JP2005340122A - Organic electroluminescent element, lighting system, and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element, a lighting system, and a display that have high external takeout yields and a long lifetime. <P>SOLUTION: In the organic electroluminescent element having at least an emission layer and a hole-blocking layer as structure layers, the emission layer contains a compound expressed by a formula (1), and the hole-blocking layer contains at least one compound selected from six kinds of compound groups containing a compound expressed by the formula (1). In the expression, Z1, Z2, Z3, and R101 indicate an aromatic series heterocycle that may have a substituent, an aromatic series heterocycle or an aromatic series hydrocarbon ring that may have each substituent, a divalent linkage group or a simple linkage, and a hydrogen atom or a substituent, respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also abbreviated 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 electroluminescence 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 (exciton) are injected by injecting electrons and holes into the light emitting layer and recombining them. ), Which emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Since it is a type, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoint of space saving, portability, and the like.

  For the development of organic EL elements for practical application in the future, organic EL elements that emit light with high power and efficiency with low power consumption are desired, such as stilbene derivatives, distyrylarylene derivatives, or tristyryl. A technique for doping an arylene derivative with a small amount of a phosphor to improve emission luminance and extend the lifetime of the device (see, for example, Patent Document 1), and 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light-emitting layer doped with a phosphor (for example, see Patent Document 2), a device having an organic light-emitting layer doped with a quinacridone-based dye as an 8-hydroxyquinoline aluminum complex as a host compound (for example, Patent Document 3) is known.

In the technique disclosed in the above document, when the 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 light extraction efficiency is about 20%, the limit of the external extraction quantum efficiency (η _ext ) is set to 5%.

  On the other hand, since the University of Princeton has reported on organic EL devices that use phosphorescence from excited triplets (see, for example, Non-Patent Document 1), research on materials that exhibit phosphorescence at room temperature has become active. (For example, refer nonpatent literature 2 and patent literature 4.).

  When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so in principle the luminous efficiency is four times that of excited singlets, and the performance is almost the same as that of cold cathode tubes. It can be applied to and attracts attention.

  On the other hand, it has been proposed to provide a hole blocking layer that restricts the movement of holes from the light emitting layer between the light emitting layer and the cathode in order to improve the light emission luminance and the light emission lifetime of the organic EL element. By efficiently accumulating holes in the light emitting layer by this hole blocking layer, it is possible to improve the recombination probability with electrons and achieve high efficiency of light emission. It has been reported that the use of a phenanthroline derivative or a triazole derivative alone as a hole blocking material is effective (see Patent Documents 5 and 6). In addition, a long-life organic EL element is realized by using a specific aluminum complex for the hole blocking layer (see Patent Document 7).

  As described above, with the introduction of the hole blocking layer, in the organic EL element using the phosphorescent compound, the internal quantum efficiency in green is almost 100% and the lifetime is 20,000 hours (see Non-Patent Document 3). There is still room for improvement in terms of luminance.

  In addition, when a blue to blue-green phosphorescent compound is used as a dopant, there is an example in which a carbazole derivative such as CBP is used as a host compound, but the external extraction quantum efficiency is 6%, which is an insufficient result. Yes (see Non-Patent Document 4), there remains room for improvement. For blue, light emission from fluorescent compounds is used, but a linking group is introduced into the middle biaryl moiety of the carbazole derivative molecule to create an organic EL device with excellent blue color purity and long life. (For example, see Patent Document 8). Further, in addition to the above compound, when a specific pentacoordinate metal complex is used for the hole blocking layer and a phosphorescent compound is used as a dopant, a longer lifetime is achieved (for example, patents). Reference 9).

Furthermore, other organic EL elements using carbazole derivatives have been produced (for example, Patent Documents 10 to 21). However, the carbazole derivatives described in the above patents have not yet reached luminous efficiency and heat resistance that can withstand practical use. In the organic EL element for practical use in the future, it is desired to develop an organic EL element that emits light efficiently and with high luminance with low power consumption and has a longer lifetime.
Japanese Patent No. 3093796 Japanese Unexamined Patent Publication No. 63-264692 JP-A-3-255190 US Pat. No. 6,097,147 JP-A-8-109373 JP-A-10-233284 JP 2001-284056 A JP 2000-21572 A Japanese Patent Laid-Open No. 2002-8860 JP 2002-203663 A JP-A-8-3547 Japanese Patent Laid-Open No. 8-143861 JP-A-8-143862 Japanese Patent Laid-Open No. 9-249876 Japanese Patent Laid-Open No. 11-144866 JP-A-11-144867 JP-A-8-60144 Japanese Patent Laid-Open No. 2002-8860 Japanese Patent Laid-Open No. 2003-77664 WO03 / 50201 JP 2003-231692 A M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) 62nd Japan Society of Applied Physics Academic Lecture Proceedings 12-a-M7, Pioneer Technical Information Magazine, Vol. 11, No. 1 Proceedings of the 62nd Japan Society of Applied Physics, 12-a-M8

  An object of the present invention is to provide an organic electroluminescence element, a lighting device, and a display device that have a high external extraction efficiency and a long lifetime.

  The above object of the present invention has been achieved by the following configurations 1 to 63.

(Claim 1)
In the organic electroluminescence device having at least a light emitting layer and a hole blocking layer as a constituent layer,
The light emitting layer contains a compound represented by the following general formula (1), and the hole blocking layer includes the following general formulas (2) to (5), the general formula (1) and the following general formula (B). An organic electroluminescence device comprising at least one compound selected from the group consisting of:

[Wherein, Z ₁ represents an aromatic heterocyclic ring which may have a substituent, Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may each have a substituent, Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent. ]

_{Wherein, R a1 ~R a3, R b1} ~R b4, R c1, R c2 , each may have a substituent, an alkyl group, an aryl group or an aromatic heterocyclic group, A _ra -A _rc represents an aryl group or an aromatic heterocyclic group, each optionally having a substituent. ]

[Wherein, Ra to Rg each represents a hydrogen atom or a substituent, and the substituents represented by Ra to Rg may be the same or different. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. ]
(Claim 2)
2. The organic electroluminescence device according to claim 1, wherein Z _{1 of the} compound represented by the general formula (1) is a 6-membered ring.

(Claim 3)
The organic electroluminescence device according to claim 1 or 2, wherein Z _{2 of the} compound represented by the general formula (1) is a 6-membered ring.

(Claim 4)
The organic electroluminescent element according to claim 1, wherein Z _{3 of the} compound represented by the general formula (1) is a bond.

(Claim 5)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) has a molecular weight of 450 or more.

(Claim 6)
The compound represented by said general formula (1) is represented by the following general formula (1-1), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{501 to} R ₅₀₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 7)
The compound represented by said general formula (1) is represented by the following general formula (1-2), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{511 to} R ₅₁₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 8)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-3).

[Wherein, R _{521 to} R ₅₂₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 9)
The compound represented by said general formula (1) is represented by the following general formula (1-4), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{531 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 10)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-5).

Wherein, R ₅₄₁ to R ₅₄₈ each independently represents a hydrogen atom or a substituent. ]
(Claim 11)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-6).

[Wherein, R _{551 to} R ₅₅₈ each independently represents a hydrogen atom or a substituent. ]
(Claim 12)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-7).

[Wherein, R _{561 to} R ₅₆₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 13)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-8).

[Wherein, R _{571 to} R ₅₇₇ each independently represents a hydrogen atom or a substituent. ]
(Claim 14)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ]
(Claim 15)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-10).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ]
(Claim 16)
The compound represented by the general formula (1) has at least one group represented by any one of the following general formulas (2-1) to (2-8). Organic electroluminescent element of any one of these.

_{Wherein, R 502 ~R 507, R 512} ~R 517, R 522 ~R 527, R 532 ~R 537, R 542 ~R 548, R 552 ~R 558, R 562 ~R 567, R 572 ~R ₅₇₇ each independently represents a hydrogen atom or a substituent, and the substituents may be the same or different. ]
(Claim 17)
The compound represented by said general formula (1) is represented by the following general formula (3), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{601 to} R ₆₀₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 18)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (4).

[Wherein, R _{611 to} R ₆₂₀ each independently represents a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 19)
The compound represented by said general formula (1) is represented by the following general formula (5), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{621 to} R ₆₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{621 to} R ₆₂₃ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 20)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (6).

[Wherein R _{631 to} R ₆₄₅ each independently represents a hydrogen atom or a substituent, and at least one of R _{631 to} R ₆₄₅ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 21)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (7).

[Wherein, R _{651 to} R ₆₅₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6. ]
(Claim 22)
The compound represented by said general formula (1) is represented by the following general formula (8), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein R _{661 to} R ₆₇₂ each independently represents a hydrogen atom or a substituent, and at least one of R _{661 to} R ₆₇₂ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 23)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (9).

[Wherein, R _{681 to} R ₆₈₈ independently represent a hydrogen atom or a substituent, and at least one of R _{681 to} R ₆₈₈ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ]
(Claim 24)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (10).

[Wherein, R _{691 to} R ₇₀₀ each independently represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group. At least one of R _{691 to} R ₇₀₀ represents at least one group selected from the groups represented by the general formulas (2-1) to (2-4). ]
(Claim 25)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (11).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
(Claim 26)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (12).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
(Claim 27)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
(Claim 28)
The compound represented by said general formula (1) is represented by the following general formula (14), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
(Claim 29)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (15).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom. ]
(Claim 30)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (16).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ and Z ₂ each represent a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ]
(Claim 31)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (17).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent a divalent arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ]
(Claim 32)
The phosphorescent light emitting layer as the constituent layer, and the phosphorescent light emitting layer contains the compound represented by the general formula (1). Organic electroluminescence element.

(Claim 33)
At least 1 layer of the said structural layer is a hole-blocking layer, The said hole-blocking layer contains the compound represented by the said General formula (1), The any one of Claims 1-32 characterized by the above-mentioned. The organic electroluminescent element according to item.

(Claim 34)
A display device comprising the organic electroluminescence element according to claim 1.

(Claim 35)
Luminescence is substantially white, The organic electroluminescent element of any one of Claims 1-33 characterized by the above-mentioned.

(Claim 36)
36. A display device comprising the organic electroluminescence element according to claim 35.

(Claim 37)
36. An illumination device comprising the organic electroluminescence element according to claim 35.

(Claim 38)
38. A display device comprising the illumination device according to claim 37 and a liquid crystal element as display means.

  According to the present invention, an organic electroluminescence element, an illuminating device, and a display device having high external extraction efficiency and a long lifetime can be provided.

  In the organic electroluminescent element of the present invention (hereinafter also referred to as an organic El element), any one of claims 1 to 35, any one of claims 37 to 45, and any one of claims 47 to 53. The organic EL device having a high external extraction yield and a long life could be obtained by adopting the constitutions defined in any one of Items Nos. 55 to 62.

  In addition, using the organic EL element exhibiting the above characteristics, a high-luminance and long-life lighting device and display device could be obtained.

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

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.

  As a result of intensive studies, the present inventors have used the compound represented by the general formula (1) in the light emitting layer, thereby increasing the light emission efficiency of the organic EL element and extending the life. The combined use with a compound selected from the compound group consisting of the general formulas (2) to (5), the general formula (1) and the general formula (B) further increases the luminous efficiency and further increases the length. It was found that the life could be extended.

  As described above, the compound represented by the general formula (1) is used in the light-emitting layer, and it is also found that it is one of the materials preferably used as the hole blocking material in the hole blocking layer. It was.

In the general formula (1), Z ₁ represents an aromatic heterocyclic ring which may have a substituent, and Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may have a substituent. , Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent.

In the general formula (1), examples of the aromatic heterocycle represented by Z ₁ and Z ₂ include a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, Diazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring And a ring in which the carbon atom of the hydrocarbon ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁₀₁ described later.

In the general formula (1), examples of the aromatic hydrocarbon ring represented by Z ₂ include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene. Ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene Ring, pyranthrene ring, anthraanthrene ring and the like. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁₀₁ described later.

In the general formula (1), examples of the substituent represented by R ₁₀₁ include an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group). Group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.) Etc.), aryl groups (eg phenyl group, naphthyl group etc.), aromatic heterocyclic groups (eg furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group) , Thiazolyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg Pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cyclo An alkoxyl group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), an aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, Octylthio group, dodecylthio group etc.), cycloalkylthio group (eg cyclopentylthio group, cyclohexylthio group etc.), arylthio group (eg phenylthio group, naphthylthio group etc.), alkoxycarbonyl group (eg meso Ruoxycarbonyl 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, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclyl group) Hexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group) Octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonyl) Amino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthy Carbonylamino group, etc.), carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylamino) Carbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group) , Dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethyl) Rufinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) , Butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (for example, amino group, ethyl group) Amino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridy Amino groups, etc.), halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, etc.), fluorinated hydrocarbon groups (eg, fluoromethyl groups, trifluoromethyl groups, pentafluoroethyl groups, pentafluorophenyl groups, etc.), And cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.).

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

  Preferred substituents are an alkyl group, a cycloalkyl group, a fluorinated hydrocarbon group, an aryl group, and an aromatic heterocyclic group.

  As the divalent linking group, in addition to hydrocarbon groups such as alkylene, alkenylene, alkynylene, and arylene, those containing a hetero atom may be used, and a thiophene-2,5-diyl group, pyrazine-2, It may be a divalent linking group derived from a compound having an aromatic heterocyclic ring (also called a heteroaromatic compound) such as a 3-diyl group, or may be a chalcogen atom such as oxygen or sulfur. . Further, it may be a group such as an alkylimino group, a dialkylsilanediyl group, or a diarylgermandiyl group that connects and connects heteroatoms.

  A mere bond is a bond that directly bonds the connecting substituents together.

In the present invention, Z _{1 in the} general formula (1) is preferably a 6-membered ring. Thereby, luminous efficiency can be made higher. Furthermore, the lifetime can be further increased.

In the present invention, it is preferable that the Z ₂ in the general formula (1) is a 6-membered ring. Thereby, luminous efficiency can be made higher. Furthermore, the lifetime can be further increased.

Furthermore, it is preferable that Z ₁ and Z _{2 in} the general formula (1) are both 6-membered rings because the luminous efficiency can be further increased. Furthermore, it is preferable because the lifetime can be further increased.

  Preferred among the compounds represented by the general formula (1) are compounds represented by the general formulas (1-1) to (1-13).

In the general formula (1-1), R _{501 to} R ₅₀₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-1), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-2), R _{511 to} R ₅₁₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-2), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-3), R _{521 to} R ₅₂₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-3), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-4), R _{531 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-4), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In Formula (1-5), R ₅₄₁ ~R ₅₄₈ each independently represents a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-5), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-6), R _{551 to} R ₅₅₈ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-6), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-7), R _{561 to} R ₅₆₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-7), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-8), R _{571 to} R ₅₇₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-8), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

  In the general formula (1-9), R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.

  By using the compound represented by the said General formula (1-9), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as a longer life organic EL element.

  In the general formula (1-10), R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.

  By using the compound represented by the general formula (1-10), an organic EL device with higher luminous efficiency can be obtained. Furthermore, a long-life organic EL element can be obtained.

In addition, the compound represented by the general formula (1) is preferably a compound having at least one group represented by any one of the general formulas (2-1) to (2-8). In particular, it is more preferable to have 2 to 4 groups represented by any one of the general formulas (2-1) to (2-8) in the molecule. In this case, the structure represented by the general formula (1) includes a case where the portion excluding R ₁₀₁ is replaced by the general formulas (2-1) to (2-8).

  At this time, the compounds represented by the general formulas (3) to (17) are particularly preferable for obtaining the effects of the present invention.

In the general formula (3), R _{601 to} R ₆₀₆ represent a hydrogen atom or a substituent, and at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (3), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (4), R _{611 to} R ₆₂₀ represent a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (4), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (5), R _{621 to} R ₆₂₃ represent a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (5), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (6), R _{631 to} R ₆₄₅ represent a hydrogen atom or a substituent, and at least one of R _{631 to} R ₆₄₅ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (6), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (7), R _{651 to} R ₆₅₆ represent a hydrogen atom or a substituent, and at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented. na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6.

  By using the compound represented by the general formula (7), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (8), R _{661 to} R _{672 each} represents a hydrogen atom or a substituent, and at least one of R _{661 to} R ₆₇₂ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (8), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (9), R _{681 to} R ₆₈₈ represent a hydrogen atom or a substituent, and at least one of R _{681 to} R ₆₈₈ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (9), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (10), R _{691 to} R ₇₀₀ represent a hydrogen atom or a substituent, and at least one of R _{691 to} R ₇₀₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

In the general formula (10), the divalent linking group represented by L ₁ is an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene). Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.) ), Cyclopentylene group (for example, 1,5-cyclopentanediyl group, etc.), alkenylene group (for example, vinylene group, propenylene group, etc.), alkynylene group (for example, ethynylene group, 3-pentynylene group, etc.), In addition to hydrocarbon groups such as arylene groups, groups containing heteroatoms (eg, —O , —S— and the like, a divalent group containing a chalcogen atom, —N (R) — group, wherein R represents a hydrogen atom or an alkyl group, and the alkyl group in the general formula (1), And the same as the alkyl group represented by R ₁₀₁ .

  In each of the alkylene group, alkenylene group, alkynylene group, and arylene group, at least one of carbon atoms constituting the divalent linking group is a chalcogen atom (oxygen, sulfur, etc.) or -N (R). -It may be substituted with a group or the like.

Furthermore, as the divalent linking group represented by L ₁ , for example, a group having a divalent heterocyclic group is used. For example, an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, a pyrrolindiyl group. Group, imidazoline diyl group, imidazolidine diyl group, pyrazolidine diyl group, pyrazoline diyl group, piperidine diyl group, piperazine diyl group, morpholine diyl group, quinuclidine diyl group and the like, and thiophene-2,5- A divalent linking group derived from a compound having an aromatic heterocycle (also referred to as a heteroaromatic compound) such as a diyl group or a pyrazine-2,3-diyl group may be used.

  Further, it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilanediyl group, or a diarylgermandiyl group.

  By using the compound represented by the general formula (10), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the compounds represented by the general formula (11) to the general formula (15), the substituents represented by R ₁ and R ₂ are the substituents represented by R ₁₀₁ in the general formula (1). At the same time as the group.

In the general formula (15), examples of the 6-membered aromatic heterocyclic ring each containing at least one nitrogen atom represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ include a pyridine ring and a pyridazine ring. , Pyrimidine ring, pyrazine ring and the like.

In the general formula (16), examples of the 6-membered aromatic heterocycle each containing at least one nitrogen atom represented by Z ₁ and Z ₂ include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Etc.

In the general formula (16), the arylene groups represented by Ar ₁ and Ar ₂ include o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, and pyrenediyl group. Group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group, sexi Examples thereof include a phenyldiyl group, a septiphenyldiyl group, an octylphenyldiyl group, a nobiphenyldiyl group, and a deciphenyldiyl group. The arylene group may further have a substituent described later.

In the general formula (16), the divalent aromatic heterocyclic groups represented by Ar ₁ and Ar ₂ are furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzo Imidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, And divalent groups derived from a ring in which the carbon atom of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic group may have a substituent represented by R ₁₀₁ .

In the general formula (16), the divalent linking group represented by L has the same meaning as the divalent linking group represented by L ₁ in the general formula (10), but is preferably an alkylene group. , —O—, —S— and the like, are divalent groups containing a chalcogen atom, most preferably an alkylene group.

In the general formula (17), in Ar _1, Ar _2, the arylene group represented by each, in the general formula (16), it is synonymous with the arylene group represented by each of Ar _1, Ar _2.

In the general formula (17), an aromatic heterocyclic group represented by each of Ar _1, Ar _2, in the general formula (16), the divalent aromatic heterocyclic ring represented by each of Ar _1, Ar ₂ Synonymous with group.

In the general formula (17), examples of the 6-membered aromatic heterocycle each containing at least one nitrogen atom represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ include a pyridine ring and a pyridazine ring. , Pyrimidine ring, pyrazine ring and the like.

In the general formula (17), the divalent linking group represented by L has the same meaning as the divalent linking group represented by L ₁ in the general formula (10), but is preferably an alkylene group. , —O—, —S— and the like, are divalent groups containing a chalcogen atom, most preferably an alkylene group.

  Although the specific example of a compound represented by General formula (1) based on this invention below is shown, this invention is not limited to these.

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

  << Synthesis of Exemplified Compound 73 >>

  To a mixed solution obtained by adding 6.87 g of 4,4′-diiodobiphenyl and 6.00 g of β-carboline in 50 ml of N, N-dimethylacetamide, 4.5 g of copper powder and 7.36 g of potassium carbonate were added for 15 hours. Heated to reflux. After allowing to cool, water chloroform was added, and insolubles were removed by filtration. The organic layer was separated, washed with water and saturated brine, and concentrated under reduced pressure. The obtained residue was dissolved in acetic acid, treated with activated carbon, and recrystallized to give 4.2 g of colorless crystals of Exemplified Compound 73. Got.

The structure of Exemplified Compound 73 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplified compound 73 are shown below.

Colorless crystals, melting point 200 ° C
MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.3-7.5 (m, 2H), 7.5-7.6 (m, 4H), 7.7-7.8 (m, 4H), 7.9-8.0 (m, 4H), 8.06 (d, J = 5.1 Hz, 2H), 8.24 (d, J = 7.8 Hz, 2H), 8.56 ( d, J = 5.1 Hz, 2H), 8.96 (s, 2H)
<< Synthesis of Exemplary Compound 74 >>

  0.32 g of palladium acetate and 1.17 g of tri-tert-butylphosphine were dissolved in 10 ml of anhydrous toluene, 50 mg of sodium borohydride was added, and the mixture was stirred at room temperature for 10 minutes, then δ-carboline 5.00 g, 4, 4 5.87 g of '-diiodobiphenyl and 3.42 g of sodium tert-butoxide were dispersed in 50 ml of anhydrous xylene and stirred at reflux temperature for 10 hours under a nitrogen atmosphere. The resulting reaction mixture was allowed to cool, chloroform and water were added to separate the organic layer, the organic layer was washed with water and saturated brine, and then concentrated under reduced pressure. The resulting residue was dissolved in tetrahydrofuran. After the activated carbon treatment, 5.0 g of colorless crystals of Exemplified Compound 74 was obtained by recrystallization.

The structure of exemplary compound 74 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplified compound 74 are shown below.

MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.37 (dd, J = 4.7 Hz, J = 8.3 Hz, 2H), 7.4-7.5 (m, 2H), 7. 5-7.6 (m, 4H), 7.7-7.8 (m, 4H), 7.81 (dd, J = 1.2 Hz, J = 8.3 Hz, 2H), 7.9-8 0.0 (m, 4H), 8.48 (d, J = 7.8 Hz, 2H), 8.65 (dd, J = 1.2 Hz, J = 4.6 Hz, 2H)
<< Synthesis of Exemplary Compound 60 >>

  To a mixed solution in which 6.87 g of 4,4′-diiodobiphenyl and 6.00 g of γ-carboline were added to 50 ml of N, N-dimethylacetamide, 4.5 g of copper powder and 7.36 g of potassium carbonate were added for 15 hours. Heated to reflux. After allowing to cool, water chloroform was added, and insolubles were removed by filtration. The organic layer was separated, washed with water and saturated brine, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography and crystallized in dichloromethane / cyclohexane to give colorless crystals of Exemplified Compound 60. 4.3 g was obtained.

The structure of the exemplary compound 60 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplary compound 60 are shown below.

MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.4-7.4 (m, 4H), 7.4-7.5 (m, 4H), 7.7-7.8 (m, 4H) 7.9-8.0 (m, 4H), 8.25 (d, J = 7.8 Hz, 2H), 8.57 (d, J = 5.6 Hz, 2H), 9.42 (s) , 1H)
<< Synthesis of Exemplary Compound 144 >>

  0.16 g of palladium acetate and 0.58 g of tri-tert-butylphosphine are dissolved in 10 ml of anhydrous toluene, 25 mg of sodium borohydride is added and stirred for 10 minutes at room temperature, then 2.00 g of δ-carboline, intermediate a3 20 g and 1.37 g of sodium tert-butoxide were dispersed in 50 ml of anhydrous xylene and stirred at reflux temperature for 10 hours under a nitrogen atmosphere. After allowing to cool, chloroform and water are added to separate the organic layer. The organic layer is washed with water and saturated brine and then concentrated under reduced pressure. The resulting residue is recrystallized from acetic acid to give colorless colorless compound of Exemplified Compound 144. 1.5 g of crystals were obtained.

The structure of the exemplary compound 144 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 144 are as follows.

MS (FAB) m / z: 647 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 1.80 (S, 12H), 7.27 (S, 4H), 7.34 (dd, J = 4.9 Hz, J = 8.3 Hz, 2H ), 7.3-7.4 (m, 2H), 7.4-7.5 (m, 12H), 7.76 (dd, J = 1.3 Hz, J = 8.3 Hz, 2H), 8 .45 (d, J = 7.8 Hz, 2H), 8.63 (dd, J = 1.3 Hz, J = 4.9 Hz, 2H)
<< Synthesis of Exemplary Compound 143 >>

  Add 4,5'-dichloro-3,3'-bipyridyl 0.85 g, diamine b 0.59 g, dibenzylideneacetone palladium 44 mg, imidazolium salt 36 mg, sodium tert-butoxide 1.09 g to 5 ml dimethoxyethane, 80 The mixture was stirred at 24 ° C. for 24 hours. After allowing to cool, chloroform and water were added to separate the organic layer, and the organic layer was washed with water and saturated brine and then concentrated under reduced pressure. The obtained residue was recrystallized from ethyl acetate to give Example Compound 143. 0.3 g of colorless crystals was obtained.

The structure of the exemplary compound 143 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 143 are shown below.

MS (FAB) m / z 639 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.46 (d, J = 5.7 Hz, 4H), 7.6-7.7 (m, 4H), 7.8-7.9 ( m, 4H), 8.67 (d, J = 5.7 Hz, 4H), 9.51 (S, 4H)
<< Synthesis of Exemplary Compound 145 >>
In the synthesis of Exemplified Compound 143, the same procedure was carried out except that one pyridine ring of 4,4'-dichloro-3,3'-bipyridyl was changed to benzene and 3- (2-chlorophenyl) -4-chloropyridine was used. Example compound 145 was synthesized.

The structure of exemplary compound 145 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 145 are shown below.

MS (FAB) m / z 637 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 7.3-7.4 (m, 2H), 7.6-7.7 (m, 4H), 7.7-7.8 (m, 4H) ) 7.8-7.9 (m, 4H), 8.06 (d, J = 5.3 Hz, 2H), 8.23 (d, J = 7.8 Hz, 2H), 8.56 (d, J = 5.3 Hz, 2H), 8.96 (S, 2H)
In addition to the above synthesis examples, the azacarbazole rings and chloroplasts of these compounds are described in J. Org. Chem. Soc. Perkin Trans. 1, 1505-1510 (1999), Pol. J. et al. Chem. , 54, 1585 (1980), (Tetrahedron Lett. 41 (2000), 481-484). Introduction of the synthesized azacarbazole ring or its chloroplast to the core or linking group of an aromatic ring, heterocycle, alkyl group, etc. is well known, such as Ullman coupling, coupling using Pd catalyst, Suzuki coupling, etc. This method can be used.

  The compound according to the present invention preferably has a molecular weight of 400 or more, more preferably 450 or more, still more preferably 600 or more, and particularly preferably a molecular weight of 800 or more. Thereby, the glass transition temperature is raised, the thermal stability is improved, and the life can be further extended.

<< Compounds Represented by General Formulas (2) to (5) >>
The compounds represented by the general formulas (2) to (5) according to the present invention will be described.

  The compounds represented by the general formulas (2) to (5) according to the present invention are preferably used as a hole blocking material in the hole blocking layer of the organic EL device of the present invention.

In the general formulas (2) to (5), examples of the alkyl group represented by R _{a1 to} R _a3 , R _{b1 to} R _b4 , R _c1 , R _c2 include a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and the like.
In the general formulas (2) to (5), examples of the aryl group represented by R _{a1 to} R _a3 , R _{b1 to} R _b4 , R _c1 , and R _c2 include a phenyl group, a tolyl group, a xylyl group, Biphenylyl group, naphthyl group, anthryl group, phenanthryl group and the like can be mentioned.

In the general formulas (2) to (5), examples of the aromatic heterocyclic group represented by R _{a1 to} R _a3 , R _{b1 to} R _b4 , R _c1 , and R _c2 include a furyl group, a thienyl group, Pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (for example, constituting carboline ring of carbolinyl group) One in which one of the carbon atoms is replaced with a nitrogen atom.), A phthalazinyl group, and the like.

In the general formulas (2) to (5), the aryl group and the heterocyclic group which may have a substituent represented by A _{ra to} A _rc are R _{a1 to} R _a3 , R _{b1 to} R _b4 , R _c1 and _{Rc2 have the same meanings} as the aryl group and aromatic heterocyclic group, respectively.

  Hereinafter, although the specific example of a compound represented by General formula (2)-(5) is enumerated below, this invention is not limited to these.

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

  The compound represented by the general formula (B) according to the present invention is preferably used as a hole blocking material in the hole blocking layer of the organic EL device of the present invention.

In the general formula (B), the substituents represented by Ra to Rg have the same meaning as the substituent represented by R ₁₀₁ in the general formula (1).

  Hereinafter, although the specific example of a compound represented by general formula (B) is shown, this invention is not limited to these.

  Moreover, you may use said compound based on this invention for the other structural layer of an organic EL element as needed from a viewpoint of various physical-property control of an organic EL element.

  The compound according to the present invention is a material for organic EL elements (backlight, flat panel display, illumination light source, display element, electrophotographic light source, recording light source, exposure light source, reading light source, sign, signboard, interior, optical communication device, etc.) Other uses include organic semiconductor laser materials (recording light source, exposure light source, reading light source optical communication device, electrophotographic light source, etc.), electrophotographic photosensitive material, organic TFT element It can be used in a wide range of fields such as materials (organic memory elements, organic arithmetic elements, organic switching elements), organic wavelength conversion element materials, photoelectric conversion element materials (solar cells, optical sensors, etc.).

  Next, the constituent layers of the organic EL device of the present invention will be described in detail.

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 << Anode >>
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (100 μm or more) Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the 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 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

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

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

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, 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. You may let them.

  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 desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

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

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

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

  In this invention, it is preferable to contain the compound which concerns on this invention mentioned above as a hole blocking material of a hole blocking layer. Thereby, it can be set as an organic EL element with much higher luminous efficiency. Furthermore, the lifetime can be further increased.

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

<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.

(Host compound)
The light emitting layer of the organic EL device of the present invention preferably contains the following host compound and phosphorescent compound (also referred to as phosphorescent compound). Preference is given to using the compounds according to the invention. Thereby, the luminous efficiency can be further increased. Moreover, you may contain compounds other than the compound which concerns on said this invention as a host compound.

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

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

  As these known host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable.

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

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

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

(Phosphorescent compound (phosphorescent compound))
The material used for the light emitting layer (hereinafter referred to as a light emitting material) preferably contains a phosphorescent compound at the same time as the host compound. Thereby, it can be set as an organic EL element with higher luminous efficiency.

  The phosphorescent compound according to the present invention is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0.2 at 25 ° C. 01 or more compounds. The phosphorescence quantum yield is preferably 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.

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

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

  The phosphorescent compound used in the present invention is preferably a complex compound containing a group 8 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex system). Compound) and rare earth complexes, and most preferred is an iridium compound.

  Although the specific example of a phosphorescent compound is shown below, this invention is not limited to these. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

  In the present invention, the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited. In principle, the phosphorescent compound can be obtained by selecting a central metal, a ligand, a ligand substituent, and the like. However, it is preferable that the phosphorescent compound has a maximum phosphorescence emission wavelength of 380 nm to 480 nm. With such a blue phosphorescent organic EL element and a white phosphorescent organic EL element, the luminous efficiency can be further increased.

  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 Minolta) is applied to the CIE chromaticity coordinates.

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

《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, stilbenes Derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like can be given.

  As the hole transport material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 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.

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

《Electron transport layer》
The electron transport layer 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), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as an electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and similarly to the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC can be used. A semiconductor can also be used as an electron transport 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.

<Substrate>
The organic EL device of the present invention is preferably formed on a substrate.

  The substrate (hereinafter also referred to as a substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc. Although there is no restriction | limiting in particular, As a board | substrate used preferably, glass, quartz, and a transparent resin film can be mentioned, for example. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

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

  The external extraction efficiency at room temperature for light emission of the organic electroluminescence device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

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

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

  First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode. To do. Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, is formed thereon.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (for example, a spin coating method, a casting method, an ink jet method, a printing method) as described above. From the viewpoint of difficulty in generating pinholes, vacuum deposition, spin coating, ink jet, and printing are particularly preferable. Further, a different film forming method may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 ° C. to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, a vapor deposition rate of 0. It is desirable to select appropriately within the range of 01 nm / second to 50 nm / second, substrate temperature −50 ° C. to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 nm to 200 nm.

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

  The multi-color display device of the present invention is provided with a shadow mask only at the time of forming a light emitting layer, and other layers are common, so patterning such as a shadow mask is unnecessary, and vapor deposition, casting, spin coating, inkjet A film can be formed by a method or a printing method.

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

  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 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

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

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Illumination devices include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. However, it is not limited to these. Moreover, you may use as an organic EL element which gave the organic EL element of this invention the resonator structure.

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

  The organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of three primary colors of blue, green, and blue, or two using a complementary color relationship such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

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

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, an ortho metalated complex (Ir complex, so that it may suit the wavelength range corresponding to CF (color filter) characteristic) Pt complex etc.) or any known light emitting material may be selected and combined to whiten.

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

  Others such as backlights for watches, signboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. There are a wide range of uses such as household appliances.

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

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

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

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

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

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

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below. FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at orthogonal positions (details are shown in FIG. Not shown).

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.

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

  FIG. 3 is a schematic diagram of a pixel.

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

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

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

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

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

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

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

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

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

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

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

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 is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD is put in a molybdenum resistance heating boat, and 200 mg of CBP as a host compound is put in another resistance heating boat made of molybdenum. 200 mg of bathocuproin (BCP) was put in a molybdenum resistance heating boat, 100 mg of Ir-12 was put in another resistance heating boat made of molybdenum, and 200 mg of Alq ₃ was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus. .

Next, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is heated by heating, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and hole transport A layer was provided. Further, the heating boat containing CBP and Ir-12 is energized and heated, and a light emitting layer is provided by co-deposition on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature. Further, the heating boat containing B-1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer. Further, the heating boat containing Alq ₃ is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-15 >>
In the production of the organic EL device 1-1, CBP used as the host compound of the light emitting layer is replaced with a material for the organic EL device shown in Table 1 to make the host compound, and B-1 used as the hole blocking compound is shown. 1-2 to 1-15 were produced in the same manner as the organic EL element 1-1 except that the hole transport material shown in 1 was used.

<< Evaluation of Organic EL Elements 1-1 to 1-15 >>
The following evaluation was performed about obtained organic EL element 1-1 to 1-15.

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

"lifespan"
When driving at a constant current of ^2.5 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured, and this was calculated as the half-life time (
It was used as an index of life as τ0.5). For measurement, the spectral radiance meter CS-100
0 (Minolta) was used.

  Moreover, the measurement results of the external extraction quantum efficiency and lifetime in Table 1 are expressed as relative values when the measured value of the organic EL element 1-1 is 100.

  From Table 1, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 2
<< Preparation of Organic EL Element 2-1 >>
In the production of the organic EL element 1-1 of Example 1, an organic EL element 2-1 was produced in the same manner except that the dopant compound of the light emitting layer was changed to Ir-1.

<< Production of Organic EL Elements 2-2 to 2-15 >>
Subsequently, in the production of the organic EL device 2-1, the CBP used as the host compound of the light emitting layer is replaced with a material for the organic EL device shown in Table 2 to be used as a host compound, and B- Organic EL elements 2-2 to 2-15 were produced in the same manner except that the compounds shown in Table 2 were used instead of 1.

  For each of the obtained organic EL elements 2-1 to 2-15, the external extraction quantum efficiency and lifetime were measured and evaluated in the same manner as described in Example 1. Moreover, the measurement results of the external extraction quantum efficiency and lifetime in Table 2 were expressed as relative values when the measured value of the organic EL element 2-1 was 100.

  The obtained results are shown in Table 2.

  From Table 2, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 3: (Example of lighting device, using white organic EL element)
In the organic EL element 2-19 produced in Example 2, it was the same as the organic EL element 2-3 except that Ir-1 used in the light emitting layer was changed to a mixture of Ir-1, Ir-9, and Ir-12 The organic EL element 2-19W produced by the method was used. The non-light emitting surface of the organic EL element 2-19W was covered with a glass case to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life. FIG. 5 is a schematic view of the lighting device, and FIG. 6 is a cross-sectional view of the lighting device. The organic EL element 101 is covered with a glass cover 102 and connected with a power line (anode) 103 and a power line (cathode) 104. 105 is a cathode and 106 is an organic EL layer. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

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

Explanation of symbols

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

Claims (38)

In the organic electroluminescence device having at least a light emitting layer and a hole blocking layer as a constituent layer,
The light emitting layer contains a compound represented by the following general formula (1), and the hole blocking layer includes the following general formulas (2) to (5), the general formula (1) and the following general formula (B). An organic electroluminescence device comprising at least one compound selected from the group consisting of:

[Wherein, Z ₁ represents an aromatic heterocyclic ring which may have a substituent, Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may each have a substituent, Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent. ]

_{Wherein, R a1 ~R a3, R b1} ~R b4, R c1, R c2 , each may have a substituent, an alkyl group, an aryl group or an aromatic heterocyclic group, A _ra -A _rc represents an aryl group or an aromatic heterocyclic group, each optionally having a substituent. ]

[Wherein, Ra to Rg each represents a hydrogen atom or a substituent, and the substituents represented by Ra to Rg may be the same or different. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. ] 2. The organic electroluminescence device according to claim 1, wherein Z _{1 of the} compound represented by the general formula (1) is a 6-membered ring. The organic electroluminescence device according to claim 1 or 2, wherein Z _{2 of the} compound represented by the general formula (1) is a 6-membered ring. The organic electroluminescent element according to claim 1, wherein Z _{3 of the} compound represented by the general formula (1) is a bond. The organic electroluminescence device according to any one of claims 1 to 4, wherein the compound represented by the general formula (1) has a molecular weight of 450 or more. The compound represented by said general formula (1) is represented by the following general formula (1-1), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{501 to} R ₅₀₇ each independently represents a hydrogen atom or a substituent. ] The compound represented by said general formula (1) is represented by the following general formula (1-2), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{511 to} R ₅₁₇ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-3).

[Wherein, R _{521 to} R ₅₂₇ each independently represents a hydrogen atom or a substituent. ] The compound represented by said general formula (1) is represented by the following general formula (1-4), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{531 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-5).

Wherein, R ₅₄₁ to R ₅₄₈ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-6).

[Wherein, R _{551 to} R ₅₅₈ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-7).

[Wherein, R _{561 to} R ₅₆₇ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-8).

[Wherein, R _{571 to} R ₅₇₇ each independently represents a hydrogen atom or a substituent. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-10).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ] The compound represented by the general formula (1) has at least one group represented by any one of the following general formulas (2-1) to (2-8). Organic electroluminescent element of any one of these.

_{Wherein, R 502 ~R 507, R 512} ~R 517, R 522 ~R 527, R 532 ~R 537, R 542 ~R 548, R 552 ~R 558, R 562 ~R 567, R 572 ~R ₅₇₇ each independently represents a hydrogen atom or a substituent, and the substituents may be the same or different. ] The compound represented by said general formula (1) is represented by the following general formula (3), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{601 to} R ₆₀₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (4).

[Wherein, R _{611 to} R ₆₂₀ each independently represents a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The compound represented by said general formula (1) is represented by the following general formula (5), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R _{621 to} R ₆₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{621 to} R ₆₂₃ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (6).

[Wherein R _{631 to} R ₆₄₅ each independently represents a hydrogen atom or a substituent, and at least one of R _{631 to} R ₆₄₅ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (7).

[Wherein, R _{651 to} R ₆₅₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6. ] The compound represented by said general formula (1) is represented by the following general formula (8), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein R _{661 to} R ₆₇₂ each independently represents a hydrogen atom or a substituent, and at least one of R _{661 to} R ₆₇₂ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (9).

[Wherein, R _{681 to} R ₆₈₈ independently represent a hydrogen atom or a substituent, and at least one of R _{681 to} R ₆₈₈ is represented by the general formulas (2-1) to (2-4). Represents at least one group selected from the following groups. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (10).

[Wherein, R _{691 to} R ₇₀₀ each independently represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group. At least one of R _{691 to} R ₇₀₀ represents at least one group selected from the groups represented by the general formulas (2-1) to (2-4). ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (11).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (12).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The compound represented by said general formula (1) is represented by the following general formula (14), The organic electroluminescent element of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (15).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom. ] The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (16).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ and Z ₂ each represent a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (17).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent a divalent arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ] The phosphorescent light emitting layer as the constituent layer, and the phosphorescent light emitting layer contains the compound represented by the general formula (1). Organic electroluminescence element. At least 1 layer of the said structural layer is a hole-blocking layer, The said hole-blocking layer contains the compound represented by the said General formula (1), The any one of Claims 1-32 characterized by the above-mentioned. The organic electroluminescent element of the item. A display device comprising the organic electroluminescence element according to claim 1. Luminescence is substantially white, The organic electroluminescent element of any one of Claims 1-33 characterized by the above-mentioned. 36. A display device comprising the organic electroluminescence element according to claim 35. 36. An illumination device comprising the organic electroluminescence element according to claim 35. 38. A display device comprising the illumination device according to claim 37 and a liquid crystal element as display means.

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