JP5600891B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Organic electroluminescence element, display device and lighting device Download PDF

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JP5600891B2
JP5600891B2 JP2009118617A JP2009118617A JP5600891B2 JP 5600891 B2 JP5600891 B2 JP 5600891B2 JP 2009118617 A JP2009118617 A JP 2009118617A JP 2009118617 A JP2009118617 A JP 2009118617A JP 5600891 B2 JP5600891 B2 JP 5600891B2
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雅人 西関
栄作 加藤
大 池水
智寛 押山
信也 大津
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コニカミノルタ株式会社
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  The present invention relates to an organic electroluminescence element, a display device, and a lighting device.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. The device emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  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 (η) 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. 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 ortho-metalated 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 Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

  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 an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, a cyano group or the like into phenylpyridine as a substituent, and picolinic acid or a pyrazabole-based ligand as a ligand. It is known to introduce.

  However, with these ligands, the emission wavelength of the light-emitting material is shortened to achieve blue, and a high-efficiency device can be achieved. On the other hand, the light-emitting lifetime of the device is greatly deteriorated, so an improvement in the trade-off is required. It was.

  It is disclosed that a metal complex having phenylpyrazole as a ligand is a light-emitting material having a short emission wavelength (see, for example, Patent Documents 1 and 2). Furthermore, a metal complex formed from a ligand having a partial structure in which a 6-membered ring is condensed to a 5-membered ring of phenylpyrazole is disclosed (for example, see Patent Documents 3 and 4). There is disclosure of metal complexes having a phenanthridine skeleton. (For example, refer to Patent Documents 5 and 6.)

  However, with the metal complexes described in the above-mentioned known documents, the external extraction quantum efficiency is not improved, and a practically sufficient improvement effect is not obtained for the light emission lifetime, and there is a need for improvement. Yes.

  The problems of the prior art are listed below.

Conventionally, a compound having a plurality of carbazole rings in the molecule is known as a good host compound. Also in the compound having the phenanthridine skeleton, a combination example with m-CBP is disclosed. (For example, see Patent Documents 5 and 6)
However, as is clear from the above-mentioned patent documents, in the combined use with various phenanthridine compounds, a compound having a plurality of carbazole rings in the molecule is still insufficient in terms of lifetime and efficiency. Therefore, further improvement is necessary.

International Publication No. 2004/085450 Pamphlet JP 2005-53912 A JP 2006-28101 A US Pat. No. 7,147,937 US Patent No. 20070190359 International Publication No. 2007/095118 Pamphlet

  The present invention has been made in view of the above problems, and an object of the present invention is to use an organic EL element material that exhibits specific short-wave emission, exhibits high emission efficiency, and has a long emission lifetime. An organic electroluminescence element, an illumination device, and a display device are provided.

  In particular, it is to provide an organic electroluminescence element material which exhibits high luminous efficiency with short-wave light emission of blue to blue-green, low driving voltage, and long emission lifetime.

  1. In the organic electroluminescence device having at least one light emitting layer sandwiched between an anode and a cathode, the light emitting layer contains a phosphorescent dopant and has the following general formula (5), (6) or (7) It has an organic layer containing the compound containing the partial structure represented by these, The organic electroluminescent element characterized by the above-mentioned.

[ Wherein , A 1a , A 1b and A 1c each independently represent a single bond, an arylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.

E 2a to E 2j each independently represent a carbon atom or a nitrogen atom. In E 2a to E 2j , the number of nitrogen atoms is 1 to 4, and two or more adjacent E 2 * s do not become nitrogen atoms at the same time. Further, at least one of E 2a to E 2h is a nitrogen atom. Here, * represents an arbitrary character from a to j.

R 2a to R 2k each independently represents a hydrogen atom or a substituent.

However, any one of next A 1a of R 2a to R 2d, one of R 2e or R 2h is A 1 c, and the any one of the R 2i to R 2k becomes A 1b.
However, in General formula (6), when E2d, E2e, and E2i are all nitrogen atoms, E2d, E2h, and E2i are all nitrogen atoms, or when E2a, E2h, and E2i are all nitrogen atoms. . ]
2. 2. Said phosphorescent dopant is at least 1 sort (s) of the compound containing the partial structure represented by the following general formula (1), (2), (3), or (4), Organic electroluminescence element.

[ Wherein , E 1a and E 1q are different and each represents a carbon atom or a nitrogen atom. E 1b to E 1p each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and the skeleton composed of E 1a to E 1q has a total of 18π electrons.

R 1a to R 1i each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1h is a substituent.

However, when E 1 * to which R 1 * is bonded is an oxygen atom or a sulfur atom, R 1 * does not exist. In addition, when E 1 * to which R 1 * is bonded is a nitrogen atom, R 1 * may not exist. Here, * represents any character of a to i.

M represents a group 8-10 transition metal element in the periodic table. ]
3. Formula (5), (6) or a compound containing the partial structure represented by (7) of the general formula (8) to (13) according to 2 before Symbol characterized by being represented by any one of Organic electroluminescence element.

  [Wherein, m1 to m3 and n1 to n3 are each an integer of 0 to 6, and m1 + n1 ≦ 6, m2 + n2 ≦ 6, and m3 + n3 ≦ 6.

  m4 to m6 and n4 to n6 are each an integer of 1 to 5, and m4 + n4 ≦ 6, m5 + n5 ≦ 6, and m6 + n6 ≦ 6.

X 1 to X 6 are each independently a single bond, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an amino which may have a substituent. It represents a my + ny-valent group formed by combining groups selected from groups. Here, y represents any one of 1-6.

A 11a , A 21a , A 11b , A 21b , A 11c and A 21c are each independently a single bond, an arylene group which may have a substituent, or a divalent complex which may have a substituent. Represents a cyclic group.

E 11a to E 11j , E 21a to E 21j , E 31a to E 31j , E 41a to E 41j , E 51a to E 51j , E 61a to E 61j each independently represent a carbon atom or a nitrogen atom. In E za to E zj , the number of nitrogen atoms is 1 to 4, and two or more adjacent E Z * do not simultaneously become nitrogen atoms. In addition, at least one of E za to E zh is a nitrogen atom. Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61, and * represents an arbitrary character selected from a to j.

R 11a to R 11k , R 21a to R 21k , R 31a to R 31k , R 41a to R 41k , R 51a to R 51k , and R 61a to R 61k each independently represent a hydrogen atom or a substituent.

Any one of R 11a to R 11d is A 11a and any one of R 21a to R 21d is A 21a .

Any one of R 31i to R 31k is A 11b , and any one of R 41i to R 41k is A 21b .

Any one of R 51e to R 51h is A 11c , and any one of R 61e to R 61h is A 21c .
However, in general formula (9), general formula (11) or general formula (13),
When E 31d , E 31e and E 31i are all nitrogen atoms,
When E 31d , E 31h and E 31i are all nitrogen atoms,
When E 31a , E 31h and E 31i are all nitrogen atoms,
When E 41d , E 41e and E 41i are all nitrogen atoms,
When E 41d , E 41h and E 41i are all nitrogen atoms, or
Except when E 41a , E 41h and E 41i are all nitrogen atoms. ]

5. The groups represented by X 1 to X 6 in the general formulas (8) to (13) are a phenyl group, a biphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, and an anthracenyl group. 5. The organic electroluminescence device as described in 3 or 4 above, which is a divalent group obtained by further removing one hydrogen atom from the above, and a group comprising a combination thereof.

6). 6. The organic electroluminescence device according to any one of 3 to 5, wherein the compounds represented by the general formulas (8) to (13) have a glass transition temperature of 100 ° C. or higher.

7). R 11a to R 11k , R 21a to R 21k , R 31a to R 31k , R 41a to R 41k , R 51a to R 51k , R 61a to R 61k in the general formulas (8) to (13) 7. The organic electroluminescence device according to any one of 3 to 6, wherein at least one of the substituents is a polymerizable substituent.

8). Any of 3 to 7 above, wherein the ring composed of E 1a to E 1e in the general formula (1), (2), (3), or (4) is an imidazole ring or a pyrazole ring. 2. The organic electroluminescence device according to item 1.

9. As a constituent layer, it has an organic layer containing at least one compound containing a partial structure represented by any one of the general formulas (1) to (4), and the organic layer was formed using a wet process The organic electroluminescence device according to any one of 3 to 8, wherein the organic electroluminescence device is characterized in that

10. It has an organic layer containing at least one compound represented by any one of the general formulas (8) to (13) as a constituent layer, and the organic layer is formed using a wet process 10. The organic electroluminescence device according to any one of 3 to 9 above.

11. In any one of 3 to 10 above, the organic layer containing at least one compound represented by any one of the general formulas (8) to (13) as a constituent layer is a light emitting layer. The organic electroluminescent element of description.

12 Any one of 3 to 11 above, comprising an organic layer containing at least one polymer having a partial structure of the compound represented by any one of the general formulas (8) to (13). The organic electroluminescent element of description.

13. The 3-12 any one of which is characterized by containing at least one kind of polymer to compound a partial structure containing a partial structure represented by any one of formulas (1) to (4) The organic electroluminescent element of description.

14 14. The organic electroluminescence device according to any one of 3 to 13, wherein M in the general formula (1), (2), (3), or (4) is platinum or iridium.

  15. 15. A display device comprising the organic electroluminescence element according to any one of 1 to 14 above.

  16. 15. An illumination device comprising the organic electroluminescence element according to any one of 1 to 14 above.

  According to the present invention, there are provided an organic electroluminescence element material that exhibits specific short-wave emission, exhibits high emission efficiency, and has a long emission lifetime, and an organic EL element, an illumination device, and a display device using the same. Can do.

  In particular, it is possible to provide an organic electroluminescent element material that exhibits high light emission efficiency with short-wave light emission of blue to blue-green, has a low driving voltage, and has a long light emission lifetime.

  Further, as a result of the study by the present inventors, the present invention was able to significantly reduce the initial deterioration at the start of element driving. Furthermore, the generation of dark spots in the light emitting device during device driving was successfully reduced, and a useful organic electroluminescence device could be provided.

  In addition, an illumination device and a display device using the element could be provided.

  Furthermore, the useful organic electroluminescent element material for organic electroluminescent elements was able to be obtained.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  In the organic electroluminescent element of this invention, the structure prescribed | regulated in any one of Claims 1-16 WHEREIN: The organic electroluminescent element which shows high luminous efficiency and has a long light emission lifetime, and illumination using this element A device and a display device could be provided.

  In the organic electroluminescence device of the present invention, the light emitting layer contains at least one phosphorescent dopant and at least one compound containing a partial structure represented by the general formula (5), (6) or (7). It has an organic layer to be contained, and the phosphorescent dopant is selected from compounds containing a partial structure represented by the general formula (1), (2), (3) or (4). preferable.

  In addition, the present inventors succeeded in molecular design of an organic EL element material useful for the organic electroluminescence element of the present invention. The organic electroluminescence element material of the present invention was observed to emit light with a specific short wave, and the lifetime of the organic electroluminescence element of the present invention could be remarkably improved.

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

《Phosphorescent dopant》
A metal complex compound (also referred to as a transition metal complex compound) which is a phosphorescent dopant (also referred to as a phosphorescent dopant) according to the present invention will be described.

  The present inventors have introduced a substituent into the basic skeleton of a metal complex, and thus it is not a conventionally known approach to control the wavelength or improve the lifetime, but to expand the π-conjugated surface of the condensed ring. Various complexes were studied under the focus of increasing stability.

  As a result, the improvement tendency of lifetime was found in several condensed ring structures. However, when a fused ring as known so far is introduced, the red shift of the emission wavelength is remarkable, resulting in green and red emission.

  The present inventors have further studied, and compounds (metal complexes, metals) in which a condensed ring as shown in the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is introduced. When it is applied to a luminescent material, it is a preferable characteristic as a phosphorescent dopant (phosphorescent dopant) that has a small emission wavelength shift and has a long lifetime at a desired emission wavelength. It was found that

  Further examination of this new basic skeleton has the disadvantage that the π-conjugate plane becomes larger, and the planarity becomes higher, so that the association between metal complexes becomes a problem, and the lifetime of the device is remarkably reduced. all right.

  As for the waveform, sub-luminescence is seen on the long wave side, and a decrease in color purity has become a problem. As a result of various investigations, by introducing at least one substituent into the ligand moiety, association between molecules can be prevented, side-light emission on the long wave side can be suppressed, and the stability of the metal complex (metal complex compound). It was found to improve.

In addition, these metal complexes are characterized by significant oxidative degradation due to oxygen and light, and there has been concern over degradation over time during handling. As a result of various studies, R in a transition metal complex compound containing at least one substituent in the ligand portion, particularly a partial structure represented by any one of the general formulas (1) to (4) according to the present invention. It has been found that by introducing a substituent into at least one of 1a to R 1h , oxidative degradation is greatly reduced and the stability of the compound is greatly improved.

Preferably, at least one of R 1a or R 1b is a substituent, more preferably, at least two of R 1a to R 1h are substituents, and most preferably R 1a or R 1b. In which at least one of is a substituent and at least one of R 1c to R 1h is a substituent.

  The transition metal complex compound containing the partial structure represented by any one of the general formulas (1) to (4) according to the present invention has a plurality of ligands depending on the valence of the transition metal element represented by M. The ligands may all be the same, or may have ligands each having a different structure.

  Here, the ligand is a portion obtained by removing the transition metal element M from the partial structure represented by any one of the general formulas (1) to (4).

(Conventionally known ligand)
Moreover, as what is called a ligand, the said trader can use together a well-known ligand (it is also called a coordination compound) as a ligand as needed.

  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.

  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 in 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabo Company, Akio Yamamoto, published in 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).

(Transition metal element of group 8-10 of the periodic table)
Formation of a compound (also referred to as a transition metal complex, metal complex, or metal complex compound) containing a partial structure represented by any one of the general formulas (1), (2), (3), or (4) according to the present invention As the metal used in the above, a transition metal element belonging to Group 8 to 10 of the periodic table (also simply referred to as a transition metal) is used. Among them, iridium and platinum are preferable transition metal elements.

(Contained layer of transition metal complex according to the present invention)
The transition metal complex compound-containing layer containing the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is not particularly limited as long as it is a layer that transports charges (charge transport layer). However, a hole transport layer or a light emitting layer, a light emitting layer or an electron blocking layer is preferable, a light emitting layer or an electron blocking layer is more preferable, and a light emitting layer is particularly preferable.

  Moreover, when it contains in a light emitting layer, by using as a light emission dopant in a light emitting layer, the efficiency improvement (high brightness) of the external extraction quantum efficiency of the organic EL element of this invention and the lifetime improvement of a light emission lifetime are achieved. be able to. The constituent layers of the organic EL element of the present invention will be described in detail later.

  First, the partial structure represented by any of the general formulas (1) to (4) according to the present invention will be described.

<< Partial structure represented by any one of general formulas (1) to (4) >>
In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E 1a to E 1e represents a 5-membered aromatic heterocycle, such as an oxazole ring, thiazole ring, oxa Examples include a diazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, an isothiazole ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, and a triazole ring.

  Among these, a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring are preferable, and a pyrazole ring and an imidazole ring are particularly preferable. Each of these rings may further have a substituent described later.

In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E 1f to E 1k is a 6-membered aromatic hydrocarbon ring, or a 5-membered or 6-membered aromatic ring. Represents a heterocycle. Examples of the 6-membered aromatic hydrocarbon ring formed by E 1f to E 1k include a benzene ring. Furthermore, you may have the substituent mentioned later.

Examples of the 5-membered or 6-membered aromatic heterocycle formed by E 1f to E 1k include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Etc. Each of these rings may further have a substituent described later.

In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E 11 to E 1q is a 6-membered aromatic hydrocarbon ring, or a 5-membered or 6-membered aromatic ring. Although this represents a heterocyclic ring, these rings are synonymous with a 6-membered aromatic hydrocarbon ring formed by E 1f to E 1k or a 5-membered or 6-membered aromatic heterocyclic ring, respectively.

In the partial structure represented by any one of the general formulas (1) to (4), each of the substituents represented by R 1a to R 1i includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group). Group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl) Group, allyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (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 group, fluorenyl group, Nantril group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, , 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, Thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group) One is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy) Group, 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 groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (for example, cyclopentylthio group, cyclohexylthio group, etc.) An arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl Group (for example, 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.), a Group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc. ), Acyloxy groups (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonyl) Amino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonyl group Group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentyl) Aminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (eg methyl Ureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido naphthyl Raid group, 2-pyridylaminoureido group, etc.), 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 (eg 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, dimethyl) Mino 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.), phosphono group and the like. These substituents may be further substituted with the above substituents.

  A plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. It may be formed.

In the partial structure represented by any one of the general formulas (1) to (4), the substituents represented by R 1a to R 1i are styryl, epoxy, oxetanyl, You may have polymerizable groups, such as an acryl group and a methacryl group. Furthermore, the compound represented by the partial structure represented by any one of the general formulas (1) to (4) can react with the polymerizable groups or with other polymerizable monomers to form a polymer. .

  When a plurality of partial structures are present in the polymer, the partial structures represented by any one of the general formulas (1) to (4) may be the same or different.

<Method for Polymerizing Partial Structure Represented by any of General Formulas (1) to (4)>
The polymer (polymer) of the partial structure represented by any one of the general formulas (1) to (4) is “Revised Polymer Synthesis Chemistry” Chemistry “Polymer Synthesis Experimental Method” Chemistry Dojin “4th Edition Experiment It can be synthesized using the method described in Chemistry Lecture 28 “Polymer Synthesis” Maruzen et al.

  Preferable polymerization methods include 1) polycondensation, 2) radical polymerization, 3) ionic polymerization, 4) polyaddition, addition condensation, and the like, which can be used depending on the type of polymerizable group.

  The polymer having a partial structure represented by any one of the general formulas (1) to (4) can be made into a homopolymer using the above method, or can be made into a copolymer in combination with a plurality of monomers. is there.

  Hereinafter, specific examples of the compound (also referred to as a metal complex or a metal complex compound) including a partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be shown. It is not limited.

  These metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 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), Organic Letter, vol. 3, pages 415 to 418 (2006), and further by applying methods such as references described in these documents.

  Although the synthesis example of the metal complex based on this invention is shown below, this invention is not limited to these.

  << Synthesis Example: Synthesis of Exemplary Compound A-97 >>

Step 1: Synthesis of Complex A A 100 ml four-necked flask was charged with 1.5 g of 2-methylimidazo [1,2-f] phenanthridine, 13 ml of 2-ethoxyethanol, and 3 ml of water, a nitrogen blowing tube, a thermometer, a condenser And set on an oil bath stirrer. To this, 0.55 g of IrCl 3 .3H 2 O and 0.16 g (0.001560 mol) of triethylamine were added, and the reaction was completed by boiling and refluxing at an internal temperature of about 100 ° C. for 6 hours under a nitrogen stream. .

  After completion of the reaction, the reaction mixture was cooled to room temperature, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was thoroughly washed with methanol and dried to obtain 1.37 g (77.0%) of complex A.

Step 2: Synthesis of complex B In a 50 ml four-necked flask, 1.0 g (0.0007244 mol) of complex A, 0.29 g of acetylacetone, 1.0 g of sodium carbonate, and 24 ml of 2-ethoxyethanol were introduced, and nitrogen was blown into the flask. A tube, a thermometer and a condenser were attached and set on an oil bath stirrer. Under nitrogen flow, the mixture was heated and stirred at an internal temperature of about 80 ° C. for 1.5 hours.

  After completion of the reaction, the reaction solution was cooled to room temperature, methanol was added to the reaction solution, and the precipitated crystals were filtered. The crystals were washed with 30 ml of water, 10 ml of MeOH and dried to obtain 0.42 g of complex D (38.5%).

Step 3: Synthesis of Exemplified Compound A-97 In a 50 ml four-necked flask, 0.386 g (0.0005120 mol) of Complex B, 0.357 g of 2-methylimidazo [1,2-f] phenanthridine, glycerin 20 ml was added, and a nitrogen blowing tube, a thermometer, and an air cooling tube were attached and set on an oil bath stirrer. The reaction was completed by heating and stirring for 4.5 hours at an internal temperature of 150 ° C. under nitrogen flow.

  After completion of the reaction, the mixture was cooled to room temperature, methanol was added and dispersed, and the crystals were collected by filtration to obtain 0.38 g of crude crystals.

  The crystals are purified by column chromatography (developing solvent: toluene / ethyl acetate), and the obtained crystals are heated and suspended in a mixed solvent of tetrahydrofuran and ethyl acetate, filtered, and 0.3 g (66.66) of Exemplified Compound A-97 is filtered. 6%).

The structure of the obtained exemplary compound A-97 was confirmed using 1 H-NMR (nuclear magnetic resonance spectrum). Measurement conditions, chemical shift of each peak of the obtained spectrum, proton number, etc. are shown below.

1 H-NMR (400 MHz, tetrahydrofuran-d8)
Measuring device: JEOL JNM-AL400 (400 MHz): JEOL Ltd.

  Spectral assignment (chemical shift δ, proton number, peak shape): 8.48 (3H, d), 7.93 (3H, d), 7.75 (3H, s), 7.64 (3H, d) 7.54 (3H, t), 7.46 (3H, t), 6.95 (3H, t), 6.83 (3H, d), 1.85 (9H, s). In addition, the emission maximum wavelength in 77K in 2-methyltetrahydrofuran solution of exemplary compound A-97 was 455 nm.

  << Synthesis Example: Synthesis of Exemplary Compound F-8 >>

Step 1: Synthesis of Complex C A 100 ml four-necked flask was charged with 2.3 g of 3-mesityl-6-methylimidazo [1,2-f] phenanthridine, 13 ml of 2-ethoxyethanol, 3 ml of water, a nitrogen blowing tube, A thermometer and a condenser were attached and set on an oil bath stirrer. To this, 0.55 g of IrCl 3 .3H 2 O and 0.16 g (0.001560 mol) of triethylamine were added, and the reaction was completed by bubbling and refluxing at about 100 ° C. for 6 hours under a nitrogen stream. .

  After completion of the reaction, the reaction mixture was cooled to room temperature, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was thoroughly washed with methanol and dried to obtain 2.08 g (72.0%) of Complex C.

Step 2: Synthesis of Complex D In a 50 ml four-necked flask, 1.0 g (0.000540 mol) of Complex C, 0.25 g of acetylacetone, 1.0 g of sodium carbonate, and 24 ml of 2-ethoxyethanol were introduced, and nitrogen was blown into the flask. A tube, a thermometer and a condenser were attached and set on an oil bath stirrer. The mixture was heated and stirred for 1.5 hours at about 80 ° C. under nitrogen flow.

  After completion of the reaction, the reaction solution was cooled to room temperature, methanol was added to the reaction solution, and the precipitated crystals were filtered. The crystals were washed with water (30 ml), MeOH (10 ml) and dried to obtain 0.37 g of Complex D (35%).

Step 3: Synthesis of Exemplified Compound F-8 In a 50 ml four-necked flask, 0.370 g (0.0003740 mol) of Complex D, 0.540 g of 3-mesityl-6-methylimidazo [1,2-f] fe Nanthridine and 20 ml of glycerin were added, and a nitrogen blowing tube, a thermometer, and an air cooling tube were attached and set on an oil bath stirrer. The reaction was completed by heating and stirring for 4.5 hours at an internal temperature of 150 ° C. under nitrogen flow.

  After completion of the reaction, the mixture was cooled to room temperature, methanol was added and dispersed, and the crystals were collected by filtration to obtain 0.37 g of crude crystals.

  The crystal was purified by column chromatography (developing solvent: toluene / ethyl acetate), and the obtained crystal was heated and suspended in a mixed solvent of tetrahydrofuran and ethyl acetate, followed by filtration, and 0.3 g (64.64) of Exemplified Compound F-8. 7%).

  The structure of the obtained exemplary compound A-65 was confirmed using 1H-NMR (nuclear magnetic resonance spectrum). Measurement conditions, chemical shift of each peak of the obtained spectrum, proton number, etc. are shown below.

1 H-NMR (400 MHz, dichloromethane-d2)
Measuring device: JEOL JNM-AL400 (400 MHz): JEOL Ltd.

  Spectral assignment (chemical shift δ, proton number, peak shape): 8.32 (3H, d), 7.64 (3H, d), 7.22 (3H, d), 7.13 (3H, t) , 7.05 (3H, d), 7.01 (3H, s), 6.98 (3H, s), 6.91 (3H, s), 6.85 (3H, s), 2.36 ( 3H, s), 2.13 (3H, s), 2.00 (3H, s), 1.86 (3H, s).

  In addition, the emission maximum wavelength in 77K in 2-methyltetrahydrofuran solution of exemplary compound F-8 was 456 nm.

  In the present invention, the emission wavelength of the exemplified compound was measured as follows. First, an absorption spectrum of the exemplary compound is measured, and an absorption maximum wavelength in the range of 300 to 350 nm is set as excitation light.

  Using the set excitation light, the emission wavelength is measured with a fluorometer F-4500 (manufactured by Hitachi, Ltd.) while performing nitrogen bubbling.

In addition, although there is no restriction | limiting in the solvent which can be used, 2-methyltetrahydrofuran, a dichloromethane, etc. are used preferably from a soluble viewpoint of a compound. The concentration at the time of measurement is preferably sufficiently diluted, and specifically, it is preferably measured in the range of 10 −6 to 10 −4 mol / l. Moreover, there is no restriction | limiting in particular as temperature at the time of measurement, However, Generally, it is preferable that temperature setting of the range of room temperature-77K is performed.

In order for the organic EL device of the present invention to achieve the effects described in the present invention, a phosphorescent light-emitting dopant is contained in the light-emitting layer that is a component layer of the device, and the general formulas (5) to (7) It is necessary that an organic layer containing a compound represented by any one of the above is provided as a constituent layer of the organic EL element.
<< Organic Compound Containing Partial Structure Represented by General Formulas (5) to (7) >>
The organic compound including the partial structure represented by the general formulas (5) to (7) will be described.

  The organic compound containing the partial structure represented by the general formulas (5) to (7) of the present invention contains one or more dibenzoindole rings, phenanthroimidazole rings, dibenzoindazole rings, and dibenzoindole rings in the molecule. Nitrogen-containing heterocycles in which one or more atoms have been replaced with nitrogen atoms, nitrogen-containing heterocycles in which the carbon atom of the phenanthroimidazole ring has been replaced by one nitrogen atom, or one or more carbon atoms in the dibenzoindazole ring It has a nitrogen-containing heterocycle substituted with an atom. Since these nitrogen-containing condensed heterocyclic groups have higher electron mobility than carbazole groups, when the substituents are almost the same, the overall electron mobility is higher than that of a compound having one or more carbazolyl groups in the molecule. Is slightly higher.

  On the other hand, the transition metal complex compound including the partial structure represented by the general formula (1), (2), (3), or (4) of the present invention has a hole transporting property as compared with a conventional transition metal complex. Due to the improvement, the combined use of a conventional host compound composed of a plurality of carbazolyl groups cannot fully balance the hole transfer and electron transfer, and has not exhibited sufficient performance.

  As a result of examination of the optimum host compound to be used in combination with the transition metal complex compound containing the partial structure represented by the general formula (1), (2), (3), or (4) of the present invention, By using an organic compound containing a partial structure represented by the general formulas (5) to (7) of the invention as a host compound, the balance between hole transfer and electron transfer can be perfectly matched, and thereby a specific short wave Light emission was seen, an organic EL device having a high light emission efficiency and a long light emission lifetime could be provided. Furthermore, as an unexpected effect, the initial deterioration at the start of element driving can be greatly reduced, and further, the dark spot of the light emitting element has been successfully reduced to provide a useful organic EL element. I was able to do it.

  Furthermore, the preferable embodiment of the organic compound containing the partial structure represented by General formula (5)-(7) is demonstrated.

  The optimum host compound for use in combination with the transition metal complex compound containing the partial structure represented by the general formula (1), (2), (3), or (4) of the present invention is the above general formula (5). It is an organic compound containing the partial structure represented by (7).

In the general formulas (5) to (7), A 1a , A 1b and A 1c are each independently a single bond, an arylene group which may have a substituent, or a divalent which may have a substituent. Represents a heterocyclic group.

As the arylene group represented by A 1a , A 1b and A 1c , a divalent group obtained by removing any hydrogen atom of any aryl group can be used. Examples of aryl groups include phenyl Group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.

Examples of the divalent heterocyclic group represented by A 1a , A 1b, and A 1c include a divalent group obtained by removing any hydrogen atom of any heterocyclic group. The heterocyclic group may be aromatic or non-aromatic.

  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-triazole-1- Yl, 1,2,3-triazol-1-yl, etc.), oxazolyl, benzoxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl Group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), Quinoxalinyl group, pyridazinyl group, triazinyl group, quina Riniru group, phthalazinyl group, and the like.

  Examples of non-aromatic heterocyclic groups include pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, tetrahydrofuranyl group, tetrahydrothiophenyl group, and the like.

  The arylene group or divalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group). Group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl Group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, Naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, inde Group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1, 2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, A quinolyl group, a benzofuryl group, a dibenzofuryl group, a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is a nitrogen atom) ), Quinoxalinyl group, Dazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyl) Oxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (For example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, Phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group) , Dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl) Group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, , Acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino) Group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbo Ruamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexyl). Aminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido) Group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridyl Aminoureido groups, etc.), sulfinyl groups (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Etc.), alkylsulfonyl groups (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl groups or heteroarylsulfonyl groups (for example, phenylsulfonyl) Group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino) , Cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, diphenylamino group, phenylnaphthylamino group, etc., halogen atom (for example, fluorine atom, chlorine atom, bromine) Atoms), fluorinated hydrocarbon groups (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.), phosphono group and the like. These substituents may be further substituted with the above substituents. A plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. May be formed.

E 2a to E 2j each independently represent a carbon atom or a nitrogen atom. In E 2a to E 2j , the number of nitrogen atoms is 1 to 4, and two or more adjacent E 2 * s do not become nitrogen atoms at the same time. Further, at least one of E 2a to E 2h is a nitrogen atom. Here, * represents an arbitrary character from a to j.
In the present invention, the compound having a partial structure represented by the general formula (6) is a compound having a structure in which E2d, E2e and E2i are all nitrogen atoms, and E2d, E2h and E2i are all nitrogen atoms. A compound having a structure or a compound having a structure in which E2a, E2h and E2i are all nitrogen atoms is excluded.

  In the following, one or more carbon atoms of the nitrogen-containing heterocycle represented by the general formulas (5) to (7), that is, dibenzoindole ring, phenanthroimidazole ring, dibenzoindazole ring, dibenzoindole ring are nitrogen atoms. Replaced nitrogen-containing heterocycles, nitrogen-containing heterocycles in which the carbon atom of the phenanthroimidazole ring is replaced by one nitrogen atom, or nitrogen-containing heterocycles in which one or more carbon atoms of the dibenzoindazole ring are replaced with nitrogen atoms Are specifically listed.

  Each structure has a name and abbreviation. Abbreviations are used in the following compound examples.

  Hereinafter, in this specification, the position number for designating the position of a substituent or a bond is not represented by a number unique to each heterocycle, but is represented using a position number on a dibenzoindole skeleton that is a common skeleton.

In General Formulas (5) to (7), R 2a to R 2k each independently represent a hydrogen atom or a substituent.

Examples of the substituent include those having the same meaning as the substituent that the arylene group or valent heterocyclic group represented by A 1a , A 1b, and A 1c may have.

  In the general formula (5), A1a is a nitrogen-containing compound in which one or more of R2a to R2d is substituted with one or more nitrogen atoms in the dibenzoindole ring, phenanthroimidazole ring, dibenzoindazole ring, or dibenzoindole ring. Bonded to a heterocycle, a nitrogen-containing heterocycle in which one carbon atom of the phenanthroimidazole ring is replaced by a nitrogen atom, or a nitrogen-containing heterocycle in which one or more carbon atoms of a dibenzoindazole ring are replaced with a nitrogen atom Yes.

  In general formula (6), A1b is a nitrogen-containing nitrogen atom in which one or more of R2i or R2k is substituted with one or more carbon atoms of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring. Bonded to a heterocycle, a nitrogen-containing heterocycle in which one carbon atom of the phenanthroimidazole ring is replaced by a nitrogen atom, or a nitrogen-containing heterocycle in which one or more carbon atoms of a dibenzoindazole ring are replaced with a nitrogen atom Yes.

  In the general formula (7), A1c is a nitrogen-containing compound in which one or more of R2e to R2h are substituted with one or more nitrogen atoms in the dibenzoindole ring, phenanthroimidazole ring, dibenzoindazole ring, or dibenzoindole ring. Bonded to a heterocycle, a nitrogen-containing heterocycle in which one carbon atom of the phenanthroimidazole ring is replaced by a nitrogen atom, or a nitrogen-containing heterocycle in which one or more carbon atoms of a dibenzoindazole ring are replaced with a nitrogen atom Yes.

  The preferable embodiment of the organic compound containing the partial structure represented by general formula (5)-(7) of this invention is a case where a compound is represented by either of the said general formula (8)-(14). is there.

  In general formulas (8) to (14), m1 to m3 and n1 to n3 are each an integer of 0 to 6, and m1 + n1 ≦ 6, m2 + n2 ≦ 6, and m3 + n3 ≦ 6.

  m4 to m6 and n4 to n6 are each an integer of 1 to 5, and m4 + n4 ≦ 6, m5 + n5 ≦ 6, and m6 + n6 ≦ 6.

X 1 to X 6 are each independently a single bond, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an amino which may have a substituent. It represents a my + ny-valent group formed by combining groups selected from groups. Here, y represents any one of 1-6.

Examples of the aryl group represented by X 1 to X 6 include phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group. , Indenyl group, pyrenyl group, biphenylyl group and the like.

The heterocyclic group represented by X 1 to X 6 may be aromatic or non-aromatic.

  Examples of aromatic heterocyclic groups include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl 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, dibenzo Furyl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazinyl group, Zoriniru group, phthalazinyl group, and the like. Examples of non-aromatic heterocyclic groups include pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, tetrahydrofuranyl group, tetrahydrothiophenyl group, and the like.

Examples of the substituents represented by X 1 to X 6 include those having the same meaning as those described above in the description of the general formulas (5) to (7).

A 11 a, A 21a , A 11b , A 21b , A 11c and A 21c are each independently a single bond, an arylene group which may have a substituent, or a divalent which may have a substituent Represents a heterocyclic group. Examples of the arylene group and the divalent heterocyclic group include those having the same meanings as those described above in connection with the general formulas (5) to (7).

E 11a to E 11j , E 21a to E 21j , E 31a to E 31j , E 41a to E 41j , E 51a to E 51j , E 61a to E 61j each independently represent a carbon atom or a nitrogen atom. In E za to E zj , the number of nitrogen atoms is 1 to 4, and two or more adjacent E Z * do not simultaneously become nitrogen atoms. In addition, at least one of E za to E zh is a nitrogen atom. Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61, and * represents an arbitrary character selected from a to j.
However, in general formula (9), general formula (11) or general formula (13),
When E 31d , E 31e and E 31i are all nitrogen atoms,
When E 31d , E 31h and E 31i are all nitrogen atoms,
When E 31a , E 31h and E 31i are all nitrogen atoms,
When E 41d , E 41e and E 41i are all nitrogen atoms,
When E 41d , E 41h and E 41i are all nitrogen atoms, or
Except when E 41a , E 41h and E 41i are all nitrogen atoms.

R 11a to R 11k , R 21a to R 21k , R 31a to R 31k , R 41a to R 41k , R 51a to R 51k , and R 61a to R 61k each independently represent a hydrogen atom or a substituent. Similarly, examples of the substituent include those having the same meaning as those described in the description of the general formulas (5) to (7).

In the general formulas (8), (11), and (12), A 11a represents a carbon atom of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring as any one of R 11a to R 11d. Nitrogen-containing heterocycles in which one or more nitrogen atoms have been replaced, nitrogen-containing heterocycles in which the carbon atom of the phenanthroimidazole ring has been replaced with a nitrogen atom one position higher, or one or more carbon atoms in the dibenzoindazole ring Bonded to the replaced nitrogen-containing heterocycle.

In General Formulas (9), (11), and (13), A 11b represents a carbon atom of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring as any one of R 31i to R 31k. Nitrogen-containing heterocycles in which one or more nitrogen atoms have been replaced, nitrogen-containing heterocycles in which the carbon atom of the phenanthroimidazole ring has been replaced with a nitrogen atom one position higher, or one or more carbon atoms in the dibenzoindazole ring Bonded to the replaced nitrogen-containing heterocycle.

In general formulas (10), (12), and (13), A 11c represents one carbon atom of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring as any one of R51e to R51h. Nitrogen-containing heterocycles that have been replaced with nitrogen atoms, nitrogen-containing heterocycles in which the carbon atom of the phenanthroimidazole ring has been replaced by one nitrogen atom, or one or more carbon atoms of the dibenzoindazole ring have been replaced with nitrogen atoms Bonded to a nitrogen-containing heterocycle.

  In the general formula (8), A21a represents any one of R21a to R21d as a nitrogen-containing complex in which one or more carbon atoms of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring are replaced with a nitrogen atom. Bonded to a nitrogen-containing heterocycle in which one or more carbon atoms of the ring or phenanthroimidazole ring are replaced with a nitrogen atom, or a nitrogen-containing heterocycle in which one or more carbon atoms of a dibenzoindazole ring are replaced with nitrogen atoms .

In General Formula (9), A 21b is one of R 41i to R 41k in which one or more carbon atoms of a dibenzoindole ring, a phenanthroimidazole ring, a dibenzoindazole ring, or a dibenzoindole ring are replaced with a nitrogen atom. Bonded to nitrogen-containing heterocycles, nitrogen-containing heterocycles in which one or more carbon atoms of the phenanthroimidazole ring are replaced with nitrogen atoms, or nitrogen-containing heterocycles in which one or more carbon atoms of the dibenzoindazole ring are replaced with nitrogen atoms doing.

In general formula (10), A 21c is one of R 61e to R 61h and one or more carbon atoms of the dibenzoindole ring, phenanthroimidazole ring, dibenzoindazole ring or dibenzoindole ring are replaced with a nitrogen atom. A nitrogen-containing heterocyclic ring, a nitrogen-containing heterocyclic ring in which one carbon atom of the phenanthroimidazole ring is replaced with a nitrogen atom, or a nitrogen-containing heterocyclic ring in which one or more carbon atoms of a dibenzoindazole ring are replaced with nitrogen atoms Are connected.
《Molecular weight》
The upper limit of the molecular weight of the compound containing the partial structure represented by the general formulas (5) to (7) of the present invention or the compound represented by any one of the general formulas (8) to (13) of the present invention is vapor deposition. From the viewpoint of minimizing the content of impurities during purification using the method, it is preferably 4000 or less, more preferably 3000 or less, and particularly preferably 2000 or less. The lower limit of the molecular weight is preferably 200 or more, more preferably 300 or more, from the viewpoint of maintaining the glass transition temperature, melting point, vaporization temperature, etc. at a certain level and improving the heat resistance of the compound. Especially preferably, it is 400 or more.
<Physical properties>
Although the compound containing the partial structure represented by the general formulas (5) to (7) of the present invention usually has a glass transition temperature of 50 ° C. or higher, when used in an organic electroluminescent device, its heat resistance From the viewpoint, the glass transition temperature is preferably 90 ° C. or higher, and more preferably 110 ° C. or higher. The upper limit of the glass transition temperature is usually about 400 ° C.

  The compound containing the partial structure represented by the general formulas (5) to (7) of the present invention usually has a vaporization temperature of 800 ° C. or lower under normal pressure. From the viewpoint of the stability of the film forming process, the vaporization temperature is preferably 700 ° C. or lower, and more preferably 600 ° C. or lower. The lower limit of the vaporization temperature is usually about 300 ° C.

  The organic compound containing the partial structure represented by the general formulas (5) to (7) of the present invention usually has a melting point of 100 ° C. or higher. However, when used in an organic electroluminescent device, its heat resistance viewpoint. Therefore, the melting point is preferably 150 ° C. or higher, and more preferably 200 ° C. or higher. The upper limit of the melting point is usually about 500 ° C.

  Hereinafter, although the specific example of the organic compound containing the partial structure represented by General formula (5)-(7) which concerns on this invention is shown, this invention is not limited to these.

Hereinafter, although the specific example of the organic compound containing the partial structure represented by General formula (5), (6) or (7) based on this invention and the compound of a reference example are shown, this invention is not limited to these.

  The structures of the substituents R-1 to R-74 and the linking groups A-1 to A-45 and Y-1 to Y-45 are shown below. * Of a substituent or a linking group represents a bond at a binding site with another part of the molecule.

  The compound having a partial structure represented by the general formula (5), (6) or (7) of the present invention can be synthesized in a higher yield than a commercially available compound by appropriately combining known synthesis methods.

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

  Synthesis of exemplary compound HB-1

In a 50 ml three-headed flask, 6.52 g (30.0 mmol) of 1H-dibenzo [e, g] indole, 6.09 g (15.0 mmol) of 3,3′-diiodobiphenyl, 5.53 g (40 mmol) of Potassium carbonate, 5 ml of tetralin and 0.24 g (3.8 mmol) of activated copper powder were charged, heated to 200 ° C. and stirred at this temperature for 24 hours. The reaction mixture was cooled to 140 ° C. and then mixed with 50 ml of ethyl acetate. The suspension was heated to boiling point under reflux for 1 hour and subsequently filtered hot. The filtrate was diluted with 20 ml of methanol, during which time a precipitate precipitated, which was separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 6.3 g of pale yellowish white solid was obtained. It was confirmed by MASS and NMR that the produced compound was the target product.
1H-NMR (400 MHz, CDCl 3 ) (chemical shift δ, peak shape, proton number): δ = 6.50 (d, 2H), 7.45 to 7.55 (m, 6H), 7.58 (d , 2H), 7.80 to 7.90 (m, 8H), 8.05 to 8.15 (m, 6H), 8.85 to 8.95 (m, 4H).
Synthesis of exemplary compound HB-134

  In a 50 ml three-headed flask, 6.52 g (30.0 mmol) of 1H-dibenzo [e, g] indole, 4.95 g (15.0 mmol) of 1,3-diiodobenzene, 5.53 g (40 mmol) of carbonic acid. Potassium, 5 ml of tetralin and 0.24 g (3.8 mmol) of activated copper powder were charged and heated to 200 ° C. and stirred at this temperature for 24 hours. The reaction mixture was cooled to 140 ° C. and then mixed with 50 ml of ethyl acetate. The suspension was heated to boiling point under reflux for 1 hour and subsequently filtered hot. The filtrate was diluted with 20 ml of methanol, during which time a precipitate precipitated, which was separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 5.3 g of a pale yellowish white solid was obtained.

It was confirmed by MASS and NMR that the produced compound was the target product.
1H-NMR (400 MHz, CDCl 3 ) (chemical shift δ, peak shape, proton number): δ = 6.51 (d, 2H), 7.45 to 7.55 (m, 4H), 7.59 (d , 2H), 7.80 to 7.90 (m, 8H), 8.05 to 8.15 (m, 4H), 8.85 to 8.95 (m, 4H)
Synthesis of exemplary compound HC-59

  5.58 g (15.0 mmol) of 5-bromo-1-phenyl-1H-1H-dibenzo [e, g] indole 2.95 g (7.0 mmol) of 2,2′-bibenzobenzofuran in a 50 ml three-headed flask -8,8'-diboronic acid, 1.94 g (14 mmol) of potassium carbonate, 10 ml of toluene and 5.8 g (0.5 mmol) of tetrakis (triphenylphosphine) palladium were added and heated to reflux temperature. Stir for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 50 ml of acetic acid ethyl ester. The solution was washed several times with water, dried over sodium sulfate and filtered. When the filtrate was concentrated under reduced pressure, crystals were precipitated. It was suctioned off, washed with methanol and dried in vacuo at 80 ° C. 4.69 g of pale yellowish white solid was obtained.

It was confirmed by MASS and 1H-NMR that the resulting compound was the target product.
1H-NMR (400 MHz, CDCl 3 ) (chemical shift δ, peak shape, proton number): δ = 6.50 (d, 2H), 7.45 to 7.55 (m, 10H), 7.59 (d , 2H), 7.70 to 7.90 (m, 16H), 8.05 to 8.15 (m, 4H), 8.32 (d, 2H), 8.85 to 8.95 (m, 4H) )
Other compounds of the present invention can also be synthesized with good yield by using the same synthesis method as in the above synthesis examples and using appropriate raw materials.

  Next, the light emitting element, illumination device, and image display device of the present invention will be described.

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

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode In the organic EL device of the present invention, the blue light emitting layer preferably has a light emission maximum wavelength of 430 nm to 480 nm, and the green light emitting layer has a light emission maximum wavelength of 510 nm to 550 nm, The red light emitting layer is preferably a monochromatic light emitting layer having a light emission maximum wavelength in the range of 600 nm to 640 nm, and is preferably a display device using these. Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.

  Each layer which comprises the organic EL element of this invention is demonstrated.

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

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

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

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

(Host compound (also called luminescent host))
The host compound used in the present invention will be described.

  Here, the host compound in the present invention is a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is defined as a compound of less than 0.1. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  As the host compound of the present invention, an organic compound containing a partial structure represented by the general formulas (5) to (7) according to the present invention is preferable, and a known host compound may be used in combination, or a plurality of them may be used. It may be used in combination with seeds. 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. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). A light emitting host), or one or more compounds such as the material C may be used.

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

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

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent dopant)
The light emitting dopant according to the present invention will be described.

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

(Phosphorescent dopant)
The phosphorescent dopant according to the present invention will be described.

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

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

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

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.

  The phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), Rare earth complexes, most preferably iridium compounds.

  The compound used as the phosphorescent dopant according to the present invention is preferably a transition metal complex compound including a partial structure represented by any one of the general formulas (1) to (4) according to the present invention.

  Moreover, you may use together a conventionally well-known light emission dopant as shown below.

(Fluorescent dopant (also called fluorescent compound))
Fluorescent dopants (fluorescent compounds) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

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

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

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

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

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

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

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

  Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

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

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

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

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

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

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

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

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

  The hole transport material has any 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, and also 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.

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

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

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

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

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.

  Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

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

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

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

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

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.

Alternatively, an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

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

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

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

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m 2 · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 −3 ml / (m 2 · 24 h · atm) or less and a water vapor permeability of 10 −5 g / (m 2 · 24 h) or less is preferable.

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

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

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

  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 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

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

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

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

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

  In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.

Furthermore, the polymer film has an oxygen permeability of 1 × 10 −3 ml / (m 2 · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 −3 g / (m 2 · 24 h) or less.

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

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive.

  Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, plasma CVD method, laser CVD method, thermal CVD method, coating method, or the like can be used.

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

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

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

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

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

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

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

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

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

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

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

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

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

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

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

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

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

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

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

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< 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 will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, to form an anode.

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

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

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

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

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

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

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the device may be patterned. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with 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 CIE 1931 color system at 1000 cd / m 2 is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the structure of the compound used in an Example is shown below.

Example 1
<< Production of Organic EL Element 1-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was put in a molybdenum resistance heating boat, and 200 mg of H-1 as a host compound was put in another molybdenum resistance heating boat, 200 mg of BAlq was put into another resistance heating boat made of molybdenum, 100 mg of Ir-12 was put into another resistance heating boat made of molybdenum, and 200 mg of Alq 3 was put into another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum chamber to 4 × 10 −4 Pa, the heating boat containing α-NPD was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The hole transport layer was provided.

  Further, the heating boat containing H-1 and Ir-12 (FIrpic) is energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. Thus, a light emitting layer having a thickness of 40 nm was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

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

In addition, the heating boat containing Alq 3 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. 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 organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-21 >>
In the production of the organic EL device 1-1, the organic EL device 1-2 was similarly prepared except that H-1 as the host compound of the light emitting layer and Ir-12 as the dopant compound were replaced with the compounds shown in Table 5. 1-21 was produced.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-21, 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 photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as 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. 3 and 4 was formed and evaluated.

  FIG. 3 is a schematic diagram 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).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, 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 light 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.

(Half life)
The half-life was evaluated according to the measurement method shown below.

Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / m 2, obtains the time to be 1/2 (500cd / m 2) of the initial luminance, which was used as a measure of the half-life. The half life was expressed as a relative value when the comparative organic EL element 1-1 was set to 100.

(Initial deterioration)
The initial deterioration was evaluated according to the measurement method shown below.

  When the half-life was measured, the time required for the luminance to reach 90% was measured and used as a measure of initial deterioration. The initial deterioration was 100 for the comparative organic EL element 1-1.

The initial deterioration was calculated based on the following formula.
Initial deterioration = (luminance 90% arrival time of organic EL element 1-1) / (luminance 90% arrival time of each element) × 100
That is, the smaller the initial deterioration value is, the smaller the initial deterioration is.

(Dark spot)
The light emitting surface when each organic EL element was continuously lit under a constant current condition of 2.5 mA / cm 2 at room temperature was visually evaluated. The dark spot resistance was evaluated according to the following evaluation criteria for each element after 10 hours of continuous lighting by visual observation by 10 randomly extracted persons.
×: When the number of confirmed dark spots is 5 or more Δ: When the number of confirmed dark spots is 1-4 persons ○: When the number of confirmed dark spots is 0 persons The above evaluation results are shown in Table 1. Show.

  From Table 1, it can be seen that the organic EL device of the present invention has a higher external extraction quantum efficiency, less initial luminance degradation, and a longer lifetime as compared with the comparative device.

  It can also be seen that the generation of dark spots is suppressed.

Example 2
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL device 1-9 of Example 1 was used as a blue light emitting device.

(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 Ir-12 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 Ir-12 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 3
<< Preparation of White Light Emitting Element and White Lighting Device-1 >>
The electrode of the transparent electrode substrate of Example 1 was patterned to 50 mm × 50 mm, and α-NPD was formed thereon with a thickness of 25 nm as a hole injection / transport layer in the same manner as in Example 1, and further HB— The heated boat containing 1 and the boat containing Exemplified Compound A-97 and the boat containing Ir-9 were energized independently, and HB-1 as a luminescent host and Exemplified Compound A-97 as a luminescent dopant, In addition, the evaporation rate of Ir-9 was adjusted to be 100: 5: 0.6, vapor deposition was performed so that the film thickness was 30 nm, and a light emitting layer was provided.

Next, 10 nm of BAlq was deposited to provide a hole blocking layer. Furthermore, it was deposited Alq 3 at 40nm an electron transporting 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 transport layer, and lithium fluoride 0.5 nm as the cathode buffer layer and aluminum 150 nm as the cathode. Vapor deposition and film formation were performed.

  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. 3 and 4 was produced. When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 4
<< 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 obtained by dissolving HB-689 (60 mg), F-8 (3.0 mg), and Ir-14 (3.0 mg) in 6 ml of toluene, it was manufactured by spin coating under conditions of 1000 rpm and 30 seconds. Filmed. 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.

  Furthermore, a film in which compound F (20 mg) was 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 vapor deposition apparatus, and 200 mg of Alq 3 was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus. After depressurizing the vacuum chamber to 4 × 10 −4 Pa, energizing and heating the heating boat containing Alq 3 , depositing on the hole blocking layer at a deposition rate of 0.1 nm / second, 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.

  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. 3 and 4 was produced.

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

Example 5
<< Production of Organic EL Element 5-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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 of compound E (60 mg) and Ir-12 (3.0 mg) dissolved in 6 ml of toluene, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds to form a light emitting layer.

  Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of BAlq was put into a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus.

After the vacuum chamber was depressurized to 4 × 10 −4 Pa, the heating boat containing BAlq was energized and heated, deposited on the light emitting layer at a deposition rate of 0.1 nm / second, and a film thickness of 40 nm. The electron transport layer 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.

<< Production of Organic EL Elements 5-2 to 5-10 >>
In the production of the organic EL device 5-1, the organic EL devices 5-2 to 10 were similarly prepared except that the compound E as the host compound of the light emitting layer and the dopant compound Ir-12 were replaced with the compounds shown in Table 2. Was made.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 5-1 to 5-10, 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 photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as 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. 3 and 4 was formed and evaluated.

  FIG. 3 is a schematic diagram 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).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, 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 light 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 5-1 as 100.

(Half life)
The half-life was evaluated according to the measurement method shown below.

Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / m 2, obtains the time to be 1/2 (500cd / m 2) of the initial luminance, which was used as a measure of the half-life. The half life was expressed as a relative value with the comparative organic EL element 5-1 of Example 5 as 100.

(Initial deterioration)
The initial deterioration was evaluated according to the measurement method shown below.

  At the time of measuring the half-life, a time for 90% of the initial luminance was obtained and used as a measure of initial deterioration. In addition, initial stage deterioration was represented by the relative value which sets the comparison organic EL element 5-1 of Example 5 to 100.

The initial deterioration was calculated based on the following formula.
Initial degradation = (90% reach time of luminance of organic EL element 5-1) / (90% reach time of brightness of each element) × 100
That is, the smaller the initial deterioration value is, the smaller the initial deterioration is.

(Dark spot resistance)
The light emitting surface when the organic EL element was continuously lit under a constant current condition of 2.5 mA / cm 2 at room temperature was visually evaluated. The dark spot resistance of each element was evaluated according to the following evaluation criteria by visual observation by 10 people extracted at random.
×: When the number of confirmed dark spots is 5 or more. Δ: When the number of confirmed dark spots is 1-4. ○: When the number of confirmed dark spots is 0. The above evaluation results are shown in Table 2. Show.

  From Table 2, it can be seen that the organic EL device of the present invention has a higher external extraction quantum efficiency, less initial luminance degradation, and a longer lifetime as compared with the comparative device. It can also be seen that the generation of dark spots is suppressed.

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

Claims (16)

  1. In the organic electroluminescence device having at least one light emitting layer sandwiched between an anode and a cathode, the light emitting layer contains a phosphorescent dopant and has the following general formula (5), (6) or (7) It has an organic layer containing the compound containing the partial structure represented by these, The organic electroluminescent element characterized by the above-mentioned.
    [ Wherein , A 1a , A 1b and A 1c each independently represent a single bond, an arylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.
    E 2a to E 2j each independently represent a carbon atom or a nitrogen atom. In E 2a to E 2j , the number of nitrogen atoms is 1 to 4, and two or more adjacent E 2 * s do not become nitrogen atoms at the same time. Further, at least one of E 2a to E 2h is a nitrogen atom. Here, * represents an arbitrary character from a to j.
    R 2a to R 2k each independently represents a hydrogen atom or a substituent.
    However, any one of next A 1a of R 2a to R 2d, one of R 2e or R 2h is A 1 c, and the any one of the R 2i to R 2k becomes A 1b.
    However, in General formula (6), when E2d, E2e, and E2i are all nitrogen atoms, E2d, E2h, and E2i are all nitrogen atoms, or when E2a, E2h, and E2i are all nitrogen atoms. . ]
    ]
  2. 2. The phosphorescent dopant is at least one compound including a partial structure represented by the following general formula (1), (2), (3), or (4). The organic electroluminescent element of description.
    [ Wherein , E 1a and E 1q are different and each represents a carbon atom or a nitrogen atom. E 1b to E 1p each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and the skeleton composed of E 1a to E 1q has a total of 18π electrons.
    R 1a to R 1i each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1h is a substituent.
    However, when E 1 * to which R 1 * is bonded is an oxygen atom or a sulfur atom, R 1 * does not exist. In addition, when E 1 * to which R 1 * is bonded is a nitrogen atom, R 1 * may not exist. Here, * represents any character of a to i.
    M represents a group 8-10 transition metal element in the periodic table. ]
  3. Formula (5), according to claim 2, characterized by being represented by any one of (6) or a compound containing the partial structure represented by (7) of the general formula (8) to (13) Organic electroluminescence element.
    [Wherein, m1 to m3 and n1 to n3 are each an integer of 0 to 6, and m1 + n1 ≦ 6, m2 + n2 ≦ 6, and m3 + n3 ≦ 6.
    m4 to m6 and n4 to n6 are each an integer of 1 to 5, and m4 + n4 ≦ 6, m5 + n5 ≦ 6, and m6 + n6 ≦ 6.
    X 1 to X 6 are each independently a single bond, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an amino which may have a substituent. It represents a my + ny-valent group formed by combining groups selected from groups. Here, y represents any one of 1-6.
    A 11a , A 21a , A 11b , A 21b , A 11c and A 21c are each independently a single bond, an arylene group which may have a substituent, or a divalent complex which may have a substituent. Represents a cyclic group.
    E 11a to E 11j , E 21a to E 21j , E 31a to E 31j , E 41a to E 41j , E 51a to E 51j , E 61a to E 61j each independently represent a carbon atom or a nitrogen atom. In E za to E zj , the number of nitrogen atoms is 1 to 4, and two or more adjacent E Z * do not simultaneously become nitrogen atoms. In addition, at least one of E za to E zh is a nitrogen atom. Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61, and * represents an arbitrary character selected from a to j.
    R 11a to R 11k , R 21a to R 21k , R 31a to R 31k , R 41a to R 41k , R 51a to R 51k , and R 61a to R 61k each independently represent a hydrogen atom or a substituent.
    Any one of R 11a to R 11d is A 11a and any one of R 21a to R 21d is A 21a .
    Any one of R 31i to R 31k is A 11b , and any one of R 41i to R 41k is A 21b .
    Any one of R 51e to R 51h is A 11c , and any one of R 61e to R 61h is A 21c .
    However, in general formula (9), general formula (11) or general formula (13),
    When E 31d , E 31e and E 31i are all nitrogen atoms,
    When E 31d , E 31h and E 31i are all nitrogen atoms,
    When E 31a , E 31h and E 31i are all nitrogen atoms,
    When E 41d , E 41e and E 41i are all nitrogen atoms,
    When E 41d , E 41h and E 41i are all nitrogen atoms, or
    Except when E 41a , E 41h and E 41i are all nitrogen atoms. ]
  4. 4. The organic group according to claim 3, wherein the groups represented by X 1 to X 6 in the general formulas (8) to (13) are an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Electroluminescence element.
  5. The groups represented by X 1 to X 6 in the general formulas (8) to (13) are a phenyl group, a biphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, and an anthracenyl group. 5. The organic electroluminescence device according to claim 3, wherein the organic electroluminescence device is a divalent group obtained by further removing one hydrogen atom from the group and a combination thereof.
  6.   The organic electroluminescence device according to claim 3, wherein the compounds represented by the general formulas (8) to (13) have a glass transition temperature of 100 ° C. or higher.
  7. R 11a to R 11k , R 21a to R 21k , R 31a to R 31k , R 41a to R 41k , R 51a to R 51k , R 61a to R 61k in the general formulas (8) to (13) The organic electroluminescence device according to claim 3, wherein at least one of the substituents is a polymerizable substituent.
  8. Formula (1), (2), (3), or ring comprised of E 1a to E 1e in (4), according to claim 3-7, characterized in that the imidazole ring or pyrazole ring The organic electroluminescent element of any one of Claims.
  9. As a constituent layer, it has an organic layer containing at least one compound containing a partial structure represented by any one of the general formulas (1) to (4), and the organic layer was formed using a wet process The organic electroluminescence device according to claim 3 , wherein the organic electroluminescence device is a liquid crystal display device.
  10.   It has an organic layer containing at least one compound represented by any one of the general formulas (8) to (13) as a constituent layer, and the organic layer is formed using a wet process The organic electroluminescent element according to any one of claims 3 to 9.
  11.   The organic layer containing at least one compound represented by any one of the general formulas (8) to (13) as a constituent layer is a light emitting layer. The organic electroluminescent element of description.
  12.   The organic layer containing at least one polymer having a partial structure of the compound represented by any one of the general formulas (8) to (13). The organic electroluminescent element of description.
  13. The polymer according to any one of claims 3 to 12, comprising at least one polymer having a partial structure of a compound including the partial structure represented by any one of the general formulas (1) to (4). The organic electroluminescent element of the item.
  14. 14. The organic electroluminescent element according to claim 3 , wherein M in the general formulas (1), (2), (3), or (4) is platinum or iridium.
  15.   A display device comprising the organic electroluminescence element according to claim 1.
  16.   The illuminating device provided with the organic electroluminescent element of any one of Claims 1-14.
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