JP5509634B2 - ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE, LIGHTING DEVICE, AND ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL - Google Patents

Description

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

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of 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, and there is a possibility that almost the same performance as a cold cathode tube can be obtained. Therefore, it is attracting attention as a lighting application.

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

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

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

  Conventionally, a compound having a plurality of carbazole rings in the molecule is known as a good host compound. Patent Documents 5 and 6 disclose a combination example with m-CBP even in the compound having the phenanthridine skeleton.

  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. 04/085450 Pamphlet JP 2005-53912 A JP 2006-28101 A US Pat. No. 7,147,937 US Patent Application Publication No. 2007/190359 International Publication No. 07/95118 Pamphlet

  The present invention has been made in view of such problems, and an object of the present invention is to use an organic EL device material that exhibits specific short-wave light emission, exhibits high light emission efficiency, and has a long light emission lifetime. An organic EL element, an illumination device, and a display device are provided. Another object of the present invention is to provide an organic EL device material that exhibits high light emission efficiency with a short wavelength light emission of blue to blue green, has a low driving voltage, and has a long light emission lifetime.

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

  1. In an organic electroluminescence device comprising at least one light emitting layer sandwiched between an anode and a cathode, the light emitting layer contains at least one phosphorescent dopant, and the following general formula (5), (6) or (7 And an organic layer containing at least one compound containing a partial structure represented by formula (1).

(In the formula, A _1a , A _1b and A _1c each represent a single bond or an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. E _2a to E _2k represents a carbon atom or a nitrogen atom, and any one of E _{2i to} E _2k is a nitrogen atom, and the number of nitrogen atoms in E _{2a to} E _2k is 1 to 4, and two or more adjacent ones E _{2 *} is not a nitrogen atom at the same time, where * represents an arbitrary letter from a to _k, R _{2a to} R _2k each independently represents a hydrogen atom or a substituent, and R _2a to Any of R _2d is A _1a , any of R _2e or R _2h is A _1c , and any of R _{2i to} R _2k is A _1b , provided that E _2i represents a nitrogen atom, and When R _2j and R _2k both represent a substituent R _2j or R _2k is a substituted or unsubstituted C3-C40 cycloalkyl group; a substituted or unsubstituted C6-C60 aryl group; a substituted or unsubstituted C2-C40 alkenyl group; a substituted or unsubstituted It is not a C2-C60 heterocyclic group or an aromatic heterocyclic ring, and R _2j and R _2k are not bonded to each other to form an aliphatic, aromatic or heteroaromatic ring.
2. 2. The organic electroluminescent device according to 1 above, wherein the phosphorescent dopant is selected from compounds containing a partial structure represented by the following general formula (1), (2), (3) or (4).

(In the formula, E ^1a and E ^1q are different from each other and represent a carbon atom or a nitrogen atom. E ^{1b to} E ^1p represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and are composed of E ^{1a to} E ^1q . The skeleton has a total of 18π electrons, R ^{1a to} R ¹ⁱ each represent a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^1h is a substituent, provided that R ^{1 *} is bonded to E ^{When 1 *} is an oxygen atom or a sulfur atom, R ^{1 *} does not exist, and when E ^{1 *} to which R ^{1 *} is bonded is a nitrogen atom, R ^{1 *} may not exist. Here, * represents an arbitrary letter from a to i. M represents a transition metal element of Group 8 to Group 10 in the periodic table.)
3. 3. The organic electroluminescence device according to 2 above, wherein the ring composed of E ^{1a to} E ^1e in the general formulas (1) to (4) is an imidazole ring or a pyrazole ring.

  4). The compound containing the partial structure represented by the general formula (5), (6) or (7) is represented by any one of the general formulas (8) to (13). The organic electroluminescent element of any one of Claims.

(In the formula, 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 integers of 1 to 5, respectively. M4 + n4 ≦ 6, m5 + n5 ≦ 6, m6 + n6 ≦ 6, X _{1 to} X ₆ are each a single bond, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. , Or a linking group composed of a my + ny valent group formed by combining groups selected from optionally substituted amino groups, where y represents any one of 1 to 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 heterocyclic group which may have a substituent. E _{11a to} E _{11 k, E} 21a _~E 21k, represents _{E 31a ~E 31k, E 41a ~E} 41k, the _{E 51a ~E 51k, E 61a ~E} 61k each carbon atom or a nitrogen _atom, E _zi, E _zj, the _{E zk} Any one is a nitrogen atom, and the number of nitrogen atoms is 1 to 4 in E _{za to} E _zk , and two or more adjacent E _{Z *} cannot be a nitrogen atom at the same time, where z is Represents any number selected from ₁₁ , ₂₁ , ₃₁ , ₄₁ , 51, 61, and * represents any character selected from a to _k , R _{11a to} R _11k , R _{21a to} R _21k , R _{31a to} R _{31k, R} 41a _{to R 41k,} represents a _{R 51a ~R 51k, R 61a ~R} 61k are each independently hydrogen atom or a substituent. _also, one of R 11a _{to R 11d} is in _{a 11a Ri,} either R 21a _{to R 21d} is _{A 21a. Also,} one of R 51e _{to R 51h} is _{A 11c,} one of R 61e _{to R 61h} is _{A 21c. Further, R 31i} either to R _31k are _{a 11b,} one of R 41i _{to R 41k} are _{a 21b.}
However, when E _zi represents a nitrogen atom and R _zj and R _zk both represent a substituent, R _zj or R _zk represents a substituted or unsubstituted C3-C40 cycloalkyl group; a substituted or unsubstituted It is not a C6-C60 aryl group; a substituted or unsubstituted C2-C40 alkenyl group; a substituted or unsubstituted C2-C60 heterocyclic group or an aromatic heterocyclic ring. Further, R _zj and R _zk are not bonded to each other to form an aliphatic, aromatic or heteroaromatic ring. Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61 in each condensed ring bonded via X _{1 to} X ₆ in each formula . )
5. 5. The organic electroluminescence as described in 4 above, wherein the linking group represented by X _{1 to} X ₆ in the general formulas (8) to (13) is composed of an aromatic ring group or an aromatic heterocyclic group. element.

6). The aromatic ring group or an aromatic heterocyclic group is a phenyl group, Ru Oh biphenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, fluorenyl group, pyrenyl group, anthracenyl group, and a group comprising a combination thereof the organic electroluminescent device according to the 5, wherein the this.

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 4 to 6, wherein at least one of the substituents is a polymerizable substituent.

  8). 8. The organic electroluminescence device according to any one of 4 to 7, wherein a glass transition temperature in the compounds represented by the general formulas (8) to (13) is 100 ° C. or higher.

  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 9. The organic electroluminescence device according to any one of 1 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 The organic electroluminescent element according to any one of 1 to 9 above.

  11. 11. The organic electroluminescence device as described in 10 above, wherein the organic layer is a light emitting layer.

  12 Any one of 1 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. Said M is platinum or iridium, The organic electroluminescent element of any one of said 2-12 characterized by the above-mentioned.

  14 14. A display device comprising the organic electroluminescence element according to any one of 1 to 13 above.

  15. 14. An illumination device comprising the organic electroluminescence element according to any one of 1 to 13 above.

16. Formula (1) to (4) an organic electroluminescence device material characterized by having including a partial structure including the polymer represented by any one of claim 2.

  According to the present invention, it has been possible to provide an organic EL device that exhibits specific short-wave light emission, exhibits high light emission efficiency, has a low driving voltage, and has a long light emission lifetime. Further, as a result of investigations by the inventors, the present invention has been able to significantly reduce 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 EL device could be provided. In addition, an illumination device and a display device using the element could be provided. Furthermore, the organic EL element material useful for organic EL 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, the present invention will be described in detail.

  In the organic electroluminescent element of this invention, by the structure prescribed | regulated in any one of Claims 1-13, the organic electroluminescent element which shows high luminous efficiency and has a long light emission lifetime, and the illuminating device using this element 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 device material of the present invention was observed to emit light with a specific short wave, and the lifetime of the organic electroluminescence device 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 (also referred to as a metal complex compound) that is a phosphorescent dopant according to the present invention will be described.

  The present inventors paid attention to the organic EL element material used for the light emitting layer of the organic EL element, and examined various metal complex compounds used as a light emitting dopant.

  The present inventors have introduced a substituent into the basic skeleton of the metal complex, so that it is not a conventionally known approach to control the wavelength or improve the lifetime, but it is possible to stabilize the compound by expanding the π-conjugated surface of the condensed ring. Various complexes were examined under the focus of increasing the properties. 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. It was found that when the light-emitting material is applied to the light-emitting material, the light-emitting wavelength shift is small, and it exhibits favorable characteristics as a phosphorescent dopant that achieves a long lifetime at a desired light-emitting wavelength.

  Further investigation on this new basic skeleton has the disadvantage that the π-conjugated 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 ^1a in a 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 was found that by introducing a substituent into at least one of ~ R ^1h , the oxidative degradation was greatly reduced and the stability of the compound was 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 at least one of R ^1a or R ^1b is a substituent. And at least one of R ^{1c to} R ^1h is a substituent.

  The transition metal complex compound including 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. However, the ligands may all be the same or may have ligands each having a different structure.

  Here, the part with a ligand remove | excluding the transition metal element M from the partial structure represented by either of General formula (1)-(4) is a ligand, respectively.

(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 of group 8 to 10 of the periodic table (also simply referred to as a transition metal) is used, among which 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.

<< Compounds including partial structures represented by general formulas (5) to (7) >>
The compound containing the partial structure represented by the general formulas (5) to (7) will be described.

  The compound containing the partial structure represented by the general formulas (5) to (7) according to the present invention includes one or more imidazophenanthridine rings, pyrazolophenanthridine rings, and imidazophenanthridine rings in the molecule. It has a nitrogen-containing heterocycle in which one or two carbon atoms are replaced with a nitrogen atom, or a nitrogen-containing heterocycle in which one or two carbon atoms of a pyrazolophenanthridine ring are replaced with a nitrogen 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) according to the present invention has a hole transport property as compared with a conventional transition metal complex. Therefore, the combined use of a conventional host compound composed of a plurality of carbazolyl groups cannot achieve a perfect balance between hole transfer and electron transfer, so that sufficient performance cannot be exhibited.

  As a result of investigating an optimal host compound to be used in combination with a transition metal complex compound containing a partial structure represented by the general formula (1), (2), (3), or (4) according to the present invention, By using the compound containing the partial structure represented by the general formulas (5) to (7) according to the present invention as the host compound, the balance of hole transfer and electron transfer can be perfectly matched, Short-wave light emission was observed, high light emission efficiency was exhibited, and an organic EL element having a long light emission lifetime could be provided.

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

  Furthermore, the preferable embodiment of the 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) according to the present invention is represented by the general formula (5). It is a compound containing the partial structure represented by-(7).

In the formula, each of A _1a , A _1b and A _1c represents a single bond or an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.

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

  As a bivalent heterocyclic group, the bivalent group obtained by remove | excluding the arbitrary hydrogen atoms of arbitrary heterocyclic groups is mentioned. 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.

  Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aromatic hydrocarbon ring group (aromatic carbon) Also referred to as ring 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, phenanthryl group, indenyl group, pyrenyl Group, biphenylyl group, etc.), aromatic heterocyclic group (for example, Zyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazole- 1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl Group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group , Phthalazinyl group, etc.) Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloalkoxy groups (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), alkylthio groups (eg methylthio group, ethylthio group, propylthio group, pentylthio group) Hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (example) For example, 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) 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, cyclohexyl group) Carbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino , Naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexyl) Aminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido) Group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group) , Ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethyl Sulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), Amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group) Group, anilino group, naphthylamino group, 2-pyridylamino group, diphenylamino group, phenylnaphthylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, Fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group) , 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. You may form.
However, in General Formula (5) to General Formula (7), when E _2i represents a nitrogen atom and R _2j and R _2k both represent a substituent, R _2j or R _2k is a substituted or unsubstituted group. A C3-C40 cycloalkyl group; a substituted or unsubstituted C6-C60 aryl group; a substituted or unsubstituted C2-C40 alkenyl group; a substituted or unsubstituted C2-C60 heterocyclic group or an aromatic heterocyclic ring; Never. Also, R _2j and R _2k are not bonded to each other to form an aliphatic, aromatic or heteroaromatic ring.

E _{2a to} E _2k represent a carbon atom or a nitrogen atom, and any one of E _{2i to} E _2k is a nitrogen atom. In E _{2a to} E _2k , 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.

  In the following, the nitrogen-containing heterocycle represented by the general formulas (5) to (7), that is, one or two carbon atoms of the imidazophenanthridine ring, pyrazolophenanthridine ring, imidazophenanthridine ring is nitrogen. Specific examples include nitrogen-containing heterocycles substituted with atoms or nitrogen-containing heterocycles in which one or two carbon atoms of the pyrazolophenanthridine ring are replaced with nitrogen atoms. 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 a number unique to each heterocycle, but on the common skeleton pyrazolo [1,2-f] phenanthridine skeleton. The position number is used.

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 the same as those exemplified in the description of the substituents of A _1a to A _1c.

In General Formula (5), A _1a represents one of R _{2a to} R _2d as one or two nitrogen atoms of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. It is bonded to a nitrogen-containing heterocyclic ring in which the carbon atom of the substituted nitrogen-containing heterocyclic ring or the pyrazolophenanthridine ring is replaced with one or two nitrogen atoms.

In the general formula (6), A _1b represents one of R _{2i and} R _2k as one or two carbon atoms of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. It is bonded to a nitrogen-containing heterocyclic ring in which the carbon atom of the substituted nitrogen-containing heterocyclic ring or the pyrazolophenanthridine ring is replaced with one or two nitrogen atoms.

In General Formula (7), A _1c represents one of R _{2e to} R _2h as one or two nitrogen atoms of an imidazophenanthridine ring, a pyrazolophenanthridine ring, or an imidazophenanthridine ring. It is bonded to a nitrogen-containing heterocyclic ring in which the carbon atom of the substituted nitrogen-containing heterocyclic ring or the pyrazolophenanthridine ring is replaced with one or two nitrogen atoms.

  A preferred embodiment of the compound including the partial structure represented by the general formulas (5) to (7) according to the present invention is a case where the compound is represented by any one of the general formulas (8) to (13). .

  In the formula, m1 to m3 and n1 to n3 are integers of 0 to 6, respectively, 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 selected from a single bond, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an amino group which may have a substituent. Represents a my + ny-valent group formed by combining these groups. Here, y represents any one of 1-6.

  Examples of aryl groups include phenyl, p-chlorophenyl, mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl Etc.

  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.

  Examples of the substituent are the same as those described in the description of the general formulas (5) to (7).

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 which may have a substituent A heterocyclic group is shown. Examples of the arylene group and the divalent heterocyclic group are the same as those described in the description of the general formulas (5) to (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 , and R _{61a to} R _61k each independently represent a hydrogen atom or a substituent. Similarly, examples of the substituent include the same as those described in the description of the general formulas (5) to (7).

In the general formulas (8), (11), and (12), A _11a is any one of R _{11a to} R _11d as a carbon atom of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. Are bonded to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms are replaced, or to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms of the pyrazolophenanthridine ring are replaced.

In General Formulas (9), (11), and (13), A _11b is any one of R _{31i to} R _31k , and is a carbon atom of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. Are bonded to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms are replaced, or to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms of the pyrazolophenanthridine ring are replaced.

In the general formulas (10), (12), and (13), A _11c is any one of R _{51e to} R _51h , and is a carbon atom of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. Are bonded to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms are replaced, or to a nitrogen-containing heterocyclic ring in which one or two nitrogen atoms of the pyrazolophenanthridine ring are replaced.

In General Formula (8), A _21a represents any one of R _{21a to} R _21d as one or two nitrogen atoms of an imidazophenanthridine ring, pyrazolophenanthridine ring, or imidazophenanthridine ring. Or a nitrogen-containing heterocycle in which one or two carbon atoms of the pyrazolophenanthridine ring are replaced with one or two nitrogen atoms.

In General Formula (9), A _21b represents any one of R _{41i to} R _41k as one or two carbon atoms of an imidazophenanthridine ring, a pyrazolophenanthridine ring, or an imidazophenanthridine ring. Or a nitrogen-containing heterocycle in which one or two carbon atoms of the pyrazolophenanthridine ring are replaced with one or two nitrogen atoms.

In General Formula (10), A _21c represents one of R _{61e to} R _61h as one or two carbon atoms of an imidazophenanthridine ring, a pyrazolophenanthridine ring, or an imidazophenanthridine ring. Or a nitrogen-containing heterocycle in which one or two carbon atoms of the pyrazolophenanthridine ring are replaced with one or two nitrogen atoms.

(Molecular weight)
The upper limit of the molecular weight of the compound containing the partial structure represented by the general formulas (5) to (7) according to the present invention or the compound containing the partial structure represented by the general formulas (8) to (13) according to the present invention Is preferably 4000 or less, more preferably 3000 or less, and particularly preferably 2000 or less from the viewpoint of minimizing the content of impurities during purification using a vapor deposition method. The lower limit of the molecular weight is preferably 200 or more, more preferably 300 or more, particularly preferably 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. 400 or more.

(Physical properties)
The compound containing the partial structure represented by the general formulas (5) to (7) according to the present invention usually has a glass transition temperature of 50 ° C. or higher, but when used in an organic electroluminescent device, its heat resistance From this 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) according to the present invention usually has a vaporization temperature of 800 ° C. or lower under normal pressure, but when used in an organic electroluminescence device, From the viewpoint of the stability of the vapor deposition film forming step, 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.

  Although the compound containing the partial structure represented by the general formulas (5) to (7) according to the present invention usually has a melting point of 100 ° C. or higher, when used in an organic electroluminescence 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. Here, the chemical formulas 92 to 243 are represented based on the general formula (14) of the chemical formula 92, the chemical formula 105, the chemical formula 152, and the general formula (15) of the chemical formula 199.

Het substituents and R, A in Chemical Formula 92 to Chemical Formula 104 based on general formula (14), and further, Het1 and Het2 substituents in Chemical Formula 105 to Chemical formula 243 based on general formula (15), X, A ₁ and A ₂ Is as follows. Note that * indicates 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) according to the present invention can be synthesized with higher yield than commercially available compounds by appropriately combining known synthesis methods.

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

<< Synthesis of Exemplified Compound HA-1 >>
Step 1: Synthesis of 2- (3-bromophenyl) imidazo [1,2-f] phenanthridine

  In a 1 L three-head flask, 12.5 g (62 mmol) of 1-bromo-2-nitrobenzene, 11.3 g (93 mmol) of phenylboronic acid, 40 g (186 mmol) of tripotassium phosphate and tetrakis (triphenylphosphine) in a nitrogen atmosphere Palladium (0) (3.5 g, 3.1 mmol) was added, and 300 ml of dehydrated toluene was added and stirred. Heating was started as it was, and the mixture was reacted for 8 hours under reflux with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. 300 ml of ethyl acetate was added to the reaction solution to extract the product. The extract was concentrated under reduced pressure to obtain 32 g of a crude product. The crude product was purified by column gel chromatography (hexane-ethyl acetate = 4: 1) to obtain 10.1 g of 2-nitrobiphenyl.

  In a Erlenmeyer flask for the hydrogenation reaction, a methanol 200 ml-tetrahydrofuran 100 ml solution of 2-nitrobiphenyl 10.1 g (51 mmol) was added, and 2.4 g of a highly active palladium carbon catalyst (palladium content 20%) was further added. Added. A connector for introducing and discharging gas was attached, and the air in the container was replaced with nitrogen. Next, hydrogen gas was introduced, and the inside of the container was replaced with hydrogen gas. The hydrogenation reaction was performed for 10 hours at room temperature while supplying hydrogen gas.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The palladium carbon catalyst was filtered and removed from the reaction solution, and concentrated under reduced pressure to obtain 8.7 g of a crude product. This crude product was purified by column gel chromatography (hexane-tetrahydrofuran = 2: 1) to obtain 8.5 g of 2-aminobiphenyl.

  In a 500 ml three-headed flask, 8.5 g (50 mmol) of 2-aminobiphenyl, 12 g (260 mmol) of formic acid, and 140 ml of toluene were added and reacted for 2 hours under superheated reflux.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was concentrated under reduced pressure, dissolved again in toluene, and concentrated under reduced pressure twice to remove excess formic acid and used as it was in the next reaction.

  N- (biphenyl-2-yl) formamide, which is the product of the previous step, was placed in a 500 ml three-headed flask, and 160 g of polyphosphoric acid (a high-viscosity bowl) was added. After mounting the mechanical stirrer, heating was started, and the reaction was carried out for 4 hours while heating in a 140 ° C. oil bath with sufficient stirring. The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred until a homogeneous solution was obtained. The product was extracted from the homogeneous solution with methylene chloride (200 ml x 3).

  The extract was concentrated under reduced pressure to obtain 15 g of a crude product. This crude product was purified by column gel chromatography (hexane-ethyl acetate = 10: 1 to 4: 1) to obtain 4.2 g of phenanthridine.

  In a 300 ml three-headed flask, 4.0 g (22 mmol) of phenanthridine and 200 ml of xylene were added and stirred at room temperature for a while to obtain a uniform solution. 8.6 g (220 mmol) of sodium amide was added thereto, and heating was started. The mixture was reacted for 1.5 hours under reflux while heating in an oil bath at 170 ° C. with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The toluene layer was separated and concentrated under reduced pressure to obtain 8 g of crude crystals. The crude crystals were suspended in hot toluene, and the crystals were filtered when cooled to room temperature. After washing with hexane and drying by heating, 3.5 g of phenanthridine-6-amine was obtained.

  In a 100 ml three-headed flask, a solution of 1.55 g (8.0 mmol) of phenanthridine-6-amine in 50 ml of toluene, 3.34 g (12.0 mmol) of 2-bromo-3′-bromoacetophenone, 1.2 g of triethylamine (12 0.0 mmol), and the mixture was reacted for 3 hours under reflux with heating in an oil bath at 140 ° C.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was filtered to remove insolubles, and then concentrated under reduced pressure until the volume was reduced to about half. The solution was purified by column gel chromatography (hexane-tetrahydrofuran = 10: 1 to 5: 1) to obtain 2.33 g of 2- (3-bromophenyl) imidazo [1,2, f] phenanthridine. .

  Step 2: Synthesis of Exemplified Compound HA-1

  In a 100 ml three-headed flask, 2.46 (6.6 mmol) 2- (3-bromophenyl) imidazo [1,2, f] phenanthridine, 1.27 g (6.0 mmol) dibenzofuran-2-boronic acid 2.8 g (20 mmol) of potassium carbonate, 20 ml of toluene and 0.58 g (0.5 mmol) of tetrakis (triphenylphosphine) palladium were heated to reflux temperature and stirred at this temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 2.1 g of a white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.32 to 7.49 (m, 5H), 7.55 to 7.82 (m, 10H), 7.86-7.94 (m, 2H), 8.06 (m, 1H), 8.58 (m, 1H), 9.60 (s, 1H).

<< Synthesis of Exemplified Compound HA-110 >>
Step 1: Synthesis of 3- (9- (3-bromophenyl) -9H-carbazol-3-yl) pyrazolo [1,5-f] phenanthridine

  A 300 ml three-headed flask was charged with 10.9 g (50.0 mmol) of pyrazolo [1,5-f] phenanthridine and 80 ml of glacial acetic acid, and stirred at room temperature for a while to obtain a uniform solution. This solution was heated to reflux temperature, and a solution of 12.8 g (80 mmol) of bromine in 20 ml of glacial acetic acid was added over 3 hours. After completion of the addition, the mixture was further reacted for 3 hours under reflux.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The precipitated crystals were filtered and dried by heating to obtain 13.9 g of crude crystals. This crude product was purified by silica gel column chromatography (hexane-ethyl acetate = 10: 1) to obtain 12.6 g of 3-bromopyrazolo [1,5-f] phenanthridine.

  In a 500 ml three-headed flask, under a nitrogen atmosphere, 3-bromopyrazolo [1,5-f] phenanthridine 11.9 g (40 mmol), 9H-carbazole-3-boronic acid 12.6 g (60 mmol), tripotassium phosphate 40 g (186 mmol) and 3.5 g (3.1 mmol) of tetrakis (triphenylphosphine) palladium (0) were added, and 200 ml of dehydrated toluene was added and stirred. Heating was started as it was, and the mixture was reacted for 8 hours under reflux with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. 300 ml of ethyl acetate was added to the reaction solution to extract the product. The extract was concentrated under reduced pressure to obtain 16 g of a crude product. This crude product was purified by column gel chromatography (hexane-ethyl acetate = 8: 1) to obtain 11.6 g of 3- (9H-carbazol-3-yl) pyrazolo [1,5-f] phenanthridine. It was.

  In a 50 ml three-headed flask, 5- (9H-carbazol-3-yl) pyrazolo [1,5-f] phenanthridine 5.75 g (15.0 mmol), 5.66 g (20.0 mmol) 1-bromo. -3-iodobenzene, 3.46 g (25 mmol) of potassium carbonate, 5 ml of tetralin, and 0.12 g (1.9 mmol) of activated copper powder are charged and heated to 200 ° C. Stir for 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 concentrated under reduced pressure and diluted with 20 ml of methanol to precipitate a precipitate which was separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 4.2 g of 3- (9- (3-bromophenyl) -9H-carbazol-3-yl) pyrazolo [1,5-f] phenanthridine pale yellowish white solid was obtained.

  Step 2: Synthesis of exemplary compound HA-110

  In a 100 ml three-headed flask, 3.55 g (6.6 mmol) 3- (9- (3-bromophenyl) -9H-carbazol-3-yl) pyrazolo [1,5-f] phenanthridine, 1.27 g ( 6.0 mmol) dibenzofuran-2-boronic acid, 2.8 g (20 mmol) potassium carbonate, 20 ml toluene and 0.58 g (0.5 mmol) tetrakis (triphenylphosphine) palladium were heated to reflux temperature, Stir at temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 2.7 g of a white solid was obtained.

  MASS confirmed that the produced compound was the target product.

<< Synthesis of Exemplified Compound HB-1 >>
Step 1: Synthesis of (imidazo [1,2-f] phenanthridin-2-yl) -3-phenylboronic acid

  A 100 ml three-headed flask was charged with 2.24 g (6.0 mmol) of 2- (3-bromophenyl) imidazo [1,2, f] phenanthridine in 30 ml of tetrahydrofuran under a nitrogen atmosphere, and dried ice-acetone It cooled with the bath and cooled to internal temperature -78 degreeC. Into this, 4.2 ml of hexane solution of n-butyllithium (1.6M solution manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the internal temperature was raised to -15 ° C, and then cooled again in a dry ice-acetone bath to cool to an internal temperature of -78 ° C. To this, a solution of trimethyl borate 0.83 g (8.0 mmol) in 10 ml of tetrahydrofuran was added dropwise over 30 minutes, and then reacted as it was for 30 minutes. Furthermore, the temperature was raised to room temperature and reacted at room temperature for 5 hours. Subsequently, 40 ml of 10% sulfuric acid aqueous solution was added to the reaction solution and reacted at room temperature for 3 hours.

  Since the reaction solution had two layers, a solvent layer and an aqueous layer, the aqueous layer was removed, and then the solvent layer was washed with brine three times. The solvent layer was concentrated under reduced pressure to obtain 2.40 g of a crude product.

  This crude product was purified by column gel chromatography (hexane-ethyl acetate = 3: 1) to obtain 1.49 g of (imidazo [1,2-f] phenanthridin-2-yl) -3-phenylboronic acid. Obtained.

  Step 2: Synthesis of exemplary compound HB-1

  In a 50 ml three-headed flask, 1.31 g (3.5 mmol) 2- (3-bromophenyl) imidazo [1,2, f] phenanthridine, 1.18 g (3.5 mmol) (imidazo [1,2 -F] phenanthridin-2-yl) -3-phenylboronic acid, 4.15 g (30 mmol) of potassium carbonate, 20 ml of toluene and 0.23 g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were refluxed. Heated to temperature and stirred at this temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 1.60 g of a white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.4 to 7.5 (m, 6H), 7.54 to 7.63 (m, 4H), 7.70-7.79 (m, 8H), 7.93 (m, 2H), 8.05 (m, 2H), 8.61 (m, 2H), 9.56 (s, 2H).

<< Synthesis of Exemplified Compound HB-104 >>
Step 1: Synthesis of 2- (6-bromo-9,9'-dimethyl-9H-fluoren-3-yl) imidazo [1,2-f] phenanthridine

  A 500 ml three-headed flask is charged with 40 g (0.3 mmol) of finely crushed anhydrous aluminum chloride and 200 ml of methylene chloride, cooled to 0 ° C. and stirred. Into this, 39.4 g (0.25 mmol) of 2-bromoacetyl chloride is added dropwise over 20 minutes. Subsequently, a solution of 54.6 g (0.2 mmol) of 3-bromo-9,9-dimethyl-9H-fluorene in 100 ml of methylene chloride was added dropwise over 30 minutes, and further reacted at room temperature for 3 hours. The reaction mixture was poured into 300 g of ice, and the precipitated aluminum hydroxide was dissolved by adding a small amount of concentrated hydrochloric acid and water.

  When the aluminum hydroxide was dissolved, the solvent layer was separated and the aqueous layer was extracted with methylene chloride. The solvent layers were combined, dried over sodium sulfate, and concentrated under reduced pressure to obtain 65 g of a crude product.

  This was purified by column gel chromatography (hexane-ethyl acetate = 20: 1 to 2: 1) to obtain 59 g of 3-bromoacetyl-6-bromo-9,9′-dimethyl-9H-fluorene. .

  In a 100 ml three-headed flask, a solution of 3.10 g (16.0 mmol) of phenanthridine-6-amine in 50 ml of toluene, 9.46 g of 3-bromoacetyl-6-bromo-9,9′-dimethyl-9H-fluorene (24 0.0 mmol) and 2.4 g (24.0 mmol) of triethylamine were added and reacted under reflux for 3 hours while heating in an oil bath at 140 ° C.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was filtered to remove insolubles, and then concentrated under reduced pressure until the volume was reduced to about half. The solution was purified by column gel chromatography (hexane-tetrahydrofuran = 10: 1 to 2: 1) to give 2- (6-bromo-9,9′-dimethyl-9H-fluoren-3-yl) imidazo [1 , 2-f] phenanthridine was obtained.

  Step 2: Synthesis of 6- (imidazo [1,2-f] phenanthridin-2-yl) -9,9'-dimethyl-9H-fluorene-3-boronic acid

  In a 100 ml three-headed flask, under a nitrogen atmosphere, 5.87 g (12.0 mmol) of 2- (6-bromo-9,9′-dimethyl-9H-fluoren-3-yl) imidazo [1,2-f] A solution of phenanthridine in 50 ml of tetrahydrofuran was added, cooled in a dry ice-acetone bath, and cooled to an internal temperature of -78 ° C. 8.4 ml of n-butyllithium hexane solution (1.6M solution manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into this over 10 minutes.

  After completion of the dropwise addition, the internal temperature was raised to -15 ° C, and then cooled again in a dry ice-acetone bath to cool to an internal temperature of -78 ° C. To this, a solution of trimethyl borate 1.66 g (16.0 mmol) in 20 ml of tetrahydrofuran was added dropwise over 30 minutes, and then reacted as it was for 30 minutes. Furthermore, the temperature was raised to room temperature and reacted at room temperature for 5 hours. Subsequently, 60 ml of 10% sulfuric acid aqueous solution was added to the reaction solution, and reacted at room temperature for 3 hours.

  Since the reaction solution had two layers, a solvent layer and an aqueous layer, the aqueous layer was removed, and then the solvent layer was washed with brine three times. The solvent layer was concentrated under reduced pressure to obtain 3.6 g of a crude product.

  The crude product was purified by column gel chromatography (hexane-ethyl acetate = 3: 1) to give 6- (imidazo [1,2-f] phenanthridin-2-yl) -9,9′-dimethyl- 3.2 g of 9H-fluorene-3-boronic acid was obtained.

  Step 2: Synthesis of exemplary compound HB-104

  In a 50 ml three-head flask, 1.71 g (3.5 mmol) 2- (6-bromo-9,9′-dimethyl-9H-fluoren-3-yl) imidazo [1,2-f] phenanthridine, .59 g (3.5 mmol) of 6- (imidazo [1,2-f] phenanthridin-2-yl) -9,9′-dimethyl-9H-fluorene-3-boronic acid, 4.15 g (30 mmol) ), 20 ml of toluene, and 0.23 g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were heated to reflux temperature and stirred at this temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 2.11 g of a white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 1.68 (s, 12H), 7.40 to 7.63 (m, 14H), 7.76 to 7.79 (m, 4H), 7.93 (m, 2H), 8.04 (m, 6H), 8.61 (m, 2H), 9.58 (s, 2H).

  << Synthesis of Exemplified Compound HB-134 >>

  In a 100 ml three-headed flask, a solution of 3.50 g (18.0 mmol) of phenanthridine-6-amine in 50 ml of toluene, 2.56 g (8.0 mmol) of 1,3-bis (2-bromoacetyl) benzene, 2. 0 g (20.0 mmol) was added, and the mixture was reacted under reflux for 3 hours while heating in an oil bath at 140 ° C.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was filtered to remove insolubles, and then concentrated under reduced pressure until the volume was reduced to about half. The solution was purified by silica gel column chromatography (hexane-tetrahydrofuran = 10: 1 to 5: 1) to obtain 3.06 g of white crystals.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.4 to 7.5 (m, 4H), 7.6 to 7.8 (m, 10H), 7.90 (m, 2H), 8.05 (m, 2H), 8.60 (m, 2H), 9.58 (s, 2H).

<< Synthesis of Exemplary Compound HC-1 >>
Step 1: Synthesis of 3-bromophenanthridine-6 (5H) -one

  In a 1 L three-headed flask, 20.3 g (62 mmol) of 1-iodo-2-nitro-4-bromobenzene, 11.3 g (93 mmol) of phenylboronic acid, 40 g (186 mmol) of tripotassium phosphate and acetic acid under a nitrogen atmosphere Palladium (II) 1.1 g (5.0 mmol) was added, and 300 ml of dehydrated toluene was added and stirred. Heating was started as it was, and the mixture was reacted for 8 hours under reflux with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. 300 ml of ethyl acetate was added to the reaction solution to extract the product. The extract was concentrated under reduced pressure to obtain 32 g of a crude product.

  This crude product was purified by column gel chromatography (hexane-ethyl acetate = 4: 1) to obtain 14.2 g of 4-bromo-2-nitrobiphenyl.

  In a Erlenmeyer flask for hydrogenation reaction, a solution of 14.2 g (51 mmol) of 4-bromo-2-nitrobiphenyl in methanol 200 ml-tetrahydrofuran 100 ml was added, and a highly active palladium carbon catalyst (palladium content 20%). 2.4 g was added. A gas inlet / outlet connector was attached, and the air in the container was replaced with nitrogen. Next, hydrogen gas was introduced, and the inside of the container was replaced with hydrogen gas. The hydrogenation reaction was performed for 10 hours at room temperature while supplying hydrogen gas.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The palladium carbon catalyst was filtered and removed from the reaction solution, and concentrated under reduced pressure to obtain 12.7 g of a crude product.

  This crude product was purified by column gel chromatography (hexane-tetrahydrofuran = 2: 1) to obtain 12.5 g of 4-bromo-2-aminobiphenyl.

  A 500 ml three-headed flask was charged with 12.4 g (50 mmol) of 4-bromo-2-aminobiphenyl, 6.5 g (60 mmol) of ethyl chloroformate and 140 ml of toluene, and reacted as it was under reflux for 2 hours.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was concentrated under reduced pressure, dissolved again in toluene, and concentrated under reduced pressure twice to remove excess ethyl chloroformate and used as it was in the next reaction.

  Ethyl-4-bromobiphenyl-2-yl-carbamate, which is the product of the previous step, was placed in a 500 ml three-head flask, and 160 g of polyphosphoric acid (high viscosity rod) was added. After mounting the mechanical stirrer, heating was started, and the reaction was carried out for 4 hours while heating in a 140 ° C. oil bath with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred until a homogeneous solution was obtained. The product was extracted from the homogeneous solution with methylene chloride (200 ml x 3).

  The extract was concentrated under reduced pressure to obtain 15 g of a crude product. This crude product was purified by column gel chromatography (hexane-ethyl acetate = 10: 1 to 4: 1) to obtain 10.6 g of 3-bromophenanthridin-6 (5H) -one.

  Step 2: Synthesis of 6-bromo-imidazo [1,2-f] phenanthridine

  In a 300 ml three-headed flask, 9.6 g (35 mmol) of 3-bromophenanthridine-6 (5H) -one and 200 ml of toluene were added, and stirred at room temperature for a while to obtain a uniform solution. To this, 15.3 g (100 mmol) of phosphoryl chloride was added, and heating was started. The mixture was reacted for 1.5 hours under reflux with heating in an oil bath at 160 ° C. with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The toluene layer was separated and concentrated under reduced pressure to obtain 4.8 g of crude crystals. The crude crystals were suspended in hot toluene, and the crystals were filtered when cooled to room temperature. After washing with hexane and drying by heating, 9.7 g of 3-bromo-6-chlorophenanthridine was obtained.

  In a 200 ml three-headed flask, 8.8 g (30 mmol) of 3-bromo-6-chlorophenanthridine, 4.2 g (40 mmol) of aminoacetaldehyde dimethyl acetal and 100 ml of ethylene glycol dimethyl ether are heated under a nitrogen atmosphere. Started. The mixture was reacted for 20 hours under reflux with heating in a 160 ° C. oil bath with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The solvent layer was separated and concentrated under reduced pressure to obtain 9.1 g of crude crystals. The crude crystals were suspended in hot toluene, and the crystals were filtered when cooled to room temperature. After washing with hexane and drying by heating, 8.7 g of 6-bromo-imidazo [1,2-f] phenanthridine was obtained.

  Step 3: Synthesis of imidazo [1,2-f] phenanthridine-6-boronic acid

  In a 100 ml three-headed flask, 3.57 g (12.0 mmol) of 6-bromo-imidazo [1,2-f] phenanthridine in 50 ml of tetrahydrofuran was placed in a nitrogen atmosphere and cooled in a dry ice-acetone bath. The internal temperature was cooled to -78 ° C. 8.4 ml of n-butyllithium hexane solution (1.6M solution manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into this over 10 minutes. After completion of the dropwise addition, the internal temperature was raised to -15 ° C, and then cooled again in a dry ice-acetone bath to cool to an internal temperature of -78 ° C.

  To this, a solution of trimethyl borate 1.66 g (16.0 mmol) in 20 ml of tetrahydrofuran was added dropwise over 30 minutes, and then reacted as it was for 30 minutes. Furthermore, the temperature was raised to room temperature and reacted at room temperature for 5 hours. Subsequently, 60 ml of 10% sulfuric acid aqueous solution was added to the reaction solution, and reacted at room temperature for 3 hours.

  Since the reaction solution had two layers, a solvent layer and an aqueous layer, the aqueous layer was removed, and then the solvent layer was washed with brine three times. The solvent layer was concentrated under reduced pressure to obtain 3.6 g of a crude product.

  This crude product was purified by column gel chromatography (hexane-ethyl acetate = 3: 1) to obtain 3.0 g of imidazo [1,2-f] phenanthridine-6-boronic acid.

  Step 4: Synthesis of 6- (3-bromophenyl) imidazo [1,2-f] phenanthridine

  In a 100 ml three-head flask, 3.4 g (12 mmol) of 1-bromo-3-iodobenzene, 2.9 g (11 mmol) of imidazo [1,2-f] phenanthridine-6-boronic acid, phosphorus, under a nitrogen atmosphere 17 g (80 mmol) of tripotassium acid and 0.11 g (0.5 mmol) of palladium palladium (II) acetate were added, and 60 ml of dehydrated toluene was added and stirred. Heating was started as it was, and the mixture was reacted for 8 hours under reflux with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. 50 ml of ethyl acetate was added to the reaction solution to extract the product. The extract was concentrated under reduced pressure to obtain 3.5 g of a crude product.

  The crude product was purified by column gel chromatography (hexane-ethyl acetate = 4: 1) to obtain 3.2 g of 6- (3-bromophenyl) imidazo [1,2-f] phenanthridine.

  Step 5: Synthesis of HC-1

  In a 50 ml three-headed flask, 1.31 g (3.5 mmol) 6- (3-bromophenyl) imidazo [1,2-f] phenanthridine, 1.18 g (3.5 mmol) (imidazo [1,2 -F] Phenanthridin-2-yl) -3-phenylboronic acid, 2.8 g (20 mmol) of potassium carbonate, 20 ml of toluene and 0.23 g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were added and refluxed. Heated to temperature and stirred at this temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 1.75 g of pale yellowish white crystals were obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.40-7.50 (m, 9H), 7.56-7.62 (m, 3H), 7.70 (s, 2H), 7.74-7.80 (m, 4H), 7.90 (m, 2H), 8.02 (d, 1H), 8.05 (m, 1H), 8 .10 (d, 1H), 8.24 (s, 1H), 8.60 (m, 1H), 9.53 (m, 1H).

  << Synthesis of Exemplified Compound HC-59 >>

  To a 50 ml three-head flask, 4.46 g (15.0 mmol) of 6-bromo-imidazo [1,2-f] phenanthridine, 3.19 g (7.0 mmol) of 2,2′-bibenzobenzofuran-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, heated to reflux temperature, and stirred at this temperature for 12 hours. did. The reaction mixture was cooled to room temperature and then mixed with 50 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals. It was suctioned off, washed with methanol and dried in vacuo at 80 ° C. 8.28 g of pale yellowish white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.40 to 7.52 (m, 8H), 7.68 (s, 2H), 7.70 ( s, 2H), 7.71 to 7.73 (m, 4H), 7.75 (m, 2H)) 7.80 to 7.82 (m, 4H), 7.90 (m, 2H)) 8 .02 (m, 2H), 8.11 (m, 2H), 8.25 (s, 2H).

<< Synthesis of Exemplary Compound HD-149 >>
Step 1: Synthesis of 8-bromophenanthridin-6 (5H) -one

  In a 1 L three-headed flask, under a nitrogen atmosphere, 15.4 g (62 mmol) of 1-iodo-2-nitrobenzene, 18.7 g (93 mmol) of 3-bromophenylboronic acid, 40 g (186 mmol) of tripotassium phosphate and palladium acetate (II ) 1.1 g (5.0 mmol) was added, and 300 ml of dehydrated toluene was added and stirred. Heating was started as it was, and the mixture was reacted for 8 hours under reflux with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. 300 ml of ethyl acetate was added to the reaction solution to extract the product. The extract was concentrated under reduced pressure to obtain 26 g of a crude product. This crude product was purified by column gel chromatography (hexane-ethyl acetate = 4: 1) to obtain 14.2 g of 4′-bromo-2-nitrobiphenyl.

  In a Erlenmeyer flask for hydrogenation reaction, a solution of 14.2 g (51 mmol) of 4'-bromo-2-nitrobiphenyl in methanol 200 ml-tetrahydrofuran 100 ml was added, and a highly active palladium carbon catalyst (palladium content 20%). ) 2.4g was added. A gas inlet / outlet connector was attached, and the air in the container was replaced with nitrogen. Next, hydrogen gas was introduced, and the inside of the container was replaced with hydrogen gas. The hydrogenation reaction was performed for 10 hours at room temperature while supplying hydrogen gas.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The palladium carbon catalyst was filtered and removed from the reaction solution, and concentrated under reduced pressure to obtain 12.7 g of a crude product. This crude product was purified by column gel chromatography (hexane-tetrahydrofuran = 2: 1) to obtain 12.4 g of 4'-bromo-2-aminobiphenyl.

  A 500 ml three-headed flask was charged with 12.4 g (50 mmol) of 4'-bromo-2-aminobiphenyl, 6.5 g (60 mmol) of ethyl chloroformate, and 140 ml of toluene, and reacted under heating and reflux for 2 hours.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was concentrated under reduced pressure, dissolved again in toluene, and concentrated under reduced pressure twice to remove excess ethyl chloroformate and used as it was in the next reaction.

  Ethyl-4'-bromobiphenyl-2-yl-carbamate, which was the product of the previous step, was placed in a 500 ml three-headed flask, and 160 g of polyphosphoric acid (high viscosity rod-like material) was added. After mounting the mechanical stirrer, heating was started, and the reaction was carried out for 4 hours while heating in a 140 ° C. oil bath with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred until a homogeneous solution was obtained. The product was extracted from the homogeneous solution with methylene chloride (200 ml x 3).

  The extract was concentrated under reduced pressure to obtain 15 g of a crude product. The crude product was purified by column gel chromatography (hexane-ethyl acetate = 10: 1 to 4: 1) to obtain 10.6 g of 8-bromophenanthridin-6 (5H) -one.

  Step 2: Synthesis of 11-bromo-imidazo [1,2-f] phenanthridine

  9.6 g (35 mmol) of 8-bromophenanthridine-6 (5H) -one and 200 ml of toluene were placed in a 300 ml three-headed flask and stirred for a while at room temperature to obtain a uniform solution. To this, 15.3 g (100 mmol) of phosphoryl chloride was added, and heating was started. The mixture was reacted for 1.5 hours under reflux with heating in a 160 ° C. oil bath with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The toluene layer was separated and concentrated under reduced pressure to obtain 4.8 g of crude crystals. The crude crystals were suspended in hot toluene, and the crystals were filtered when cooled to room temperature. After washing with hexane and drying by heating, 9.7 g of 8-bromo-6-chlorophenanthridine was obtained.

  A 200 ml three-headed flask is charged with 8.8 g (30 mmol) of 8-bromo-6-chlorophenanthridine, 4.2 g (40 mmol) of aminoacetaldehyde dimethyl acetal and 100 ml of ethylene glycol dimethyl ether and heated under a nitrogen atmosphere. Started. The mixture was reacted for 20 hours under reflux while heating in an oil bath at 160 ° C. with sufficient stirring.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction was poured into ice water and stirred for 30 minutes. The solvent layer was separated and concentrated under reduced pressure to obtain 9.1 g of crude crystals. The crude crystals were suspended in hot toluene, and the crystals were filtered when cooled to room temperature. After washing with hexane and drying by heating, 8.7 g of 11-bromo-imidazo [1,2-f] phenanthridine was obtained.

  Step 3: Synthesis of exemplary compound HD-149

  In a 100 ml three-headed flask, 3.56 g (12.0 mmol) of 11-bromo-imidazo [1,2-f] phenanthridine 2.49 g (5.0 mmol) of 1,3-phenylene-bis (dibenzofuran-8 2-diyl) -8,8'-diboronic acid, 2.8 g (20 mmol) of potassium carbonate, 40 ml of toluene and 0.58 g (0.5 mmol) of tetrakis (triphenylphosphine) palladium were added and heated to reflux temperature. The mixture was stirred at this temperature for 12 hours. The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 2.8 g of a pale yellowish white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.40-7.50 (m, 6H), 7.55 (m, 1H), 7.58 ( m, 2H), 7.70-7.75 (m, 9H), 7.78-7.85 (m, 10H), 8.04 (m, 2H), 8.07 (m, 2H), 8 .60 (m, 2H).

Synthesis of Exemplary Compound D-269 Step 1: Synthesis of 2- (9- (3-bromophenyl) -9H-carbazol-3-yl) imidazo [1,2-f] phenanthridine

  A 500 ml three-headed flask is charged with 40 g (0.3 mmol) of finely crushed anhydrous aluminum chloride and 200 ml of methylene chloride, cooled to 0 ° C. and stirred. Into this, 39.4 g (0.25 mmol) of 2-bromoacetyl chloride is added dropwise over 20 minutes. Subsequently, a solution of 64.4 g (0.2 mmol) of -9- (3-bromophenyl) -9H-carbazole in 100 ml of methylene chloride was added dropwise over 30 minutes, and further reacted at room temperature for 3 hours.

  The reaction mixture was poured into 300 g of ice and the precipitated aluminum hydroxide was dissolved by adding a small amount of concentrated hydrochloric acid and water. When the aluminum hydroxide was dissolved, the solvent layer was separated and the aqueous layer was extracted with methylene chloride. The solvent layers were combined, dried over sodium sulfate, and concentrated under reduced pressure to obtain 65 g of a crude product.

  This was purified by column gel chromatography (hexane-ethyl acetate = 20: 1 to 2: 1) to obtain 68 g of 3-bromoacetyl-9- (3-bromophenyl) -9H-carbazole.

  In a 100 ml three-head flask, a solution of 3.10 g (16.0 mmol) of phenanthridine-6-amine in 50 ml of toluene, 10.6 g (24.0 mmol) of 3-bromoacetyl-9- (3-bromophenyl) -9H-carbazole ), 2.4 g (24.0 mmol) of triethylamine was added, and the mixture was reacted under reflux for 3 hours while heating in an oil bath at 140 ° C.

  The reaction was completed after confirming the disappearance of the raw materials by thin layer chromatography. The reaction solution was filtered to remove insolubles, and then concentrated under reduced pressure until the volume was reduced to about half. The solution was purified by column gel chromatography (hexane-tetrahydrofuran = 10: 1 to 2: 1) to give 2- (9- (3-bromophenyl) -9H-carbazol-3-yl) imidazo [1,2 -F] Phenanthridine 9.3 g was obtained.

  Step 2: Synthesis of 3- (imidazo [1,2-f] phenanthridin-2-yl) -9H-carbazol-9-yl) -phenylboronic acid

  In a 100 ml three-headed flask, under a nitrogen atmosphere, 6.46 g (12.0 mmol) of 2- (9- (3-bromophenyl) -9H-carbazol-3-yl) imidazo [1,2-f] phenance A 50 ml solution of lysine in tetrahydrofuran was added, cooled in a dry ice-acetone bath, and cooled to an internal temperature of -78 ° C. 8.4 ml of n-butyllithium hexane solution (1.6M solution manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into this over 10 minutes.

  After completion of the dropwise addition, the internal temperature was raised to -15 ° C, and then cooled again in a dry ice-acetone bath to cool to an internal temperature of -78 ° C. To this, a solution of trimethyl borate 1.66 g (16.0 mmol) in 20 ml of tetrahydrofuran was added dropwise over 30 minutes, and then reacted as it was for 30 minutes. Furthermore, the temperature was raised to room temperature and reacted at room temperature for 5 hours. Subsequently, 60 ml of 10% sulfuric acid aqueous solution was added to the reaction solution, and reacted at room temperature for 3 hours.

  Since the reaction solution had two layers, a solvent layer and an aqueous layer, the aqueous layer was removed, and then the solvent layer was washed with brine three times. The solvent layer was concentrated under reduced pressure to obtain 3.6 g of a crude product.

  The crude product was purified by column gel chromatography (hexane-ethyl acetate = 3: 1) to give 3- (imidazo [1,2-f] phenanthridin-2-yl) -9H-carbazol-9-yl. ) -Phenylboronic acid 5.1 g was obtained.

  Step 3: Synthesis of exemplary compound HD-269

  In a 50 ml three-head flask, 1.04 g (3.5 mmol) of 11-bromo-imidazo [1,2-f] phenanthridine, 1.76 g (3.5 mmol) of 3- (imidazo [1,2-f ] Phenanthridin-2-yl) -9H-carbazol-9-yl) -phenylboronic acid, 4.15 g (30 mmol) of potassium carbonate, 30 ml of toluene and 0.23 g of tetrakis (triphenylphosphine) palladium. 2 mmol) was heated to reflux temperature and stirred at this temperature for 12 hours.

  The reaction mixture was cooled to room temperature and then mixed with 300 ml of ethyl acetate. The solution was washed several times with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to precipitate crystals, which were separated by suction, washed with methanol and dried at 80 ° C. in vacuo. 1.87 g of a white solid was obtained.

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

¹ H-NMR (400 MHz, CDCl ₃ ) (chemical shift δ, peak shape, proton number): δ = 7.26 (m, 1H), 7.42 to 7.55 (m, 8H), 7.60 to 7.63 (m, 3H), 7.75 to 7.85 (m, 6H), 7.92 (m, 1H), 8.00 to 8.10 (m, 6H), 8.17 (m, 1H), 8.61 (m, 2H), 9.58 (s, 1H).

  Other compounds according to the present invention can 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 to 480 nm, and the green light emitting layer has a light emission maximum wavelength of 510 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 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 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 a high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust to the range of 2-5 micrometers, More preferably, it adjusts to the range of 2-200 nm, Especially preferably, it is the range of 10-20 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 host compound and at least one kind of light emitting dopant (phosphorescent dopant, fluorescent dopant, etc.).

(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 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 according to the present invention, a compound containing a partial structure represented by the general formulas (5) to (7) is preferable, and a known host compound may be used in combination, or a plurality of types may be used in combination. It may be used. 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.

  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.

  Although the specific example of the host compound which can be used together by this invention is shown below, this invention is not limited to these.

(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 or a phosphorescent dopant can be used. From the viewpoint of obtaining an organic EL element with higher luminous efficiency, it is used for the light-emitting layer and the light-emitting unit of the organic EL element of the present invention. The light emitting dopant (sometimes simply referred to as a light emitting material) preferably contains a phosphorescent dopant simultaneously with the host compound.

<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. The compound has a phosphorescence quantum yield of 0.1 or more, although it is a compound of 0.01 or more at ° C.

  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 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>
Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, or rare earth complex phosphors.

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

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

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

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. 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.

  In the hole blocking layer, the carbazole derivative, carboline derivative, diazacarbazole derivative (shown by replacing one of the carbon atoms constituting the carboline ring of the carboline derivative with a nitrogen atom) as the host compound described above. 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 electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.

  (1) 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, is used as a keyword. The ionization potential can be obtained as a value obtained by rounding off the second decimal place of a 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 using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki.

  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 transporting layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 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 5-200 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, 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.

  In addition, 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), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

  In addition, 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 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 5-200 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 is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / ° C. or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

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

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / ° C. 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 with a film thickness of 1-20 nm on a cathode, a 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., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Polyetherimide, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (manufactured by JSR) or APEL (manufactured by Mitsui Chemicals).

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 more preferably oxygen permeability measured by a method according to JIS K 7126-1987. A high barrier property film having a degree 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, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

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

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

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

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light 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 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 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, Sumitomo 3M brightness enhancement film (BEF) 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 by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, thereby producing 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 a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.

  In addition, it is 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, Although it does not limit to this, It can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination especially.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned, and a conventionally known method may be used in the fabrication of the element. it can.

  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.

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 = It is in the region of 0.33 ± 0.07, 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 >>
A transparent support substrate provided with this ITO transparent electrode after patterning a substrate (NH45 made of NH technoglass) 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 Was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed 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 tank 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 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.023 nm / second, respectively. A 60 nm light emitting layer 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 deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

Further, the heating boat containing Alq ₃ was further energized and heated, and was 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. . 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 light emitting dopant were replaced with the compounds shown in Table 1. 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 (Luxe 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, the smaller the initial deterioration.

(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. For each element after 10 hours of continuous lighting by visual evaluation by 10 randomly extracted people, the following was set.

×: When the number of confirmed dark spots is 5 or more Δ: When the number of confirmed dark spots is 1 to 4 ○: When the number of confirmed dark spots is 0

  From Table 1, it can be seen that the organic EL device of the present invention has a high external extraction quantum efficiency, less initial luminance degradation, and has a long 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 as a hole injection / transport layer with a thickness of 25 nm thereon as in Example 1, and further HB-1 The heated boat containing NO, the boat containing Exemplified Compound A-97, and the boat containing Ir-9 are energized independently, and HB-1 as a luminescent host and Illustrative Compound A-97 as a luminescent dopant, and The vapor deposition rate of Ir-9 was adjusted to 100: 12: 0.6, vapor deposition was performed to a thickness of 60 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 >>
A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed 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 film formation by a spin coating method, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 20 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound D 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, a solution obtained by dissolving HA-417 (60 mg), F-9 (8.0 mg), and Ir-14 (3.0 mg) in 6 ml of toluene was prepared by spin coating under the 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. It was irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated 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 >>
A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed 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 film formation by a spin coating method, 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 D 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 Compound E (60 mg) and Ir-12 (8.0 mg) in 6 ml of toluene, a film was formed by a spin coating method at 1000 rpm for 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.

The vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing the heating boat containing BAlq, and deposited on the light emitting layer at a deposition rate of 0.1 nm / sec. 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 emission organic EL element 5-1 was produced.

<< Production of Organic EL Elements 5-2 to 5-10 >>
In the production of the organic EL element 5-1, the organic EL elements 5-2 to 10 are similarly manufactured except that the compound E as the host compound of the light emitting layer and the light emitting dopant Ir-12 are 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 (Luxe 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, the smaller the initial deterioration.

(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. For each element after 10 hours of continuous lighting by visual evaluation by 10 randomly extracted people, the following was set.

×: When the number of confirmed dark spots is 5 or more Δ: When the number of confirmed dark spots is 1 to 4 ○: When the number of confirmed dark spots is 0

  From Table 2, it can be seen that the organic EL device of the present invention has higher external extraction quantum efficiency and less initial luminance deterioration, and has 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)

In an organic electroluminescence device comprising at least one light emitting layer sandwiched between an anode and a cathode, the light emitting layer contains at least one phosphorescent dopant, and the following general formula (5), (6) or (7 And an organic layer containing at least one compound containing a partial structure represented by formula (1).

(In the formula, A _1a , A _1b and A _1c each represent a single bond or an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. E _2a to E _2k represents a carbon atom or a nitrogen atom, and any one of E _{2i to} E _2k is a nitrogen atom, and the number of nitrogen atoms in E _{2a to} E _2k is 1 to 4, and two or more adjacent ones E _{2 *} is not a nitrogen atom at the same time, where * represents an arbitrary letter from a to _k, R _{2a to} R _2k each independently represents a hydrogen atom or a substituent, and R _2a to Any of R _2d is A _1a , any of R _2e or R _2h is A _1c , and any of R _{2i to} R _2k is A _1b , provided that E _2i represents a nitrogen atom, and When R _2j and R _2k both represent a substituent R _2j or R _2k is a substituted or unsubstituted C3-C40 cycloalkyl group; a substituted or unsubstituted C6-C60 aryl group; a substituted or unsubstituted C2-C40 alkenyl group; a substituted or unsubstituted It is not a C2-C60 heterocyclic group or an aromatic heterocyclic ring, and R _2j and R _2k are not bonded to each other to form an aliphatic, aromatic or heteroaromatic ring. 2. The organic electroluminescent device according to claim 1, wherein the phosphorescent dopant is selected from compounds including a partial structure represented by the following general formula (1), (2), (3) or (4). .

(In the formula, E ^1a and E ^1q are different from each other and represent a carbon atom or a nitrogen atom. E ^{1b to} E ^1p represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and are composed of E ^{1a to} E ^1q . The skeleton has a total of 18π electrons, R ^{1a to} R ¹ⁱ each represent a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^1h is a substituent, provided that R ^{1 *} is bonded to E ^{When 1 *} is an oxygen atom or a sulfur atom, R ^{1 *} does not exist, and when E ^{1 *} to which R ^{1 *} is bonded is a nitrogen atom, R ^{1 *} may not exist. Here, * represents an arbitrary letter from a to i. M represents a transition metal element of Group 8 to Group 10 in the periodic table.) The organic electroluminescent device according to claim 2, wherein the ring composed of E ^{1a to} E ^1e in the general formulas (1) to (4) is an imidazole ring or a pyrazole ring. The compound containing the partial structure represented by the general formula (5), (6) or (7) is represented by any one of the general formulas (8) to (13). Organic electroluminescent element of any one of these.

(In the formula, 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 integers of 1 to 5, respectively. M4 + n4 ≦ 6, m5 + n5 ≦ 6, m6 + n6 ≦ 6, X _{1 to} X ₆ are each a single bond, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. , Or a linking group composed of a my + ny valent group formed by combining groups selected from optionally substituted amino groups, where y represents any one of 1 to 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 heterocyclic group which may have a substituent. E _{11a to} E _{11 k, E} 21a _~E 21k, represents _{E 31a ~E 31k, E 41a ~E} 41k, the _{E 51a ~E 51k, E 61a ~E} 61k each carbon atom or a nitrogen _atom, E _zi, E _zj, the _{E zk} Any one is a nitrogen atom, and the number of nitrogen atoms in E _{za to} E _zk is 1 to 4, and two or more adjacent E _{Z *} do not simultaneously become nitrogen atoms.
Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61, and * represents an arbitrary character selected from a to k. 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 of R _{11a to} R _11d is A _11a , and any of R _{21a to} R _21d is A _21a . Any of R _{51e to} R _51h is A _11c , and any of R _{61e to} R _61h is A _21c . Further, any of R _{31i to} R _31k is A _11b , and any of R _{41i to} R _41k is A _21b .
However, when E _zi represents a nitrogen atom and R _zj and R _zk both represent a substituent, R _zj or R _zk represents a substituted or unsubstituted C3-C40 cycloalkyl group; a substituted or unsubstituted It is not a C6-C60 aryl group; a substituted or unsubstituted C2-C40 alkenyl group; a substituted or unsubstituted C2-C60 heterocyclic group or an aromatic heterocyclic ring. Further, R _zj and R _zk are not bonded to each other to form an aliphatic, aromatic or heteroaromatic ring. Here, z represents an arbitrary number selected from 11, 21, 31, 41, 51, 61 in each condensed ring bonded via X _{1 to} X ₆ in each formula . ) 5. The organic electro according to claim 4, wherein the linking group represented by X _{1 to} X ₆ in the general formulas (8) to (13) includes an aromatic ring group or an aromatic heterocyclic group. Luminescence element.   The aromatic ring group or aromatic heterocyclic group is a group comprising a phenyl group, a biphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, an anthracenyl group, and a combination thereof. The organic electroluminescent element according to claim 5. 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 any one of claims 4 to 6, wherein at least one of the substituents is a polymerizable substituent.   The organic electroluminescence device according to any one of claims 4 to 7, wherein a glass transition temperature of the compounds represented by the general formulas (8) to (13) is 100 ° C or higher.   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 electroluminescent element according to any one of claims 1 to 8, wherein   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 1 to 9.   The organic electroluminescence device according to claim 10, wherein the organic layer is a light emitting layer.   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.   The organic electroluminescent element according to claim 2, wherein M is platinum or iridium.   A display device comprising the organic electroluminescence element according to claim 1.   An illuminating device comprising the organic electroluminescent element according to claim 1.   An organic electroluminescent element material comprising a polymer including a partial structure represented by any one of the general formulas (1) to (4) according to claim 2.

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