JP5359088B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic EL element which is high in external takeoff quantum efficiency, long in half life span, small in dark spot, long in drive life span at 50&deg;C, and small in change of dope concentration, and also to provide a display device using the same. <P>SOLUTION: In the organic electroluminescence element including an emission layer with at least one layer sandwiched between an anode and a cathode, the emission layer contains at least one metal complex having a ligand consisting of a six-member ring aromatic group which is substituted with a pyrazole ring or an imidazole ring and has an organic layer containing at least one compound expressed in a general formula (PA)(R0)n1-Ar0-(Ar1)m1, where Ar0 expresses: a group of (n1+m1) valency; Ar1 expresses an aromatic hydrocarbon ring radical or an aromatic heterocyclic group; R0 expresses a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group; n1 expresses an integer from 0 to 7; and m1 expresses an integer from 3 to 10. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

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

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

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

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

  However, for organic EL elements for practical use in the future, further development of organic EL elements that emit light efficiently and with high luminance with low 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), and has a phenanthridine skeleton. There is disclosure about metal complexes. (For example, refer to Patent Documents 5 and 6.)

  However, with the metal complexes described in the above-mentioned known documents, the external extraction quantum efficiency is not improved, and a practically sufficient improvement effect is not obtained for the light emission lifetime, and there is a need for improvement. Yes. CBP, mCP, Alq3, etc. are disclosed as a luminescent host used in combination with the compound having the phenanthridine skeleton. (For example, refer to Patent Documents 5 and 6).

  However, as a light-emitting host material used in combination with various phenanthridine compounds, the life and efficiency are still insufficient, and further improvement is necessary.

  There is a disclosure of using a polysubstituted benzene derivative in a light emitting layer as a phosphorescent light emitting host material (see, for example, Patent Documents 7, 8, and 9), and there are good effects such as improvement in luminance and lifetime of the element. Has been found.

  However, the use of the compounds described in the above-mentioned known documents does not improve the external extraction quantum efficiency and does not provide a practically sufficient improvement effect on the light emission lifetime. ing.

  Furthermore, there has been no example of use as a luminescent host material for the metal complex having the phenanthridine skeleton.

  In recent years, derivatives having a plurality of benzene rings or heterocyclic rings have been disclosed as hole blocking materials or electron transport materials (see, for example, Patent Documents 10 and 11). Good effects have been found.

  However, the use of the compounds described in the above-mentioned known documents does not improve the external extraction quantum efficiency, and the practically sufficient improvement effect is not obtained in the light emission lifetime, and there is a need for improvement. Yes.

Furthermore, there has been no example used as a hole blocking material or an electron transporting material for the metal complex having the phenanthridine skeleton.
International Publication No. 04/085450 Pamphlet JP 2005-53912 A JP 2006-28101 A US Pat. No. 7,147,937 US 2007/0190359 specification International Publication No. 07/095118 Pamphlet JP 2003-27048 A JP 2006-135160 A JP 2004-14334 A Japanese Patent No. 3925265 JP 2006-135155 A

  An object of the present invention is to provide an organic EL element that emits short-wave blue light, exhibits high light emission efficiency, and has a long emission lifetime, an organic EL material used for the element, a display device and an illumination device including the element Is to provide.

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

〔式中、Ｅ１ａ〜Ｅ１ｑは、各々炭素原子、窒素原子、酸素原子または硫黄原子を表し、Ｅ１ａ〜Ｅ１ｑで構成される骨格は合計で１８π電子を有する。Ｅ１ａとＥ１ｐは各々異なり、炭素原子または窒素原子を表す。Ｒ１ａ〜Ｒ１ｉは、各々水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、芳香族炭化水素環基、芳香族複素環基、複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、スルファモイル基、アシル基、アシルオキシ基、アミド基、カルバモイル基、ウレイド基、スルフィニル基、アルキルスルホニル基、アリールスルホニル基もしくはヘテロアリールスルホニル基、アミノ基、ハロゲン原子、フッ化炭化水素基、シアノ基、ニトロ基、ヒドロキシ基、メルカプト基、シリル基またはホスホノ基を表す。Ｍは元素周期表における８族〜１０族の遷移金属元素を表す。〕

〔式中、Ａｒ１、Ａｒ２は、各々芳香族炭化水素環基または芳香族複素環基を表す。Ｒ０は、水素原子、アルキル基、アルコキシ基、ハロゲン原子、シアノ基または複素環基を表す。Ｘ２１〜Ｘ２５は、各々窒素原子または−Ｃ（Ｒｂ１）＝基を表す。Ｒｂ１は、水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、芳香族炭化水素環基、芳香族複素環基、複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、スルファモイル基、アシル基、アシルオキシ基、アミド基、カルバモイル基、ウレイド基、スルフィニル基、アルキルスルホニル基、アリールスルホニル基もしくはヘテロアリールスルホニル基、アミノ基、ハロゲン原子、フッ化炭化水素基、シアノ基、ニトロ基、ヒドロキシ基、メルカプト基、シリル基またはホスホノ基を表す。ｎ２は０から３の整数を表し、ｍ２は２〜５の整数を表す。〕
（２）前記一般式（ＰＢ−１）で表される化合物が下記一般式（ＰＢ−２）で表される化合物であることを特徴とする前記（１）に記載の有機エレクトロルミネッセンス素子。

〔式中、Ａｒ１、Ａｒ２は、各々芳香族炭化水素環基または芳香族複素環基を表す。Ｒ０は、水素原子、アルキル基、アルコキシ基、ハロゲン原子、シアノ基または複素環基を表す。ｎ２は０〜３の整数、ｍ２は２〜５の整数を表す。〕
（３）前記一般式（ＰＢ−２）で表される化合物が下記一般式（ＰＢ−３）で表される化合物であることを特徴とする前記（２）に記載の有機エレクトロルミネッセンス素子。

〔式中、Ｒ０は、水素原子、アルキル基、アルコキシ基、ハロゲン原子、シアノ基または複素環基を表す。Ｒ１、Ｒ２は、各々水素原子、アルキル基、芳香族炭化水素環基、芳香族複素環基、アルコキシ基、アルキルスルホニル基、ハロゲン原子、フッ化炭化水素基またはシアノ基を表す。ｎ２は０〜３の整数を表し、ｎ３、ｎ４は、各々０〜５の整数を表す。ｍ２は２〜５の整数を表す。〕
（４）前記一般式（ＰＢ−２）で表される化合物が下記一般式（ＰＢ−４）で表される化合物であることを特徴とする前記（２）に記載の有機エレクトロルミネッセンス素子。

〔式中、Ｒ０は、水素原子、アルキル基、アルコキシ基、ハロゲン原子、シアノ基または複素環基を表す。Ｒ１、Ｒ２は、各々水素原子、アルキル基または芳香族炭化水素環基を表す。ｎ２は０〜３の整数を表し、ｎ３、ｎ４は、各々０〜４の整数を表す。ｍ２は２〜５の整数を表す。〕
（５）前記（１）に記載の一般式（ＰＢ−１）で表される化合物、前記（２）に記載の一般式（ＰＢ−２）で表される化合物、前記（３）に記載の一般式（ＰＢ−３）で表される化合物及び前記（４）に記載の一般式（ＰＢ−４）で表される化合物からなる群から選択される化合物の少なくとも１種が分子中に少なくとも一つの重合性基を有することを特徴とする前記（１）〜（４）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（６）前記Ｅ１ａ〜Ｅ１ｅで構成される環が、イミダゾール環またはピラゾール環であることを特徴とする前記（１）〜（５）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（７）構成層として、前記一般式（１）〜（４）のいずれかで表される部分構造を含む化合物を少なくとも１種含有する有機層を有し、該有機層がウェットプロセスを用いて形成されたことを特徴とする前記（１）〜（６）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（８）構成層として、前記（１）に記載の一般式（ＰＢ−１）で表される化合物、前記（２）に記載の一般式（ＰＢ−２）で表される化合物、前記（３）に記載の一般式（ＰＢ−３）で表される化合物及び前記（４）に記載の一般式（ＰＢ−４）で表される化合物からなる群から選択される少なくとも１種の化合物を含有する有機層を有し、該有機層がウェットプロセスを用いて形成されたことを特徴とする前記（１）〜（７）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（９）構成層として、前記（１）に記載の一般式（ＰＢ−１）で表される化合物、前記（２）に記載の一般式（ＰＢ−２）で表される化合物、前記（３）に記載の一般式（ＰＢ−３）で表される化合物及び前記（４）に記載の一般式（ＰＢ−４）で表される化合物からなる群から選択される化合物を少なくとも１種を含有する有機層が発光層であることを特徴とする前記（１）〜（８）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（１０）構成層として、前記（１）に記載の一般式（ＰＢ−１）で表される化合物、前記（２）に記載の一般式（ＰＢ−２）で表される化合物、前記（３）に記載の一般式（ＰＢ−３）で表される化合物及び前記（４）に記載の一般式（ＰＢ−４）で表される化合物からなる群から選択される化合物を少なくとも１種を含有する有機層が正孔阻止層または電子輸送層であることを特徴とする前記（１）〜（８）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（１１）前記一般式（１）〜（４）のいずれかで表される化合物のＲ１ａ〜Ｒ１ｉが重合性基を有し、該重合性基が結合して構成された重合体を少なくとも１種含有する発光層を有することを特徴とする前記（１）〜（１０）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（１２）前記Ｍが白金またはイリジウムであることを特徴とする前記（１）〜（１１）のいずれか１項に記載の有機エレクトロルミネッセンス素子。
（１３）前記（１）〜（１２）のいずれか１項に記載の有機エレクトロルミネッセンス素子を備えたことを特徴とする表示装置。
（１４）前記（１）〜（１２）のいずれか１項に記載の有機エレクトロルミネッセンス素子を備えたことを特徴とする照明装置。
なお、以下１〜２１については、参考とされる構成である。 The object of the present invention has been achieved by the following constitutions (1) to (14) .
(1) In an organic electroluminescence device containing at least one light emitting layer sandwiched between an anode and a cathode,
The light emitting layer contains at least one compound containing a partial structure represented by the following general formula (1), (2), (3) or (4), and represented by the following general formula (PB-1) It has an organic layer containing at least 1 compound represented, The organic electroluminescent element characterized by the above-mentioned.

[In formula, E1a-E1q represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom respectively, and the frame | skeleton comprised by E1a-E1q has a total of 18 (pi) electrons. E1a and E1p are different from each other and represent a carbon atom or a nitrogen atom. R1a to R1i are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, Alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroaryl A sulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, or a phosphono group is represented. M represents a group 8-10 transition metal element in the periodic table. ]

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. X21 to X25 each represent a nitrogen atom or —C (Rb1) = group. Rb1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, Cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroarylsulfonyl group, An amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, or a phosphono group is represented. n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ]
(2) The organic electroluminescence device according to (1), wherein the compound represented by the general formula (PB-1) is a compound represented by the following general formula (PB-2).

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ]
(3) The organic electroluminescence device according to (2), wherein the compound represented by the general formula (PB-2) is a compound represented by the following general formula (PB-3).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom, an alkyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkoxy group, an alkylsulfonyl group, a halogen atom, a fluorinated hydrocarbon group, or a cyano group. n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 5. m2 represents an integer of 2 to 5. ]
(4) The organic electroluminescence device according to (2), wherein the compound represented by the general formula (PB-2) is a compound represented by the following general formula (PB-4).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon ring group. n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 4. m2 represents an integer of 2 to 5. ]
(5) The compound represented by the general formula (PB-1) described in (1), the compound represented by the general formula (PB-2) described in (2), At least one compound selected from the group consisting of the compound represented by the general formula (PB-3) and the compound represented by the general formula (PB-4) described in the above (4) is at least one in the molecule. The organic electroluminescence device according to any one of (1) to (4), wherein the organic electroluminescence device has one polymerizable group.
(6) The organic electroluminescent element according to any one of (1) to (5), wherein the ring composed of E1a to E1e is an imidazole ring or a pyrazole ring.
(7) 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 uses a wet process. The organic electroluminescence device according to any one of (1) to (6), wherein the organic electroluminescence device is formed.
(8) As a constituent layer, the compound represented by the general formula (PB-1) described in (1) above, the compound represented by the general formula (PB-2) described in (2) above, (3 And at least one compound selected from the group consisting of the compound represented by the general formula (PB-4) described in (4) above The organic electroluminescent element according to any one of (1) to (7), wherein the organic layer is formed using a wet process.
(9) As a constituent layer, the compound represented by the general formula (PB-1) described in the above (1), the compound represented by the general formula (PB-2) described in the above (2), the above (3 And at least one compound selected from the group consisting of the compound represented by the general formula (PB-3) described in (4) and the compound represented by the general formula (PB-4) described in (4). The organic electroluminescent element according to any one of (1) to (8), wherein the organic layer is a light emitting layer.
(10) As a constituent layer, the compound represented by the general formula (PB-1) described in the above (1), the compound represented by the general formula (PB-2) described in the above (2), the above (3 And at least one compound selected from the group consisting of the compound represented by the general formula (PB-3) described in (4) and the compound represented by the general formula (PB-4) described in (4). The organic electroluminescent element according to any one of (1) to (8), wherein the organic layer is a hole blocking layer or an electron transporting layer.
(11) R1a to R1i of the compound represented by any one of the general formulas (1) to (4) have a polymerizable group, and at least one polymer constituted by bonding of the polymerizable group. The organic electroluminescent element according to any one of (1) to (10), wherein the organic electroluminescent element has a light emitting layer to be contained.
(12) The organic electroluminescence element according to any one of (1) to (11), wherein the M is platinum or iridium.
(13) A display device comprising the organic electroluminescence element according to any one of (1) to (12).
(14) An illuminating device comprising the organic electroluminescent element according to any one of (1) to (12).
In addition, about the following 1-21, it is a structure used as a reference.

1. In an organic electroluminescence device containing at least one light emitting layer sandwiched between an anode and a cathode,
The light emitting layer contains at least one compound containing a partial structure represented by the following general formula (1), (2), (3) or (4), and is represented by the following general formula (PA). An organic electroluminescence device comprising an organic layer containing at least one compound.

[In formula, E1a-E1q represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom respectively, and the frame | skeleton comprised by E1a-E1q has a total of 18 (pi) electrons. E1a and E1p are different from each other and represent a carbon atom or a nitrogen atom. R1a to R1i each represents a hydrogen atom or a substituent. M represents a group 8-10 transition metal element in the periodic table. ]
General formula (PA)
(R0) n1-Ar0- (Ar1) m1
[In the formula, Ar0 represents a (n1 + m1) -valent group, and Ar1 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. n1 represents an integer of 0 to 7, and m1 represents an integer of 3 to 10. ]
2. 2. The organic electroluminescent device according to 1 above, wherein the compound represented by the general formula (PA) is a compound represented by the following general formula (PB-1).

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. X21 to X25 each represent a nitrogen atom or —C (Rb1) = group. Rb1 represents a hydrogen atom or a substituent. n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ]
3. 3. The organic electroluminescence device according to 2 above, wherein the compound represented by the general formula (PB-1) is a compound represented by the following general formula (PB-2).

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ]
4). 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (PB-2) is a compound represented by the following general formula (PB-3).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom or a substituent. n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 5. p1 represents an integer of 2 to 5. ]
5. 5. The organic electroluminescence device as described in 4 above, wherein the compound represented by the general formula (PB-3) is a compound represented by the following general formula (PB-4).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom or a substituent. n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 4. p2 represents an integer of 2 to 5. ]
6). 3. The organic electroluminescence device as described in 2 above, wherein the compound represented by the general formula (PB-1) is a compound represented by the following general formula (PC-1).

[Wherein Ar3 and Ar4 each represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R2 and R3 each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. X31 to X40 each represents a nitrogen atom or -C (Rb1) = group. Rb1 represents a hydrogen atom or a substituent. X represents a direct bond or a divalent linking group. m5 and m6 each represent an integer of 2 to 5, and m3 and m4 each represent an integer of 0 to 3. k represents an integer of 0 or 1. ]
7). 7. The organic electroluminescence device as described in 6 above, wherein the compound represented by the general formula (PC-1) is a compound represented by the following general formula (PC-2).

[Wherein Ar3 and Ar4 each represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R2 and R3 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. X represents a direct bond or a divalent linking group. m3 and m4 each represent an integer of 0 to 3. m5 and m6 each represents an integer of 2 to 5. k represents an integer of 0 or 1. ]
8). 8. The organic electroluminescence device as described in 7 above, wherein the compound represented by the general formula (PC-2) is a compound represented by the general formula (PC-3).

[Wherein R 2, R 3 and R 4 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. m3 and m4 each represent an integer of 0 to 3. X represents a direct bond or a divalent linking group. n5 and n6 each represents an integer of 0 to 5. p3 and p4 each represent an integer of 2 to 5. k represents an integer of 0 or 1. ]
9. 8. The organic electroluminescence device as described in 7 above, wherein the compound represented by the general formula (PC-2) is a compound represented by the following general formula (PC-4).

[Wherein R 2, R 3, R 4 and R 5 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a cyano group. X represents a direct bond or a divalent linking group. m3 and m4 each represent an integer of 0 to 3. n5 and n6 each represents an integer of 0 to 4. p4 and p5 each represent an integer of 2 to 5. k represents an integer of 0 or 1. ]
10. The compound represented by the general formula (PA) described in 1 above, the compound represented by the general formula (PB-1) described in 2 above, and the general formula (PB-2) described in 3 above Compound, compound represented by general formula (PB-3) described in 4 above, compound represented by general formula (PB-4) described in 5 above, general formula (PC-1) described in 6 above , A compound represented by the general formula (PC-2) described in 7 above, a compound represented by the general formula (PC-3) described in 8 above and (PC- 4) The organic electro of any one of 1 to 9 above, wherein at least one compound selected from the group consisting of compounds represented by 4) has at least one polymerizable group in the molecule. Luminescence element.

  11. 11. The organic electroluminescence device according to any one of 1 to 10, wherein the ring composed of E1a to E1e is an imidazole ring or a pyrazole ring.

  12 As a constituent layer, it has an organic layer containing at least one compound containing a partial structure represented by any one of the general formulas (1) to (4), and the organic layer was formed using a wet process The organic electroluminescence device according to any one of 1 to 11, wherein the organic electroluminescence device is characterized in that

  13. As a constituent layer, the compound represented by the general formula (PA) described in 1 above, the compound represented by the general formula (PB-1) described in 2 above, the general formula (PB-2) described in 3 above A compound represented by the general formula (PB-3) described in 4 above, a compound represented by the general formula (PB-4) described in 5 above, a general formula ( 10. A compound represented by PC-1), a compound represented by Formula (PC-2) described in 7 above, a compound represented by Formula (PC-3) described in 8 above, and 9 The organic layer containing at least one compound selected from the group consisting of the compounds represented by (PC-4) of the above, wherein the organic layer is formed using a wet process The organic electroluminescent element of any one of 1-12.

  14 As a constituent layer, the compound represented by the general formula (PA) described in 1 above, the compound represented by the general formula (PB-1) described in 2 above, the general formula (PB-2) described in 3 above A compound represented by the general formula (PB-3) described in 4 above, a compound represented by the general formula (PB-4) described in 5 above, a general formula ( 10. A compound represented by PC-1), a compound represented by Formula (PC-2) described in 7 above, a compound represented by Formula (PC-3) described in 8 above, and 9 14. The organic layer containing at least one compound selected from the group consisting of compounds represented by (PC-4) is a light emitting layer, Organic electroluminescence device.

  15. As a constituent layer, the compound represented by the general formula (PA) described in 1 above, the compound represented by the general formula (PB-1) described in 2 above, the general formula (PB-2) described in 3 above A compound represented by the general formula (PB-3) described in 4 above, a compound represented by the general formula (PB-4) described in 5 above, a general formula ( 10. A compound represented by PC-1), a compound represented by Formula (PC-2) described in 7 above, a compound represented by Formula (PC-3) described in 8 above, and 9 Any one of 1 to 13 above, wherein the organic layer containing at least one compound selected from the group consisting of compounds represented by (PC-4) is a hole blocking layer or an electron transporting layer 2. The organic electroluminescence device according to item 1.

  16. Any one of 1 to 15 above, which has a light emitting layer containing at least one polymer having a partial structure of the compound represented by any one of the general formulas (1) to (4). The organic electroluminescent element of description.

  17. 17. The organic electroluminescent element according to any one of 1 to 16, wherein M is platinum or iridium.

  18. 2. An organic electroluminescent device material comprising at least one compound containing a partial structure represented by any one of the general formulas (1) to (4) described in 1 above.

  19. 19. The organic electroluminescent device material as described in 18 above, wherein M is platinum or iridium.

  20. 18. A display device comprising the organic electroluminescence element according to any one of 1 to 17 above.

  21. 18. An illumination device comprising the organic electroluminescence element according to any one of 1 to 17 above.

  According to the present invention, it is possible to provide an organic EL element that exhibits short-wave blue light emission, exhibits high light emission efficiency, has a low driving voltage, and has a long light emission lifetime. In addition, as a result of the study by the inventors, the present invention can provide a useful organic EL element that greatly reduces initial deterioration during driving of the element and also greatly reduces dark spots of the light emitting element. It was.

  In addition, an illumination device and a display device using the element can be provided. Furthermore, the organic EL element material useful for organic EL elements was able to be obtained.

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

  In 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.

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

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

<< Partial structure represented by any one of general formulas (1) to (4) >>
The partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be described.

  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. In the case where a complex compound) is applied to a light emitting material, the present inventors have succeeded in developing a light emitting dopant having a small emission wavelength shift and a long lifetime at a desired emission wavelength.

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

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

  Regarding the waveform, a shift in chromaticity caused by changing the concentration of the compound having a partial structure represented by any one of the general formulas (1) to (4) has become a problem. As a result of various studies, the general formulas (1) to (4) are represented by the following formulas (PA), (PB-1), (PB-2), (PB-3), ( PB-4), general formula (PC-1), general formula (PC-2), general formula (PC-3), and a compound represented by general formula (PC-4) are used together to shift this chromaticity. Can be greatly reduced.

  The driving voltage can also be significantly reduced by using the compounds represented by the above general formula in combination with the general formulas (1) to (4).

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

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

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

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

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

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

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

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

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

<< Partial structure represented by any one of general formulas (1) to (4) >>
The partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be described.

  In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E1a to E1e represents a 5-membered aromatic heterocycle, such as an oxazole ring, thiazole ring, or oxadi Examples thereof include an azole 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 E1f to E1k is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle. Represent.

  Examples of the 6-membered aromatic hydrocarbon ring formed by E1f to E1k include a benzene ring. Furthermore, you may have the substituent mentioned later.

  Examples of the 5- or 6-membered aromatic heterocycle formed by E1f to E1k 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. Can be mentioned.

  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 E1l to E1p is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle. These rings are each synonymous with a 6-membered aromatic hydrocarbon ring or 5-membered or 6-membered aromatic heterocycle formed by E1f to E1k.

  In the partial structure represented by any one of the general formulas (1) to (4), each of the substituents represented by R1a to R1i includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl 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), 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, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenyl 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) Noxalinyl 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.), Arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (Eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octyl) Aminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), 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.) An acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group) Group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group Group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylamino) Carbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido) Group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group naphthyluree Id 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 (Eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group, dimethyla 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. May be formed.

  In the partial structure represented by any one of the general formulas (1) to (4), the substituents represented by R1a to R1i are each a styryl group, an epoxy group, an oxetanyl group, an acryloyl group in addition to the alkenyl group described above. And may have a polymerizable group such as a methacryloyl 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.

(Polymer having a partial structure represented by any one of the 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 Chemistry of Chemical Synthesis” Chemistry “Experimental Method of Polymer Synthesis” It can be synthesized using the method described in Chemistry Course 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 properly used depending on the type of polymerizable group.

  In addition, the polymer of the 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 combined with a plurality of monomers. Is possible.

  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 2: Synthesis of Exemplified Compound A-97 >>

  Step 1: Synthesis of complex C, except that 1.5 g of 2-methylimidazo [1,2-f] phenanthridine was used instead of 3-methylimidazo [1,2-f] phenanthridine Reaction and post-treatment were performed in the same manner as in Step 1 of Synthesis Example 1 to obtain 1.37 g (77.0%) of Complex C.

  Step 2: Synthesis of Complex D Except that 1.0 g (0.0007244 mol) of Complex C was used, the reaction and post-treatment were performed in the same manner as in Step 2 of Synthesis Example 1 to obtain 0.42 g (38.5%) of Complex D. )Obtained.

Step 3: Synthesis of Exemplified Compound A-97 In a 50 ml four-necked flask, 0.386 g (0.0005120 mol) of Complex D, 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 were purified by column chromatography (developing solvent: toluene / ethyl acetate), and the obtained crystals were purified by suspension in a mixed solvent of tetrahydrofuran and ethyl acetate, and 0.3 g (66.6%) of Exemplified Compound A-97 was obtained. )Obtained.

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 apparatus: JEOL JNM-AL400 (400 MHz): manufactured by JEOL Ltd. Spectrum attribution (chemical shift δ, proton number, peak shape)
8.48 (1H, d), 7.93 (1H, d), 7.75 (1H, s), 7.64 (1H, d), 7.54 (1H, t), 7.46 (1H) , T), 6.95 (1H, t), 6.83 (1H, d), 1.85 (3H, s) The emission wavelength in the solution of Exemplified Compound A-81 was 455 nm (emission wavelength) Is measured in 2-methyltetrahydrofuran.)
The compound including the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is a phosphorescent dopant (a kind of light emitting dopant) in the light emitting layer of the organic EL device of the present invention. However, the compound may be contained in a layer other than the light emitting layer of the organic EL device of the present invention.

  The light emitting layer according to the present invention is characterized in that the above phosphorescent metal complex and a host compound having a glass transition temperature of 110 ° C. or higher are used in combination, but there is no particular limitation, and even a low molecular weight compound is a repeating unit. May be a high molecular compound having a low molecular weight compound (deposition polymerization light-emitting host) having a polymerizable group such as a vinyl group or an epoxy group, or one or more of them may be used.

<< Compound Represented by Formula (PA) >>
The compound represented by formula (PA) according to the present invention will be described.

  At least one of the organic layers, which is a constituent layer of the organic EL device of the present invention, contains the compound represented by the general formula (PA) according to the present invention.

  Moreover, it is preferable that the compound represented by general formula (PA) based on this invention is used for a light emitting layer, a hole-blocking layer, or an electron carrying layer as a structural layer of the organic EL element of this invention.

  The constituent layers of the element will be described later in detail in the constituent layers of the organic EL element of the present invention.

  As the organic layer containing the compound represented by the general formula (PA) according to the present invention, a light emitting layer, a hole blocking layer or an electron transporting layer is preferable.

  In the general formula (PA), the (n1 + m1) -valent group represented by Ar0 is a hydrogen atom or a substituent (n1 + m1) from any position of any aromatic hydrocarbon ring compound or aromatic heterocyclic compound. It is a residue removed and may be a group derived from any aromatic hydrocarbon ring or a group derived from any aromatic heterocycle, and further includes the aromatic hydrocarbon ring, the aromatic Each group heterocyclic ring may be a condensed ring.

  In the general formula (PA), as an arbitrary aromatic hydrocarbon ring used for deriving the (n1 + m1) -valent group represented by Ar0, for example, a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, Phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, Examples include a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

  Furthermore, the aromatic hydrocarbon ring may have a substituent represented by each of R1a to R1i in the partial structure represented by any of the general formulas (1) to (4).

  In the general formula (PA), examples of the aromatic heterocycle used for deriving the (n1 + m1) -valent group represented by Ar0 include, for example, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, and a pyridazine. Ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, A quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, a diazacarbazole ring (showing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), and the like.

  Furthermore, the aromatic heterocycle may have a substituent represented by each of R1a to R1i in the partial structure represented by any of the general formulas (1) to (4).

  In the general formula (PA), examples of the aromatic hydrocarbon ring group represented by Ar1 include a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, and an acenaphthenyl group. Group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.

  These groups may have substituents represented by R1a to R1i in the partial structure represented by any one of the general formulas (1) to (4).

  In the general formula (PA), examples of the aromatic heterocyclic group represented by Ar1 include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a pyrazinyl group, and a 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)

  These groups may have substituents represented by R1a to R1i in the partial structure represented by any one of the general formulas (1) to (4).

  In the general formula (PA), examples of the alkyl group represented by R0 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, and a tridecyl group. , Tetradecyl group, pentadecyl group and the like.

  In the general formula (PA), examples of the alkoxy group represented by R0 include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

  In the general formula (PA), examples of the halogen atom represented by R0 include a fluorine atom, a chlorine atom, and a bromine atom.

  In the general formula (PA), the alkyl group, the aromatic hydrocarbon ring group, or the aromatic heterocyclic group represented by R0 is, in the partial structure represented by any one of the general formulas (1) to (4), R1a May have a substituent represented by each of R1i, and a plurality of these alkyl groups, aromatic hydrocarbon ring groups, and aromatic heterocyclic groups may be bonded to each other to form a ring. Good.

<< Preferred Aspect 1 of Compound Represented by General Formula (PA) >>
Next, preferred embodiment 1 of the compound represented by formula (PA) according to the present invention will be described.

  Among the compounds represented by the general formula (PA) according to the present invention, the compounds represented by the above general formula (PB-1) are preferable, and among these, the compounds represented by the above general formula (PB-2) are preferable. Furthermore, the compound represented by the general formula (PB-3) is preferable, and among them, the general formula (PB-4) is particularly preferable.

(Compound represented by formula (PB-1))
In the general formula (PB-1), the aromatic hydrocarbon ring group represented by Ar1 and Ar2 has the same meaning as the aromatic hydrocarbon ring group represented by Ar1 in the general formula (PA).

  In general formula (PB-1), the aromatic heterocyclic group represented by Ar1 and Ar2 has the same meaning as the aromatic heterocyclic group represented by Ar1 in general formula (PA).

  In General Formula (PB-1), R0 has the same meaning as R0 in General Formula (PA).

  In the general formula (PB-1), the substituent represented by Rb1 of —C (Rb1) = group represented by X21 to X25 is represented by any one of the general formulas (1) to (4). In a partial structure, it is synonymous with the substituent respectively represented by R1a-R1i.

(Compound represented by formula (PB-2))
In the general formula (PB-2), the aromatic hydrocarbon ring group represented by Ar1 and Ar2 has the same meaning as the aromatic hydrocarbon ring group represented by Ar1 in the general formula (PA).

  In general formula (PB-1), the aromatic heterocyclic group represented by Ar1 and Ar2 has the same meaning as the aromatic heterocyclic group represented by Ar1 in general formula (PA).

  In General Formula (PB-2), R0 has the same meaning as R0 in General Formula (PA).

(Compound represented by formula (PB-3))
In general formula (PB-3), the alkyl group, alkoxy group, or halogen atom represented by R0 has the same meaning as R0 in general formula (PA).

  In the general formula (PB-3), examples of the heterocyclic group represented by R0 include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

(Compound represented by formula (PB-4))
In general formula (PB-4), the alkyl group, alkoxy group, or halogen atom represented by R0 has the same meaning as R0 in general formula (PA).

  In the general formula (PB-4), examples of the heterocyclic group represented by R0 include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

<< Another Preferred Embodiment 2 of the Compound Represented by General Formula (PA) >>
Next, another preferred embodiment 2 of the compound represented by the general formula (PA) according to the present invention will be described.

  Among the compounds represented by the general formula (PA) according to the present invention, the compounds represented by the above general formula (PB-1) are preferable, and among them, the compounds represented by the above general formula (PC-1) are different. Among them, the compound represented by the general formula (PC-2) is preferable, the general formula (PC-3) is more preferable, and the general formula (PC-4) is particularly preferable. The compounds represented are preferred.

(Compound represented by formula (PC-1))
In the general formula (PC-1), each aromatic hydrocarbon ring group represented by Ar3 and Ar4 has the same meaning as the aromatic hydrocarbon ring group represented by Ar1 in the general formula (PA). is there.

  In the general formula (PC-1), the aromatic heterocyclic group represented by Ar3 and Ar4 has the same meaning as the aromatic heterocyclic group represented by Ar1 in the general formula (PA).

  R2 and R3 in General Formula (PC-1) have the same meanings as R0 in General Formula (PA), respectively.

  In the general formula (PC-1), the substituent represented by Rb1 of —C (Rb1) = group represented by X31 to X40 is represented by any one of the general formulas (1) to (4). In a partial structure, it is synonymous with the substituent respectively represented by R1a-R1i.

  In the general formula (PC-1), the divalent linking group represented by X is an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group). ), Cycloalkylene group (for example, cyclohexane-1,6-diyl group, etc.), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methylpentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group, etc.), alkynylene group (For example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, -Hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl-1-propynylene group, 3-methyl-1-butynylene group, etc.), arylene group (for example, phenylene group, naphthalenediyl group) It represents a divalent linking group selected from the group consisting of an oxy group, a thio group, and a dialkylsilane-1,1-diyl group.

(Compound represented by formula (PC-2))
In the general formula (PC-2), each of the aromatic hydrocarbon ring groups represented by Ar3 and Ar4 has the same meaning as the aromatic hydrocarbon ring group represented by Ar1 in the general formula (PA). is there.

  In the general formula (PC-2), the aromatic heterocyclic group represented by Ar3 and Ar4 has the same meaning as the aromatic heterocyclic group represented by Ar1 in the general formula (PA).

  R2 and R3 in General Formula (PC-2) have the same meanings as R0 in General Formula (PA), respectively.

(Compound represented by general formula (PC-3))
R2, R3, R4 and R5 in the general formula (PC-3) have the same meaning as R0 in the general formula (PA).

(Compound represented by formula (PC-4))
R2, R3, R4 and R5 in the general formula (PC-4) have the same meaning as R0 in the general formula (PA).

(Polymer of compound represented by general formula (PA), (PB-1 to 3), (PC-1 to 4))
It is represented by the general formula (PA), (PB-1), (PB-2), (PB-3), (PC-1) (PC-2), (PC-3) or (PC-4). The Tg (glass transition temperature) of the compound is preferably 100 ° C. or higher and lower than 400 ° C., more preferably 100 ° C. or higher and lower than 350 ° C.

  In addition, Tg (it is also called a glass transition temperature, a glass transition point, etc.) concerning this invention can be calculated | required using a commercially available DSC (differential scanning calorimetry) measuring apparatus.

  In addition, the general formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or The molecular weight of the compound represented by (PC-4) is preferably 600 or more and less than 2000. However, general formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or ( When the compound represented by PC-4) forms a polymer (polymer), the molecular weight of the monomer is preferably 600 or more and less than 2000.

  The general formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or (PC The compound represented by -4) may have a polymerizable group such as a styryl group, an epoxy group, an oxetanyl group, an acryloyl group, and a methacryloyl group in addition to the alkenyl group described above.

  Furthermore, general formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or ( The compound represented by PC-4) can react with the polymerizable groups or other polymerizable monomers to form a polymer (polymer).

  When a plurality of partial structures are present in the polymer, each of the general formulas (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) The partial structures represented by any of (PC-2), (PC-3) or (PC-4) may be the same or different.

  Formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or (PC- The polymer (polymer) of the compound represented by 4) can be synthesized according to the polymerization method of the partial structure represented by any one of the general formulas (1) to (4).

  Formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or (PC- The polymer (polymer) of the compound represented by 4) can be a homopolymer using the above-described method, or a copolymer in combination with a plurality of monomers.

  General formulas (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) according to the present invention Alternatively, when the molecular weight of the compound represented by (PC-4) is less than 2000, it can be determined by mass spectrometry well known to those skilled in the art.

  Moreover, general formula (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or ( When the molecular weight of the compound represented by PC-4) exceeds 1000, the molecular weight can be measured using GPC (gel permeation chromatography) well known to those skilled in the art. The average molecular weight (Mw) and the number average molecular weight (Mn) can be measured.

  The molecular weight of the polymer itself can be measured by a conventionally known method.

  Specifically, 1 ml of THF (using a degassed sample) is added to 1 mg of a measurement sample, and the sample is stirred using a magnetic stirrer at room temperature to be sufficiently dissolved. Subsequently, after processing with a membrane filter having a pore size of 0.45 μm to 0.50 μm, it is injected into a GPC (gel permeation chromatograph) apparatus.

  GPC measurement conditions are measured by stabilizing the column at 40 ° C., flowing THF (tetrahydrofuran) at a flow rate of 1 ml / min, and injecting about 100 μl of a sample having a concentration of 1 mg / ml.

  As the column, it is preferable to use a combination of commercially available polystyrene gel columns. For example, Shodex GPC KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko KK, TSKgel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, TSK guard, etc. manufactured by Tosoh Corporation A combination of these is preferred.

  As the detector, a refractive index detector (RI detector) or a UV detector is preferably used. In the measurement of the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points are preferably used as polystyrene for preparing a calibration curve.

  In the present invention, the molecular weight was measured under the following measurement conditions.

(Measurement condition)
Equipment: Tosoh High Speed GPC Equipment HLC-8220GPC
Column: TOSOH TSKgel Super HM-M
Detector: RI and / or UV
Eluent flow rate: 0.6 ml / min Sample concentration: 0.1% by mass
Sample volume: 100 μl
Calibration curve: prepared with standard polystyrene: standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 100000 to 500-500 calibration curves (also referred to as calibration curves) were used to calculate the molecular weight. . It is preferable that the 13 samples are substantially equally spaced.

  In the following formulas (PA), (PB-1), (PB-2), (PB-3), (PB-4), (PC-1) (PC-2), (PC-3) or Specific examples of the compound represented by any of (PC-4) are shown below, but the present invention is not limited thereto.

  The compound represented by any one of the general formulas (PA-1), (PB-1) to (PB-4) or (PC-1) to (PC-4) according to the present invention is a known method. Can be synthesized.

  For example, synthesis is performed using the methods described in JP 2004-14334 A, JP 2006-135184 A, JP 2003-27048 A, JP 2003-135160 A, JP 2003-135155 A, and the like. Is possible.

<< 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 (vi) Anode / hole transport layer / electron block layer / light emitting layer / hole block layer / electron transport layer / cathode In the organic EL device of the present invention, blue light emission The light emission maximum wavelength of the layer is preferably in the range of 430 nm to 480 nm, the green light emission layer is preferably a monochromatic light emission layer having a light emission maximum wavelength in the range of 510 nm to 550 nm, and the red light emission layer is in the range of 600 nm to 640 nm. This is a display device using these. It is preferred. Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.

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

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

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

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

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

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

  Here, in the present invention, the host compound is defined as a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.1 at room temperature (25 ° C.). 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, known host compounds may be used alone or in combination of two or more. 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.

  In addition, the light emitting host used in the present invention is represented by any one of the general formulas (PA-1), (PB-1) to (PB-4), or (PC-1) to (PC-4). A compound is preferably used.

  Moreover, you may use together a conventionally well-known light emission dopant as shown below. It may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). As known host compounds that may be used in combination with the present invention, there are compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature). preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The hole blocking layer contains the carbazole derivative, carboline derivative, diazacarbazole derivative (one in which one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced with a nitrogen atom) mentioned as the host compound. It is preferable to do.

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

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

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

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

  The partial structure represented by any one of the general formulas (1) to (4), the partial structure represented by any one of the general formulas (5) to (8), and the general formula (9) according to the present invention. To (12) or a compound having a partial structure represented by any one of the general formulas (13) to (16) may be contained in the hole blocking layer. .

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

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

  The partial structure represented by any one of the general formulas (1) to (4), the partial structure represented by any one of the general formulas (5) to (8), and the general formula (9) according to the present invention. It is also possible to contain in the electron blocking layer a compound having a partial structure represented by any one of (12) or a partial structure represented by any one of the general formulas (13) to (16).

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

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

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

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

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

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

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

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 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 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

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

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

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

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method. A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

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

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

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

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

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., 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 Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described.

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

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

  Examples of the method for forming each layer include a vapor deposition method and a wet process (also referred to as a coating method, such as a spin coating method, a casting method, an ink jet method, and a printing method) as described above. In the present invention, film formation by a wet process (coating method) such as a spin coating method, an ink jet method, or a printing method is preferable.

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

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

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. 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 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

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

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

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

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

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

  The structures of the compounds used in the following examples are shown below.

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

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

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

  Further, the heating boat containing H-1 and Compound 1 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.006 nm / second, respectively. A 40 nm light emitting layer was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Furthermore, it supplied with electricity to the said heating boat containing BAlq, it heated, and it vapor-deposited on the said light emitting layer with the vapor deposition rate of 0.1 nm / second, and provided the electron carrying layer with a film 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 1-27 >>
In the production of the organic EL element 1-1, the organic EL elements 1-2 to 1 were similarly performed except that H-1 as the host compound of the light emitting layer and the compound 1 as the dopant compound were replaced with the compounds shown in Table 1. -27 was produced.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-27, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 3 and 4 was formed and evaluated.

  FIG. 3 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

(External quantum efficiency)
By lighting the organic EL element under a constant current condition of room temperature (about 23 ° C. 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.

(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. Rank evaluation was performed as follows by visual evaluation by 10 people extracted at random.

×: The number of people who confirmed dark spots was 5 or more. △: The number of people confirmed dark spots was 1-4. ○: The number of people confirmed dark spots was 0. (Luminescent color)
In the production of the light emitting layer of the organic EL device 1-1, the film was co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.024 nm / second of H-1 and the compound (1), An organic EL device 1-1A of the present invention was produced in the same manner except that a 40 nm thick light emitting layer was provided.

  Similarly, in the production of the light emitting layers of the organic EL elements 1-2 to 1-27, the organic EL elements 1-2A to 1-27A were respectively produced.

The CIE chromaticity of the device was measured using CS-1000 (manufactured by Konica Minolta Sensing) as the emission color when the obtained organic EL device was continuously lit at a constant current of ^2.5 mA / cm ² at room temperature. Coordinates were measured.

  For example, in the case of the organic EL element 1-1 and the organic EL element 1-1A, the CIE chromaticity coordinates of the organic EL element 1-1 are (x1, y1), and the CIE chromaticity coordinates of the organic EL element 1-1A are , (X2, y2), the DC value was obtained using the following formula (1).

Formula (1)
DC = [(x2-x1) ² + (y2-y1) ² ] ^1/2
The obtained results are shown in Table 1.

  From Table 1, the organic EL device of the present invention has higher efficiency (external extraction quantum efficiency), longer half-life, no dark spots, and a mixture ratio of the host and the dopant, as compared with the comparative device. It is clear that there is no deviation of the emission color.

Example 2
<< Preparation of Organic EL Element 2-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

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

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

  Furthermore, the heating boat containing H-1 and Compound 1 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. A 40 nm light emitting layer was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Furthermore, it supplied with electricity to the said heating boat containing BAlq, it heated, and it vapor-deposited on the said light emitting layer with the vapor deposition rate of 0.1 nm / second, and provided the electron carrying layer with a film thickness of 40 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Subsequently, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited to form a cathode, and an organic EL element 2-1 was produced.

<< Production of Organic EL Elements 2-2 to 2-26 >>
In the production of the organic EL element 2-1, the organic EL elements 2-2 to 2-26 were similarly performed except that the compound shown in Table 2 was replaced with the compound BALq that is the compound of the electron transport layer and the compound 1 that was the dopant compound. Was made.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 2-1 to 2-26, the non-light-emitting surface of each organic EL element after production is covered with a glass case, and a glass substrate having a thickness of 300 μm is used as a sealing substrate. An epoxy photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 3 and 4 was formed and evaluated.

  FIG. 3 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

  In the evaluation of the obtained organic EL elements 2-1 to 2-33, efficiency (external extraction quantum efficiency), lifetime (half-life), and dark spots were the same as in Example 1. Further, the driving voltage and voltage increase (storage element voltage increase) of the organic EL element were evaluated as follows.

(Drive voltage)
Each voltage was measured when the organic EL element was driven at room temperature (about 23 to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and the measurement results are shown below. The organic EL element 2-1 (comparative example) of Example 2 was set as 100, and each was shown as a relative value.

Voltage = (drive voltage of each element / drive voltage of the organic EL element 2-1) × 100
A smaller value indicates a lower drive voltage for comparison.

(Storage element voltage rise)
Each organic EL element was stored for 1 week under conditions of 50 ° C. and humidity 80%, and then the voltage when driven under a constant current condition of ^2.5 mA / cm ² was measured and compared with the driving voltage before storage.

Voltage rise after storage = (drive voltage after storage of each element / drive voltage before storage of each element)
Note that the closer the value is to 1, the smaller the increase in drive voltage before and after storage.

  The obtained results are shown in Table 2.

  From Table 2, the organic EL device of the present invention has higher efficiency (external extraction quantum efficiency), longer half-life, no dark spots, lower driving voltage, and storage compared to the comparative device. It is clear that the voltage rise at the time is small.

Example 3
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL device 1-12 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 the compound (1) was changed to Ir-1, and this was used as a green light emitting device.

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

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.

  That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see Not shown).

  The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing red, green, and blue pixels.

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

Example 4
<< Preparation of white light emitting element and white lighting device >>
The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm × 20 mm, and α-NPD was formed thereon with a thickness of 25 nm as a hole injection / transport layer in the same manner as in Example 1; The heated boat containing 1 and the boat containing Exemplified Compound A-97 and the boat containing Ir-9 were energized independently, and H-1 as a luminescent host and Exemplified Compound A-97 as a luminescent dopant, And the vapor deposition rate of Ir-9 was adjusted to be 100: 5: 0.6, vapor deposition was performed so as to have a thickness of 40 nm, and a light emitting layer was provided.

  Next, PX-1 was deposited to a thickness of 30 nm to provide an electron transport layer.

  Next, as in Example 1, a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron 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 5
<< Production of Organic EL Element 5-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

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

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound 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 of H-1 (60 mg) and compound (1) (3.0 mg) dissolved in 6 ml of toluene, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds to form a light emitting layer. .

  Subsequently, BAlq was deposited on the light emitting layer to provide an electron transport layer having a thickness of 40 nm.

  Further, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited to form a cathode, thereby producing an organic EL element 5-1.

<< Production of Organic EL Elements 5-2 to 5-26 >>
Organic EL elements 5-2 to 5-26 were prepared in the same manner as in the preparation of organic EL element 5-1, except that compound 1 as H-1 and the dopant compound was replaced with the compounds shown in Table 5.

<< Evaluation of organic EL elements >>
Evaluation of the efficiency (external extraction quantum efficiency), lifetime (half-life), and dark spot of the obtained organic EL elements 5-1 to 5-26 was performed in the same manner as in Example 1.

  The obtained results are shown in Table 3.

  From Table 3, the organic EL device of the present invention has higher efficiency (external extraction quantum efficiency), longer half-life, no dark spots, lower driving voltage, and storage compared to the comparative device. It is clear that the voltage rise at the time is small.

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

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

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound 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 H-5 (60 mg) and compound (1) (3.0 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, using a solution of BC (50 mg) dissolved in 6 ml of methanol, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds. Heating was performed in vacuum at 80 ° C. for 1 hour to obtain an electron transport layer.

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

<< Production of Organic EL Elements 6-2 to 6-23 >>
In the production of the organic EL element 6-1, the compound (1), which is a dopant compound, and an electron transport compound (electron transport material)
Organic EL elements 6-2 to 6-29 were produced in the same manner except that was replaced with the compounds shown in Table 4.

<< Evaluation of organic EL elements >>
In the evaluation of the obtained organic EL elements 6-1 to 6-23, efficiency (external extraction quantum efficiency), life (half-life), and dark spot were performed in the same manner as in Example 1. Further, the drive voltage and voltage increase (storage element voltage increase) of the organic EL element were evaluated in the same manner as in Example 2.

  Table 4 shows the obtained results.

  From Table 4, it can be seen that the organic EL device of the present invention has little increase in voltage after storage, has a long life, and further suppresses the generation of dark spots as compared with the comparison.

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.

Explanation of symbols

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 (14)

In an organic electroluminescence device containing at least one light emitting layer sandwiched between an anode and a cathode,
The light emitting layer contains at least one compound containing a partial structure represented by the following general formula (1), (2), (3) or (4), and represented by the following general formula (PB-1) It has an organic layer containing at least 1 compound represented, The organic electroluminescent element characterized by the above-mentioned.

[In formula, E1a-E1q represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom respectively, and the frame | skeleton comprised by E1a-E1q has a total of 18 (pi) electrons. E1a and E1p are different from each other and represent a carbon atom or a nitrogen atom. R1a to R1i are each a hydrogen atom , an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, Alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroaryl A sulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, or a phosphono group is represented. M represents a group 8-10 transition metal element in the periodic table. ]

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. X21 to X25 each represent a nitrogen atom or —C (Rb1) = group. Rb1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, Cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroarylsulfonyl group, An amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, or a phosphono group is represented. n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ] The organic electroluminescent element according to claim 1 , wherein the compound represented by the general formula (PB-1) is a compound represented by the following general formula (PB-2).

[Wherein, Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group. R0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom , a cyano group or a heterocyclic group . n2 represents an integer of 0 to 3, and m2 represents an integer of 2 to 5. ] The organic electroluminescent element according to claim 2 , wherein the compound represented by the general formula (PB-2) is a compound represented by the following general formula (PB-3).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom , an alkyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkoxy group, an alkylsulfonyl group, a halogen atom, a fluorinated hydrocarbon group, or a cyano group . n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 5. m2 represents an integer of 2 to 5. ] The organic electroluminescent element according to claim 2 , wherein the compound represented by the general formula (PB-2) is a compound represented by the following general formula (PB-4).

[Wherein R 0 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a cyano group or a heterocyclic group. R1 and R2 each represent a hydrogen atom , an alkyl group or an aromatic hydrocarbon ring group . n2 represents an integer of 0 to 3, and n3 and n4 each represents an integer of 0 to 4. m2 represents an integer of 2 to 5. ] The compound represented by formula (PB-1) according to 請 Motomeko 1, compounds represented by the general formula of claim 2 (PB-2), the general formula of claim 3 (PB- at least one polymerizable group and at least one is in the molecule of the compound represented and claim 4 in formula (PB-4) a compound selected from the compounds or Ranaru group represented by the described 3) the organic electroluminescent device according to any one of claims 1 to 4, characterized in that it has a. It said ring consisting of E1a~E1e The organic electroluminescent device according to any one of claims 1 to 5, characterized in that an imidazole ring or a pyrazole ring. 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 device according to any one of claims 1 to 6, characterized in that. A structure layer, the compound represented by formula (PB-1) according to 請 Motomeko 1, compounds represented by the general formula of claim 2 (PB-2), generally according to claim 3 the organic layer containing at least one compound selected from the compounds or Ranaru group represented by the formula compounds represented by (PB-3) and the general formula of claim 4 (PB-4) has organic electroluminescent device according to any one of claims 1 to 7, the organic layer is characterized by being formed using a wet process. A structure layer, the compound represented by formula (PB-1) according to 請 Motomeko 1, compounds represented by the general formula of claim 2 (PB-2), generally according to claim 3 the organic layer containing at least one formula (PB-3) and the compound represented by claim 4 formula according to (PB-4) a compound selected from the compounds or Ranaru group represented is It is a light emitting layer, The organic electroluminescent element of any one of Claims 1-8 characterized by the above-mentioned. A structure layer, the compound represented by formula (PB-1) according to 請 Motomeko 1, compounds represented by the general formula of claim 2 (PB-2), generally according to claim 3 the organic layer containing at least one formula (PB-3) and the compound represented by claim 4 formula according to (PB-4) a compound selected from the compounds or Ranaru group represented is the organic electroluminescent device according to any one of claims 1 to 8, characterized in that a hole blocking layer or an electron transport layer. Luminescence containing at least one polymer in which R1a to R1i of the compound represented by any one of the general formulas (1) to (4) have a polymerizable group and the polymerizable group is bonded. It has a layer, The organic electroluminescent element of any one of Claims 1-10 characterized by the above-mentioned. The organic electroluminescent device according to any one of claims 1 to 11, wherein M is platinum or iridium. Display apparatus comprising the organic electroluminescent element of any one of claims 1 to 12. An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 12 .

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