JP2006120689A - Organic electroluminescence element, display device and illumination device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic EL element which can finely adjust a luminescent color and which has high emission efficiency and a long life, and to provide a display device using the element and an illumination device. <P>SOLUTION: In the organic electroluminescent element having a structure layer between a cathode and an anode, the structure layer has a plurality of light emitting layers. At least one layer of the structure layer comprises at least one type of compound shown by a general formula (1). In the general formula (1), Z<SB>1</SB>shows an aromatic heterocycle, and Z<SB>2</SB>shows the aromatic heterocycle or an aromatic hydrocarbon cycle. Z<SB>3</SB>shows a divalent link group or a simple joint hand. R<SB>101</SB>shows a hydrogen atom or substituent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic electroluminescence element, a display device using the same, and an illumination device.

  Organic electroluminescence elements (hereinafter also referred to as organic EL elements or simply elements) that can be used as display devices and planar light sources are injected from the anode and the cathode by applying a current to a specific organic material. It is a self-luminous element that utilizes the principle that an organic material emits light by the combination of generated electrons.

  The light emission of such organic materials has been known for a long time, but it has not received much attention because of its very low luminous efficiency.

  However, in 1987, Tang et al. Stacked organic compounds with different hole and electron carrier transport properties to increase the efficiency of the organic EL device, and the holes and electrons were injected in a balanced manner from the anode and cathode, respectively. In addition, by using a thin film having a thickness of 2000 mm or less between the anode and the cathode, it has succeeded in flowing a current using a space charge limited current to a non-conductive organic material (Tang et al., Appl. Phys. Lett., 51, 913). With these ideas, they succeeded in driving the electroluminescence of organic materials, which previously required a high driving voltage, at a lower voltage of 10 V or less.

  Since such a report by Tang et al. Was made, research on organic EL element materials and organic EL elements having organic materials as constituent elements has become active. Compared to inorganic compounds, organic compounds give various emission peaks due to their diversity. Therefore, even in organic EL elements, it is possible to obtain desired emission peaks by appropriate molecular design of organic materials.

  Further, by using a plurality of light emitting materials for the organic EL element, it is possible to adjust the color more delicately, and it is possible to design a more efficient organic EL element.

  As the luminescent molecule, organic EL element development using mainly a fluorescent luminescent organic material was performed, but the generation probability of singlet excitons that give fluorescence emission among excitons generated by carrier binding is 25%, Since the external extraction efficiency is about 20%, the upper limit of the external quantum efficiency is about 5%, and high efficiency has been desired.

  On the other hand, an organic EL material using a phosphorescent organic material utilizing light emission from triplet excitons, which account for 75% of excitons generated by carrier bonding, has been reported. As a result, the upper limit of the external quantum efficiency is improved up to 20%, so that full-scale practical research and development of organic EL elements are being conducted.

  However, no organic EL element having high characteristics that can be put into practical use has been reported so far. This is because there is a problem of the lifetime of the organic EL element which can be said to be the fate of the charge injection type device.

  As described above, the light emission of the organic EL element is caused by the combination of holes injected into the organic material and carriers called electrons. Considering the behavior of an organic material from a chemical point of view, it can be said that carrier injection occurs from a stable neutral molecule via an unstable radical state and gives light emission by carrier injection.

  Injecting a high-density current to obtain high brightness means that these unstable radical states are frequently generated, and it is easily imagined that there is a trade-off between current density and lifetime. It is a problem.

  Therefore, what is important is an organic material constituting the organic EL element. As an organic material, a material resistant to redox, in other words, a chemically stable organic compound capable of stably presenting a radical anion and a radical cation state, and less susceptible to heat generated by outside temperature and carrier bonding, By using a thermally stable organic compound as a material, the lifetime of the organic EL element can be extended.

  Furthermore, in order to facilitate the injection of carriers as well as the light emitting layer between the cathode and the anode, an electron transport layer and an electron injection layer are provided on the cathode side of the light emitting layer, and a hole transport layer and a hole injection layer are provided on the anode side. A device configuration in which layers are stacked, and a device configuration having a hole blocking layer on the cathode side of the light emitting layer and an electron blocking layer on the anode side for confining excitons have been reported.

  Furthermore, several methods are conceivable for realizing an organic EL element with high efficiency and long life, and an element configuration having a charge generation layer between the cathode and the anode is also considered as one of the promising methods. Incorporation of a charge generation layer into an organic EL element has been reported by Kido et al. Since 2002 (see, for example, Patent Document 1 and Non-Patent Document 1).

  The charge generation layer is one of the constituent layers constituting the organic EL element, and is a layer that is between the organic layers including the light emitting layer and electrically insulates the organic layer. The charge generation layer is formed by joining an organic layer including a light emitting layer sandwiched between a cathode and an anode in series, and when a predetermined voltage is applied to the element, holes are formed from the anode to the cathode and from the cathode to the anode. At the same time as electrons flow, holes can be injected from the charge generation layer to the cathode side of the device and electrons can be injected to the anode side. As a result, although all the organic layers including the light emitting layer sandwiched between the cathode and the anode are electrically insulated, as a result, the organic layers can behave as being arranged in series.

  By using the charge generation layer, it is possible to generate photons by the number of light emitting layers having the charge generation layer between the number of electrons measured by an external circuit. In other words, compared to an organic EL device composed of only one light-emitting unit, an organic EL device having n light-emitting layers and a charge generation layer between each light-emitting layer means that the internal quantum efficiency is simply multiplied by n. To do.

  According to this, the upper limit of the internal quantum efficiency and the external quantum efficiency is theoretically eliminated, and a more efficient organic EL element can be manufactured.

  Furthermore, if the luminous efficiency is increased by a factor of k, the amount of current that gives the same luminance as in the case of an organic EL device having only one light emitting layer is 1 / k. The burden can be reduced, and thereby the life of the element can be extended.

However, the organic materials used in the devices disclosed so far have not yet provided a device life sufficient for practical use.
JP 2003-272860 A 49th Japan Society of Applied Physics Related Lectures Proceedings, P1308

  The present invention has been made in view of the above circumstances, and provides an organic EL element that can finely adjust a light emission color and has high light emission efficiency and long life, and a display device and an illumination device using the organic EL element. That is.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In an organic electroluminescence device having a constituent layer between a cathode and an anode, the constituent layer has a plurality of light emitting layers, and at least one of the constituent layers contains at least one compound represented by the following general formula (1) An organic electroluminescence element characterized by comprising:

(In the formula, Z ₁ represents an aromatic heterocyclic ring, Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring, Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom. Or represents a substituent.)
(Claim 2)
The organic electroluminescence device according to claim 1, wherein at least one of the plurality of light emitting layers contains at least one compound represented by the general formula (1).

(Claim 3)
The constituent layer has at least one hole blocking layer, and at least one layer of the hole blocking layer contains at least one compound represented by the general formula (1). 2. The organic electroluminescence device according to 2.

(Claim 4)
The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-1).

(In the formula, R _{501 to} R ₅₀₇ each independently represent a hydrogen atom or a substituent.)
(Claim 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 (1-2).

(Wherein R _{511 to} R ₅₁₇ each independently represents a hydrogen atom or a substituent)
(Claim 6)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-3).

(Wherein R _{521 to} R ₅₂₇ each independently represents a hydrogen atom or a substituent)
(Claim 7)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-4).

(In the formula, R _{531 to} R ₅₃₇ 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 (1-5).

(Wherein, represents a hydrogen atom or a substituent each independently R ₅₄₁ to R ₅₄₈ in.)
(Claim 9)
The organic electroluminescent element 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 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 (1-7).

(In the formula, R _{561 to} R ₅₆₇ each independently represents a hydrogen atom or a substituent.)
(Claim 11)
The organic electroluminescent element 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 12)
The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

(In the formula, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.)
(Claim 13)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-10).

(In the formula, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.)
(Claim 14)
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 (2-10). The organic electroluminescent element of any one of Claims.

(In the formula, R _{502 to} R ₅₀₇ , R _{512 to} R ₅₁₇ , R _{522 to} R ₅₂₇ , R _{532 to} R ₅₃₇ , R _{542 to} R ₅₄₈ , R _{552 to} R ₅₅₈ , R _{562 to} R ₅₆₇ , R _{572 to} R ₅₇₇ , R _{582 to} R ₅₈₈ and R _{592 to} R ₅₉₈ each independently represent a hydrogen atom or a substituent, and the substituents may be the same or different.
(Claim 15)
The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (3).

(Wherein R _{601 to} R ₆₀₆ each independently represents a hydrogen atom or a substituent, but at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-10)). Represents at least one group selected from the group)
(Claim 16)
The organic electroluminescence device according to any one of claims 1 to 3, 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 (2-10)). Represents at least one group selected from the group)
(Claim 17)
The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (5).

(Wherein R _{621 to} R ₆₂₃ each independently represents a hydrogen atom or a substituent, but at least one of R _{621 to} R ₆₂₃ is represented by the general formulas (2-1) to (2-10)). Represents at least one group selected from the group)
(Claim 18)
The organic electroluminescence device according to any one of claims 1 to 3, 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 (2-10)). Represents at least one group selected from the group)
(Claim 19)
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 represent a hydrogen atom or a substituent, but at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-10)) And at least one group selected from the group, na represents an integer of 0 to 5, nb represents an integer of 1 to 6, and the sum of na and nb is 6.)
(Claim 20)
The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (8).

(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 above general formulas (2-1) to (2-10)) Represents at least one group selected from the group)
(Claim 21)
The organic electroluminescence device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (9).

(Wherein R _{681 to} R ₆₈₈ each independently represents 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 (2-10)). Represents at least one group selected from the group)
(Claim 22)
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, L ₁ represents a divalent linking group. At least one of R _{691 to} R ₇₀₀ represents the above general formula (2-1). ) Represents at least one group selected from the groups represented by (2-10).
(Claim 23)
The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (11).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5.)
(Claim 24)
The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (12).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5.)
(Claim 25)
The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5.)
(Claim 26)
The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (14).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that 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 (15).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5 Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocycle containing at least one nitrogen atom.
(Claim 28)
The organic electroluminescence device according to any one of claims 1 to 3, 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, Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ and Z ₂ each represent at least one nitrogen atom. A 6-membered aromatic heterocyclic ring containing 1 and L represents a divalent linking group.)
(Claim 29)
The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (17).

(In the formula, o and p each represent an integer of 1 to 3, Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ and Z ₄ are Each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group.)
(Claim 30)
30. The organic electroluminescent element according to claim 1, further comprising a charge generation layer in at least one layer between the plurality of light emitting layers.

(Claim 31)
31. The organic electroluminescence device according to claim 30, further comprising a charge generation layer in each layer between the plurality of light emitting layers.

(Claim 32)
32. The organic electroluminescent element according to claim 1, wherein the light emission colors of at least two layers of the plurality of light emitting layers are the same.

(Claim 33)
The organic electroluminescent element according to claim 1, wherein at least one light emitting layer of the plurality of light emitting layers contains a phosphorescent compound.

(Claim 34)
The plurality of light emitting layers include a light emitting layer containing at least one blue fluorescent compound, a light emitting layer containing at least one red phosphorescent compound, and a light emitting layer containing at least one green phosphorescent compound. The organic electroluminescence element according to claim 1, wherein the organic electroluminescence element is contained.

(Claim 35)
The organic electroluminescence element according to claim 1, which emits white light.

(Claim 36)
A display device comprising the organic electroluminescence element according to claim 1.

(Claim 37)
An illuminating device comprising the organic electroluminescent element according to any one of claims 1 to 35.

  According to the present invention, it is possible to provide an organic EL element that can finely adjust a luminescent color and has high luminous efficiency and long life, and a display device and an illumination device using the organic EL element.

  The organic EL element in the present invention has a structure in which a plurality of constituent layers are sandwiched between a cathode and an anode, and a structure in which a plurality of light emitting layers are included in the constituent layers. Another feature is that at least one of the constituent layers contains at least one compound represented by the general formula (1). Thereby, a highly efficient and long-life organic electroluminescence element, a display device using the same, and a lighting device using the same can be provided.

  Moreover, since the compound represented by the general formula (1) has a wide band gap, it is possible to achieve further higher efficiency of the organic EL device by using this in the light emitting layer.

  Moreover, since most of the compounds represented by the general formula (1) have a deep HOMO level lower than 6.0 eV, they can be used for the hole blocking layer. By this configuration, exciton confinement in the light-emitting layer can achieve further efficient light emission.

  In addition, the organic EL element of the present invention can have an element configuration having a charge generation layer. A well-known thing can be utilized as a structure. In addition, although a part of the structure having two or three light emitting layers and a charge generation layer in the present invention is shown below, the present invention is not limited to this.

  Hereinafter, the present invention will be described in detail.

[Compound represented by the general formula (1)]
The compound represented by the general formula (1) according to the present invention will be described.

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.

Examples of the aromatic heterocycle represented by Z ₁ and Z ₂ include furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole Ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, diazacarbazole ring (hydrocarbons constituting carboline ring) A ring in which one of the carbon atoms of the ring is further substituted with a nitrogen atom). Further, the aromatic heterocyclic ring may have a substituent represented by R ₁₀₁ described later.

The aromatic hydrocarbon ring represented by Z _2, a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o- terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene A ring etc. are mentioned. Further, the aromatic hydrocarbon ring may have a substituent represented by R ₁₀₁ described later.

Examples of the substituent represented by R ₁₀₁ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group). , Pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.), aryl group (eg , Phenyl group, naphthyl group, etc.), aromatic heterocyclic group (for example, 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, imi Dazolidyl 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.), cycloalkoxyl group (for example, Cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group) Etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, etc.) 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, cyclohexylcarbonyl group) Octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group) Group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2 -Ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc. ), Carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylamino) Carbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, Phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butyl) Rufinyl 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, ethylamino group, dimethyl) Amino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen Atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, Examples thereof include a hydroxyl group, a mercapto group, and a silyl group (for example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a phenyldiethylsilyl group, and the like).

  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.

  The divalent linking group may be a hydrocarbon group such as alkylene, alkenylene, alkynylene, arylene, etc., and may contain a hetero atom, and may be a thiophene-2,5-diyl group or pyrazine-2,3- It may be a divalent linking group derived from a compound having an aromatic heterocycle such as a diyl group (also referred to as a heteroaromatic compound), or may be a chalcogen atom such as oxygen or sulfur. Moreover, the group which connects and connects hetero atoms, such as an alkylimino group, a dialkylsilane diyl group, and a diaryl germane diyl group, may be sufficient.

  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. Further, the life can be extended. In the present invention, Z ₂ is preferably a 6-membered ring. Thereby, luminous efficiency can be made higher. Further, the lifetime can be further increased. Furthermore, it is preferable to make both Z ₁ and Z _{2 a} 6-membered ring because the luminous efficiency can be further increased. Further, 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 (1-10).

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 General formula (1-1), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 General formula (1-2), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

In the general formula (1-3), R _{521 to} R ₅₂₇ each independently represents a hydrogen atom or a substituent. By using the compound represented by general formula (1-3), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

In the general formula (1-4), R _{531 to} R ₅₃₇ each independently represent a hydrogen atom or a substituent. By using the compound represented by general formula (1-4), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

In the general formula (1-5) represents a hydrogen atom or a substituent each independently R ₅₄₁ to R ₅₄₈ is. By using the compound represented by general formula (1-5), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 General formula (1-6), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 General formula (1-7), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 General formula (1-8), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

  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 General formula (1-9), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

  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 general formula (1-10), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as a long-life organic EL element.

Moreover, what is preferable among the compounds represented by the general formula (1) is a compound having at least one group represented by any one of the general formulas (2-1) to (2-10). In particular, it is more preferable to have 2 to 4 groups represented by any one of the general formulas (2-1) to (2-10) 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 (2-10).

  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 any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (3), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (4), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

In the general formula (5), R _{621 to} R ₆₂₃ represent a hydrogen atom or a substituent, and at least one of R _{621 to} R ₆₂₃ is any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (5), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (6), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 any one of the general formulas (2-1) to (2-10). Represents a group represented by 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 General formula (7), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

In the general formula (8), R _{661 to} R ₆₇₂ represent a hydrogen atom or a substituent, and at least one of R _{661 to} R ₆₇₂ is any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (8), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 any one of the general formulas (2-1) to (2-10). Represents a group represented by By using the compound represented by General formula (9), it can be set as an organic EL element with higher luminous efficiency. Furthermore, it can be set as an organic EL element of longer life.

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 any one of the general formulas (2-1) to (2-10). Represents a group represented by

Examples of the divalent linking group represented by L ₁ include 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 groups (for example, vinylene group, propenylene group, etc.), alkynylene groups (for example, ethynylene group, 3-pentynylene group, etc.), and hydrocarbon groups such as arylene groups. In addition, a group containing a hetero atom (for example, containing a chalcogen atom such as —O— or —S—) Valent group, -N (R) - group, wherein R represents a hydrogen atom or an alkyl group, the alkyl group has the same meaning as the alkyl group represented by R ₁₀₁ in the general formula (1)) or the like Is mentioned. 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 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-diyl group Alternatively, it may be a divalent linking group derived from a compound having an aromatic heterocyclic ring (also referred to as a heteroaromatic compound) such as a pyrazine-2,3-diyl group. 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 an organic EL element of longer life.

In the compounds represented by the general formulas (11) to (15), the substituents represented by R ₁ and R ₂ are the substituents represented by R ₁₀₁ in the general formula (1). It is synonymous with.

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.

Examples of 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, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyl. Diyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl Group, octylphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group and the like. The arylene group may further have a substituent described later. The divalent aromatic heterocyclic group represented by each of Ar ₁ and Ar ₂ is a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, an 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, hydrocarbon ring constituting carboline ring And a divalent group derived from a ring in which the carbon atom is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic group may have a substituent represented by R ₁₀₁ .

The divalent linking group represented by L is the same as the divalent linking group represented by L ₁ in the general formula (10), but preferably an alkylene group, -O-, -S-. A divalent group containing a chalcogen atom such as an alkylene group, most preferably an alkylene group.

In the general formula (17), an arylene group represented by each of Ar _1, Ar ₂ has the same meaning as the arylene group represented by each in the general formula (16) in Ar _1, Ar _2. Aromatic heterocyclic group each represented by Ar _1, Ar ₂ have the same meanings as divalent aromatic heterocyclic group represented by each in the general formula (16) in Ar _1, Ar _2.

Examples of 6-membered aromatic heterocycles each containing at least one nitrogen atom represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Can be mentioned.

The divalent linking group represented by L is the same as the divalent linking group represented by L ₁ in the general formula (10), but preferably an alkylene group, -O-, -S-. A divalent group containing a chalcogen atom such as an alkylene group, most preferably an alkylene group.

  Specific examples of the compounds represented by the general formulas (1) to (17) according to the present invention are shown below, but the present invention is not limited thereto.

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

  (Synthesis of Exemplary 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 cooling, chloroform and water are added to separate the organic layer. The organic layer is washed with water and saturated brine and concentrated under reduced pressure. The resulting residue is recrystallized from acetic acid to give colorless crystals of Exemplified Compound 144. 1.5 g was obtained.

The structure of 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 are added to separate the organic layer, and the organic layer is washed with water and saturated brine and then concentrated under reduced pressure. The resulting residue is recrystallized from ethyl acetate to give colorless compound of Exemplified Compound 143. 0.3 g of 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 synthesized azacarbazole ring or its chloroplast and aromatic ring, heterocyclic ring, alkyl group, etc. to the core or linking group is known as Ullman coupling, coupling using Pd catalyst, Suzuki coupling, etc. The 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. As a result, the glass transition temperature is raised, the thermal stability is improved, and the life can be further extended.

  The present invention has a constituent layer between a cathode and an anode, the constituent layer has a plurality of light emitting layers, and at least one of the constituent layers is represented by these general formulas (1) to (17). It is characterized by containing at least one compound.

  Below, each structural layer of an organic EL element is demonstrated.

[Light emitting layer]
The total thickness of the light emitting layer is not particularly limited, but is preferably 5 to 100 nm. More preferably, it is 7-50 nm, Most preferably, it is 10-40 nm.

  The thickness of each light emitting layer constituting the light emitting layer is preferably 1 to 20 nm, more preferably 2 to 10 nm.

  These can be selected depending on the element driving voltage, the chromaticity shift with respect to the voltage (current), the energy transfer, and the difficulty of production.

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

<Luminescent dopant>
The light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

  A typical example of the phosphorescent dopant is preferably a complex compound containing a metal of group 8 to 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound, and most preferably an iridium compound. It is.

  Specific examples of the phosphorescent dopant include compounds described in the following patent publications. International Publication No. 00/70655, JP-A Nos. 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060 2001-313178, 2002-302671, 2001-345183, 2002-324679, WO 02/15645, JP-A 2002-332291, 2002-50484, 2002-332292. No. 2002-83684, No. 2002-540572, JP 2002-117978, 2002-338588, 2002-170684, 2002-352960, WO 01/93642, JP 2002 No. 50483, No. 2002-1000047, No. 2002-173684, No. 2002-359082, No. 2002-17584, No. 2002-363552, No. 2002-184582, No. 2003-7469, Special Table No. 2002-525808 JP, 2003-7471, JP, 2002-525833, JP, 2003-31366, JP, 2002-226495, JP, 2002-234894, JP, 2002-235076, JP, 2002-241751, and 2001. 319779, 2001-319780, 2002-62824, 2002-1000047, 2002-203679, 2002-343572, 2002-203678, and the like.

  Some examples are shown below.

<Light emitting host>
As the luminescent host compound used in the present invention, the compounds represented by the general formulas (1) to (17) are most preferable.

  Other compounds can also be used, and those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic borane derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, or carbolines Derivatives and diazacarbazole derivatives (herein, diazacarbazole derivatives are those in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom). It is done.

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

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

  As specific examples of the light-emitting host, compounds described in the following documents are suitable. For example, JP-A Nos. 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, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003-3165, 2002-234888, 2003-27048, No. 2002-255934, the 2002-260861 JP, same 2002-280183 JP, same 2002-299060 JP, same 2002-302516 JP, same 2002-305083 JP, same 2002-305084 JP, same 2002-308837 Patent Publication.

  In addition, it is preferable that two or more of the plurality of light emitting layers exhibit the same light emission color. Here, the same luminescent color is a luminescent color that appears to have the same color system with little difference in emission peak. The difference in emission peak is preferably 20 nm or less, and more preferably 10 nm or less. By having two or more light-emitting layers that exhibit the same luminescent color, it is possible to increase the external extraction efficiency of the corresponding color and not only increase the degree of freedom in selecting organic materials, but also adjust the light emission luminance and subtle color adjustment. Is possible.

  In addition, as described above, it is known that an internal quantum efficiency of about 4 times that of fluorescent light emission is achieved by using a phosphorescent material for the organic EL element. For this reason, in the organic EL device of the present invention, at least one light emitting layer can emit light with higher efficiency by containing a phosphorescent compound.

  In addition, it is known that energy transfer from a high-energy excited state caused by the combination of carriers to an organic compound having a lower-energy excited energy state occurs due to the combination of organic materials used in the organic EL element. . In the organic EL device of the present invention, at least one of the blue light-emitting layers containing the blue light-emitting material having the highest excitation energy has a fluorescent light-emitting compound, and at least each of the red light-emitting layer and the green light-emitting layer. By including a phosphorescent light emitting material in one layer, it is possible to emit light with higher efficiency without causing a change in chromaticity due to energy transfer.

  In addition, demand for white light emitting devices as applications such as planar light sources and lighting fixtures has been increasing in recent years, and white light emitting devices using two-color mixed colors or three-color mixed colors have been reported for organic EL elements. Since the organic EL element in the present invention has a plurality of light emitting layers and can emit light with high efficiency, it can be used as a white light emitting device to meet the above requirements.

  Further, the organic EL element of the present invention can be used as a display device and an illumination device using the organic EL element because it is capable of adjusting a luminescent color delicately and emitting light with high efficiency.

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

  Examples of the hole blocking layer include those disclosed in JP-A-11-204258, JP-A-11-204359, and “Organic EL device and its forefront of industrialization (issued by NTS, Inc. on November 30, 1998)”. The hole blocking (hole block) layer described in page 237 and the like can be applied as the hole blocking layer according to the present invention. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  In the present invention, it is preferable to use compounds represented by the general formulas (1) to (17) for the hole blocking layer.

(Electron blocking layer)
The electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and blocks electrons while transporting holes. Thus, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

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

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

  The hole transport material is not particularly limited, and is conventionally used as a hole charge injection / transport material in an optical transmission material or a well-known material used for a hole injection layer or a hole transport layer of an EL element. Any one can be selected and used.

  The hole transport material has one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, 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-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 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 material preferably has a high Tg.

  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, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, it is about 5-5000 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.

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

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

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

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

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives. 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.

Further, metal complexes of 8-quinolinol derivatives, such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum. Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and similarly to the hole injection layer and the hole transport layer, inorganics such as n-type-Si and n-type-SiC are 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, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, it is about 5-5000 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

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

[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 lower drive voltage or improve light emission luminance. “Organic EL element and its forefront of industrialization (issued on November 30, 1998 by NTS Corporation) 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 Nos. 9-45479, 9-260062, and 8-288069. Typical examples thereof include copper phthalocyanine. Phthalocyanine buffer layers, oxide buffer layers typified by vanadium oxide, amorphous carbon buffer layers, polymer buffer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Examples include a metal buffer layer represented by an alkali metal compound buffer layer represented by lithium fluoride, an alkaline earth metal compound buffer layer represented by magnesium fluoride, and an oxide buffer layer represented by aluminum oxide.

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

  This injection layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an injection | pouring layer, Usually, it is about 5-5000 nm. This injection layer may have a single-layer structure made of one or more of the above materials.

(Charge generation layer)
The charge generation layer in the present invention may be an inorganic substance, an organic substance, or a composite thereof as long as it can perform electron injection on the anode side and hole injection on the cathode side. As a characteristic, an electrically insulating material having a specific resistance of 1.0 × 10 ² Ω · cm or more and a high visible light transmittance is desirable. Preferably, it is an organic EL element material used for the hole transport layer, and an inorganic substance or an organic substance that causes a charge transfer reaction with the material. As the latter, metal oxides, metal halides, and compounds having an electron injecting property are suitable, and examples thereof include V ₂ O ₅ , Re ₂ O ₇ , ITO, and TCNQ derivatives.

  In the present invention, it is preferable to have a charge generation layer between at least one of a plurality of light emitting layers or between each light emitting layer.

  The charge generation layer will be described in more detail.

  In the organic EL device of the present invention, the material forming the charge generation layer is preferably a layer having a visible light transmittance of 50% or more. If the transmittance of visible light is less than 50%, the generated light is absorbed when passing through the charge generation layer, and a desired quantum efficiency (current efficiency) cannot be obtained even if it has a plurality of light emitting units. . The material for forming the charge generation layer may be either an inorganic substance or an organic substance as long as it has the above specific resistance, but the preferred structure of the charge generation layer in the present invention is two different types. A charge transfer complex consisting of a radical cation and a radical anion formed by a redox reaction is formed between two types of substances, consisting of a laminate or mixed layer of substances, and the radical cation state and radical anion state in the charge transfer complex are By moving in the cathode direction and the anode direction when a voltage is applied, holes are injected into the organic layer in contact with the cathode side of the charge generation layer, and electrons are injected into the organic layer in contact with the anode side of the charge generation layer. .

The specific resistance of the charge generating layer in the present invention is 1.0 × 10 ² Ω · cm or more, preferably 1.0 × 10 ⁵ Ω · cm or more intentionally conductive material such as ITO (to 10 ^-4 It is preferable to use one in a region far higher than Ω · cm), and the same deposition area regulating shadow mask can be used during the film formation process of the charge generation layer as in the organic film formation process. There can be a great productivity advantage that the shadow mask does not require frequent replacement and alignment except during film formation.

  In the organic EL element, it is said that the work function, which is one of the properties of the electrode material, affects the element characteristics (such as drive voltage). The charge generation layer in the organic EL device of the present invention is not an electrode, but electrons are injected in the anode electrode direction and holes are injected in the cathode electrode direction. The formation method of the electron injection (transport) layer and the hole injection (transport) layer is an important element for reducing the energy barrier when injecting charges (electrons and holes) into each light emitting layer.

  For example, when electrons are injected from each charge generation layer in the positive electrode direction, they are in contact with the anode side of the charge generation layer as disclosed in JP-A-10-270171 and JP-A-2001-102175. The layer preferably has an electron injection layer composed of a mixed layer of an organic compound and a metal functioning as an electron donating (donor) dopant. Here, the donor dopant is preferably made of one or more metals selected from alkali metals, alkaline earth metals, and rare earth metals. Moreover, it is preferable that the molar ratio of the donor dopant metal in said electron injection layer is 0.1-10 with respect to an organic compound. If the molar ratio is less than 0.1, the concentration of the molecule reduced by the dopant (hereinafter referred to as reducing molecule) is too low, the doping effect is small, and if it exceeds 10 times, the dopant concentration in the film far exceeds the organic molecule concentration. Since the concentration of the reducing molecule in the film is extremely reduced, the doping effect is also lowered. By using the light emitting unit having the above-described electron injection layer, electron injection without an energy barrier is realized in each light emitting unit regardless of the work function of the material forming the charge generation layer.

  In addition, as a layer in contact with the anode side of the charge generation layer, an electron having a thickness of 5 nm or less, preferably 0.2 to 5 nm, made of a metal selected from alkali metals, alkaline earth metals, and rare earth metals. A structure having an injection layer may also be used. If the film thickness exceeds 5 nm, the light transmittance is decreased, and at the same time, the presence of the excessively unstable metal in the air, which may make the device unstable. Are known. In addition, it is considered that most of the metal layer having a film thickness of 5 nm or less is diffused into the organic material layer, and as a result, a film having almost the same composition as the metal doping layer is formed. There is no metal film body having the property.

Further, for example, when electrons are injected from each charge generation layer in the positive electrode direction, JP-A Nos. 11-233262 and 2000-182774 (corresponding US Pat. No. 6,396,209) (reference paper: J. Pat. Endo, T. Matsumoto, and J. Kido, Jpn. J. Appl. Phys. Vol. 41 (2002) pp. L800-L803) are provided on the anode side of the charge generation layer. Is also preferable. This type of electron injection layer is formed by depositing a heat-reducible metal such as aluminum on a compound containing alkali metal ions, alkaline earth metal ions, and rare earth metal ions, and reducing the metal ions to a metallic state. In the case of the device of the present invention, it is preferable that the thermally reducible metal is made extremely thin and only the minimum amount necessary for the reduction reaction is supplied onto the compound. The heat-reduced metal used at this time is oxidized by itself when reducing metal ions in the compound to become an insulating compound having a specific resistance of 1.0 × 10 ² Ω · cm or more. (The ultra-thin here means a film thickness of 10 nm or less, and when the film thickness of the thermally reduced metal exceeds 10 nm, metal atoms that do not contribute to the reduction reaction remain (electrical) insulation. As well as loss of transparency.)
Further, for example, the compounds containing alkali metal ions, alkaline earth metal ions, and rare earth metal ions used in the “in situ reaction product layer” described above are disclosed in the above patent documents (Japanese Patent Laid-Open Nos. 11-233262 and In addition to the organometallic complex compounds described in JP-A-2000-182774, inorganic compounds may be used. Specifically, oxides and halides containing alkali metal ions, alkaline earth metal ions, rare earth metal ions However, any inorganic compound may be used as long as it contains alkali metal ions, alkaline earth metal ions, and rare earth metal ions.

  Furthermore, the different types of electrons disclosed in the above-mentioned JP-A-10-270171, JP-A-2001-102175, JP-A-11-233262, and JP-A-2000-182774 (corresponding US Pat. No. 6,396,209). It is also suitable to use an injection (transport) layer in an overlapping manner. Specifically, a metal doping layer described in JP-A-10-270171 or JP-A-2001-102175 is first laminated (as a low resistance electron transport layer) on an organic layer including a light emitting layer (in the order of vapor deposition). Next, it is preferable to form an “in-situ reaction product layer” described in JP-A-11-233262 and JP-A-2000-182774. The idea of forming an electron injection layer in contact with the cathode of a conventional organic EL device by using different types of electron injection (transport) layers in this manner is described in detail in Japanese Patent Application No. 2002-273656. It is written. In this case, it is the “in situ reaction product layer” that contacts the charge generation layer (on the anode side), but an undesirable interaction between the substance used for the charge generation layer and a chemically reactive metal such as an alkali metal. This is a preferable method for forming the electron injection layer in that the barrier for electron injection from the charge generation layer can be reduced as a result.

  Further, for example, when holes are injected from each charge generation layer in the negative electrode direction, the organic substances described in JP-A Nos. 11-251067 and 2001-244079 can be oxidized by Lewis oxidization. If a hole injection layer doped with an electron-accepting compound (Lewis acid compound) is formed as a layer in contact with the cathode side of the charge generation layer, the work function of the material forming the charge generation layer 4-n is used. , Hole injection without energy barrier can be realized. Furthermore, a very thin electron-accepting compound (Lewis acid compound) layer that can ensure transparency may be formed as a hole injection layer. In this case, the film thickness is preferably 30 nm or less, and preferably in the range of 0.5 to 30 nm. If the film thickness exceeds 30 nm, the light transmittance decreases, and at the same time, the presence of the Lewis acid compound that is highly reactive and unstable in the air makes the device unstable. Is also not preferable.

  The electron accepting compound (Lewis acid compound) is not particularly limited. For example, ferric chloride, ferric bromide, ferric iodide, aluminum chloride, aluminum bromide, aluminum iodide, gallium chloride. , Gallium bromide, gallium iodide, indium chloride, indium bromide, indium iodide, antimony pentachloride, arsenic pentafluoride, boron trifluoride and other inorganic compounds such as DDQ (dicyano-dichloroquinone), TNF (trinitro Organic compounds such as fluorenone), TCNQ (tetracyanoquinodimethane), and 4F-TCNQ (tetrafluoro-tetracyanoquinodimethane) can be used. The molar ratio between the organic compound and the electron-accepting compound (dopant compound) in the hole injection layer is preferably in the range of 0.01 to 10 with respect to the organic compound. If the dopant ratio is less than 0.01, the concentration of molecules oxidized by the dopant (hereinafter sometimes referred to as oxidized molecules) is too low, the effect of doping is small, and if it exceeds 10 times, the dopant in the film Since the concentration greatly exceeds the concentration of organic molecules and the concentration of oxidized molecules in the film is extremely reduced, the effect of doping is also reduced.

  In addition, if the work function of the substance forming the charge generation layer is 4.5 eV or more, holes may be injected into each light emitting unit without using a separate electron accepting compound (Lewis acid compound). is there. Conversely, the Lewis acid compound may function as a component of the charge generation layer as it is.

  In the constituent layers used in the present invention, the layers in direct contact with the cathode and the anode may be the same as the layers in contact with the anode side of the charge generation layer and the layers in contact with the cathode side of the charge generation layer, respectively. Different electron injection layers and hole injection layers may be used. Of course, the electron injection layer and the hole injection layer which have been used in the conventional organic EL element can be preferably used as they are.

  As the charge generation layer, a metal thin film, a metal oxide thin film, an organic conductor thin film, or a combination thereof can be used. For example, a metal oxide (ITO) is applied to an organic conductor thin film (BCP doped with Cs). Laminated ones can be used. In addition, on both sides of the charge generation layer, an inorganic dielectric thin film such as LiF, a metal oxide such as Li oxide, an organic thin film layer containing an alkali metal or alkaline earth metal ion, or the like is inserted as a cathode side buffer layer. In some cases, copper phthalocyanine or the like may be used as the anode buffer layer.

  In consideration of driving the device of the present invention with an AC bias, the charge generation layer needs to be designed so that both hole and electron carriers can be injected. When the charge generation layer is formed of a single material, a semiconductor with a wide band gap (for example, an intrinsic semiconductor) having holes in the valence band and electrons in the conductor, or a redox polymer that can perform both oxidation and reduction, etc. Conceivable.

Specific examples of semiconductors having a wide band gap include III-N compounds such as GaN, AlN, BN, AlGaN, InGaN, and InAlGaN, II-VI such as ZnS, MgS, ZnSe, MgSe, ZnMgSSe, CdS, ZnO, and BeO. In addition to group compounds, diamond, SiC, ZnGaSSe, CaF ₂ , AlP, and the like can be given. Redox polymers include emeraldine base polyaniline (EB-PAni).

  Here, it is also effective to use an organic conductor as the charge generation layer. For example, there is a method of mixing a p-type organic semiconductor and an n-type organic semiconductor. As a typical example of the p-type organic semiconductor, other metal phthalocyanines, metal-free phthalocyanines, and the like can be applied in addition to copper phthalocyanine (abbreviation: CuPc) represented by the following structural formula (1). Typical examples of the n-type organic semiconductor include F16-CuPc represented by the following structural formula (2), the following structural formula (3) (abbreviation: PV), and structural formula (4) (abbreviation: Me-PTC). And a 3,4,9,10-perylenetetracarboxylic acid derivative represented by the structural formula (5) (abbreviation: PTCAD).

  There is also a method of using an organic conductor that has conductivity by mixing an acceptor (electron acceptor) of an organic compound and a donor (electron donor) of an organic compound to form a charge transfer complex. Some of the charge transfer complexes are easy to crystallize and have poor film formability, but the charge generation layer of the present invention may be formed in a thin layer or a cluster (as long as carriers can be injected), so no major problem occurs. .

  Typical examples of the acceptor include TCNQ represented by the following structural formula (6) and derivatives thereof, a nickel complex represented by the following structural formula (7), and the like. Typical examples of donors include TTF represented by the following structural formula (8) and derivatives thereof.

  As another example of the organic conductor, there is a technique in which an organic semiconductor is doped with an acceptor or a donor to impart dark conductivity. As the organic semiconductor, an organic compound having a π-conjugated system such as a conductive polymer may be used. In addition to the examples described above, a Lewis acid such as iron (III) chloride or a halogen compound may be used as the acceptor (Lewis acid can act as an acceptor). In addition to the examples described above, a Lewis base such as an alkali metal or an alkaline earth metal may be used as the donor (the Lewis base can act as a donor).

  In the above, an example in which the charge generation layer is formed of a single layer has been described, but a method of forming the charge generation layer with a plurality of materials is more preferable.

  For example, a charge generation layer having a structure in which a conductive film is sandwiched between intrinsic semiconductors is provided between two electroluminescent layers. With such a structure, carriers can be injected with either bias. Here, the intrinsic semiconductor is preferably in ohmic contact with the conductive film. The conductive film may be not only a metal but also various inorganic compound conductors and organic conductors as described above. Moreover, you may use a redox polymer and an organic conductor instead of an intrinsic semiconductor.

  Another example is a structure of a charge generation layer in which cluster-like electron injection regions are provided above and below a conductive film having a large work function. With such a structure, holes are injected from the conductive film and electrons are injected from the electron injection region, so that carriers can be injected with either bias. As the conductive film having a large work function, ITO, Au, or the like can be considered, but the organic conductor as described above may be used. The cluster-like electron injection region may be formed by forming a conventional electron injection material in a cluster shape such as an Al: Li alloy, a metal such as Ca, an inorganic electron injection material such as LiF, or an organic compound having a high electron affinity.

  It is also possible to reverse this configuration. That is, a cluster-shaped hole injection region is provided above and below a conductive film having a small work function. In this case, as the conductive film having a small work function, an Al: Li alloy, Ca, or the like can be considered, but an organic conductor as described above may be used. The cluster-like hole injection region may be formed by forming a conventional hole injection material in a cluster shape, such as a metal and inorganic compound conductor such as Au or ITO, or an organic compound having a relatively low ionization potential.

〔anode〕
As the anode according to the organic EL device of the present invention, an electrode having a work function (4 eV or more) metal, alloy, electrically conductive compound and a mixture thereof as an electrode material is preferably used. Specific examples of such electrode 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 to 1000 nm, preferably 10 to 200 nm.

〔cathode〕
As the cathode according to the present invention, a cathode having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof 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 to 1000 nm, preferably 50 to 200 nm. In order to transmit light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

[Substrate (also referred to as substrate, substrate, support, etc.)]
The substrate of the organic EL device of the present invention is not particularly limited to the type of glass, plastic, etc., and is not particularly limited as long as it is transparent. Examples of substrates that are preferably used include glass, quartz, A light transmissive resin film can be mentioned. 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 triacetate. Examples thereof include films made of (TAC), cellulose acetate propionate (CAP) and the like.

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

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 2% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

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

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

[Method for producing organic EL element]
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising anode / hole transport layer / light emitting layer 1 / light emitting layer 2 / electron transport layer / electron injection layer (cathode buffer 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 to 200 nm, thereby producing an anode. To do. Next, a thin film containing an organic compound such as a hole transport layer, a light emitting layer 1, a light emitting layer 2, and an electron transport layer, which are element materials, is formed thereon.

As a method for thinning a thin film containing an organic compound, there are a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but a uniform film is easily obtained and pinholes are not easily generated. In view of the above, the vacuum deposition method or the spin coating method is particularly preferable. Further, different film forming methods may be applied for each layer. When employing a vapor deposition method for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 It is desirable to select appropriately within a range of ˜50 nm / second, a substrate temperature of −50 to 300 ° C., and a thickness of 0.1 to 5 μm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably 50 to 200 nm, and by providing a cathode, A desired organic EL element is obtained. The organic EL device is preferably produced from the hole transport layer layer to the cathode consistently by a single evacuation, but it 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.

[Display device]
The display device of the present invention will be described.

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

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

  Moreover, it is also possible to reverse the production order and produce the cathode, the electron injection layer (cathode buffer layer), the electron transport layer, the light emitting layer 2, the light emitting layer 1, the hole transport 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. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, or 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.

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

[Lighting device]
The lighting device of the present invention will be described.

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The use of the organic EL element having such a resonator structure is as a light source for an optical storage medium, an electrophotographic copying machine, and the like. Light sources, optical communication processor light sources, optical sensor light sources, and the like.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display 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 two or more organic EL elements of the present invention having different emission colors.

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

  FIG. 1 is a schematic 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.

  In the figure, 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 lattice shape and are connected to the pixels 3 at the 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.

  When the organic EL device of the present invention is used as a white light emitting device, full color display can be performed by combination with a BGR color filter.

  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 a white light-emitting organic EL element as the organic EL element 10 divided into a plurality of pixels and combining it with a BGR color filter.

  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.

  The organic EL element according to the present invention can also be applied to an organic EL element that emits substantially white light as a lighting device.

  In the white organic EL element concerning this invention, you may pattern by a metal mask, an inkjet printing method, etc. at the time of film forming as needed. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  Thus, in addition to the display device and display, the white light-emitting organic EL element of the present invention can be used as various light sources, lighting devices, household lighting, interior lighting, and a kind of lamp such as an exposure light source. It is also useful for display devices such as backlights for liquid crystal display devices.

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

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
[Production of Organic EL Elements 1-1 to 1-15]
(Organic EL device 1-1)
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm × 100 mm × 1.1 mm glass substrate is formed as an anode on a 100 nm ITO (indium tin oxide) film The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.

Next, the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, and the heating boat containing α-NPD was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. A transport layer was provided.

  Thereafter, Compound H-6 and Compound Ir-12 were co-deposited as the first light-emitting layer A (Compound H-6: Compound Ir-12 = 97: 3) to form a light-emitting layer A having a thickness of 15 nm.

Subsequently, Compound H-6 and Compound Ir-9 were co-deposited as the second light-emitting layer B (Compound H-6: Compound Ir-9 = 92: 8) to form a light-emitting layer B having a thickness of 10 nm. This was prepared, and Alq ₃ was deposited thereon to provide an electron transport layer having a thickness of 20 nm. In addition, the substrate temperature at the time of the above vapor deposition was performed at room temperature.

  Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 100nm was vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

(Organic EL device 1-2)
An organic EL element 1-2 was produced in the same manner as the organic EL element 1-1 except that H-12 was used as the host material and hole blocking layer material of the light emitting layer.

(Organic EL element 1-3)
Except for the light emitting layer, an element EL element 1-3 having three light emitting units was produced in the same manner as the organic EL element 1-1.

  As the first light-emitting layer A, compound H-12 and compound Ir-13 were co-evaporated (compound H-12: compound Ir-13 = 98: 2) to form a light-emitting layer A having a thickness of 40 nm.

  As the second light-emitting layer B, Compound H-6 and Compound Ir-1 were co-evaporated (Compound H-6: Compound Ir-1 = 92: 8) to prepare a light-emitting layer B having a thickness of 40 nm.

  Further, as the third light-emitting layer C, Compound H-6 and Compound Ir-5 were co-evaporated (Compound H-6: Compound Ir-5 = 93: 7) to form a light-emitting layer C having a thickness of 40 nm.

(Organic EL elements 1-4 to 1-15)
Organic EL elements 1-4 to 1-15 were produced by the same method as the organic EL elements 1-1 to 1-3 so as to have the layer configuration shown in Table 3.

[Evaluation of organic EL elements]
The obtained organic EL device was evaluated by the following method, and the results are shown in Table 3.

(External 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. The external extraction quantum efficiency was expressed using a relative value when the organic EL element 1-13 was set to 100.

(Luminescent life)
When driving at a constant current of ^2.5 mA / cm ^{2 in} a dry nitrogen gas atmosphere at 23 ° C., the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. Was used as an index of life as half-life time (τ0.5). For the measurement, a spectral radiance meter CS-1000 (manufactured by Minolta) was used. The light emission lifetime was expressed using a relative value when the organic EL element 1-13 was set to 100.

  From Table 3, it can be seen that the organic EL device of the present invention is superior in external extraction quantum efficiency and emission lifetime as compared with the comparative example.

Example 2
[Production of Organic EL Elements 2-1 to 2-15]
(Organic EL device 2-1)
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm × 100 mm × 1.1 mm glass substrate is formed as an anode on a 100 nm ITO (indium tin oxide) film The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.

Next, the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, and the heating boat containing α-NPD was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. A transport layer was provided.

Thereafter, Compound H-6 and Compound Ir-12 were co-deposited as the first light-emitting layer A (Compound H-6: Compound Ir-12 = 97: 3) to form a light-emitting layer A having a thickness of 40 nm. On top of that, 20 nm of Alq ₃ was deposited as an electron transport layer.

Further, V ₂ O ₅ (vanadium pentoxide) was formed to a thickness of 10 nm as a charge generation layer.

Subsequently, α-NPD was deposited as a hole transporting layer at 60 nm, and then Compound H-6 and Compound Ir-9 were co-deposited as the second light emitting layer B (Compound H-6: Compound Ir-9 = 92). 8), a light emitting layer B having a thickness of 40 nm was prepared, and Alq ₃ was deposited thereon to provide an electron transport layer having a thickness of 20 nm. The substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 100nm was vapor-deposited, the cathode was formed, and the organic EL element 2-1 was produced.

(Organic EL device 2-2)
An organic EL element 2-2 was produced in the same manner as the organic EL element 2-1, except that H-13 was used as the host material and hole blocking layer material of the light emitting layer.

(Organic EL element 2-3)
Except for the light emitting layer, an element EL element 2-3 having three light emitting units was produced in the same manner as the organic EL element 2-1.

  As the first light-emitting layer A, compound H-12 and compound Ir-13 were co-evaporated (compound H-12: compound Ir-13 = 98: 2) to form a light-emitting layer A having a thickness of 40 nm.

  As the second light-emitting layer B, Compound H-6 and Compound Ir-1 were co-evaporated (Compound H-6: Compound Ir-1 = 92: 8) to prepare a light-emitting layer B having a thickness of 40 nm.

  Further, as the third light-emitting layer C, Compound H-6 and Compound Ir-5 were co-evaporated (Compound H-6: Compound Ir-5 = 93: 7) to form a light-emitting layer C having a thickness of 40 nm.

(Organic EL elements 2-4 to 2-15)
It laminated | stacked so that it might become each layer structure shown in Table 4 like organic EL element 2-1 to 2-3, and organic EL element 2-4 to 2-15 was produced.

[Evaluation of organic EL elements]
The obtained organic EL element was evaluated in the same manner as in Example 1, and the results are shown in Table 4.

  From Table 4, it can be seen that the organic EL device of the present invention has higher external extraction efficiency than the comparative organic EL device.

Example 3
The non-light-emitting surface of the organic EL element produced with the organic EL element 1-7 and the organic EL element 2-9 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 perspective view of the lighting device, and FIG. 6 is a cross-sectional view of the lighting device. In the figure, the organic EL element 10 has an organic EL layer 106 and a cathode 105 laminated on a glass substrate 107 with an ITO transparent electrode. In the lighting device 100, the organic EL element 101 is covered with a glass case 102, and a power line (anode) 103 and a power line (cathode) 104 are connected. The glass case 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. 4 is a schematic diagram of a display unit A. FIG. It is a schematic diagram of a pixel. It is a schematic diagram of the display apparatus by a passive matrix system. It is a schematic perspective view of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

A Display unit B Control unit 102 Glass case 103 Power line (anode)
104 Power line (cathode)
105 Cathode 106 Organic EL layer 107 Glass substrate with ITO transparent electrode 108 Nitrogen gas 109 Water trapping agent

Claims (37)

In an organic electroluminescence device having a constituent layer between a cathode and an anode, the constituent layer has a plurality of light emitting layers, and at least one of the constituent layers contains at least one compound represented by the following general formula (1) An organic electroluminescence element characterized by comprising:

(In the formula, Z ₁ represents an aromatic heterocyclic ring, Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring, Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom. Or represents a substituent.) The organic electroluminescence device according to claim 1, wherein at least one of the plurality of light emitting layers contains at least one compound represented by the general formula (1). The constituent layer has at least one hole blocking layer, and at least one layer of the hole blocking layer contains at least one compound represented by the general formula (1). 2. The organic electroluminescence device according to 2. The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-1).

(In the formula, R _{501 to} R ₅₀₇ each independently represent 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 (1-2).

(Wherein R _{511 to} R ₅₁₇ 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 (1-3).

(Wherein R _{521 to} R ₅₂₇ 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 (1-4).

(In the formula, R _{531 to} R ₅₃₇ 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 (1-5).

(Wherein, represents a hydrogen atom or a substituent each independently R ₅₄₁ to R ₅₄₈ in.) The organic electroluminescent element 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 electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-7).

(In the formula, R _{561 to} R ₅₆₇ each independently represents a hydrogen atom or a substituent.) The organic electroluminescent element 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 electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

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

(In the formula, 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 (2-10). The organic electroluminescent element of any one of Claims.

(In the formula, R _{502 to} R ₅₀₇ , R _{512 to} R ₅₁₇ , R _{522 to} R ₅₂₇ , R _{532 to} R ₅₃₇ , R _{542 to} R ₅₄₈ , R _{552 to} R ₅₅₈ , R _{562 to} R ₅₆₇ , R _{572 to} R ₅₇₇ , R _{582 to} R ₅₈₈ and R _{592 to} R ₅₉₈ each independently represent a hydrogen atom or a substituent, and the substituents may be the same or different. The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (3).

(Wherein R _{601 to} R ₆₀₆ each independently represents a hydrogen atom or a substituent, but at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-10)). Represents at least one group selected from the group) The organic electroluminescence device according to any one of claims 1 to 3, 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 (2-10)). Represents at least one group selected from the group) The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (5).

(Wherein R _{621 to} R ₆₂₃ each independently represents a hydrogen atom or a substituent, but at least one of R _{621 to} R ₆₂₃ is represented by the general formulas (2-1) to (2-10)). Represents at least one group selected from the group) The organic electroluminescence device according to any one of claims 1 to 3, 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 (2-10)). Represents at least one group selected from the group) 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 represent a hydrogen atom or a substituent, but at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-10)) And at least one group selected from the group, na represents an integer of 0 to 5, nb represents an integer of 1 to 6, and the sum of na and nb is 6.) The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (8).

(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 above general formulas (2-1) to (2-10)) Represents at least one group selected from the group) The organic electroluminescence device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (9).

(Wherein R _{681 to} R ₆₈₈ each independently represents 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 (2-10)). Represents at least one group selected from the group) 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, L ₁ represents a divalent linking group. At least one of R _{691 to} R ₇₀₀ represents the above general formula (2-1). ) Represents at least one group selected from the groups represented by (2-10). The organic electroluminescent device according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is represented by the following general formula (11).

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

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5.) The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5.) The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (14).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that 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).

(In the formula, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. N and m each represents an integer of 1 to 2, and k and l each represents an integer of 3 to 4, provided that n + k. = 5 and l + m = 5 Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocycle containing at least one nitrogen atom. The organic electroluminescence device according to any one of claims 1 to 3, 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, Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ and Z ₂ each represent at least one nitrogen atom. A 6-membered aromatic heterocyclic ring containing 1 and L represents a divalent linking group.) The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (17).

(In the formula, o and p each represent an integer of 1 to 3, Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ and Z ₄ are Each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group.) 30. The organic electroluminescent element according to claim 1, further comprising a charge generation layer in at least one layer between the plurality of light emitting layers. 31. The organic electroluminescence device according to claim 30, further comprising a charge generation layer in each layer between the plurality of light emitting layers. 32. The organic electroluminescent element according to claim 1, wherein the light emission colors of at least two layers of the plurality of light emitting layers are the same. The organic electroluminescent element according to claim 1, wherein at least one light emitting layer of the plurality of light emitting layers contains a phosphorescent compound. The plurality of light emitting layers include a light emitting layer containing at least one blue fluorescent compound, a light emitting layer containing at least one red phosphorescent compound, and a light emitting layer containing at least one green phosphorescent compound. The organic electroluminescence element according to claim 1, wherein the organic electroluminescence element is contained. The organic electroluminescence element according to claim 1, which emits white light. A display device comprising the organic electroluminescence element according to claim 1. An illuminating device comprising the organic electroluminescent element according to any one of claims 1 to 35.

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