the organometallic complex in an uninclusion state, and the degree of suppression of concentration quenching is calculated. The degree of was estimated.

  Specifically, it can be calculated by the following operation. The synthesized complex (also referred to as clathrate) was purified by gel filtration chromatography, column chromatography, or the like, then fluorescence was measured at different concentrations (N = 3 for each measurement), and the average value was used. .

  The concentration [C] indicating concentration quenching was determined from the fluorescence intensity at each concentration. Similarly, the concentration [C0] indicating concentration quenching of the organometallic complex of the non-inclusion body serving as a blank is determined, and when the relationship between the two is (C / C0)> 1.1, the inclusion body (organic Metal complex is included by the inclusion compound). Here, in this invention, it is preferable that the value of (C / C0) is 1.2 or more, More preferably, it is the range of 1.4-3.0.

  The concentration of the phosphorescent dopant in the clathrate was determined and calculated by ICP (inductively coupled plasma) emission analysis, which is a well-known inorganic metal quantitative method.

  From the above, the present inventors considered the balance between the inclusion effect and the charge injection by considering the intermolecular interaction between the inclusion compound and the organometallic complex from the above-mentioned inclusion degree (concentration quenching suppression degree). And an organic EL device having a long light emission lifetime has been developed while taking advantage of the high light emission efficiency of the phosphorescent organic EL device. Moreover, it turned out that the organic EL element of this invention shows the outstanding characteristic that a drive voltage is also low.

  In addition, as one method for controlling the inclusion state of the organometallic complex in a complex formed by an inclusion compound and an organometallic complex that exhibits phosphorescence and is included in the inclusion compound, By selecting a combination of a compound and a phosphorescent dopant, the inclusion compound and the organometallic complex (phosphorescent dopant) at the time of inclusion, such as 1: 1 inclusion and 2: 1 inclusion, for example ) And the inclusion ratio can be adjusted. As described above, as a result of the control of the inclusion state (specifically, the balance adjustment between the inclusion effect and the intermolecular interaction), the external extraction quantum efficiency and In addition to improving the light emission lifetime, the effect of reducing the driving voltage of the element can also be realized.

《Specific examples of inclusion compounds》
The inclusion compound according to the present invention refers to a compound having an inclusion function shown below, for example, a crown ether derivative, a cyclophane derivative, a calixarene derivative, a carbon nanotube derivative, a cyclodextrin derivative, a cyclotriphosphazene derivative, Among them, cryptand derivatives, potando derivatives and the like can be mentioned, among which calixarene derivatives, crown ether derivatives and cyclodextrin derivatives are preferable, and calixarene derivatives and crown ether derivatives are more preferable.

  Further, calixarene derivatives, carbon nanotube derivatives, and cyclodextrin derivatives that are preferably used as the inclusion compound according to the present invention will be specifically described below.

(Calixarene derivative)
The calixarene derivative according to the present invention is a generic name for compounds having a cyclic structure in which a phenol derivative is bonded with an alkylene group or an oxyalkylene group, and the phenolic hydroxyl group in the molecule may be substituted with a substituent. .

(Crown ether derivative)
The crown ether derivative according to the present invention is a cyclic polyether, the whole ring is a polydentate ligand, and is a generic name for compounds having a function of inclusion with metal ions or organic ions, and instead of oxygen atoms. A part or all of them may be substituted with nitrogen or sulfur.

(Cyclodextrin derivative)
The cyclodextrin derivative according to the present invention is a general term for compounds having a structure in which a plurality of D-glucopyranose groups are cyclized by α-1,4 glycosidic bonds. The primary and secondary hydroxyl groups present in the molecule may be substituted with a substituent.

  The inclusion compound according to the present invention preferably has at least a hole transporting group or an electron transporting group from the viewpoint of improving the light emission efficiency of the device. Below, the hole transportable group and the electron transportable group which the clathrate compound concerning this invention has are demonstrated.

(Hole transporting group possessed by the inclusion compound)
The hole transporting group possessed by the clathrate compound according to the present invention will be described.

  The hole transporting group possessed by the clathrate compound according to the present invention is a substitution derived from a hole transporting material contained in a hole transporting layer used as a constituent layer of the organic EL device of the present invention described later. A group is preferably used.

  The hole transport material containing the substituent (hole transportable group) as a partial structure in the molecule has either hole injection or transport or electron barrier property, and is either organic or inorganic. For example, a triazole derivative, an oxadiazole derivative, an imidazole derivative, a carbazole derivative, a carboline derivative, a diazacarbazole derivative (here, diazacarbazole is a carbon constituting a carboline ring of the carboline derivative. One of the atoms is replaced by a nitrogen atom.), Polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazones Invitation , Stilbene derivatives, silazane derivatives, aniline-based copolymers, and conventionally known materials such as conductive polymer oligomers, particularly thiophene oligomers, porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, aromatic And tertiary amine compounds.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in No. 88 are linked in a starburst type ) And the like.

(Partial structure represented by general formula (1A))
Among these, carbazole derivatives, carboline derivatives, and diazacarbazole derivatives are preferably used, and particularly preferably used are carbazole derivatives, carboline derivatives, having a partial structure represented by the above general formula (1A), It is a diazacarbazole derivative.

In the general formula (1A), the substituents represented by R _{1 to} R ₅ are each an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group). Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, allyl group etc.), alkynyl group (eg, Ethynyl group, propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), aromatic heterocyclic group (eg furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, Imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, phthalazinyl, etc.), Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloalkoxyl groups (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group) Hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (Eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl Groups (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylamino group) Sulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbo group) Group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butyl) Carbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group) Cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, Group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2 -Ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, Octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group) Group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group) , Ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (for example, Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group 2-pyridylamino group, etc.), halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon groups (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.) ), Cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.).

  These substituents may be further substituted with the above substituents. A plurality of these substituents may be bonded to each other to form a ring.

  In the general formula (1A), a 5-membered to 6-membered aromatic hydrocarbon ring formed by Q, and a 5-membered to 6-membered aromatic heterocyclic ring containing at least one nitrogen atom as a constituent atom include benzene Examples include a ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.

Moreover, said ring may have the substituent respectively represented by R < ₁ > -R < ₅ > in general formula (1A).

(Electron transporting group possessed by the inclusion compound)
The electron transporting group possessed by the clathrate compound according to the present invention will be described.

  The electron transporting group possessed by the clathrate compound according to the present invention is preferably a substituent derived from an electron transporting material contained in an electron transporting layer used as a constituent layer of the organic EL device of the present invention described later. Used.

  Examples of electron transport materials containing the substituent (electron transporting group) as a partial structure in the molecule include heterocyclic tetracarboxylic anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, etc. Products, 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, a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group, and the like are also included.

  Among them, a substituent derived from the compound represented by the general formula (2A) or (2B) is preferably used as the electron transporting group according to the present invention.

In the general formula (2A), the substituents represented by R ₆ and R ₇ , respectively, and in the general formula (2B), the substituents represented by R _{8 to} R ₁₅ in the general formula (1A) , R _{1 to} R ₅ are the same as the substituents represented by each.

  In the present invention, a carbazole derivative, a carboline derivative, a diazacarbazole derivative having a partial structure represented by the general formula (1A) (here, a diazacarbazole derivative is a carbon atom constituting a carboline ring) A group having a ring structure in which any one of the above is replaced by a nitrogen atom is a diazacarbazole ring, and represents a compound having the diazacarbazole ring.) Is also an electron transporting group according to the present invention. It can be preferably used.

In addition, as the clathrate compound according to the present invention, a compound that is generally marketed as a clathrate compound can be used as it is, but the solubility of the clathrate compound itself or an organic compound that exhibits phosphorescence with the clathrate compound. In order to adjust the intermolecular interaction with the metal complex, it is preferable to introduce a substituent. As the substituent for adjusting the intermolecular interaction, R _{1 to} R ₅ in the general formula (1A) Each of the substituents represented can be used.

  Hereinafter, although the specific example of the clathrate compound which concerns on this invention is shown, this invention is not limited to these.

  Although the synthesis example of the inclusion compound which concerns on this invention below is shown, this invention is not limited to these.

<< Synthesis Example 1: Synthesis of inclusion compound CA-5 (n = 5) >>
1.3 g (1.0 mmol) of 4-tertbutylcalix [8] arene was dissolved in 10 ml of pyridine, 0.6 g (6.0 mmol) of acetic anhydride was added, and the mixture was heated to reflux for 2 hours. The reaction mixture is an acetylated 4-tertbutylcalix [8] arene mixture in which 4 to 8 hydroxyl groups are acetylated and purified by silica gel chromatography (eluent: hexane: toluene 1/1). [4] Acetylated 4-tertbutylcalix [8] arene [inclusion compound CA-5 (n = 5)] was obtained in a yield of 58% (0.8 g).

The structure of the resulting inclusion compound CA-5 (n = 5) was identified by ¹ H-NMR and mass spectrometry.

<< Synthesis Example 2: Synthesis of inclusion compound CA-6 (n = 5) >>
28.7 g (100 mmol) of 4-carbazolyl-2,6-dimethylphenol and 39.2 g (220 mmol) of N-bromosuccinimide were dissolved in 100 ml of toluene and heated to reflux. The reaction mixture was purified by silica gel chromatography (eluent: hexane: toluene 7/3) to obtain 4-carbazolyl- (2,6-bromomethyl) phenol in a yield of 63% (28.0 g).

  The obtained 22.3 g (50 mmol) of 4-carbazolyl- (2,6-bromomethyl) phenol, 13.0 g (50 mmol) of 4-carbazolylphenol was added to 100 ml of N, N-dimethylformamide (DMF). After dissolution, 1.0 g (5 mmol) of titanium tetrachloride was added, and heating under reflux was performed for 20 hours.

  The resulting reaction mixture was purified using gel filtration chromatography to obtain calix [8] arene (inclusion compound CA-6 (n = 5)) in a yield of 3% (0.7 g).

The structure of inclusion compound CA-6 (n = 5) was identified by ¹ H-NMR and mass spectrometry.

<< Synthesis Example 3: Synthesis of inclusion compound CE-10 (n = 3) >>
3.6 g (10 mmol) of dibenzo18 crown 6 was added to 15 ml of chloroform and stirred for 15 minutes. To this solution, 3.5 g (20 mmol) of N-bromosuccinimide was added and further stirred for 3 hours.

  After completion of the reaction, the precipitate was collected by filtration and recrystallized from chloroform / 2-methoxyethanol to obtain 5.0 g (97%) of a dibromo compound.

  Next, 2.6 g (5 mmol) of the dibromo compound, 3.5 g (12 mmol) of 4-carbazolylphenylboronic acid, and 3.0 g (22 mmol) of potassium carbonate were added to 50 ml of THF / pure water (3/1). The reaction system was sufficiently purged with nitrogen while stirring, and then 0.6 g (0.5 mmol) of tetrakistriphenylphosphine palladium was added, followed by heating under reflux for 8 hours. The reaction mixture was purified using silica gel chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain the desired inclusion compound CE-10 (n = 3) in a yield of 62% (2.6 g). It was.

The structure of the inclusion compound CE-10 (n = 3) was identified by ¹ H-NMR and mass spectrometry.

  These inclusion compounds can be synthesized by referring to a synthesis method known to those skilled in the art. For example, “Supramolecular Science: Naotoshi Nakajima, Chemistry Publishing, published in March 2004” and It can also be synthesized by referring to methods described in the literature listed as references in the same book.

<< Organic metal complex that exhibits phosphorescence (phosphorescent dopant) >>
The organometallic complex that exhibits phosphorescence emission according to the present invention (also referred to as a phosphorescent dopant, a phosphorescent dopant, or the like) will be described.

  At least one of the organometallic complexes exhibiting phosphorescence emission according to the present invention is contained in the light emitting layer of the organic EL device of the present invention, which will be described later, in a state of being complexed with the above clathrate compound.

  The organometallic complex exhibiting phosphorescence emission (also referred to as phosphorescent compound) used for forming the complex of the present invention may be appropriately selected from known ones used for the light emitting layer of the organic EL device. it can. For example, an iridium complex described in JP-A No. 2001-247859, represented by a formula as described in International Publication No. 00 / 70,655, pages 16 to 18, for example, tris (2-phenylpyridine) iridium Etc., platinum complexes such as osmium complexes or 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum complexes. By using such a phosphorescent compound as a dopant, a light-emitting organic EL device with high internal quantum efficiency can be realized.

  The organometallic complex (phosphorescent compound) exhibiting phosphorescence emission according to the present invention is preferably a complex compound containing any one of the metals belonging to Groups 8, 9, and 10 of the periodic table. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  In the organometallic complex exhibiting phosphorescence emission according to the present invention, emission from an excited triplet is observed, but the phosphorescence quantum yield of the organometallic complex is preferably 0.001 or more at 25 ° C. More preferably, the phosphorescence quantum yield is 0.01 or more, and particularly preferably 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield should just be achieved in any solvent.

  Although the specific example of the organometallic complex which shows phosphorescence is shown below, this invention is not limited to these.

  Moreover, each organometallic complex of said PL-1-PL-33 may be used independently, and may use it in combination of 2 or more types of compounds. These compounds are described in, for example, Inorg. Chem. Reference can be made to the method described in Vol. 40, 1704 to 1711.

  As the organometallic complex exhibiting phosphorescence emission according to the present invention, the following blue light-emitting ortho metal complex is preferably used as a so-called blue light-emitting dopant in which light emission from an excited triplet is blue.

《Blue Luminous Orthometal Complex》
The blue light-emitting ortho metal complex used in the present invention will be described.

  The blue light-emitting ortho metal complex according to the present invention is an ortho metal complex having a light emission maximum wavelength in the range of 400 nm to 500 nm and having a transition metal as a central metal, and its shortest light emission maximum wavelength is 455 nm or less. It is preferable.

  As the blue light-emitting ortho metal complex according to the present invention, complexes classified into the following seven types are preferably used. Here, the seven modes are classified into (a) to (h), and each of the seven modes is specifically described.

  << Aspect (a) >> The blue light-emitting ortho metal complex is at least one of partial structures represented by the following general formulas (1) to (6), or a moiety represented by the general formulas (1) to (6) When having at least one tautomer of each structure as a partial structure.

[Wherein, Z11 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent. M ₁₁ represents a group 8 to group 10 metal in the periodic table. ]

[In formula, Z21 represents an atomic group required in order to form an aromatic-hydrocarbon ring or an aromatic heterocyclic ring. R ₂₁ , R ₂₂ and R ₂₃ each represents a hydrogen atom or a substituent. M ₂₁ represents a group 8 to group 10 metal in the periodic table. ]

[In formula, Z31 represents an atomic group required in order to form an aromatic-hydrocarbon ring or an aromatic heterocyclic ring. X ₃₁ , X ₃₂ and X ₃₃ are each a carbon atom, —C (R ₃ ) —, a nitrogen atom or —N (R ₃ ) — (wherein R ₃ represents a hydrogen atom or a substituent). To express. C ₃₁ represents a carbon atom. M ₃₁ represents a group 8 to group 10 metal in the periodic table. Bond between C ₃₁ and N, bond between N and X ₃₃ , bond between X ₃₂ and X ₃₃ , bond between X ₃₁ and X ₃₂ , between C ₃₁ and X ₃₁ Each of the bonds represents a single bond or a double bond. ]

[In formula, Z41 represents an atomic group required in order to form an aromatic heterocyclic ring. At least one of X ₄₁ and X ₄₂ represents a nitrogen atom or —N (R ₄ ) — (wherein R ₄ represents a hydrogen atom or a substituent). M ₄₁ represents a group 8 to group 10 metal in the periodic table. C ₄₁ , C ₄₂ and C ₄₃ each represent a carbon atom. M ₄₁ represents a group 8 to group 10 metal in the periodic table. Bond between C ₄₁ and C _42, bond between C ₄₁ and X _42, coupling between X ₄₁ and X _42, coupling between X ₄₁ and C _43, and C ₄₂ and C ₄₃ The bond between represents a single bond or a double bond. ]

[In the formula, Z51 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₅₁ represents an oxygen atom or a sulfur atom. R ₅₁ and R ₅₂ represent a hydrogen atom or a substituent. M ₅₁ represents a group 8 to group 10 metal in the periodic table. ]

[Wherein, Z61 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₆₁ , X ₆₂ and X ₆₃ each represent a carbon atom, —C (R ₆ ) —, a nitrogen atom or —N (R ₆ ) — (where R ₆ represents a hydrogen atom or a substituent). To express. M ₆₁ represents a group 8 to group 10 metal in the periodic table. ]
The light emitting layer and / or the hole blocking layer may be used as the metal complex containing layer having the partial structure of each of the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6). In addition, when it is contained in the light emitting layer, it can be used as a light emitting dopant in the light emitting layer to increase the efficiency of external extraction quantum efficiency of the organic EL device of the present invention (higher brightness) and to extend the light emitting lifetime. Can be achieved.

<< General Formula (1) or Tautomer of General Formula (1) >>
In the general formula (1) or a tautomer of the general formula (1), the aromatic hydrocarbon ring represented by Z ₁₁ includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, and a phenanthrene ring. , Pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring Perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, and the like.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the general formula (1) described later.

In the general formula (1) or a tautomer of the general formula (1), the aromatic heterocycle represented by Z ₁₁ includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring , A carboline ring, a ring in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom, and the like.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the general formula (1) described later.

In the general formula (1) or a tautomer of the general formula (1), examples of the substituent represented by R ₁₁ , R ₁₂ , and R ₁₃ include an alkyl group (for example, methyl group, ethyl group, isopropyl Group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.) , Aromatic hydrocarbon groups (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic groups (for example, furyl group) , Thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl Group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (Diazacarbazolyl group is any one of the carbon atoms constituting the carboline ring of the carbolinyl group replaced by a nitrogen atom. ), Phthalazinyl group etc.), alkoxyl group (eg ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), cyano group, hydroxyl group, Examples include alkenyl groups (for example, vinyl group), styryl groups, halogen atoms (for example, chlorine atom, bromine atom, iodine atom, fluorine atom). These groups may be further substituted.

Among these, in the present invention, at least one of the groups represented by R ₁₁ , R ₁₂ and R ₁₃ is preferably the aromatic hydrocarbon group or the aromatic heterocyclic group.

In the general formula (1) or the tautomer of the general formula (1), M ₁₁ represents a group 8 to group 10 metal (a metal atom or an ion) in the periodic table of elements, and preferably used among them. Platinum (Pt) and iridium (Ir) are used. In the metal complex having the general formula (1) or an alternate isomer of the general formula (1) as a partial structure, M ₁₁ may be a metal or an ion.

In the present invention, a coordinate bond is formed between the above general formula (1) or a tautomer of the general formula (1) and a central metal (metal or ion) represented by M ₁₁ (complex formation). A metal complex is formed.

<< General Formula (2) or Tautomer of General Formula (2) >>
In the tautomer of the general formula (2) or the general formula (2), the aromatic hydrocarbon ring represented by Z ₂₁ is in the tautomer of the general formula (1) or the general formula (1). , Z ₁₁ and the same as the aromatic hydrocarbon ring.

In the tautomer of the general formula (2) or the general formula (2), the aromatic heterocycle represented by Z ₂₁ is the general formula (1) or the tautomer of the general formula (1). it is synonymous with an aromatic heterocyclic ring represented by Z _11.

In the tautomer of the general formula (2) or the general formula (2), each of the substituents represented by R ₂₁ , R ₂₂ and R ₂₃ is represented by the general formula (1) or the general formula (1). In the tautomer, it is synonymous with the substituent represented by each of R ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (2) or the general formula (2), the metal of group 8 to group 10 (which may be an ion) in the periodic table represented by M ₂₁ is represented by the general formula (1) or in tautomers general formula (1), represented by M _11, the same meaning as metal group 8-10 of the periodic table.

<< General Formula (3) or Tautomer of General Formula (3) >>
In the general formula (3) or the tautomer of the general formula (3), the aromatic hydrocarbon ring represented by Z ₃₁ is the same as that in the general formula (1) or the tautomer of the general formula (1). , Z ₁₁ and the same as the aromatic hydrocarbon ring.

In the tautomer of the general formula (3) or the general formula (3), the aromatic heterocycle represented by Z ₃₁ is the general formula (1) or the tautomer of the general formula (1). it is synonymous with an aromatic heterocyclic ring represented by Z _11.

In the general formula (3) or a tautomer of the general formula (3), a substituent represented by R ₃ of —N (R ₃ ) — represented by X ₃₁ , X ₃₂ , or X ₃₃ , respectively, In the general formula (1) or the tautomer of the general formula (1), it is synonymous with the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (3) or the general formula (3), the metal of group 8 to group 10 (which may be an ion) in the periodic table of elements represented by M ₃₁ is represented by the general formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

<< General Formula (4) or Tautomer of General Formula (4) >>
In the tautomer of the general formula (4) or the general formula (4), the aromatic heterocycle represented by Z ₄₁ is the general formula (1) or the tautomer of the general formula (1). it is synonymous with an aromatic heterocyclic ring represented by Z _11.

In the general formula (4) or a tautomer of the general formula (4), a substituent represented by R ₄ of —N (R ₄ ) — represented by X ₄₁ and X ₄₂ is represented by the general formula ( In the tautomer of 1) or the general formula (1), it is synonymous with the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the general formula (4) or a tautomer of the general formula (4), a metal of group 8 to group 10 (which may be an ion) represented by M ₄₁ in the periodic table of elements is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

<< General Formula (5) or Tautomer of General Formula (5) >>
In the general formula (5) or the tautomer of the general formula (5), the aromatic hydrocarbon ring represented by Z ₅₁ is the general formula (1) or the tautomer of the general formula (1). , Z ₁₁ and the same as the aromatic hydrocarbon ring.

In the tautomer of the general formula (5) or the general formula (5), the aromatic heterocycle represented by Z ₅₁ is the general formula (1) or the tautomer of the general formula (1). it is synonymous with an aromatic heterocyclic ring represented by Z _11.

In the general formula (5) or the tautomer of the general formula (5), the substituents represented by R ₅₁ and R ₅₂ are the general formula (1) or the tautomer of the general formula (1). Are the same as the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the general formula (5) or a tautomer of the general formula (5), a metal of group 8 to group 10 (which may be an ion) in the periodic table represented by M ₅₁ is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

<< General Formula (6) or Tautomer of General Formula (6) >>
In the general formula (6) or the tautomer of the general formula (6), the aromatic hydrocarbon ring represented by Z ₆₁ is the general formula (1) or the tautomer of the general formula (1). , Z ₁₁ and the same as the aromatic hydrocarbon ring.

In the general formula (6) or the tautomer of the general formula (6), the aromatic heterocycle represented by Z ₆₁ is the general formula (1) or the tautomer of the general formula (1). it is synonymous with an aromatic heterocyclic ring represented by Z _11.

In the general formula (6) or a tautomer of the general formula (6), a metal of group 8 to group 10 (which may be an ion) in the periodic table of elements represented by M ₆₁ is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

  Hereinafter, specific examples of the metal complex according to the present invention having the partial structures of the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6) will be described. The invention is not limited to these.

  << Aspect (b) >> The blue light-emitting orthometal complex is represented by a platinum complex represented by the following general formula (7).

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ represent a hydrogen atom or a substituent, at least one of which is necessarily a substituent. Ra represents a substituent, and Xa represents an oxygen atom or a sulfur atom. Y ₁ -L ₁ -Y ₂ represents a bidentate ligand, Y ₁ and Y ₂ each independently represent an oxygen atom, a nitrogen atom, a carbon atom or a sulfur atom, and L ₁ together with Y ₁ and Y ₂ This represents a group of atoms necessary to form a bidentate ligand. ]
<< Metal Complex Represented by General Formula (7) >>
The platinum complex represented by the general formula (7) will be described.

In the general formula (7), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each represented by a hydrogen atom or a substituent, but at least one of them represents a substituent. Even when two or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are represented by a substituent, they are not bonded to each other to form a ring. Ra represents a substituent, and Xa represents an oxygen atom or a sulfur atom.

  In the general formula (7), the substituent represented by Ra is not particularly limited, but an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group), a cycloalkyl group (for example, Cyclohexyl group, cyclopentyl group, cyclopropyl group etc.), alkenyl group (eg vinyl group, allyl group, 2-butenyl group etc.), alkynyl group (eg ethynyl group, propynyl group etc.), aryl group (eg phenyl) Group, 2-naphthyl group, 2-pyridyl group, 2-thienyl group, 3-furyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.) and the like.

  Among these, Ra is preferably an alkyl group having 1 to 30 carbon atoms, and Ra-Xa- is preferably an alkoxyl group or an alkylthio group.

Examples of the substituent represented by R _{1 to} R ₇ include an alkyl group (for example, methyl group, isopropyl group, tert-butyl group), a cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, cyclopropyl group). Etc.), alkenyl groups (eg vinyl group, allyl group, 2-butenyl group etc.), alkynyl groups (eg ethynyl group, propynyl group etc.), aryl groups (eg phenyl group, 2-naphthyl group, 9-phenanthryl) Group, 2-pyridyl group, mesityl group, carbazolyl group, fluorenyl group, 2-thienyl group, 3-furyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.), amino group, alkylamino Group (for example, dimethylamino group, diphenylamino group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine) Element, iodine atom, etc.), alkoxyl group (eg, methoxy group, ethoxy group, isopropoxy group, etc.), aryloxy group (eg, phenoxy group, perfluorophenoxy group, etc.), acylamino group (eg, acetamido group, benzoylamide) Group), sulfonamide group (eg methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group etc.), carboalkoxyl group (eg carboethoxy group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.) ), Acyloxy groups (eg, acetoxy group, benzoyloxy group, etc.), alkylthio groups (eg, methylthio group, etc.), arylthio groups (eg, phenylthio group, etc.), cyano groups, fluorinated hydrocarbon groups (eg, trifluoromethyl) Group, pentafluorophe Nyl group, etc.).

In General Formula (7), Y ₁ -L ₂ -Y ₂ represents a bidentate ligand, and Y ₁ and Y ₂ each independently represent an oxygen atom, a nitrogen atom, a carbon atom, or a sulfur atom. , L ₁ represents an atomic group necessary for forming a bidentate ligand together with Y ₁ and Y ₂ .

Specific examples of the bidentate ligand represented by Y ₁ -L ₂ -Y ₂ include, but are not limited to, phenylpyridine, acetic acid, acetylacetone, thiocarbamic acid derivative which may have a substituent, Derivatives such as 2-acylphenol and picolinic acid are preferred.

In addition, the at least one substituent that is preferably introduced together with the alkoxyl group, the alkylthio group, and the like at positions 3p to 6p in the structure and not bonded to each other to form a ring is represented by the general formula (7). Groups represented by R ₁ , R ₂ , R ₃ and R ₄ , respectively, and at least one of the substituents represented by R _{1 to} R ₄ is an electron-donating substituent among the above-mentioned substituents. It is preferably a group. More preferably, at least two of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ are electron donating substituents.

Most preferably, R ₂ and R ₄ in the general formula (7) are electron-donating substituents.

  As the electron-donating substituent, among the above groups, an alkyl group, an alkoxyl group, and an alkylamino group are most preferable.

  Next, preferred as these substituents are halogen atoms, especially fluorine atoms. Since the fluorine atom has a π-donor property, it may function as an electron donor, and it is considered that a favorable device performance can be imparted by the effect.

  Specific examples of the platinum complex represented by the general formula (7) used in the present invention will be given below, but the present invention is not limited thereto.

  << Aspect (c) >> The blue light-emitting orthometal complex is a platinum complex represented by the following general formulas (8) and (9), respectively.

[Wherein, A, B and C represent a hydrogen atom or a substituent, and at least two of them represent -Xa- (Ra) _na (Ra represents a substituent. Xa represents an oxygen atom, a sulfur atom or a nitrogen atom. Na represents 1 or 2, and may be the same as or different from each other. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represents a hydrogen atom or a substituent. M ₁ represents an element of Group 8, 9 or 10 in the periodic table. ]

[Wherein Rb, Rc and Rd represent substituents, and Xb, Xc and Xd represent an oxygen atom, a sulfur atom or a nitrogen atom. nb, nc, and nd represent 1 or 2. R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a substituent. M ₂ represents an element of Group 8, 9 or 10 in the periodic table. ]
<< Metal Complex Represented by Formula (8) >>
The metal complex represented by the general formula (8) will be described.

  In the general formula (8), A, B, and C are represented by hydrogen atoms or substituents, but at least two of them are represented by the general formula (2) and may be different from each other. The substituent represented by A, B, or C is not particularly limited, but is preferably an alkyl group (for example, a methyl group, an isopropyl group, a tert-butyl group), a cycloalkyl group (for example, a cyclohexyl group, a cyclopentyl group). , Cyclopropyl group, etc.), alkenyl group (eg, vinyl group, allyl group, 2-butenyl group, etc.), alkynyl group (eg, ethynyl group, propynyl group, etc.), aryl group (eg, phenyl group, 2-naphthyl group, etc.) 9-phenanthryl group, 2-pyridyl group, 2-thienyl group, 3-furyl group, mesityl group, carbazolyl group, fluorenyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.), amino Group (eg, dimethylamino group, diphenylamino group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom) ), Alkoxyl groups (for example, methoxy group, ethoxy group, isopropoxy group, etc.), aryloxy groups (for example, phenoxy group, perfluorophenoxy group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group) Group, hexylthio group, octylthio group, dodecylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), cyano group, fluorinated hydrocarbon group (eg, trifluoromethyl group, pentafluorophenyl group, etc.), silyl Group (for example, triphenylsilyl group, trimethylsilyl group, etc.). Of these, amino groups, alkoxyl groups, aryloxy groups, alkylthio groups, arylthio groups, and aryl groups are particularly preferred. Most preferably, they are an amino group, an alkoxyl group, and an alkylthio group.

In General formula (8), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ >, R < ₅ > represents a hydrogen atom or a substituent. The substituents represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as those described as the substituents represented by A, B and C.

In the general formula (8), M ₁ represents an element of Group 8, 9 or 10 in the periodic table. The element of Group 8, 9 or 10 is preferably ruthenium, rhodium, palladium, osmium, iridium or platinum, and most preferably iridium or platinum.

  In general formula (2), Ra represents a substituent. As a substituent represented by Ra, it is synonymous with what was demonstrated as a substituent represented by said A, B, and C. Of these, an alkyl group is particularly preferred.

  In General formula (8), Xa represents an oxygen atom, a sulfur atom, or a nitrogen atom. na represents 1 or 2.

  In General formula (8), the case where three of A, B, and C are represented by General formula (2) is the most preferable.

  In the general formula (8), when two of A, B, and C are represented by the general formula (2), most preferably, when the general formula (2) is substituted at the 4-position and the 6p-position, preferably the general formula This is a case where (2) is substituted at positions 4 and 4p.

<< Metal Complex Represented by Formula (9) >>
The metal complex represented by the general formula (9) will be described.

  In the general formula (9), Rb, Rc and Rd represent substituents, and examples of the substituent represented by Rb, Rc and Rd include the substituents represented by A, B and C in the general formula (8). It is synonymous with what was demonstrated as. The substituent for Rb, Rc and Rd is preferably an alkyl group.

  In General formula (9), Xb, Xc, and Xd represent an oxygen atom, a sulfur atom, or a nitrogen atom. The combination of Xb, Xc, and Xd atoms includes (1) Xd is a nitrogen atom, Xb and Xc are oxygen atoms, (2) Xd is a sulfur atom, Xb and Xc are oxygen atoms, or (3) Xb Xc and Xd are preferably oxygen atoms.

  In the general formula (9), nb, nc, and nd represent 1 or 2.

In the general formula _{(9), R 6, R} 7, R 8, R 9, R 10 represents a hydrogen atom or a substituent. The substituents represented by R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described as the substituents represented by A, B and C in the general formula (8).

In the general formula (9), M ₂ represents an element of Group 8, 9 or 10 in the periodic table. The element of Group 8, 9 or 10 is preferably ruthenium, rhodium, palladium, osmium, iridium or platinum, and most preferably iridium or platinum.

  Specific examples of the complex represented by the general formula (8) or (9) are given below, but the present invention is not limited to these.

  << Aspect (d) >> The blue light-emitting orthometal complex has a metal complex having a ligand represented by the following general formula (10) and a partial structure represented by the following general formula (11) or (12) When it is a metal complex or a metal complex having each tautomer of the partial structure represented by the general formula (11) or (12).

[Wherein, X ₁ , X ₂ , X ₃ , X ₄ each independently represents a carbon atom or a nitrogen atom, C ₁ , C ₂ represent a carbon atom, and Z ₁ represents C ₁ , X ₁ , X ₃ Along with C ₂ , X ₂ , and X ₄ , Z ₂ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, respectively. A ₁ represents a nitrogen atom or a boron atom, and R ₁ represents a substituent. The bond between C ₁ and X ₁ , the bond between C ₂ and X ₂ , the bond between X ₁ and X ₃ , the bond between X ₂ and X ₄ is a single bond or a double bond Represents. ]

[Wherein C ₃ , C ₄ , C ₅ , C ₆ and C ₇ each represent a carbon atom, and Z ₃ forms an aromatic hydrocarbon ring or an aromatic heterocycle together with C ₃ , C ₄ and C ₅ Z4 represents an atomic group necessary for forming an aromatic heterocyclic ring together with C ₆ , C ₇ and N. A ₂ represents a nitrogen atom or a boron atom, R ₂ represents a substituent, and M ₁₁ represents an element belonging to Groups 8 to 10 in the periodic table. The bond between C ₃ and C ₄ , the bond between C ₄ and C ₅ , the bond between C ₆ and C _7, and the bond between C ₇ and N are single bonds or double bonds. To express. ]

[Wherein, A ₃ represents a nitrogen atom or a boron atom, R ₃ represents a substituent, and R ₄ and R ₅ represent a substituent. n1 and n2 each represents an integer of 0 to 3. M ₁₂ represents an element of Group 8 to Group 10 in the periodic table. ]
<< Metal Complex Having Ligand Represented by Formula (10) >>
The metal complex having the ligand represented by the general formula (10) will be described.

  First, the ligand represented by the general formula (10) will be described.

In the general formula (10), Z ₁ together with C ₁ , X ₁ , X ₃ and Z ₂ together with C ₂ , X ₂ , X ₄ may be, for example, benzene ring or biphenyl. Ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, Examples include a fluorene ring, a fluoranthrene ring, a naphthacene ring, a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁ in the general formula (10) described later.

In the general formula (10), the aromatic heterocycle formed by Z ₁ together with C ₁ , X ₁ and X ₃ and Z ₂ together with C ₂ , X ₂ and X ₄ may be, for example, a furan ring or a thiophene ring. , Pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole Examples thereof include a ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, a ring in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ in the general formula (10) described later.

In the general formula (10), examples of the substituent represented by R ₁ include an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group). Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aromatic hydrocarbon group (eg, phenyl group, p-chlorophenyl group, mesityl). Group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group) , Imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl Group, phthalazinyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group ( For example, a vinyl group etc.), a styryl group, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom etc.) etc. are mentioned. These groups may be further substituted.

Among them, in the present invention, at least one of the groups represented by R ₁ is preferably the above aromatic hydrocarbon group or aromatic heterocyclic group.

  A coordination bond is formed (also referred to as complex formation) between the ligand represented by the general formula (10) and the central metal (which may be a metal or an ion) to form a metal complex.

Here, a coordination bond is formed between the ligand and a central metal (described later) among the atoms constituting the ligand represented by the general formula (10). It is preferable that a coordinate bond or a covalent bond is formed between ₃ and / or X ₄ .

<< Metal Complex Having General Formula (11) or Its Tautomer as Partial Structure >>
A metal complex having the general formula (11) or a tautomer thereof as a partial structure will be described.

In the general formula (11), an aromatic hydrocarbon ring formed by Z ₃ together with C ₃ , C ₄ , and C _{5 is} formed by Z ₁ together with C ₁ , X ₁ , and X _{3 in the} general formula (10). Synonymous with aromatic hydrocarbon ring.

In the general formula (11), an aromatic heterocycle formed by Z ₃ together with C ₃ , C ₄ and C ₅ is an aromatic heterocycle formed by Z ₁ together with C ₁ , X ₁ and X _{3 in the} general formula (10). Synonymous with family heterocycle.

In the general formula (11), the aromatic heterocycle formed by Z ₄ together with C ₆ , C ₇ and N is a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, hydrocarbon ring constituting carboline ring And a ring in which at least one of the carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ in the general formula (10).

In the general formula (11), the substituent represented by R ₂ has the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula (11), the elements of Group 8 to Group 10 in the periodic table of elements represented by M ₁₁ are preferably platinum (Pt), iridium (Ir), and the like. In the general formula (11), M ₁₁ may be a metal or an ion.

<< Metal Complex Having General Formula (12) or its Tautomer as Partial Structure >>
A metal complex having the general formula (12) or a tautomer thereof as a partial structure will be described.

In the general formula (12), the substituent represented by R ₃ has the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula (12), the substituents represented by R ₄ and R ₅ have the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula (12), the element of Group 8 to Group 10 in the periodic table represented by M ₁₂ is preferably platinum (Pt), iridium (Ir), or the like. In the general formula (12), M ₁₂ may be a metal or an ion.

  Below, a metal complex having a ligand represented by the general formula (10), a metal complex having a partial structure represented by the following general formula (11) or (12), or the general formula (11) or (12 Specific examples of metal complexes having tautomers of each of the partial structures represented by) are shown below, but the present invention is not limited to these.

  << Aspect (e) >> The blue light-emitting orthometal complex has a metal complex having a ligand represented by the following general formula (13), a metal complex having a partial structure represented by the following general formula (14), A metal complex having a partial structure represented by the general formula (15) or a tautomer thereof as a partial structure, a metal complex having a ligand represented by the following general formula (16), or a general formula (17) When it is a metal complex having a partial structure represented, or a metal complex having a partial structure represented by the following general formula (18).

[Wherein, X ₁ , X ₂ , X ₃ , X ₄ each independently represents a carbon atom or a nitrogen atom, C ₁ , C ₂ each represents a carbon atom, and Z ₁ represents C ₁ , X ₁ , Along with X ₃ , Z 2 together with C ₂ , X ₂ , and X ₄ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A ₁ represents a carbon atom or a silicon atom, and R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. The bond between C ₁ and X ₁ , the bond between C ₂ and X ₂ , the bond between X ₁ and X _3, and the bond between X ₂ and X ₄ are each a single bond or two Represents a double bond. ]

[Wherein C ₃ , C ₄ , C ₅ , C ₆ , C ₇ represent a carbon atom, and Z ₃ forms an aromatic hydrocarbon ring or an aromatic heterocycle together with C ₅ , C ₃ , C _7. Z4 represents an atomic group necessary for forming an aromatic heterocyclic ring together with C ₆ , C ₄ , and N, A ₂ represents a carbon atom or a silicon atom, R ₃ , R ₄ each independently represents a hydrogen atom or a substituent. M ₁₁ represents an element of Group 8 to Group 10 in the periodic table. The bond between C ₅ and C ₃ , the bond between C ₃ and C ₇ , the bond between C ₆ and C _4, and the bond between C ₄ and N are each a single bond or a double bond Represents a bond. ]

[Wherein, A ₃ represents a carbon atom or a silicon atom, R ₅ and R ₆ each independently represent a hydrogen atom or a substituent, and R ₇ and R ₈ each independently represent a substituent. n1 and n2 each independently represents an integer of 0 to 3. M ₁₂ represents a Group 8 to Group 10 element in the periodic table. ]

[Wherein, X ₃ , X ₄ , X ₅ and X ₆ each independently represent a carbon atom or a nitrogen atom, C _{8 to} C ₁₃ each represents a carbon atom, and Z 5 represents C ₈ , X ₃ , Along with X ₅ , Z 6 is together with C ₉ , X ₄ and X ₆ , Z 7 is together with C ₁₀ and C ₁₁ , Z 8 is together with C ₁₂ and C ₁₃ , each independently an aromatic hydrocarbon ring or aromatic heterocyclic ring Represents an atomic group necessary for forming. A ₄ represents a carbon atom or a silicon atom. Bond between X ₃ and X ₅ , bond between X ₄ and X ₆ , bond between C ₈ and X ₃ , bond between C ₉ and X ₄ , C ₁₀ and C ₁₁ and And the bond between C ₁₂ and C ₁₃ each represents a single bond or a double bond. ]

Wherein, C ₁₄ -C ₂₂ each represent a carbon atom, Z9, together with _{C 16, C 14, C 18} , Z11 , together with the C _19, C _20, Z12, together with the C _21, C _22, Each represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and Z10 represents an atomic group necessary for forming an aromatic heterocyclic ring together with C ₁₇ , C ₁₅ , and N. . A ₅ represents a carbon atom or a silicon atom. M ₂₁ represents an element of Group 8 to Group 10 in the periodic table. Bond between C ₁₈ and C ₁₄ , bond between C ₁₄ and C ₁₆ , bond between C ₁₇ and C ₁₅ , bond between C ₁₅ and N, bond between C ₁₉ and C ₂₀ The bond between C ₂₁ and C ₂₂ represents a single bond or a double bond, respectively. ]

Wherein, Z13, together with the C _23, C _24, Z14, together with the C _25, C _26, each represents an atomic group necessary for forming an aromatic hydrocarbon ring or aromatic heterocyclic ring, A ₆ is Represents a carbon atom or a silicon atom. R ₉ and R ₁₀ each independently represents a substituent. n3 and n4 each independently represents an integer of 0 to 3. M ₂₂ represents a Group 8 to Group 10 element in the periodic table. Bond between C ₂₃ and C _24, bond between C ₂₅ and C ₂₆ each represents a single bond or a double bond. ]
<< Metal Complex Having Ligand Represented by General Formula (13) >>
The metal complex having a ligand represented by the general formula (13) will be described.

  First, the ligand represented by the general formula (13) will be described.

In the general formula (13), the aromatic hydrocarbon ring formed together with Z ₁ and C ₁ , X ₁ , X ₃ includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring , Chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring , Pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring and the like.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have substituents represented by R ₁ and R ₂ in the general formula (13) described later.

In the general formula (13), examples of the aromatic heterocycle formed together with Z ₁ and C ₁ , X ₁ and X ₃ include a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring And a ring in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ or R ₂ in the general formula (13) described later.

In the general formula (13), examples of the substituent independently represented by R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoro group). Methyl group, t-butyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (for example, benzyl group, 2-phenethyl group, etc.), aromatic hydrocarbon group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group) , Pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolini Group, carbazolyl group, phthalazinyl group, etc.), alkoxyl group (eg, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group ( For example, a vinyl group etc.), a styryl group, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom etc.) etc. are mentioned. These groups may be further substituted.

Among them, in the present invention, at least one of the groups represented by R ₁ and R ₂ is preferably the above aromatic hydrocarbon group or aromatic heterocyclic group.

  A coordination bond is formed (also referred to as complex formation) between the ligand represented by the general formula (13) and the central metal (which may be a metal or an ion) to form a metal complex.

Here, a coordination bond is formed between the ligand and a central metal (described later) among the atoms constituting the ligand represented by the general formula (13). It is preferable that a coordinate bond or a covalent bond is formed between ₃ and / or X ₄ .

<< Metal Complex having Partial Structure Represented by General Formula (14) >>
The metal complex having a partial structure represented by the general formula (14) will be described.

In the general formula (14), the aromatic hydrocarbon ring formed by Z ₃ together with C ₅ , C ₃ , and C _{7 is} formed by Z ₁ together with C ₁ , X ₁ , and X _{3 in the} general formula (13). Synonymous with aromatic hydrocarbon ring.

In the general formula (14), the aromatic heterocycle formed by Z ₃ together with C ₅ , C ₃ , and C ₇ is the aromatic formed by Z ₁ and C ₁ , X ₁ , and X _{3 in the} general formula (13). Synonymous with family heterocycle.

In the general formula (14), the aromatic heterocycle formed by Z ₄ together with C ₆ , C ₄ , and N includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole. Carbon, constituting the ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring Examples include a ring in which at least one of the carbon atoms of the hydrogen ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ or R ₂ in the general formula (13).

In the general formula (14), the substituents independently represented by R ₃ and R ₄ have the same meanings as the substituents independently represented by R ₁ and R ₂ in the general formula (13). .

In the general formula (14), M ₁₁ represents an element belonging to Group VIII of Group 8 to Group 10 in the periodic table, and platinum (Pt) and iridium (Ir) are preferably used among them. In the general formula (14), M ₁₁ may be a metal or an ion.

<< Metal Complex Having General Formula (15) or its Tautomer as Partial Structure >>
A metal complex having the general formula (15) or a tautomer thereof as a partial structure will be described.

In the general formula (15), the substituents independently represented by R ₅ and R ₆ and the substituents independently represented by R ₇ and R ₈ are the same as those represented by R ₁ , R 6 in the general formula (13). ₂ is synonymous with the substituent each independently represented.

In the general formula (15), at least one of R ₅ and R ₆ is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.

In the general formula (15), Group 8 to Group 10 element in the periodic table represented by M _12, in the general formula (14), M ₁₁ is the Group 8 to Group 10 in the periodic table Synonymous with element.

<< Metal complex having a ligand represented by the general formula (16) >>
The metal complex having a ligand represented by the general formula (16) will be described.

In the general formula (16), Z ₅ is together with C ₈ , X ₃ and X ₅ , Z ₆ is together with C ₉ , X ₄ and X ₆ , Z ₇ is together with C ₁₀ and C ₁₁ , Z ₈ is The aromatic hydrocarbon ring independently formed with C ₁₂ and C _{13 is the same} as the aromatic hydrocarbon ring formed with Z ₁ together with C ₁ , X ₁ and X ₃ in the general formula (13). .

In the general formula (16), Z ₅ is together with C ₈ , X ₃ and X ₅ , Z ₆ is together with C ₉ , X ₄ and X ₆ , Z ₇ is together with C ₁₀ and C ₁₁ , Z ₈ is The aromatic heterocyclic ring independently formed with C ₁₂ and C ₁₃ has the same meaning as the aromatic heterocyclic ring formed with Z ₁ together with C ₁ , X ₁ and X ₃ in the general formula (13).

<< Metal Complex having Partial Structure Represented by General Formula (17) >>
The metal complex having the partial structure represented by the general formula (17) will be described.

In the general formula (17), Z ₉ is C ₁₆ , C ₁₄ , C ₁₈ , Z ₁₁ is C ₁₉ , C ₂₀ , Z ₁₂ is C ₂₁ , C ₂₂ , and each aromatic is independently formed hydrocarbon ring, in the general formula (13) is synonymous with an aromatic hydrocarbon ring formed by Z ₁ with _{C 1, X 1, X 3} .

In the general formula (17), Z ₉ is C ₁₆ , C ₁₄ , C ₁₈ , Z ₁₁ is C ₁₉ , C ₂₀ , Z ₁₂ is C ₂₁ , C ₂₂ , and each aromatic is independently formed heterocycle, in the general formula (13), is synonymous with the aromatic heterocyclic ring formed by Z ₁ with _{C 1, X 1, X 3} .

In the general formula (17), an aromatic heterocycle formed by Z ₁₀ together with C ₁₇ , C ₁₅ and N is an aromatic heterocycle formed by Z ₄ together with C ₆ , C ₄ and N in the general formula (14). Synonymous with family heterocycle.

In the general formula (17), represented by M _21, element of groups 8 to 10 is in the periodic table, in the general formula (14), M ₁₁ is Group 8 to Group 10 in the periodic table It is synonymous with the element.

<< Metal Complex having Partial Structure Represented by General Formula (18) >>
The metal complex having a partial structure represented by the general formula (18) will be described.

In the general formula (18), Z _13, together with the C _23, C _24, Z _14, together with the C _25, C _26, an aromatic hydrocarbon ring to each form, in the general formula (13), Z ₁ is C _1, X _1, X ₃ is synonymous with an aromatic hydrocarbon ring formed together.

In the general formula (18), Z ₁₃ together with C ₂₃ and C ₂₄ , and Z ₁₄ together with C ₂₅ and C ₂₆ , the aromatic heterocyclic ring respectively formed in Z ₁ and C _1, X _1, is synonymous with the aromatic heterocyclic ring formed together with X _3.

In the general formula (18), the substituents independently represented by R ₉ and R ₁₀ have the same meanings as the substituents independently represented by R ₁ and R ₂ in the general formula (13).

In the general formula (18), represented by M _22, element of groups 8 to 10 is in the periodic table, in the general formula (14), M ₁₁ is Group 8 to Group 10 in the periodic table It is synonymous with the element.

  Hereinafter, a metal complex having a ligand represented by the general formula (13), a metal complex having a partial structure represented by the general formula (14), a partial structure represented by the general formula (15), or a combination thereof. Metal complex having mutant as partial structure, metal complex having ligand represented by general formula (16), metal complex having partial structure represented by general formula (17), or general formula (18) Although the specific example of the metal complex which has the partial structure represented by this is shown, this invention is not limited to these.

  << Aspect (f) >> The case where at least one platinum complex selected from the group consisting of the following general formulas (19) to (27) is used as the blue light-emitting orthometal complex.

[Wherein, R ₁ and R ₂ each represent a hydrogen atom or a substituent. However, at least one of R ₁ and R ₂ is the substituent. X ₁ and X ₂ each represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and Z ₁ and Z ₂ are each an atom necessary to form an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Represents a group. n1 represents an integer of 1 or 2, and when n1 is 1, L1 represents a bidentate ligand. p1 and q1 each represent an integer of 0 to 4. ]

[Wherein R ₃ and R ₄ each represent a hydrogen atom or a substituent. However, at least one of R ₃ and R ₄ is the substituent. n2 is an integer of 1 or 2, and when n2 is 1, L2 represents a bidentate ligand. p2 and q2 each represents an integer of 0 to 4. ]

[Wherein, R ₅ and R ₆ each represent a hydrogen atom or a substituent. Z ₃ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. n3 is an integer of 1 or 2, and when n3 is 1, L3 represents a bidentate ligand. p3 represents an integer of 0 to 3, and q3 represents an integer of 0 to 4. ]

[Wherein, R ₇ and R ₈ each represents a hydrogen atom or a substituent. R _{9 to} R ₁₃ each represent a hydrogen atom or a substituent. n4 is an integer of 1 or 2, and when n4 is 1, L4 represents a bidentate ligand. p4 represents an integer of 0 to 3, and q4 represents an integer of 0 to 4. ]

[Wherein, R ₁₄ and R ₁₅ each represents a hydrogen atom or a substituent. Z ₄ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. n5 is an integer of 1 or 2, and when n5 is 1, L5 represents a bidentate ligand. p5 represents an integer of 0 to 4, and q5 represents an integer of 0 to 3. ]

[Wherein, R ₁₆ and R ₁₇ each represents a hydrogen atom or a substituent. R _{18 to} R ₂₂ each represent a hydrogen atom or a substituent. n6 is an integer of 1 or 2, and when n6 is 1, L6 represents a bidentate ligand. p6 represents an integer of 0 to 3, and p7 represents an integer of 0 to 4. ]

[Wherein R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent. Z ₅ represents an atomic group necessary for forming an aromatic heterocycle with a nitrogen atom. n7 is an integer of 1 or 2, and when n7 is 1, L7 represents a bidentate ligand. p8 represents an integer of 0 to 3, and q6 represents an integer of 0 to 4. ]

[Wherein R ₂₅ and R ₂₆ each represent a hydrogen atom or a substituent. Z ₆ represents an atomic group necessary for forming an aromatic heterocycle with a nitrogen atom. n8 is an integer of 1 or 2, and when n8 is 1, L8 represents a bidentate ligand. p9 represents an integer of 0 to 3, and q7 represents an integer of 0 to 4. ]

[Wherein R ₂₇ and R ₂₈ each represent a hydrogen atom or a substituent. At least one of R ₂₇ and R ₂₈ is the substituent. L0 represents a divalent linking group. X ₃ and X ₄ each represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and Z ₇ and Z ₈ each represent an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. To express. n9 is an integer of 1 or 2, and when n9 is 1, L9 represents a bidentate ligand. p10 and q8 each represent an integer of 0 to 4. ]
<< Platinum Complex Represented by General Formula (19) >>
The platinum complex represented by the general formula (19) will be described. In this invention, what is represented by the tautomer of the said General formula (19) shall also be included.

In the general formula (19), examples of the substituent represented by R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group). Group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, p-chlorophenyl group). Mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, Triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, cal Zolyl group, phthalazinyl group, etc.), alkoxyl group (eg, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group (eg, Vinyl group, etc.), styryl group, halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.). These groups may be further substituted.

In the general formula (19), examples of the aromatic hydrocarbon ring or aromatic heterocycle formed by Z ₁ include a benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, and furan ring. Thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like. Of these, a benzene ring is preferred.

In the general formula (19), examples of the aromatic hydrocarbon ring or aromatic heterocyclic ring formed by Z ₂ include a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, benzothiazole ring, Examples thereof include a benzoxazole ring, a quinazoline ring, and a phthalazine ring. Of these, a pyridine ring is preferred.

  In the general formula (19), n1 is an integer of 1 or 2, and when n1 is 1, L1 represents a bidentate ligand. Examples of the bidentate ligand represented by L1 include oxycarboxylic acid, oxyaldehyde and derivatives thereof (for example, salicylaldehyde, oxyacetophenonate, etc.), dioxy compounds (for example, biphenolate, etc.), diketones (for example, Acetylacetonato, dibenzoylmethanato, diethylmalonate, ethylacetoacetate, etc.), oxyquinones (eg, pyromeconato, oxynaphthoquinato, oxyanthraquinato, etc.), tropolones (eg, troponato, hinokitiolato, etc.), N-oxide compounds, aminocarboxylic acids and similar compounds (for example, glycinato, alaninato, anthranilate, picolinato, etc.), hydroxylamines (for example, aminophenolato, ethanolaminato, mercaptoethylaminato, etc.), oxines (for example, 8-oxyquinolinato, etc.), aldimines (eg, salicylaldiminato, etc.), oximes (eg, benzoin oximato, salicylaldoximato, etc.), oxyazo compounds (eg, oxyazobenzonate, phenylazonaphtholato, etc.) , Nitrosonaphthols (for example, β-nitroso-α-naphtholate, etc.), triazenes (for example, diazoaminobenzenato, etc.), biurets (for example, biuretate, polypeptide group, etc.), formasenes and dithizones (for example, Diphenylcarbazonate, diphenylthiocarbazonate and the like), piguanides (for example, piguanidate and the like), glyoximes (for example, dimethylglyoximato and the like) and the like.

  Although the general formula and specific example of a bidentate ligand which are preferably used in the present invention are listed below, the present invention is not limited thereto.

  In the general formula of the above bidentate ligand, Ra to Rv are each an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc. Or a halogenated alkyl group (for example, those in which at least one hydrogen atom of the alkyl group is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like).

  In the general formula of the above bidentate ligand, Ara to Arc are aryl groups (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group). Etc.) or an aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, A diazacarbazolyl group (here, a diazacarbazolyl group is one in which any one of the carbon atoms constituting the carboline ring of the carbolinyl group is substituted with a nitrogen atom), a phthalazinyl group, etc. ).

<< Platinum Complex Represented by Formula (20) >>
The platinum complex represented by the general formula (2) according to the present invention will be described.

In the general formula (20), the substituents represented by R ₃ and R ₄ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (20), the bidentate ligand represented by L2 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (21) >>
The platinum complex represented by the general formula (21) according to the present invention will be described.

In the general formula (21), the substituents represented by R ₅ and R ₆ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19), respectively.

  In the general formula (21), the bidentate ligand represented by L3 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (21), the aromatic hydrocarbon ring formed by Z ₃ and C (carbon atom) includes a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

In the general formula (21), the aromatic heterocycle formed by Z ₃ and C (carbon atom) includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzimidazole. Ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline Examples include a ring in which at least one of the carbon atoms of the hydrocarbon ring constituting the ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (22) >>
The platinum complex represented by the general formula (22) according to the present invention will be described.

In the general formula (22), the substituents represented by R _{7 to} R ₁₃ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (22), the bidentate ligand represented by L4 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (23) >>
The platinum complex represented by the general formula (23) according to the present invention will be described.

In the general formula (23), the substituents represented by R ₁₄ and R ₁₅ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (23), the bidentate ligand represented by L5 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (23), the aromatic hydrocarbon ring formed by Z ₄ and C (carbon atom) is the same as the aromatic carbon ring formed by Z ₃ and C (carbon atom) in the general formula (21). Synonymous with hydrogen ring.

In the general formula (23), an aromatic heterocycle formed by Z ₄ and C (carbon atom) is an aromatic heterocycle formed by Z ₃ and C (carbon atom) in the general formula (21). It is synonymous with.

<< Platinum Complex Represented by Formula (24) >>
The platinum complex represented by the general formula (24) according to the present invention will be described.

In the general formula (24), the substituents represented by R _{16 to} R ₂₂ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (24), the bidentate ligand represented by L6 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (25) >>
The platinum complex represented by the general formula (25) according to the present invention will be described.

In the general formula (25), the substituents represented by R ₂₃ and R ₂₄ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (25), the bidentate ligand represented by L7 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (25), the aromatic heterocycle formed by Z ₅ and N (nitrogen atom) includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring. , Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring And a ring in which at least one of the ring carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (26) >>
The platinum complex represented by the general formula (26) according to the present invention will be described.

In the general formula (26), the substituents represented by R ₂₅ and R ₂₆ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (26), the bidentate ligand represented by L8 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (26), the aromatic heterocycle formed by Z ₆ and N (nitrogen atom) includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring. , Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring And a ring in which at least one of the ring carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (27) >>
The platinum complex represented by the general formula (27) according to the present invention will be described.

In the general formula (27), the substituents represented by R ₂₇ and R ₂₈ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (27), the bidentate ligand represented by L9 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (27), the 5-membered or 6-membered ring formed by Z ₇ has the same meaning as the 5-membered or 6-membered ring formed by Z ₁ in the general formula (19).

In the general formula (27), the 5-membered or 6-membered ring formed by Z ₈ has the same meaning as the 5-membered or 6-membered ring formed by Z ₂ in the general formula (19).

In the general formula (27), as the divalent linking group represented by L0, an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), Cyclopentylene group (for example, 1,5-cyclopentanediyl group, etc.), alkenylene group (for example, vinylene group, propenylene group, etc.), alkynylene group (for example, ethynylene group, 3-pentynylene group, etc.), arylene group In addition to hydrocarbon groups such as, a group containing a hetero atom (for example, -O-, Divalent group containing a chalcogen atom S- like, -N (R) - group, where, R represents a hydrogen atom or an alkyl group, the alkyl group in the general formula (19), R ₁ And alkyl groups described in the substituents represented by R ₂ , etc.).

  Although the specific example of the platinum complex compound used as the organic EL element material of this invention is shown below, this invention is not limited to these. In the specific examples shown below, the periphery of an aryl group that cannot rotate freely or an aromatic heterocyclic group that cannot rotate freely is indicated by a dotted line.

《Aryl group that cannot rotate freely, Aromatic heterocyclic group that cannot rotate freely》
In the present invention, “an aryl group that cannot be freely rotated and an aromatic heterocyclic group that cannot be freely rotated” represents a substituent that cannot be freely rotated due to steric hindrance.

  However, as a state where the free rotation is not possible, when the aryl group and the aromatic heterocyclic group are close to other substituents arranged in the vicinity, it is physically impossible to rotate freely. As a matter of course, an aryl which cannot rotate freely even in the presence of a bond rotation barrier derived from the conformational energy with the bond axis of the aryl group or the substituent formed through the bond axis of the aromatic heterocyclic group The group can be defined as an aromatic heterocyclic group that cannot rotate freely.

  Here, the conformational energy for generating the bond rotation barrier is preferably 25 kcal / mol or more.

  In the present invention, an aryl group and an aromatic heterocyclic group, each of which is physically incapable of free rotation, are preferred.

  Examples of the aryl group that can be used as an aryl group that cannot freely rotate include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

  Examples of the aromatic heterocyclic group that can be used as an aromatic heterocyclic group that cannot rotate freely include a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, and a pyrazolyl group. Group, thiazolyl group, quinazolinyl group, phthalazinyl group and the like.

  << Aspect g >> The case where the blue light-emitting orthometal complex includes at least one partial structure selected from the group consisting of the following general formulas (28) to (32) or a tautomer of the partial structure.

[In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₁₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₁₂ represents a non-aromatic group together with the carbon atom. This represents an atomic group necessary for forming a ring, and M represents a metal. ]

[Wherein, C represents a carbon atom, N represents a nitrogen atom, Z ₂₁ and Z ₂₂ represent an atomic group necessary for forming an aromatic ring together with the carbon atom and the nitrogen atom, respectively, and M represents a metal. ]

[Wherein, C represents a carbon atom, N represents a nitrogen atom, Z ₃₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₃₂ represents a 5-membered or It represents an atomic group composed of carbon atoms, nitrogen atoms or oxygen atoms necessary for forming a 6-membered aromatic heterocyclic ring, and M represents a metal. ]

[Wherein, C represents a carbon atom, N represents a nitrogen atom, Z ₄₁ represents an atomic group necessary for forming a ring together with the carbon atom and the nitrogen atom, and Z ₄₂ represents a ring formed together with the carbon atom. It represents a necessary atomic group, and M represents a metal. ]

[Wherein, C represents a carbon atom, N represents a nitrogen atom, Z ₅₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₅₂ represents an azulene ring together with the carbon atom. Represents an atomic group to be formed, and M represents a metal. ]
The metal complex compound having a specific structure represented by each of the general formulas (28) to (32) will be described.

In the general formula (28), Z ₁₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₁₂ is necessary for forming a non-aromatic ring together with the carbon atom. Represents an atomic group, and M represents a metal. Examples of the aromatic heterocycle formed by Z ₁₁ include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, a quinazoline ring, and a phthalazine ring. It is done. Examples of the non-aromatic ring formed by Z ₁₂ include the rings described below.

In the general formula (28), preferably non-aromatic ring represented by Z ₁₂ is an R-2 or R-6.

  Next, general formula (29) will be described.

In the general formula (29), Z ₂₁ and Z ₂₂ each represent an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and M represents a metal. Examples of the aromatic ring formed by Z ₂₁ include the same aromatic heterocycle as Z _11. Examples of the aromatic heterocycle formed by Z ₂₂ include a pyrrole ring, a pyrazole ring, an imidazole ring, and a triazole ring. , Indole ring, benzimidazole ring and the like. Preferred is a pyrrole ring or a triazole ring.

  Next, general formula (30) will be described.

In the general formula (30), Z ₃₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₃₂ is necessary for forming an aromatic 5-membered ring together with the carbon atom. Represents an atomic group composed of carbon, nitrogen or oxygen atoms, and M represents a metal. Examples of the aromatic heterocycle formed by Z ₃₁ include the same aromatic heterocycle as Z ₁₁ described above, and examples of the aromatic 5-membered ring formed by Z ₃₂ include a pyrrole ring, a furan ring, and an imidazole ring. , Pyrazole ring, oxazole ring, oxadiazole ring, and the like, preferably a nitrogen-containing aromatic heterocyclic ring, more preferably a nitrogen-containing aromatic heterocyclic ring containing a plurality of nitrogen or oxygen atoms.

  Next, general formula (31) will be described.

In the general formula (31), Z ₄₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₄₂ represents an atomic group necessary for forming a ring together with the carbon atom. , M represents a metal. Examples of the aromatic heterocycle formed by Z ₄₁ include the same aromatic heterocycles as Z ₁₁ described above, and the ring formed by Z ₄₂ may be an aromatic ring or a non-aromatic ring, but is preferably non-aromatic. It is a ring.

  Next, general formula (32) will be described.

In the general formula (32), Z ₅₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₅₂ represents an atomic group necessary for forming an azulene ring together with the carbon atom. M represents metal. Aromatic heterocyclic ring formed by Z ₅₁ may include the same aromatic heterocyclic and Z _11.

In the general formulas (28) to (32) described above, the ring formed by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₃₂ , Z ₄₁ , Z ₄₂ , Z ₅₁ and Z ₅₂ is Furthermore, you may have a substituent and substituents may couple | bond together and you may form a ring further. In the general formulas (28) to (32), M is preferably a group 8-10 metal in the periodic table, more preferably M is iridium, osmium or platinum, most preferably M is Iridium.

  Although the specific example of a compound represented by either of general formula (28)-(32) below is given, this invention is not limited to these.

  << Aspect h >> The case where the blue light-emitting orthometal complex is represented by a platinum complex having a partial structure represented by the following general formula (A) or (B).

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ each represents a hydrogen atom or a substituent, but at least one of R ₁ , R ₂ , R ₃ , R _4] One is an electron donating group. Ra and Rb each represents a substituent. ]

[Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ each represents a hydrogen atom or a substituent, at least one of R ₁₁ , R ₁₃ is an electron-withdrawing group It is. Rc and Rd represent a substituent. ]
At least one platinum complex represented by the general formula (A) or (B) will be described.

<< Platinum Complex Having Partial Structure Represented by General Formula (A) >>
The platinum complex having the partial structure represented by the general formula (A) will be described.

In the general formula (A), examples of the substituent represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ include an alkyl group (for example, a methyl group, an ethyl group, and the like). Propyl group, isopropyl group, (t) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), Alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group, biphenylyl group, anthryl group, phenanthryl group, mesityl group) Group, fluorenyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl) , Pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, carbazolyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy) Group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group ( For example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), aryl Thio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (Eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octyl) Aminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group ( For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group, Ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyl) Oxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (example) For example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenyl Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridyl group) Sulfinyl group etc.), alkylsulfonyl group or arylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2 -Pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group) 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), nitro group, cyano group, silyl group (trimethylsilyl group, t-butyldimethylsilyl group, dimethylphenylsilyl group, triphenyl) Silyl group, etc.).

In the present invention, at least one of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ is preferably an electron donating group, more preferably R ₁ , R ₂ , R ₃ , R _At least two of the groups represented by ₄ are electron donating groups, and at least one of the electron donating groups is such that σp is −0.20 or less, most preferably The electron donating group is introduced into R ₂ or R ₄ of the general formula (A).

<< Electron-donating group with σp of -0.20 or less >>
Here, as the electron donating group having σp of −0.20 or less, for example, cyclopropyl group (−0.21), cyclohexyl group (−0.22), tert-butyl group (−0.20) , —CH ₂ Si (CH ₃ ) ₃ (−0.21), amino group (−0.66), hydroxylamino group (−0.34), —NHNH ₂ (−0.55), —NHCONH ₂ ( _{-0.24), - NHCH 3 (-0.84} ), - NHC 2 H 5 (-0.61), - NHCONHC 2 H 5 (-0.26), - NHC 4 H 9 (-0.51 ), —NHC ₆ H ₅ (−0.40), —N═CHC ₆ H ₅ (−0.55), —OH (−0.37), —OCH ₃ (−0.27), —OCH _{2 COOH (-0.33), - OC 2} H 5 (-0.24), - OC 3 H 7 (-0.25), - OCH (CH 3) 2 _{-0.45), - OC 5 H 11} (-0.34), - although _{OCH 2 C 6 H 5 (-0.42} ) , and the like, the present invention is not limited thereto.

In the general formula (A), the substituents represented by Ra and Rb are respectively R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ in the general formula (A). Although it is synonymous with the substituent represented, Preferably, Ra and Rb are the cases where both are alkyl groups.

<< Platinum Complex Having Ligand Represented by Formula (B) >>
The platinum complex having the partial structure represented by the general formula (B) will be described.

In the general formula (B), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ are each a substituent represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ have the same meanings as the substituents represented by each. Provided that at least one of R _11, R ₁₃ is an electron withdrawing group, preferably R _11, R ₁₃ are both electron-withdrawing group, more preferably, .sigma.p of the electron withdrawing group is 0. 10 or more.

<< Electron withdrawing group with σp of 0.10 or more >>
Here, as an electron withdrawing group having σp of 0.10 or more, for example, —B (OH) ₂ (0.12), bromine atom (0.23), chlorine atom (0.23), iodine atom ( _{0.18), - CBr 3 (-0.29} ), - CCl 3 (0.33), - CCF 3 (0.54), - CN (0.66), - CHO (0.42), - _{COOH (0.45), CONH 2 (} 0.36), - CH 2 SO 2 CF 3 (0.31), - COCH 3 (0.45), 3- Bareniru group (0.19), - CF ( _{CF 3) 2 (0.53),} - CO 2 C 2 H 5 (0.45), - CF 2 CF 2 CF 2 CF 3 (0.52), - C 6 F 5 (0.41), 2 - benzoxazolyl group (0.33), 2-benzothiadiazolyl no doubt Lil group (0.29), - C = O (C 6 H 5) (0.43), - OCF 3 (0.35), − _{SO 2 CH 3 (0.36),} - SO 2 (NH 2) (0.57), - SO 2 CH 3 (0.72), - COCH 2 CH 3 (0.48), - COCH (CH 3 ) ₂ (0.47), —COC (CH ₃ ) ₃ (0.32) and the like, but the present invention is not limited thereto.

In the general formula (B), each of the substituents represented by Rc and Rd is represented by the following formula (1): R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ Although it is synonymous with the substituent represented, Preferably, Rc and Rd are both a case where it is an alkyl group.

  Although the specific example of the platinum complex which has the partial structure represented by general formula (A) or (B) based on this invention below is shown, this invention is not limited to these.

  The metal complex according to the organic EL device of the present invention is described in, for example, Organic Letter, vol. 16, p 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. MoI. 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, page 1171 (2002), and further by applying a method such as a reference described in these documents.

  In addition, for example, J. et al. Am. Chem. Soc. 123, 4304-4312 (2001), International Publication No. 00/70655 pamphlet, No. 02/15645 pamphlet, JP-A No. 2001-247859, No. 2001-345183, No. 2002-117978, 2002-170684, 2002-203678, 2002-235076, 2002-302671, 2002-324679, 2002-332291, 2002-332292, Examples include iridium complexes represented by the general formula described in JP 2002-338588 A, etc., iridium complexes exemplified as specific examples, iridium complexes represented by formula (IV) described in JP 2002-8860 A, and the like. It is done.

  The organometallic complex (phosphorescent compound) exhibiting phosphorescence emission according to the present invention preferably has a phosphorescence quantum yield in solution of 0.001 or more at 25 ° C., more preferably 0.01 or more. Particularly preferably, it is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the 4th edition, Experimental Chemistry Course 7.

<< Compound exhibiting fluorescence (also referred to as fluorescence-emitting dopant) >>
A compound exhibiting fluorescence (also referred to as a fluorescence emitting dopant) that can be used in combination with the organometallic complex compound exhibiting phosphorescence emission according to the present invention is described.

  As the fluorescent compound that may be used in the present invention, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, and other known fluorescent compounds.

  Moreover, in order to obtain a high fluorescence quantum yield, it is preferable that content in a light emitting layer is 10 mass% or more of the mass of the whole layer, Most preferably, it is 30% or more.

  Examples of fluorescent organic molecules having a partial structure with a high fluorescence quantum yield include conventionally known coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzoanthracene dyes, and fluorescein. Type dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and the like, and groups having these partial structures are preferably used as the fluorescent light-emitting group.

<< 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 << light emitting layer >>
The light emitting layer according to the present invention will be described.

  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.

  In the light emitting layer according to the present invention, the composite of the present invention (the above-mentioned inclusion compound includes the above-described organometallic complex (phosphorescent light-emitting dopant) that emits phosphorescence) is used. In addition, an organic EL element having high luminous efficiency and a long lifetime can be produced.

  There are two types of light emission of phosphorescent compounds 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 phosphorescent. Energy transfer type to obtain light emission from the phosphorescent compound by transferring to the compound, the other is that the phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, and from the phosphorescent compound In any case, the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  In the present invention, the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited. In principle, the phosphorescent compound can be obtained by selecting a central metal, a ligand, a ligand substituent, and the like. However, it is preferable that the phosphorescent compound has a maximum phosphorescence emission wavelength of 380 nm to 480 nm.

  Examples of such phosphorescent emission wavelengths include organic EL elements that emit blue light and organic EL elements that emit white light. These elements should be operated with lower emission voltage and lower power consumption. Can do.

  In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  The host compound used in the present invention is a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C.) among compounds contained in the light emitting layer.

  In the light emitting layer according to the present invention, a plurality of known host compounds may be used in combination as the host compound. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. As these known host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable.

  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. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Moreover, the light emitting layer may contain the host compound which has a fluorescence maximum wavelength further as a host compound. In this case, the energy transfer from the other host compound and the phosphorescent compound to the fluorescent compound allows electroluminescence as an organic EL element to be emitted from the other host compound having a fluorescence maximum wavelength. A host compound having a fluorescence maximum wavelength is preferably a compound having a high fluorescence quantum yield in a solution state. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. Specific host compounds having a maximum fluorescence wavelength include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, and pyrylium dyes. Perylene dyes, stilbene dyes, polythiophene dyes, and the like. The fluorescence quantum yield can be measured by the method described in 362 (1992, Maruzen) of Spectroscopic II of the Fourth Edition Experimental Chemistry Course 7.

  The color emitted in this specification is the spectral radiance meter CS-1000 (Minolta) in FIG. 4.16 on page 108 of “New Color Science Handbook” (Edited by the Japan Society for Color Science, University of Tokyo Press, 1985). It is determined by the color when the measured result is applied to the CIE chromaticity coordinates.

  The light emitting layer can be formed by forming the above compound 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. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5 nm-200 nm. The light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Good.

<Blocking layer: hole blocking layer, electron blocking layer>
The hole blocking layer is an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons and has a very small ability to transport holes. By blocking holes while transporting electrons, And the recombination probability of holes can be improved.

  The hole blocking layer has a role of blocking the holes moving from the hole transport layer from reaching the cathode and a compound that can efficiently transport the electrons injected from the cathode toward the light emitting layer. It is formed. The physical properties required of the material constituting the hole blocking layer are higher than the ionization potential of the light emitting layer in order to have high electron mobility and low hole mobility and to efficiently confine holes in the light emitting layer. It is preferable to have a value of ionization potential or a band gap larger than that of the light emitting layer. Use of at least one of styryl compounds, triazole derivatives, phenanthroline derivatives, oxadiazole derivatives, and boron derivatives as the hole blocking material is also effective in obtaining the effects of the present invention.

  Examples of other compounds include exemplified compounds described in JP-A Nos. 2003-31367, 2003-31368, and Japanese Patent No. 2721441.

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

  The hole blocking layer and the electron blocking layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. .

《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 any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.

  Examples of the hole transport layer according to the present invention include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives. Conventionally known materials such as styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers may be used.

  As the hole transport material, those described above can be used, 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 ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in No. 88 are linked in a starburst type ) And the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

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

《Electron transport layer》
The electron transport layer according to the present invention is only required to have a function of transmitting electrons injected from the cathode to the light emitting layer, and as the material thereof, any one of conventionally known compounds can be selected and used. Can do. The electron transport layer contains 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.

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives. Furthermore, in the 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.

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

  In addition, an example of a partial structure having a function of imparting electron transporting properties is shown below (wherein, a bond is provided at any atomic site of the partial structure shown below to form a group having electron transporting properties. However, the present invention is not limited to these.

  In addition, metal-free or metal phthalocyanine, and those having the terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Alternatively, the distyrylpyrazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC A semiconductor can also be used as an electron transport material.

  The electron transport layer can be formed by forming the above compound by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.

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

"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, a thin film may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method. Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is 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, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / 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 a 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 one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

  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.

<< Buffer layer >>: Anode buffer layer, cathode buffer layer An injection layer is provided as necessary, and includes a cathode buffer layer (electron injection layer) and an anode buffer layer (hole injection layer). You may exist between a positive hole transport layer and between a cathode and a light emitting layer or an electron carrying layer.

  The buffer layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (November 30, 1998, issued by NTT Corporation) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes an anode buffer layer and a cathode buffer layer.

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

  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. A metal buffer layer typified by lithium fluoride, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, an 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.

<< Substrate (also referred to as substrate, substrate, support, etc.) >>
The organic EL device of the present invention is preferably formed on a substrate.

  The substrate of the organic EL device of the present invention is not particularly limited to the type of glass, plastic, etc., and is not particularly limited as long as it is transparent. Examples of substrates that are preferably used include glass, quartz, A light transmissive resin film can be mentioned. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films having (TAC), cellulose acetate propionate (CAP) and the like. In addition, an inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film.

  The external extraction efficiency at room temperature for light emission of the organic electroluminescence device 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.

  In addition, 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. 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.

<< Method for producing 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 / anode buffer layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode. explain.

  First, a thin film made of a desired electrode material, for example, 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, thereby producing an anode. To do. Next, an organic compound thin film of an anode buffer layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode buffer layer, which are organic EL element materials, is formed thereon.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 ° C. to 450 ° C., a vacuum degree of 10 ⁻⁶ Pa to 10 ⁻² Pa, and a vapor deposition rate of 0 It is desirable to select appropriately within the range of 0.01 nm / second to 50 nm / second, substrate temperature −50 ° C. to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 nm to 200 nm.

  After these layers are formed, 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 thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  The multicolor display device of the present invention is provided with a shadow mask only when the light emitting layer is formed, and the other layers are common, so that patterning of the shadow mask or the like is unnecessary, and the evaporation method, the casting method, the spin coating method, the ink jet method on one side. A film can be formed by a method, a spray method, a printing method, or the like.

  When patterning is performed only on the light emitting layer, the method is not limited. However, a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  In addition, it is also possible to reverse the production order to produce a cathode, a cathode buffer layer, an electron transport layer, a hole transport layer, a light emitting layer, a hole transport layer, an anode buffer layer, and an 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.

  The display device of the present invention can be used as a display device, a display, and various light emission sources. In a display device or a display, full-color display is possible by using three types of organic EL elements of blue, red, and green 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.

  The lighting device of the present invention includes 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 sensors Although a light source etc. are mentioned, it is not limited to this.

  Further, the organic EL element according to the present invention may be used as an organic EL element having a resonator structure.

  Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

<Display device>
The organic EL element of the present invention may be used as one 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). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using three or more organic EL elements of the present invention having different emission colors. Alternatively, it is possible to make a single color emission color, for example, white emission, into BGR using a color filter to achieve full color. Further, it is possible to convert the emission color of the organic EL to another color by using a color conversion filter, and in this case, λmax of the organic EL emission is preferably 480 nm or less.

  An example of a display device having the organic EL element of the present invention as a configuration will be described with reference to the drawings.

  FIG. 1 is a schematic diagram illustrating an example of a display device including organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  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, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  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).

  The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and 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 orthogonal positions (details are shown in FIG. Not shown).

  When a scanning signal is applied 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 that emit light on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 shows a schematic diagram of a pixel.

  The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the organic EL element 10 emits light by the switching transistor 11 and the driving transistor 12 that are active elements for the organic EL elements 10 of the plurality of pixels, and the organic EL elements 10 of the plurality of pixels 3 emit light. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic view of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal. In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

  The organic EL element material of the present invention can also 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. As a combination of a plurality of luminescent colors, those containing three luminescence maximum wavelengths of three primary colors of blue, green, and blue may be used. 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 includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and the light emission. Any combination of a dye material that emits light from the material as excitation light may be used, but in the white organic electroluminescence device according to the present invention, a method of combining a plurality of light-emitting dopants is preferable.

  As a layer structure of an organic electroluminescence device for obtaining a plurality of emission colors, a method of having a plurality of emission dopants in one emission layer, a plurality of emission layers, and an emission wavelength in each emission layer And a method of forming minute pixels emitting light having different wavelengths in a matrix.

  In the white organic electroluminescence device according to the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like at the time of film formation, if necessary. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the platinum complex according to the present invention is known so as to be suitable for the wavelength range corresponding to the CF (color filter) characteristics. Any one of the light emitting materials may be selected and combined to be whitened.

  Thus, in addition to the display device and display, the white light-emitting organic EL element of the present invention can be used as a kind of lamp such as a home lighting, an interior lighting, and an exposure light source as various light emitting light sources and lighting devices. It is also useful for display devices such as backlights of liquid crystal display devices.

  Others such as backlights for watches, signboard 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. A wide range of uses such as household appliances

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<< Synthesis Example 1: Synthesis of Complex (CL-Ir-3) >>
0.6 g (0.4 mmol) of the inclusion compound CA-5 (n = 5) synthesized in Synthesis Example 1 was dissolved in 5 ml of ethyl acetate / tetrahydrofuran (THF), and tris (2-phenyl) was added thereto. Pyridine) iridium (Ir (ppy) ₃ ) (0.13 g, 0.2 mmol) was added, and the mixture was stirred for 5 hours and allowed to stand for 12 hours. After the precipitate was filtered off, Ir (ppy) ₃ complex was obtained from the filtrate. The obtained Ir (ppy) ₃ complex (CL-Ir-3) was purified using gel filtration chromatography to obtain a yield of 80% (0.6 g).

  Moreover, the suppression degree (C / C0) of concentration quenching calculated | required by said method was 1.25, and it was also confirmed that concentration quenching is suppressed with the confirmation of the production | generation of a composite_body | complex.

<< Synthesis Example 2: Synthesis of Complex (CL-Ir-5) >>
0.6 g (0.3 mmol) of inclusion compound CA-6 (n = 5) synthesized in Synthesis Example 2 above was dissolved in 5 ml of ethyl acetate / tetrahydrofuran (THF), and tris (2-phenyl) was added thereto. Pyridine) iridium (Ir (ppy) ₃ ) (0.1 g, 0.15 mmol) was added, and the mixture was stirred for 5 hours and allowed to stand for 12 hours. After the precipitate was filtered off, inclusion Ir (ppy) ₃ was obtained from the filtrate. The resulting inclusion Ir (ppy) ₃ complex (CL-Ir-5) was purified using gel filtration chromatography to obtain a yield of 71% (0.5 g).

  The concentration quenching suppression degree (C / C0) of the complex was 1.40, and it was confirmed that the complex quenching was suppressed as well as the generation of the complex.

<< Synthesis of Complex CL-Ir-1, 2, 4, 6-10 >>
In the synthesis of the complex CL-Ir-3 of Synthesis Example 1, the complex CL-Ir-1, 2, 4, 6 to 10 was changed in the same manner except that the inclusion compound was changed as shown in Table 1. Synthesized.

  The degree of inhibition of concentration quenching (C / C0) of each composite obtained was also the same as in Synthesis Example 1 and Synthesis Example 2.

  Data of inclusion complex of the obtained complex, organometallic complex exhibiting phosphorescence emission, molar ratio at the time of complex formation of the inclusion compound and organometallic complex, and concentration quenching suppression degree of the obtained complex are shown. It is shown in 1.

  From Table 1, the complex of the present invention forms an clathrate from each of the clathrate compound and the organometallic complex exhibiting phosphorescence emission, and at the same time, from the data of the concentration quenching suppression degree of the complex, It can be seen that the intermolecular interaction of the metal complex is appropriately adjusted for the balance between the inclusion effect and the charge injection.

Example 2
<< Production of Organic EL Element 1-1 >>
After patterning on a substrate (NH-Techno Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, 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, 30 mg of polyvinylcarbazole (PVK) and 1.8 mg of PL-14 (Ir (ppy) ₃ ) were dissolved in 1 ml of 1,2-dichloroethane, and spin-coated at 1000 rpm for 5 seconds. (Adjusted to a film thickness of about 100 nm) and vacuum dried at 60 degrees for 1 hour to obtain a light emitting layer.

This was attached to a vacuum deposition apparatus, and then the vacuum chamber was decompressed to 4 × 10 ⁻⁴ Pa, and lithium fluoride 0.5 nm was deposited as a cathode buffer layer and aluminum 110 nm was deposited as a cathode to form a cathode. Finally, glass sealing was performed to prepare an organic EL element 1-1.

<< Production of Organic EL Elements 1-2 to 1-13 >>
In the production of the organic EL device 1-1, except that the phosphorescent dopant PL-14 used in the light emitting layer is changed to the light emitting dopant or the composite shown in Table 2, and the dope concentration is changed, Organic EL elements 1-2 to 1-13 were produced.

<< Evaluation of Organic EL Elements 1-1 to 1-13 >>
Evaluation shown below was performed about obtained organic EL element 1-1 to 1-13.

《External extraction quantum efficiency》
The produced organic EL device was measured for external extraction quantum efficiency (%) when a constant current of ^2.5 mA / cm ² was applied at 23 ° C. in a dry nitrogen gas atmosphere. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used in the same manner.

<Luminescent life>
When driving at a constant current of ^2.5 mA / cm ^{2 in} a dry nitrogen gas atmosphere at 23 ° C., the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. Was used as an index of life as half-life time (τ0.5). For the measurement, a spectral radiance meter CS-1000 (manufactured by Minolta) was used.

<Drive voltage>
The voltage at the start of light emission was measured at a temperature of 23 ° C. and in a dry nitrogen gas atmosphere. The voltage at the start of light emission was measured when the luminance was 50 cd / m ² or more. A spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used for measuring the luminance.

  The measurement results of the external extraction quantum efficiency, the light emission lifetime, and the driving voltage of the organic EL elements 1-1 to 1-11 are shown in Table 3 as relative values when the organic EL element 1-1 is 100.

  From Table 3, it is clear that the organic EL element of the present invention has higher light emission luminance, light emission efficiency, and light emission lifetime than those of the comparison, and the driving power is further reduced.

Example 3
<Production of full-color display device>
(Blue light emitting organic EL device)
In the organic EL device 1-11 produced in Example 2 , PL-14 (Ir (ppy) ₃ ) of the complex (CL-Ir-8) including the phosphorescent dopant PL-14 was changed to PL-26. And organic EL element 1-11B produced by the method similar to organic EL element 1-11 was used except having used the adjusted composite_body | complex (CL-Ir-8B).

(Green light-emitting organic EL device)
The organic EL element 1-11G produced in Example 2 was used.

(Red light emitting organic EL device)
In the organic EL element 1-11 produced in Example 2 , PL-14 of the composite (CL-Ir-8) in which the phosphorescent dopant PL-14 was included was changed to PL-23, and an adjusted composite ( Organic EL element 1-11R produced by the same method as organic EL element 1-11 was used except that CL-Ir-8R) was used.

  The above organic EL elements emitting red, green and blue light are juxtaposed on the same substrate to produce an active matrix type full-color display device having the form shown in FIG. 1, and FIG. Only a schematic diagram of the display unit A is shown. That is, a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions ( Details are not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing the red, green, and blue pixels.

  It was confirmed that by driving the full-color display device, a full-color moving image display having a high light emission efficiency and a long light emission life can be obtained.

Example 4
<< Production of lighting device (using white organic EL element) >>
In the organic EL device 1-11 produced in Example 2 , the complex CL-Ir-8 was changed to a mixture of the complex CL-Ir-8, the complex CL-Ir-8B, and the complex CL-Ir-8R. The organic EL element 1-11W produced by the same method as that of the organic EL element 1-11 was used. The non-light-emitting surface of the organic EL element 1-11W was covered with a glass case to obtain an illumination device as shown in FIGS.

  The obtained illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

  FIG. 5 is a schematic view of the lighting device, and FIG. 6 is a cross-sectional view of the lighting device. The organic EL element 101 is covered with a glass cover 102 and connected with a power line (anode) 103 and a power line (cathode) 104. 105 is a cathode and 106 is an organic EL layer. The glass cover 102 is filled with nitrogen gas 108 and a water replenisher 109 is provided.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 102 Glass cover 103 Power supply line (anode)
104 Power line (cathode)
105 Cathode 106 Organic EL layer 107 Glass substrate with transparent electrode 108 Nitrogen gas 109 Water trapping agent

Claims (5)

A crown ether derivative having a light emitting layer between a cathode and an anode, wherein at least one of the light emitting layers has a hole transporting group or an electron transporting group having a partial structure represented by the following general formula (1A) Alternatively, an organic electroluminescence device comprising at least one kind of a complex in which an organometallic complex exhibiting phosphorescence is included in a calixarene derivative.

[Wherein, R _{1 to} R ₅ each represents a hydrogen atom or a substituent, and Q represents a 5-membered to 6-membered aromatic hydrocarbon ring or a 5-membered to 6-membered structure containing at least one nitrogen atom as a constituent atom. It represents an atomic group necessary for forming a member aromatic heterocycle. ] The organic electroluminescence device according to claim 1, which emits white light. A display device comprising the organic electroluminescence element according to claim 1. An illuminating device comprising the organic electroluminescent element according to claim 1. A display device comprising the lighting device according to claim 4 and a liquid crystal element as a display means.

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