JP5067114B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an organic EL element material that has a controlled emission wavelength, a high luminous efficiency and a long emission lifetime. <P>SOLUTION: The organic electroluminescent element material is a transition metal complex comprising a compound as a ligand in which in an azole ring-condensed phenanthridine derivative such as imidazophenanthridine, pyrazolophenanthridine etc., carbon at 1-position or 10-position of phenanthridine skeleton is substituted with nitrogen and a substituted group such as an alkyl group or an aryl group comprising a hydrocarbon is introduced to the 1-position or 10-position facing the nitrogen. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

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

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements). Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements. An organic EL device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, injects electrons and holes into the light emitting layer, and recombines them to generate excitons (exciton). It is an element that emits light by using light emission (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts, and is also self-luminous. In addition, it is attracting attention from the viewpoints of space saving, portability and the like because it is a thin film type complete solid element with a wide viewing angle and high visibility.

  However, in organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

  In Japanese Patent No. 3093796, a small amount of a phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve an improvement in light emission luminance and a longer device lifetime. Further, an element having an organic light-emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped thereto (for example, JP-A 63-264692), and an 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

  As described above, when light emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University reported on an organic EL device using phosphorescence emission from an excited triplet (MA Baldo et al., Nature, 395, 151-154 (1998)), Research on materials that exhibit phosphorescence has become active.

  For example, M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

  When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%. In principle, the luminous efficiency is four times that of the excited singlet, and there is a possibility that almost the same performance as a cold cathode tube can be obtained. Therefore, it is attracting attention as a lighting application.

  For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds are being studied for synthesis centering on heavy metal complexes such as iridium complexes.

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

In addition, M.M. E. Thompson et al., In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), used L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac), e. 0 g, Tetsuo Tsutsui, etc., again The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), the dopant as tris (2-(p-tolyl) pyridine) iridium (Ir (ptpy) _3), tris ( Studies using benzo [h] quinoline) iridium (Ir (bzq) ₃ ) and the like are being conducted (note that these metal complexes are generally called orthometalated iridium complexes).

  In addition, the S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) and Japanese Patent Application Laid-Open No. 2001-247859, etc., attempts have been made to form devices using various iridium complexes.

  In order to obtain high luminous efficiency, in the 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. Also, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

  Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. With respect to this type of complex, many examples are known in which ligands are characterized.

  In either case, the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element. As described above, it is difficult for phosphorescent highly efficient light-emitting materials to shorten the light emission wavelength and improve the light emission lifetime of the device, and the performance that can withstand practical use cannot be sufficiently achieved.

  In addition, regarding wavelength shortening, introduction of electron-withdrawing groups such as fluorine atoms, trifluoromethyl groups, and cyano groups into phenylpyridine as substituents, and picolinic acid and pyrazaball-type secondary ligands as ligands However, with these ligands, the emission wavelength of the luminescent material is shortened to achieve a blue color, and a high-efficiency device can be achieved. There was a need to improve the trade-off.

  A metal complex having phenylpyrazole substituted with a phenyl group as a ligand is known (for example, see Patent Documents 1 and 2). However, while the phenyl group substitution mode disclosed here improves the lifetime of the light emitting device, it is still not sufficient, and there is still room for improvement from the viewpoint of the light emission wavelength and the light emission efficiency.

  Examples in which various substituents are introduced using phenylimidazole as a basic skeleton as a ligand are disclosed (for example, see Patent Documents 3, 4, and 5), but the emission wavelength is not sufficiently shortened, There is room for improvement when aiming for a blue light source with high color purity.

  As another approach, an example in which a condensed structure of 18π electron system composed of four or more rings including a nitrogen atom is introduced into the structure of the ligand is disclosed (see Patent Documents 6 and 7). In particular, the compound group shown in Examples in Patent Document 7 shows short-wave light emission, and it is shown that the light emission efficiency, the light emission lifetime, and the like have good performance. However, as noted in the specification of Patent Document 7, these compounds are greatly photooxidatively deteriorated by ambient light in the air, and are sufficient as organic EL device materials if they are not synthesized with attention to the handling environment. There was a problem that a product of purity could not be obtained. Therefore, in order to obtain the compounds shown in the Examples of Patent Document 7 with high purity, the working atmosphere is an oxygen-free atmosphere, and synthesis and purification are performed under a safe light source that cuts short-wave light. That kind of response was necessary.

  The property of such compounds is that the facilities that can be used for industrially large-scale synthesis are limited, and the quality is stable when manufacturing organic EL devices by a wet process without using a vacuum environment. There was also a strong demand for a solution from the point of making it difficult. Further, there has been a demand for further shortening of the emission wavelength for the purpose of a blue light source with high color purity.

  There are various techniques for improving the light emission lifetime of the organic electroluminescence element. For example, there is a technique of increasing the molecular weight after forming a constituent layer of an organic electroluminescence element.

For example, a bifunctional triphenylamine derivative having two vinyl groups in the molecule is disclosed, and after forming the compound film, it is disclosed to form a three-dimensionally crosslinked polymer by ultraviolet irradiation ( For example, see Patent Document 8). In addition, a technique for adding a material having two or more vinyl groups to a plurality of layers is disclosed. The polymerization reaction is performed by irradiation with ultraviolet rays or heat at the time of forming an organic layer before laminating the cathode. It is disclosed (for example, see Patent Document 9). Also, AIBN (azoisobutyronitrile), which is a radical generator, is added to a mixture of comonomer having a vinyl group in the same manner as a material having a vinyl group at the end of a phosphorescent dopant, and a polymerization reaction proceeds during film formation. A manufacturing method is disclosed. (For example, see Patent Document 10)
In the method of manufacturing an organic electroluminescence device by a wet process using these polymerization reactions, there is a need for a compound having higher stability in the organic EL device material because it is accompanied by irradiation with ultraviolet rays or heat and radical species. Has been.
International Publication No. 04/085450 Pamphlet JP 2005-53912 A International Publication No. 05/007767 Pamphlet International Publication No. 06/046980 Pamphlet International Publication No. 06/121811 Pamphlet International Publication Number 06/61180 Pamphlet International Publication No. 07/95118 Pamphlet Japanese Patent Laid-Open No. 5-271166 JP 2001-297882 A Japanese Patent Laid-Open No. 2003-73666

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic EL element material having a light emission wavelength controlled, high light emission efficiency, and a long light emission lifetime. In particular, it is to provide an organic EL device material that exhibits high light emission efficiency and has a long light emission lifetime even in light emission of blue to light blue short waves. Another object of the present invention is to provide an organic EL element material that is highly suitable for manufacturing an organic EL element using a highly productive wet process and can be manufactured with sufficient purity even in a special environment. Furthermore, it is providing the organic EL element, display apparatus, and illuminating device using the same.

  The above object of the present invention has been achieved by the following constitution.

  (1) An organic electroluminescence element material, which is a transition metal complex represented by the following general formula (1).

Wherein Y ₀ and Y ₃ represent N or C, Y ₁ and Y ₂ represent R ₁ -N, N or R ₂ -C, and together with N, a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring A 5-membered nitrogen-containing aromatic heterocycle A selected from:
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B selected from a benzene ring, a pyridine ring, a pyrimidine ring or a pyridazine ring.
Y ₇ and Y ₈ are selected from carbon and nitrogen, and form an aromatic 6-membered heterocyclic ring C selected from a pyridine ring, a pyrimidine ring or a pyridazine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the aromatic 6-membered heterocyclic ring C, and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B, and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(2) The organic electroluminescence element material according to (1), wherein the transition metal complex represented by the general formula (1) is represented by the following general formula (2).

Wherein Y ₀ and Y ₃ represent N or C, Y ₁ and Y ₂ represent R ₁ -N, N or R ₂ -C, and together with N, a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring A 5-membered nitrogen-containing aromatic heterocycle A selected from:
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ , and Y ₆ are selected from carbon or nitrogen to form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ , and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(3) The organic electroluminescence element material according to (2), wherein the transition metal complex represented by the general formula (2) is represented by the following general formula (3).

(Wherein Y ₁ and Y ₂ represent N or R ₂ —C, and together with C and N, form an aromatic 5-membered heterocyclic ring A ₁ selected from an imidazole ring, a triazole ring, or a tetrazole ring.
R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ , and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(4) The organic electroluminescence element material according to (3), wherein the transition metal complex represented by the general formula (3) is represented by the following general formula (4).

(In the formula, R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0 or 1.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ , and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(5) The organic electroluminescence element material according to (2), wherein the transition metal complex represented by the general formula (2) is represented by the following general formula (5).

(Wherein Y ₁ represents N or R ₂ —C, and together with C and N forms a 5-membered nitrogen-containing aromatic heterocyclic ring A ₂ selected from an imidazole ring or a triazole ring.
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ . m represents 0, 1 or 2; When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(6) The organic electroluminescence element material according to (5), wherein the transition metal complex represented by the general formula (5) is represented by the following general formula (6).

(Wherein R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ or Y ₆ is selected from carbon or nitrogen and forms an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0 or 1.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(7) The organic electroluminescence element material according to (2), wherein the transition metal complex represented by the general formula (2) is represented by the following general formula (7).

Wherein Y ₁ and Y ₂ represent N or R ₂ —C, and together with C and N, a 5-membered nitrogen-containing aromatic heterocyclic ring A ₃ selected from a pyrazole ring, a triazole ring, or a tetrazole ring Form.
R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ . m represents 0, 1 or 2; When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(8) The organic electroluminescence element material according to (7), wherein the transition metal complex represented by the general formula (7) is represented by the following general formula (8).

(In the formula, R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0 or 1.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(9) The organic electroluminescence element material according to (2), wherein the transition metal complex represented by the general formula (2) is represented by the following general formula (9).

(Wherein Y ₂ represents N or R ₂ —C, and together with C and N, forms a 5-membered nitrogen-containing aromatic heterocyclic ring A ₄ selected from a pyrazole ring or a triazole ring.
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B ₁ selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ . m represents 0, 1 or 2; When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(10) The organic electroluminescent element material as described in (9) above, wherein the metal complex represented by the general formula (9) is represented by the following general formula (10).

(In the formula, R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B1 selected from a benzene ring or a pyridine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the pyridine ring C ₁ , and m represents 0 or 1.
G ₃ represents a substituent of the aromatic 6-membered ring B ₁ . n represents 0, 1, 2 or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. )
(11) In the general formulas (1) to (10), the central metal M ₁ is iridium. The organic electroluminescence element material according to any one of (1) to (10), wherein the center metal M ₁ is iridium.

(12) The organic electroluminescent element material according to any one of (1) to (10), wherein in the general formulas (1) to (10), the central metal M ₁ is platinum.

  (13) The organic electroluminescent element material according to any one of (1) to (12), wherein m2 is 0 in the general formulas (1) to (10).

  (14) The organic electroluminescence element material according to any one of (1) to (13), wherein the first emission wavelength at room temperature is in the range of 400 to 480 nm.

  (15) An organic electroluminescent element comprising the organic electroluminescent element material according to any one of (1) to (14).

  (16) The above (15), wherein the constituent layer has a light emitting layer, and the light emitting layer contains the organic electroluminescence element material according to any one of (1) to (14). The organic electroluminescent element of description.

  (17) The light emitting layer contains a carbazole derivative or a derivative having a ring structure in which at least one carbon atom of a hydrocarbon ring constituting the carbazole ring of the carbazole derivative is substituted with a nitrogen atom. The organic electroluminescence device according to (16).

  (18) It has a hole blocking layer as a constituent layer, and at least one of the carbon atoms of the hydrocarbon ring constituting the carbazole ring of the carbazole derivative or the carbazole ring of the carbazole derivative is substituted with a nitrogen atom. The organic electroluminescence device according to any one of (15) to (17), wherein the organic electroluminescence device comprises a derivative having a ring structure.

  (19) It has an organic layer containing the transition metal complex represented by any one of the general formulas (1) to (10) as a constituent layer, and the organic layer is formed using a wet process. The organic electroluminescence device according to any one of (15) to (18), wherein

  (20) The organic electroluminescent element as described in (19) above, wherein the organic layer is a light emitting layer.

  (21) The organic electroluminescent element as described in (19) above, wherein the organic layer is a non-light emitting charge transport layer.

  (22) An organic electroluminescence device comprising at least one organic layer sandwiched between an anode and a cathode, wherein the organic layer is represented by any one of the general formulas (1) to (10) The organic electroluminescence device according to any one of (15) to (19), wherein the organic electroluminescence device comprises a polymer having a structural unit derived from

  (23) The organic electroluminescent element as described in (22) above, wherein the organic layer is a light emitting layer.

  (24) The organic electroluminescent element as described in (22) above, wherein the organic layer is a non-light emitting charge transport layer.

  (25) The organic electroluminescence element as described in any one of (15) to (24) above, which emits white light.

  (26) A display device comprising the organic electroluminescence element according to any one of (15) to (25).

  (27) An illuminating device comprising the organic electroluminescent element according to any one of (15) to (25).

  According to the present invention, an organic EL element material useful for an organic EL element is obtained. By using the organic EL element material, an emission wavelength is controlled, high emission efficiency is exhibited, and an organic EL element having a long emission lifetime, white A light-emitting organic EL element, a lighting device, and a display device could be provided.

  In the organic EL element material of the present invention, the organic EL element material useful for the organic EL element has been successfully molecularly designed by the configuration defined in any one of (1) to (14).

  As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have greatly improved the stability of the compounds represented by the general formulas (1) to (10), so that they can be used under normal atmospheric conditions. There is no degradation or decomposition due to photo-oxidation, which is a practical problem in handling, and the organic EL element containing those transition metal complexes as organic EL element materials has a light emission efficiency and a light emission lifetime while having a short wavelength emission wavelength. The knowledge that it improved greatly was acquired.

  This makes it possible to stably manufacture an organic EL element that exhibits high light emission efficiency and has a long light emission lifetime, particularly in a manufacturing method using a wet process.

  As a result of intensive studies, the present inventors have found that among phenanthridine derivatives (A), phenanthridine derivatives condensed with an azole ring such as imidazophenanthridine (B) and pyrazolophenanthridine (C) When focusing on the nanthridine ring, the 1st or 10th carbon of the phenanthridine skeleton is replaced with nitrogen, and the 1st or 10th position opposite to it is a substituent composed of a hydrocarbon such as an alkyl group or an aryl group. The transition metal complexes having these compounds as ligands emit light at shorter wavelengths, and the stability of the complexes is higher than that of transition metal complexes having the parent phenanthridine derivative as a ligand. It has been greatly improved and it has been found that there is almost no deterioration even when handled in the atmosphere under ordinary illumination light.

Here, E _{1 to} E ₃ represent nitrogen or carbon.

  When the carbon on the phenanthridine ring was replaced with nitrogen, the stability of the transition metal complex having the derivative as a ligand was improved in the 1st or 10th position of the phenanthridine ring. In addition, they are common in that they become p-positions with respect to the transition metal coordinated when they are complexed. The same effect was not observed even if only one carbon atom at other positions was replaced with nitrogen. For example, in the case of imidazophenanthridine (B), the improvement in stability was recognized only in the 1st or 10th position of the phenanthridine ring as follows.

  Further, the present inventors have studied various changes in the number of nitrogen atoms constituting the heterocyclic ring and substitution of positions, and phenanthridine such as triazolophenanthridine (D) and tetrazolophenanthridine (E). Similar effects were confirmed for the derivatives.

  Further, in the phenanthrin derivative (F) in which the parent phenasridine is replaced with phenanthrine, phenanthroimidazole (G), phenanthropyrazole (H), and phenant, which are heterocyclic compounds in which an azole ring is condensed, are also used. In rotriazole (I) and the like, the same effect was confirmed by the same operation as that of the phenanthridine derivative (substitution of the nitrogen atom for the 4-position and substitution of a hydrocarbon group for the 5-position).

Here, E _{1 to} E ₃ represent nitrogen or carbon.

  Furthermore, the present inventors examined various effects of further replacing nitrogen on the pyridine ring and the benzene ring with nitrogen in the above-mentioned various heterocycles, and regarding the site not involved in complex formation when becoming a transition metal complex. Confirmed that the stability of the transition metal complex was not impaired, although the emission wavelength was changed by replacing the carbon atom with the nitrogen atom. In addition, the effect of the substituent is also examined in the same way, and the stability of the transition metal complex is lost although the emission wavelength is changed by the introduction of the substituent at the site that does not participate in the complex formation when the transition metal complex is formed. I confirmed that it was not possible.

  Therefore, it was confirmed that the emission wavelength can be adjusted by further replacing the carbon on the pyridine ring and the benzene ring with nitrogen or introducing a substituent in the above-mentioned various heterocyclic rings.

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

  The metal complex which concerns on the organic EL element material of this invention is demonstrated.

(Ligand)
For example, when the metal complex according to the present invention is described by the above general formula (1), the partial structure shown in parentheses having m1 or the partial structure represented by a tautomer thereof is the main ligand, and m2 A partial structure shown in parentheses or a partial structure represented by a tautomer thereof is called a subligand.

  In the present invention, as represented by the general formula (1), the metal complex is composed of a combination of a main ligand or a tautomer thereof and a subligand or a tautomer thereof, As will be described later, in the case of m2 = 0, that is, all of the ligands of the metal complex may be composed only of a partial structure represented by the main ligand or a tautomer thereof.

  Further, as a so-called ligand used for forming a conventionally known metal complex, the trader may have a known ligand (also referred to as a coordination compound) as a sub-ligand as necessary.

  From the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type. When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis.

  There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin, 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabosha, Akio Yamamoto, published by 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands). Preferred are diketones or picolinic acid derivatives.

  Although the example of a subligand is specifically mentioned below, this invention is not limited to these.

In the formula, M ₁ represents the same as that in the general formula (1). Ra and Rc each represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. Rb represents a hydrogen atom or a substituent.

(Transition metal element of group 8-11 of the periodic table)
As the metal used for forming the metal complex represented by the general formulas (1) to (10) according to the present invention, a transition metal element of group 8 to 11 of the periodic table (also simply referred to as a transition metal) is used. Among them, iridium and platinum are preferable transition metal elements in that the emission quantum yield of the transition metal complex is high.

  As the containing layer of the metal complex represented by the general formulas (1) to (10) according to the present invention, a light emitting layer and / or an electron blocking layer are preferable, and when contained in the light emitting layer, By using it as a light-emitting dopant, it is possible to improve the external extraction quantum efficiency of the organic EL device of the present invention (increase the luminance) and increase the light emission lifetime.

  Here, the metal complex represented by the general formulas (1) to (10) according to the present invention will be described.

In the general formulas (1) to (10), Y ₀ and Y ₃ represent N or C, Y ₁ and Y ₂ represent R ₁ -N, N or R ₂ -C, and together with N, a 5-membered nitrogen-containing aroma Group heterocyclic ring A or A _{1 to} A ₄ is formed.

  The nitrogen-containing aromatic heterocycle A is selected from a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring.

The nitrogen-containing aromatic heterocyclic ring A ₁ is selected from an imidazole ring, a triazole ring, or a tetrazole ring.

The nitrogen-containing aromatic heterocyclic ring A ₂ is selected from an imidazole ring or a triazole ring.

The nitrogen-containing aromatic heterocyclic ring A ₃ is selected from a pyrazole ring, a triazole ring, or a tetrazole ring.

The nitrogen-containing aromatic heterocyclic ring A ₄ is selected from a pyrazole ring or a triazole ring.

In general formulas (1) to (10),
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

  Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

  Examples of the aryl group include phenyl, mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl and the like.

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group and the like.

  These groups may be further substituted, and examples of the substituent include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl etc.) Group), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group Acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenyl Eneyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole- 1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Quinoxalinyl group, pyridazinyl group, triazi Group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, Hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, Methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, Phthalylthio group), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, Naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group) , Phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl) Propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, Ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group) Group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecyl Carbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, Octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido) Group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), Sulfinyl group (for example, methylsulfinyl 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 or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino) Group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (for example, 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. In addition, a plurality of these substituents may be bonded to each other to form a ring.

R ₂ represents a hydrogen atom or a substituent. Examples of the substituent include the same as those exemplified as the substituent of R ₁ . Preferably, it is a hydrogen atom, or a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. .

When R ₂ is a substituent, bound together with another R ₂ substituents or R ₂ of R ₁ to R ₂ are adjacent to each other adjacent may form a ring. The ring to be formed may be a saturated ring or an aromatic ring.

Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B or B ₁ . The aromatic 6-membered ring B is selected from a benzene ring, a pyridine ring, a pyrimidine ring or a pyridazine ring.

The aromatic 6-membered ring B ₁ is selected from a benzene ring or a pyridine ring.

  The aromatic 6-membered ring B is preferably selected from a benzene ring or a pyridine ring in view of easy ligand synthesis.

Y ₇ and Y ₈ are selected from carbon or nitrogen and form an aromatic 6-membered heterocyclic ring C.
The aromatic 6-membered heterocyclic ring C is selected from a pyridine ring, a pyrimidine ring or a pyridazine ring. The aromatic 6-membered heterocyclic ring C is preferably a pyridine ring because of easy ligand synthesis.

G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.

Examples of the alkyl group, cycloalkyl group, aryl group and aromatic heterocyclic group are the same as those exemplified as R ₁ . These groups may be further substituted, and examples of the substituent include the same as those exemplified as the substituent of R ₁ .

  G1 is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

G ₂ represents a substituent of an aromatic 6-membered heterocyclic ring C or a pyridine ring C ₁ , and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.

G ₂ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

G ₃ represents an aromatic 6-membered ring B or a B ₁ substituent, and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring. Examples of the substituent include the same as those exemplified as the substituent of R ₁ .

M ₁ which is a central metal represents a metal of Group 8 to 11 in the periodic table. Examples of preferred central metals include ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold and the like. More preferred are iridium and platinum.

The following is a structure of the main ligands of the present invention together with the central metal M _1.

In the formula, G ₁ , G ₂ , G ₃ , m, n, R ₁ , R ₂ , and M ₁ represent the same as those in the general formula (1).

The number of nitrogen atoms in the fused azole ring is preferably 2 in terms of high emission quantum yield, and Y ₀ , Y _{3 in} the bridgehead position of the fused azole ring in terms of shorter emission maximum wavelength. Either is preferably nitrogen, in which case Y ₂ is preferably HC.

  That is, as the structure of the main ligand, among the above, imidazonaphthyridine derivatives, pyrazolonaphthyridine derivatives, imidazobenzoquinoline derivatives, imidazophenanthroline derivatives, pyrazolobenzoquinoline derivatives, pyrazolophenanthroline derivatives, imidazoquinoline derivatives, imidazonaphthyridine Derivatives, pyrazoloisoquinoline derivatives, pyrazolonaphthyridine derivatives, imidazoquinazoline derivatives, imidazocinnoline derivatives, pyrazoloquinazoline derivatives, pyrazolocinnoline derivatives, more preferably imidazolonaftyridine derivatives, pyrazolonaphthyridine derivatives, imidazoquinoline Derivatives, imidazonaphthyridine derivatives, pyrazoloisoquinoline derivatives, pyrazolonaphthyridine derivatives.

In the general formulas (1) to (10), X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ are each independently a carbon atom, nitrogen atom, oxygen atom, phosphorus atom or Represents a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .

Specific examples of the bidentate ligand (subligand) represented by X ₁ -L ₁ -X ₂ include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, Examples include pyraza ball, acetylacetone, and picolinic acid. m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. Among these, m2 is preferably 0.

  When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis. In this case, it is preferable to introduce a reactive group into the substituent of the main ligand as a sub-ligand.

  Moreover, in the transition metal complex which is the organic EL light emitting material of the present invention, the first emission wavelength at room temperature is preferably in the range of 400 to 480 nm.

  The first emission wavelength refers to the shortest component of the emitted light that can be excited by the absorption wavelength of the metal complex, and the first emission wavelength can be obtained by measurement using a fluorometer. .

  Hereinafter, although the specific example of the transition metal complex represented by the said General Formula (1)-(10) which concerns on this invention is shown, this invention is not limited to these.

  In the following compound examples, acac and ppz each represent a sub-ligand having the following structure.

  These metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and further synthesized by applying methods such as references described in these documents. it can.

  Below, the synthesis example of a typical compound is shown.

  Synthesis of Exemplary Compound 1-1-7

  To a solution of 2.4 g (9.2 mmol) of 2,8,10-trimethylbenzo [h] imidazo [2,1, f] [1,6] -naphthyridine dissolved in 30 ml of 2-ethoxyethanol under a nitrogen atmosphere. Iridium chloride trihydrate, 1.06 g (3.0 mmol) and 10 ml of water were added, and the mixture was refluxed for 5 hours under a nitrogen atmosphere. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and dried to obtain 1.93 g (yield 86%) of complex A.

  Under a nitrogen atmosphere, Complex A, 1.50 g (1.0 mmol) and sodium carbonate, 2.2 g, were suspended in 35 ml of 2-ethoxyethanol. To this suspension, 0.4 g (4.0 mmol) of acetylacetone was added and refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by filtration under reduced pressure. The solid obtained after concentration of the solvent under reduced pressure was suspended by adding 100 ml of water, and the solid was collected by filtration. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and after drying, 1.46 g (yield 90%) of Complex B was obtained.

  Complex B, 0.73 g (0.9 mmol) and 2,8,10-trimethylbenzo [h] imidazo [2,1, f] [1,6] -naphthyridine 0.78 g (3. 0 mmol) was suspended in 40 ml of glycerin. The reaction was completed at a reaction temperature of 150 to 160 ° C. for 2 hours under a nitrogen atmosphere, and when the disappearance of the complex B was confirmed, the reaction was terminated. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and dried to obtain 0.63 g (yield 72%) of a crude product. This crude product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography (methylene chloride) to obtain 0.56 g (yield 64%) of exemplary compound 1-1-7.

  It was confirmed by MASS and 1H-NMR that the purified compound was the target product.

1H-NMR (400 MHz, THF-d8)
(Chemical shift δ, peak shape, proton number):
δ = 1.35 (s, 9H, CH ₃ −), 1.75 (s, 9H, CH ₃ −), 1.86 (s, 9H, CH ₃ −), 6.82 (s, 3H), 7.35 (t, 3H), 7.43 (t, 3H), 7.74 (s, 3H), 8.32 (t, 3H)
The PL emission maximum wavelength in the solution of Exemplified Compound 1-1-7 measured using Hitachi F-4500 was 442 nm (T = 77 K, in 2-methyltetrahydrofuran), 445 nm (room temperature, in methylene chloride). It was.

  Synthesis of Exemplary Compound 5-1-7

  In a nitrogen atmosphere, iridium chloride was added to a solution of 2.23 g (9.0 mmol) of 7,12-dimethylbenzo [c] pyrazolo [1,5, a] [1,5] naphthyridine in 30 ml of 2-ethoxyethanol. Trihydrate, 1.06 g (3.0 mmol) and 10 ml of water were added and refluxed for 5 hours under a nitrogen atmosphere. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol and dried to obtain 1.90 g (yield 88%) of Complex C.

  Complex C, 1.44 g (1.0 mmol) and sodium carbonate, 2.0 g were suspended in 35 ml of 2-ethoxyethanol under a nitrogen atmosphere. To this suspension, 0.4 g (4.0 mmol) of acetylacetone was added and refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by filtration under reduced pressure. The solid obtained after concentration of the solvent under reduced pressure was suspended by adding 100 ml of water, and the solid was collected by filtration. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and dried to obtain 1.41 g (yield 90%) of Complex D.

  Under a nitrogen atmosphere, Complex D, 0.71 g (0.9 mmol) and 7,12-dimethylbenzo [c] pyrazolo [1,5, a] [1,5] naphthyridine 0.74 g (3.0 mmol) were added. It was suspended in 40 ml of glycerin. The reaction was performed at a reaction temperature of 150 to 160 ° C. for 6 hours under a nitrogen atmosphere, and when the disappearance of the complex D was confirmed, the reaction was terminated. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and dried to obtain 0.57 g (68% yield) of a crude product. This crude product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography (methylene chloride) to obtain 0.52 g (yield 62%) of exemplary compound 5-1-7.

  It was confirmed by MASS and 1H-NMR that the purified compound was the target product.

1H-NMR (400 MHz, THF-d8)
(Chemical shift δ, peak shape, proton number):
δ = 2.07 (s, 9H, CH ₃ −), 2.42 (s, 9H, CH ₃ −), 5.98 (s, 3H), 7.05 (d, 3H), 7.06 ( t, 3H), 7.14 (t, 3H), 7.53 (s, 3H), 8.57 (d, 3H)
The PL emission maximum wavelength in a solution of Exemplified Compound 5-1-7 measured using Hitachi F-4500 was 443 nm (T = 77 K, in 2-methyltetrahydrofuran), 447 nm (room temperature, in methylene chloride). It was.

<< Application of organic EL element materials to organic EL elements >>
When producing the organic EL element of the present invention using the organic EL element material of the present invention, the organic EL element of the present invention is formed on the light emitting layer or the electron blocking layer in the constituent layers of the organic EL element (details will be described later) It is preferable to use a material. In the light emitting layer, it is preferably used as a light emitting dopant as described above.

(Light emitting host and light emitting dopant)
The mixing ratio of the light-emitting dopant to the light-emitting host, which is the host compound as the main component in the light-emitting layer, is preferably adjusted to a range of 0.1 to less than 30% by mass.

  However, the light-emitting dopant may be a mixture of a plurality of types of compounds, and the partner to be mixed may be a phosphorescent dopant or a fluorescent dopant having a different structure, other metal complexes or other structures.

  Here, the dopant that may be used in combination with the metal complex used as the light-emitting dopant will be described. Luminescent dopants are roughly classified into two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.

  Typical examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  A typical example of the latter (phosphorescent dopant) is preferably a complex compound containing a transition metal element of Group 8, 9, or 10 in the periodic table, and more preferably an iridium compound or an osmium compound. Of these, iridium compounds are most preferred.

  Specifically, it is a compound described in the following patent publications.

  WO 00/70655 pamphlet, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP 2001-247859, JP 2002-299060, JP 2001-313178, JP 2002-302671, JP 2001-345183, JP 2002-324679, International Publication No. 02/15645 pamphlet, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-2002 A. No. 117978, JP 20 JP-A-2-338588, JP-A-2002-170684, JP-A-2002-352960, WO01 / 93642, JP-A-2002-50483, JP-A-2002-1000047, JP-A-2002. No. -173744, JP-A No. 2002-359082, JP-A No. 2002-17584, JP-A No. 2002-363552, JP-A No. 2002-184582, JP-A No. 2003-7469, JP-T-2002-525808. Gazette, JP2003-7471, JP2002-525833, JP2003-31366, JP2002-226495, JP2002-234894, JP2002-2335076 JP 2002-241751 A JP 2001-319779, JP 2001-319780, JP 2002-62824, JP 2002-1000047, JP 2002-203679, JP 2002-343572, JP 2002-203678 gazette etc.

  Some specific examples are shown below.

  The host compound used in the present invention represents 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.

  The light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligoarylene. Examples thereof include compounds having a basic skeleton such as compounds, or carboline derivatives and derivatives having a ring structure in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom. Among these, carbazole derivatives, carboline derivatives, and derivatives having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom are preferably used.

  Specific examples are given below, but the present invention is not limited thereto. These compounds are also preferably used as hole blocking materials.

  In the light emitting layer according to the present invention, a plurality of known host compounds may be used in combination as a 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. These known host compounds have a hole transporting ability and an electron transporting ability and prevent emission of longer wavelengths, and have a high Tg (glass transition of 90 ° C. or higher, more preferably 100 ° C. or higher. Temperature) compounds are preferred. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

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

  As the light-emitting host, a compound having a hole transporting ability and an electron transporting ability, preventing a long wavelength of light emission, and having a high Tg (glass transition temperature) is preferable.

  As specific examples of the light-emitting host, compounds described in the following documents are suitable. For example, Japanese Patent Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, JP2002-8860, JP2002-334787, JP2002-15871, JP2002-334788, JP2002-43056, JP2002-334789, JP JP 2002-75645 A, JP 2002-338579 A, JP 2002-105445 A, JP 2002-343568 A, JP 2002-141173 A, JP 2002-352957 A, JP 2002-2002 A. No. 203683, JP-A-2002-3632 7, JP 2002-231453, JP 2003-3165, JP 2002-234888, JP 2003-27048, JP 2002-255934, JP 2002-286061. JP, JP-A-2002-280183, JP-A-2002-299060, JP-A-2002-302516, JP-A-2002-305083, JP-A-2002-305084, JP-A-2002-308837, etc. .

  The light emitting layer may further contain a host compound having a fluorescence maximum wavelength 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.

  Next, a configuration of a typical organic EL element will be described.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described.

  Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these.

(I) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (ii) Anode / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iii) Anode / Hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iv) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode ( v) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vi) Anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / Hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) Anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode 《Blocking layer (electron blocking layer, hole blocking layer)》
The blocking layer (for example, electron blocking layer, hole blocking layer) according to the present invention will be described.

  In the present invention, the organic EL device material of the present invention is preferably used for a hole blocking layer, an electron blocking layer, and the like, and particularly preferably used for a hole blocking layer.

  When the organic EL element material of the present invention is contained in the hole blocking layer and the electron blocking layer, the organic EL element material of the present invention described in any one of claims 2 to 8 is added to the hole blocking layer or It may be contained in a state of 100% by mass as a layer constituent component such as an electron blocking layer, or may be mixed with other organic compounds.

  The thickness of the blocking layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

《Hole blocking layer》
The hole blocking layer has the function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons but has a very small ability to transport holes, and blocks holes while transporting electrons. Thus, the probability of recombination of electrons and holes can be improved.

  Examples of the hole blocking layer include, for example, JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization thereof (issued by NTT Corporation on November 30, 1998)” Can be applied as the hole blocking layer according to the present invention. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  The organic EL device of the present invention has a hole blocking layer as a constituent layer, and at least one of the carbon atoms of the hydrocarbon ring constituting the carboline derivative or the carboline ring of the carboline derivative is a nitrogen atom. It is preferable to contain a derivative having a substituted ring structure.

《Electron blocking layer》
On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

《Hole transport layer》
The hole transport layer includes a 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 is not particularly limited, and is conventionally used as a hole charge injection / transport material in a photoconductive material, or used for a hole injection layer or a hole transport layer of an organic EL device. Any one of known ones can be selected and used.

  The hole transport material has one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (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, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ′, 4′-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

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

  This 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, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, it is about 5-5000 nm. The 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 is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided with a single layer or a plurality of layers.

  Conventionally, in the case of a single-layer electron transport layer and a plurality of layers, the following materials are used as the electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer. Are known.

  Further, the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material can be selected and used from conventionally known compounds.

  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, Fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, carboline derivative, or a ring in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom Examples thereof include derivatives having a structure. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as an electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  This 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, 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, it is about 5-5000 nm. This electron transport layer may have a single layer structure composed of one or more of the above materials.

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

<< Injection Layer >>: Electron Injection Layer, Hole Injection Layer An injection layer is provided as necessary, and includes an electron injection layer and a hole injection layer, and as described above, between the anode and the light emitting layer or the hole transport layer, and the cathode. Between the light emitting layer and the electron transport layer.

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

  Details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like, and a specific example is represented by copper phthalocyanine. Phthalocyanine buffer layers, oxide buffer layers typified by vanadium oxide, amorphous carbon buffer layers, polymer buffer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.

  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. Examples include a metal buffer layer represented by an alkali metal compound buffer layer represented by lithium fluoride, an alkaline earth metal compound buffer layer represented by magnesium fluoride, and an oxide buffer layer represented by aluminum oxide.

  The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 to 100 nm although it depends on the material.

  This injection 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. Although there is no restriction | limiting in particular about the film thickness of an injection | pouring layer, Usually, it is about 5-5000 nm. The injection layer may have a single layer structure composed of one or more of the above materials.

"anode"
As the anode according to the organic EL device of the present invention, an electrode having a work function (4 eV or more) metal, alloy, electrically conductive compound and a mixture thereof as an electrode material is preferably used.

Specific examples of such electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

"cathode"
On the other hand, as the cathode according to the present invention, a cathode having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 to 1000 nm, preferably 50 to 200 nm. In order to transmit light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

<< Substrate (also referred to as substrate, substrate, support, etc.) >>
The substrate of the organic EL device of the present invention is not particularly limited as to the type of glass, plastic and the like, and is not particularly limited as long as it is transparent. Examples of the substrate preferably used include glass and quartz. And a light transmissive resin film. 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. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like.

An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and the film should be a high barrier film having a water vapor transmission rate of 0.01 g / m ² · day · atm or less. preferable.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 2% 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.

  Further, a hue improving filter such as a color filter may be used in combination.

  When used in lighting applications, a film (such as an antiglare film) that has been roughened to reduce unevenness in light emission can be used in combination.

  When used as a multicolor display device, it is composed of at least two types of organic EL elements having different light emission maximum wavelengths. A suitable example for producing an organic EL element will be described.

<< 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 / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode. Will be described.

  First, a thin film made of a desired electrode material, for example, a material for an anode 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 to 200 nm to produce an anode. . Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, or an electron transport layer, which is an element material, is formed thereon.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL device is preferably manufactured from the hole injection layer to the cathode consistently by a single vacuum, 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.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

  As a method for thinning a thin film containing an organic compound, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a uniform film can be easily obtained and a pinhole is obtained. From the point of being difficult to generate, a vacuum deposition method or a spin coating method is particularly preferable. Further, a different film forming method may be applied for each layer.

When employing a vapor deposition method for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 It is desirable to select appropriately within a range of ˜50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 0.1 to 5 μm.

  In the case where a large-area organic EL device is manufactured in large quantities, film formation by a wet process such as a spin coating method, an ink jet method, a printing method or the like is preferable.

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

<Display device>
The display device of the present invention will be described. The display device of the present invention has the organic EL element.

  Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.

  When patterning is performed only on the light-emitting layer, the method is not limited, but 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.

  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. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or 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.

  Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. For example, it is not limited to this.

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

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However, It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.

  The organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display). The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

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

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

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

  FIG. 1 is a schematic view showing an example of a display device composed of 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 a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the 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.

  In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning line 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 the orthogonal positions (details are illustrated). Not)

  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 on the same substrate.

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

  FIG. 3 is 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 light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. 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 by turning on / off a predetermined light emission amount by a binary image data signal. Good. 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 diagram 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 material of the present invention can be applied as an illumination device to an organic EL element that emits substantially white light. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed. It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

  As described above, the white light emitting organic EL element according to the present invention is used as a kind of lamp such as household illumination, interior lighting, and exposure light source as various light emitting light sources and lighting devices in addition to the display device and display. It is also useful for display devices such as backlights for 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. There are 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
<< Production of Organic EL Element 1-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl alcohol. Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while α-NPD, H4, comparative compound 1, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively, and a vacuum deposition apparatus (first (Vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten.

First, after reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and the transparent support substrate was deposited at a deposition rate of 0.1 to 0.2 nm / sec. The film was deposited to a thickness of 20 nm, and a hole injection / transport layer was provided.

  Further, the heating boat containing H4 and the boat containing comparative compound 1 are energized independently to adjust the deposition rate of H4 as a light emitting host and comparative compound 1 as a light emitting dopant to 100: 6. And it vapor-deposited so that it might become a film thickness of 30 nm, and provided the light emitting layer.

Subsequently, the said heating boat containing BCP was heated by supplying electricity, and a 10-nm-thick hole blocking layer was provided at a deposition rate of 0.1-0.2 nm / second. Further, the heating boat containing Alq ₃ was energized and heated to provide an electron transport layer having a film thickness of 20 nm at a deposition rate of 0.1 to 0.2 nm / second.

  Next, after the element deposited up to the electron transport layer was transferred to the second vacuum chamber while being vacuumed, it was remotely controlled from the outside of the apparatus so that a stainless steel rectangular perforated mask was placed on the electron transport layer. Installed.

After depressurizing the second vacuum tank to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was provided at a deposition rate of 0.01 to 0.02 nm / second by energizing a boat containing lithium fluoride. Next, a boat containing aluminum was energized, a cathode having a film thickness of 150 nm was attached at a deposition rate of 1 to 2 nm / second, and an organic EL device 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-26 >>
In the production of the organic EL element 1-1, organic EL elements 1-2 to 1-26 were produced in the same manner except that the light emitting host, the light emitting dopant and the hole blocking material were changed as shown in Table 1.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-26, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side Then, it was cured and sealed, and an illumination device as shown in FIGS. 5 and 6 was formed and evaluated.

  FIG. 5 is a schematic view of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more). 6 shows a cross-sectional view of the lighting device. In FIG. 6, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

(External quantum efficiency)
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance. The external extraction quantum efficiency was expressed as a relative value with the organic EL element 1-1 as 100.

(Luminescent life)
The organic EL device was continuously lit at a constant current of 10 mA / cm ² at room temperature, and the time (τ _1/2 ) required to reach half the initial luminance was measured. The light emission lifetime was expressed as a relative value at which the organic EL element 1-1 was set to 100.

(Luminescent color)
The organic EL element was visually evaluated for the color of light emitted when the organic EL element was continuously lit at a constant current of ^2.5 mA / cm ² at room temperature.

  The obtained results are shown in Table 1.

  From Table 1, the organic EL device produced by using the metal complex according to the present invention has higher luminous efficiency and longer lifetime while having pure blue to light blue short-wave emission compared to the organic EL device of the comparative example. It is clear that can be achieved.

Example 2
<< Preparation of Organic EL Element 2-1 >>
An anode of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed on a glass support substrate of 25 mm × 25 mm × 0.5 mm by a sputtering method using a direct current power (thickness: 200 nm). The surface resistance of this anode was 10Ω / □. Polyvinylcarbazole (hole transporting binder polymer) / Ir-13 (blue light-emitting orthometalated complex) / 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4 -Oxadiazole (electron transport material) = A dichloroethane solution in which a mass ratio of 200/2/50 was dissolved was applied by a spin coater to obtain a light-emitting layer having a thickness of 100 nm. A patterned mask (a mask with a light emission area of 5 mm × 5 mm) is placed on the organic compound layer, and lithium fluoride 0.5 nm is deposited as a cathode buffer layer and aluminum 150 nm is deposited as a cathode in a deposition apparatus to form a cathode. A blue light-emitting organic EL device 2-1 was prepared.

<< Production of Organic EL Elements 2-2 to 2-10 >>
In the production of the organic EL element 2-1, organic EL elements 2-2 to 2-10 were produced in the same manner except that the luminescent dopant was changed as shown in Table 2.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 2-1 to 2-10, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 5 and 6 was formed and evaluated.

  Next, the luminous efficiency and the 50 ° C. driving life were measured as follows.

(Luminescence efficiency)
Using a source measure unit type 2400 manufactured by Toyo Technica, a direct current voltage was applied to the organic EL element to emit light, and the light emission efficiency (lm / W) when a current of ^2.5 mA / cm ² was passed was measured.

(50 ° C drive life)
The 50 ° C. driving life was evaluated according to the measurement method shown below.

Each organic EL element is driven at a constant current with a current that gives an initial luminance of 1000 cd / m ² under a constant condition of 50 ° C., and a time that is ½ of the initial luminance (500 cd / m ² ) is obtained. The life is assumed.

  The obtained results are shown in Table 2. It represents with the relative value which sets the organic EL element 2-1 to 100.

  From Table 2, the organic EL device produced using the metal complex according to the present invention can achieve high luminous efficiency and high luminance while having pure blue to light blue short-wave emission as compared with the organic EL device of the comparative example. it is obvious.

Example 3
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element 1-13 of Example 1 was used as a blue light emitting element.

(Production of green light emitting element)
A green light emitting device was produced in the same manner as in the organic EL device 1-1 of Example 1, except that the comparative compound 1 was changed to Ir-1, and this was used as a green light emitting device.
(Production of red light emitting element)
A red light emitting device was produced in the same manner as in the organic EL device 1-1 of Example 1, except that the comparative compound 1 was changed to Ir-9, and this was used as a red light emitting device.

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown. That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. 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 (for details, see FIG. 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. The 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 red, green, and blue pixels.

  It has been found that when this full-color display device is driven, a high-brightness, high durability, and clear full-color moving image display can be obtained.

Example 4
<< Preparation of White Light Emitting Element and White Lighting Device-1 >>
The electrode of the transparent electrode substrate of Example 1 is patterned to 20 mm × 20 mm, and α-NPD is formed as a hole injection / transport layer with a thickness of 25 nm thereon, as in Example 1, and further contains H4. In addition, the heating boat, the boat containing Exemplified Compound 1-1-7, the boat containing Ir-1 and the boat containing Ir-9 were energized independently to produce H4 as a light emitting host and a light emitting dopant. The vapor deposition rate of certain exemplary compounds 1-1-7, Ir-1 and Ir-9 was adjusted to be 100: 6: 1: 0.6, vapor deposition was performed to a thickness of 30 nm, and light was emitted. A layer was provided.

Next, BCP was deposited to a thickness of 10 nm to provide a hole blocking layer. Further, Alq ₃ was formed at 40 nm to provide an electron transport layer.

  Next, as in Example 1, a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron injection layer, and lithium fluoride 0.5 nm was used as the cathode buffer layer and aluminum 150 nm was used as the cathode. Evaporated film was formed.

  This element was provided with a sealing can having the same method and the same structure as in Example 1, and a flat lamp as shown in FIGS. 5 and 6 was produced. When this flat lamp was energized, white light was obtained, and it was found that it could be used as a lighting device. It has been found that white light emission can be obtained in the same manner even when the compound is replaced with other exemplified compounds.

Example 5
<< Production of White Light Emitting Element and White Lighting Device-2 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) 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, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. After the film formation by spin coating, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

  Next, using a solution prepared by dissolving Compound B (60 mg), Compound Ir-14 (2.0 mg), Compound Ir-15 (2.0 mg), and Compound Ir-16 (4.0 mg) in 6 ml of toluene, 1000 rpm, A film was formed by spin coating under conditions of 30 seconds. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer.

  Further, a solution of compound C (20 mg) dissolved in 6 ml of toluene was used to form a film by spin coating under conditions of 1000 rpm and 30 seconds. Ultraviolet light was irradiated for 15 seconds, photopolymerization / crosslinking was performed, and further heating was performed in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of Alq ₃ was placed in a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus. After reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing Alq ₃ was heated by heating, evaporated onto the electron transport layer at a deposition rate of 0.1 nm / second, and further coated with a film. An electron transport layer having a thickness of 40 nm was provided.

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

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the white light emitting organic EL element was produced.

  When this element was energized, white light was obtained, and it was found that it could be used as a lighting device.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. 4 is a schematic diagram of a display unit A. FIG. 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 a schematic diagram 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 105 Cathode 106 Organic EL layer 107 Glass substrate with a transparent electrode 108 Nitrogen gas 109 Water catcher

Claims (10)

An organic electroluminescence element material, which is a transition metal complex represented by the following general formula (1).

Wherein Y ₀ and Y ₃ represent N or C, Y ₁ and Y ₂ represent R ₁ -N, N or R ₂ -C, and together with N, a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring A 5-membered nitrogen-containing aromatic heterocycle A selected from:
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B selected from a benzene ring, a pyridine ring, a pyrimidine ring or a pyridazine ring.
Y ₇ and Y ₈ are selected from carbon and nitrogen, and form an aromatic 6-membered heterocyclic ring C selected from a pyridine ring, a pyrimidine ring or a pyridazine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the aromatic 6-membered heterocyclic ring C, and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B, and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. ) An organic electroluminescent element comprising the organic electroluminescent element material according to claim 1. The organic electroluminescence device according to claim 2, wherein the organic electroluminescence device comprises a light emitting layer as a constituent layer, and the light emitting layer contains the organic electroluminescence device material according to claim 1. The luminescent layer contains a carbazole derivative or a derivative having a ring structure in which at least one of carbon atoms of a hydrocarbon ring constituting the carbazole ring of the carbazole derivative is substituted with a nitrogen atom. The organic electroluminescent element of description. A ring structure having a hole blocking layer as a constituent layer, wherein the hole blocking layer has a carbazole derivative or at least one carbon atom of a hydrocarbon ring constituting a carbazole ring of the carbazole derivative substituted with a nitrogen atom The organic electroluminescent element of any one of Claims 2-4 containing the derivative | guide_body which has. The organic layer containing a transition metal complex represented by the general formula (1) as a constituent layer, and the organic layer is formed by using a wet process. 2. The organic electroluminescence device according to item 1. An organic electroluminescence device comprising at least one organic layer sandwiched between an anode and a cathode, wherein the organic layer comprises a polymer having a structural unit derived from a transition metal complex compound represented by the following general formula (1) An organic electroluminescence device characterized by comprising:

Wherein Y ₀ and Y ₃ represent N or C, Y ₁ and Y ₂ represent R ₁ -N, N or R ₂ -C, and together with N, a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring A 5-membered nitrogen-containing aromatic heterocycle A selected from:
R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. R ₂ represents a hydrogen atom or a substituent.
Y ₄ , Y ₅ and Y ₆ are selected from carbon or nitrogen and form an aromatic 6-membered ring B selected from a benzene ring, a pyridine ring, a pyrimidine ring or a pyridazine ring.
Y ₇ and Y ₈ are selected from carbon and nitrogen, and form an aromatic 6-membered heterocyclic ring C selected from a pyridine ring, a pyrimidine ring or a pyridazine ring.
G ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.
G ₂ represents a substituent of the aromatic 6-membered heterocyclic ring C, and m represents 0, 1 or 2. When m = 2, two substituents may be bonded to form a ring.
G ₃ represents a substituent of the aromatic 6-membered ring B, and n represents 0, 1, 2, or 3. When n ≧ 2, two or more substituents may be bonded to form a ring. When G ₁ and G ₃ are adjacent to each other, they may combine to form a ring.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .
M ₁ which is the central metal represents a group 8-11 transition metal in the periodic table.
m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2,
m1 + m2 is 2 or 3, which is the same number as the positive charge of the central metal M _1. ) The organic electroluminescence element according to claim 2, which emits white light. A display device comprising the organic electroluminescence element according to claim 2. It has an organic electroluminescent element of any one of Claims 2-8, The illuminating device characterized by the above-mentioned.

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