JPH11106746A - Organic electroluminescent material and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material capable of high efficiency light emission at a low drive voltage and excellent in stability in repeated use by selecting a specified compound. SOLUTION: A compound represented by formula I, II or the like (e.g. a compound of formula III) is selected. In the formulas, R11 , R21 and R22 are each an aliphatic hydrocarbon group, an aryl or a heterocyclic group; R12 is an aryl or an aromatic-heterocyclic group; R11 ', R12 ', R21 ' and R22 ' are each H or a substituent; Z1 , Z21 and Z22 are each an atomic group necessary to form a five- or six-membered ring; L1 , L2 , L21 and L22 are each methine; n1 , n21 and n22 are each 0 or 1; m1 is 0-2; q2 is 0-3; X1 and X2 are each an anion; and p1 and p2 are each 0 or 1, provided that they are each 0 when the compound forms an inner salt. It is desirable that this compound is used as an electroluminescent material. An electroluminescent element excellent in durability can be obtained by forming an organic electroluminescent element composed of a pair of electrodes and a luminous layer or a plurality of organic compound thin films including a luminous layer, wherein at least one of the layers is a layer made from at least one compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic electroluminescent device used for a flat light source, a display device, a communication device, a communication wiring and the like.

[0002]

2. Description of the Related Art In recent years, with the aim of constructing a super information highway, researches on light-to-electricity conversion elements and light-to-electricity conversion elements used for connection portions of information communication using optical fibers have been actively conducted. Although the photoelectric conversion element has been studied for a long time as a photoelectric conversion element, research on the organic electroluminescent element relating to the photoelectric conversion element has been mostly made for a display, and is an effective element that can be used for information communication applications. The technology has not been found yet. For information communication use, an element emitting near-infrared light is desired. As an electroluminescent element emitting light in this wavelength region, an organic electroluminescence (EL) containing Si, Ge, and Sn complexes of tetraazaporphine is used. An element has been disclosed (JP-A-9-13024).
issue). However, its electro-optical conversion efficiency is low, and there is a problem in stability during repeated use. Therefore, development of a high-efficiency, long-term stable near-infrared-emitting organic electroluminescent device has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a material for an organic EL device and an organic EL device which can emit light with high efficiency at a low voltage and have excellent stability when used repeatedly. .

[0004]

This object has been achieved by the following means. (1) An organic electroluminescent device material, which is a compound represented by the following general formulas (I) to (VII).

[0005]

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[0006]

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(Where R₁₁, R_{twenty one}, R_{twenty two}, R₃₁, R₄₁,
R₅₁, R₆₁, R₆₂, R₇₁And R₇₂Are each aliphatic
Represents a hydrocarbon group, an aryl group or a heterocyclic group.
R₁₂, R₃₂And R₄₂Is an aryl group or
Represents an aromatic heterocyclic group. R₆₃And R₇₃Is water
Element atom, aliphatic hydrocarbon group, aryl group or hetero ring
Represents a group. R '₁₁, R '₁₂, R '₂₁, R '₂₂,
R '₃₁, R '₃₂, R '₃₃ , R '₃₄, R '₃₅,
R '₄₁, R '₄₂, R '₄₃, R '₄₄, R '₄₅,
R '₅₁, R '₅₂, R '₅₃, R '₅₄, R '₅₅,
R '₆₁, R '₆₂, R '₆₃, R '₆₄, R '₆₅,
R '₇₁, R '₇₂, R '₇₃, R '₇₄And R '
₇₅Represents a hydrogen atom or a substituent, respectively. Z₁,
Z_{twenty one}, Z_{twenty two}, Z_Three, Z_Four, Z₅₁, Z₅₂, Z₆₁, Z₆₂, Z
₇₁And Z₇₂Form a 5- or 6-membered ring, respectively
Represents the group of atoms required for L₁, L_Two, L_{twenty one}, L_{twenty two},
L_Three, L_Four, L_Five, L₅₁, L₅₂, L₆, L₆₁, L₆₂, L
₇, L₇₁And L₇₂Each represents a methine group. n₁,
n_{twenty one}, N_{twenty two}, N_Three, N_Four, N_Five, N₆₁, N₆₂, N₇₁And
And n₇₂Represents 0 or 1, respectively. m₁, M_Threeand
m_FourRepresents 0, 1 or 2, respectively. q_Two, Q_Five, Q
₆And q₇Represents 0, 1, 2 or 3, respectively. X
₁, X_Two, X_Three, X_Four, X₆And X₇Represents an anion
You. p₁, P_Two, P_Three, P_Four, P₆And p₇Is 0 or
Represents 1 and 0 when the compound forms an inner salt.
You. (2) A light emitting layer or a plurality including a light emitting layer between a pair of electrodes
Organic Light-Emitting Devices with Organic Compound Thin Films
And at least one layer of the organic electroluminescent device material according to (1).
EL device characterized in that it is a layer containing a pigment
Child. (3) A light emitting layer or a plurality including a light emitting layer between a pair of electrodes
Organic Light-Emitting Devices with Organic Compound Thin Films
And at least one layer of the organic electroluminescent device material according to (1).
Organic material characterized in that it is a layer in which a filler is dispersed in a polymer
Electroluminescent device.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the general formulas (I) to (I) of the present invention will be described.
The compound represented by (VII) will be described in detail.
R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R ₅₁ , R ₆₁ , R ₆₂ , R
₇₁ and R ₇₂ each represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ ,
The aliphatic hydrocarbon group represented by R ₄₁ , R ₅₁ , R ₆₁ , R ₆₂ , R ₇₁ and R ₇₂ is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms). -20, more preferably 1-12, for example, methyl, ethyl,
iso-propyl, tert-butyl, n-octyl,
n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 30, more preferably 2 to 20, and still more preferably 2 to 12, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl), and an alkynyl group. (Preferably having 2 to 3 carbon atoms)
0, more preferably 2 to 20, even more preferably 2 to 12
And examples thereof include propargyl and 3-pentynyl. ), Preferably an alkyl group or an alkenyl group, and more preferably methyl, ethyl, propyl, butyl, or allyl.

R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R ₅₁ , R
The aryl group represented by _{61, R 62, R 71,} R 72,
It is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, etc.), more preferably phenyl or naphthyl having 6 to 20 carbon atoms, still more preferably carbon number. 6-12 phenyl.

R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R ₅₁ , R
_61, the heterocyclic group represented represented by R _62, R _71, R ₇₂ are, N, a 3 to 10 membered saturated or unsaturated heterocyclic ring containing at least one O or S atom, they May be a single ring or may form a condensed ring with another ring. As a heterocyclic group, preferably 5 to 6
A 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom, more preferably a 5- or 6-membered aromatic heterocyclic group containing 1 or 2 nitrogen atoms. Group. Specific examples of the heterocycle include
For example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole,
Pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline,
Isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene, 1,2-
Dihydro-1-azaazulen-2-one, pyrrolo [5,
1-b] quinazolin-9-one, pyrrolo [2,3-b]
Pyridine and the like. As the heterocycle, pyrrole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, thiazole, oxazole benzimidazole, benzoxazole, benzothiazole, benzotriazole, 1 , 2-dihydro-1-azaazulene-2-one, pyrrolo [5,1-b] quinazolin-9-one and pyrrolo [2,3-b] pyridine, more preferably pyrrole, pyrazole, 1,2- Dihydro-1-azaazulene-2-one, pyrrolo [5,1-b]
Quinazolin-9-one and pyrrolo [2,3-b] pyridine.

R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R ₅₁ , R
_61, R _62, R _71, aliphatic hydrocarbon groups represented by R _72, an aryl group and heterocyclic group may have a substituent, examples of the substituent include an alkyl group (preferably having a carbon number of 1 ~
20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso-
Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenyl, p-
Methylphenyl, naphthyl and the like can be mentioned. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, and dibenzylamino. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, and butoxy), and aryloxy. Group (preferably having 6 to 2 carbon atoms)
It has 0, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl,
Benzoyl, formyl, pivaloyl and the like can be mentioned. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
-20, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms.
0, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), and an alkoxycarbonylamino group. (Preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethylsulfamoyl, phenylsulfamoyl and the like can be mentioned. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl). An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 carbon atoms)
To 16, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like. ), Ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms)
12, for example, ureide, methylureide, phenylureide and the like. ), Phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfino, hydrazino,
And imino groups and heterocyclic groups (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino and the like). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent is preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonyl group. Amino group, sulfonylamino group, sulfamoyl group, carbamoyl group, hydroxy group, heterocyclic group, more preferably alkyl group, alkenyl group, aralkyl group, aryl group, amino group, carbonylamino group, sulfonylamino group, heterocyclic group And more preferably an alkyl group, an aralkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic group.

R₁₁, R_{twenty one}, R_{twenty two}, R₃₁, R₄₁, R₅₁, R
₆₁, R₆₂, R₇₁, R₇₂Is preferably an alkyl group,
Alkenyl group and aryl group, more preferably alkyl
Phenyl, allyl, phenyl, and more preferably
Is a alkyl group. Also, R₁₁, R_{twenty one}, R_{twenty two}, R₃₁,
R₄₁, R₅₁, R₆₁, R₆₂, R₇₁, R₇₂Is Z₁,
Z _{twenty one}, Z_{twenty two}, Z_Three, Z_Four, Z₅₁, Z₆₁, Z₆₂, Z₇₁, Z
₇₂Benzene fused to a 5- or 6-membered ring formed by
Condensed with a ring to further form a 5- or 6-membered ring
Is also preferred.

R ₁₂ , R ₃₂ and R ₄₂ each represent an aryl group or an aromatic heterocyclic group. R ₁₂ , R ₃₂ , R ₄₂
The aryl group represented by preferably has 6 to 6 carbon atoms.
30 monocyclic or bicyclic aryl groups (eg phenyl,
Naphthyl and the like. ), More preferably phenyl having 6 to 20 carbon atoms and naphthyl, and still more preferably phenyl having 6 to 12 carbon atoms. R ₁₂ , R ₃₂ ,
The aryl group represented by R ₄₂ may have a substituent. Examples of the substituent include R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R
The substituents listed as ₅₁ , R ₆₁ , R ₆₂ , R ₇₁ and R ₇₂ can be applied. The aryl group represented by R ₁₂ , R ₃₂ and R ₄₂ is more preferably a group represented by the following formula (a).

[0015]

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In the formula, R _a1 and R _a2 each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R _a1 and R _a2 are R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R
_{51, R 61, R 62,} R 71, the same meanings as those represented by R _72. R _a1 and R _a2 are preferably an unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl,
Butyl, hexyl, octyl, decyl, dodecyl and the like, and substituted alkyl groups (preferable substituents include, for example, carboxyl, cyano, hydroxy, sulfo,
Halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (eg, methoxy, ethoxy, benzyloxy, phenethyloxy, etc.), aryloxy Groups (eg, phenoxy, p-tolyloxy, naphthoxy, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, mesyl, etc.), carbamoyl groups (eg, carbamoyl, dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc.), and sulfamoyl (eg, sulfamoyl) Dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.), aryl groups (eg, phenyl, p-
Chlorophenyl, p-methylphenyl, naphthyl, etc.)
And the like. ). Also preferred are those in which _Ra1 and _Ra2 are linked to form a 5- or 6-membered ring, and those in which _Ra1 and _Ra2 are linked to a benzene ring to form a 5- or 6-membered ring.

R _a3 , R _a4 , R _a5 and R _a6 each represent a hydrogen atom or a substituent. Examples of the substituent of R _{a3 to} R _a6 include R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ , R ₅₁ , R ₆₁ ,
The substituents mentioned for R ₆₂ , R ₇₁ and R ₇₂ can be applied. R _a3 and R _a4 , or R _a5 and R _a6 may be linked to form a ring. Preferably, R _{a3 to} R _a6 are a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,
Dodecyl, etc.), a substituted alkyl group (preferable examples of the substituent include a carboxyl group, a cyano group, a hydroxy group,
Sulfo group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl,
Benzyloxycarbonyl, etc.), alkoxy groups (eg, methoxy, ethoxy, benzyloxy, phenethyloxy, etc.), aryloxy groups (eg, phenoxy, p
-Tolyloxy, naphthoxy, etc.), acyl groups (eg acetyl, propionyl, benzoyl, mesyl etc.),
A carbamoyl group (eg, carbamoyl, dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc.), a sulfamoyl (eg, sulfamoyl, dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.), an aryl group (eg, phenyl, p
-Chlorophenyl, p-methylphenyl, naphthyl, etc.). ), An amino group having 0 to 18 carbon atoms, a carboxyl group, a cyano group, a hydroxy group, a sulfo group, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), an alkoxycarbonyl group having 2 to 18 carbon atoms (eg, methoxycarbonyl, ethoxy Carbonyl, phenoxycarbonyl, benzyloxycarbonyl, etc.), an alkoxy group having 1 to 18 carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), an aryloxy group having 7 to 18 carbon atoms (eg, phenoxy, p-
An acyloxy group having 2 to 18 carbon atoms (such as acetyloxy and propionyloxy), an acyl group having 1 to 18 carbon atoms (such as acetyl, propionyl, benzoyl, and mesyl); A carbamoyl group (eg, carbamoyl, dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc.); and a sulfamoyl group having 0 to 18 carbon atoms (eg, sulfamoyl, dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.).

R ₆₃ and R ₇₃ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.
An aliphatic hydrocarbon group represented by R ₆₃ or R ₇₃ , an aryl group,
Heterocyclic groups _{R 11, R 21, R 22} , R 31, R 41, R 51, R
_61, R _62, R _71, the same meanings as those represented by R _72.
R ₆₃ and R ₇₃ are preferably an aliphatic hydrocarbon group and an aryl group, more preferably an alkyl group, an alkenyl group and an aryl group, still more preferably an alkyl group, an allyl group and a phenyl group, and further preferably It is an alkyl group.

R '₁₁, R '₁₂, R '₂₁,
R '₂₂, R '₃₁, R '₃₂, R '₃₃, R '₃₄,
R '₃₅, R '₄₁, R '₄₂, R '₄₃, R '₄₄,
R '₄₅, R '₅₁, R '₅₂, R '₅₃, R '₅₄,
R '₅₅, R '₆₁, R '₆₂, R '_{6 3}, R '₆₄,
R '₆₅, R '₇₁, R '₇₂, R '₇₃, R '₇₄You
And R '₇₅Represents a hydrogen atom or a substituent, respectively.
Examples of the substituent in the above case include R₁₁, R_{twenty one}, R_{twenty two},
R₃₁, R₄₁, R₅₁, R ₆₁, R₆₂, R₇₁, R₇₂And the substituent
The above can be applied. Preferred as a substituent
Is a lower alkyl group having 1 to 6 carbon atoms (eg, methyl,
Butyl, isopropyl, butyl, etc.)
Lower alkoxy groups (eg, methoxy, ethoxy, propoxy)
, Butoxy, etc.), unsubstituted or substituted amino groups (eg,
Amino, methylamino, dimethylamino, diethyla
Mino, etc.), heterocycles (eg morpholino, piperidi
, Benzoxazolyl, benzothiazolyl, benzoi
Midazolyl, benzotriazolyl, etc.), hydroxy
Group, halogen atom (for example, fluorine atom, chlorine atom, etc.)
It is. Also, R '₃₂, R '₃₃, R '₃₄, R '
₃₅, R '₄₂, R '₄₃, R '_{Four 4}, R '₄₅, R '
₅₂, R '₅₃, R '₅₄, R '₅₅, R '₆₂, R '
₆₃ , R '₆₄, R '₆₅, R '₇₂, R '₇₃, R '
₇₄, R '₇₅May be linked to form a ring.

R ′ ₁₁ , R ′ ₁₂ , R ′ ₂₁ ,
_{R '22, R' 31,} R '41, R' 51, R '61,
R ′ ₇₁ is preferably a hydrogen atom.
R ′ ₃₂ , R ′ ₄₅ , R ′ ₅₂ , R ′ ₆₂ , and R ′ ₇₅ are preferably a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, etc.), and more preferably. Is a hydrogen atom.
_{R '33, R' 35,} R '42, R' 44, R '53,
Preferred as _{R '55, R' 63,} R '65, R' 72, R '74 hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms (e.g. methyl, ethyl, isopropyl, butyl, etc.) is an alkyl group. _R'34 , _R'43 ,
R _'54, R' _64, preferably a hydrogen atom R _'73, a lower alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), unsubstituted or substituted amino group (e.g. amino, methylamino , Dimethylamino, diethylamino, etc., and those which form a ring by bonding to a benzene ring of a benzopyrylium nucleus are also preferable.) And a hydroxy group.

Z ₁ , Z ₂₁ , Z ₂₂ , Z ₃ , Z ₄ , Z ₅₁ , Z
₅₂ , Z ₆₁ , Z ₆₂ , Z ₇₁ and Z ₇₂ each represent an atom group necessary for forming a 5- or 6-membered ring. Z ₁ ,
Z ₂₁ , Z ₂₂ , Z ₃ , Z ₄ , Z ₅₁ , Z ₆₁ , Z ₆₂ , Z ₇₁ , Z
_{As the} ring containing ₇₂ , for example, a thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-thienyl) thiazole and the like), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole , 7-chlorobenzothiazole,
4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-trifluoromethylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-carboxybenzothiazole, 5-cyanobenzothiazole, 5- Fluorobenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc., naphthothiazole nucleus (for example, naphtho- [1,2-d]) Thiazole,
Naphtho- [2,1-d] thiazole, naphtho- [2,3
-D] thiazole, 5-methoxynaphtho [2,1-d]
Thiazole, 5-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [1,2-d] thiazole,
7-methoxynaphtho- [1,2-d] thiazole and the like),
Thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-phenylthiazoline, etc.), oxazole nucleus (eg, oxazole, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 5-phenyloxazole, 4,5-diphenyloxazole) Benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-
Methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5
-Methoxybenzoxazole, 5-ethoxybenzoxazole, 5-fluorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc., a naphthoxazole nucleus (for example, naphtho [1,2-d]) Oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, etc., isoxazole nucleus (eg, 5-methylisoxazole, benzoisoxazole, etc.), oxazoline nucleus (eg, 4,4-dimethyl Oxazoline, etc.), selenazole nucleus (eg, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole, etc.), benzo selenazole nucleus (eg, benzo selenazole, 5-methyl benzo selenazole, 5
-Chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, etc.),
Naphtho selenazole nucleus (for example, naphtho [1, 2-d] selenazole, naphtho [2, 1-d] selenazole, etc.),
Tellurazole nucleus (e.g. benzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 5-methoxybenzotellurazole, 5-hydroxybenzotellurazole, 5-methylthiobenzotellurazole, 5,6-dimethoxy Benzotellurazole, naphtho [1,2-d] tellurazole, 6-methylnaphtho [1,2-d] tellurazole, 6-methoxynaphtho [1,2-d] tellurazole, etc., indolenine nucleus (for example, 3,3- Dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-nitroindolenine,
3,3-dimethyl-6-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine and the like, imidazole nucleus (for example, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole) , 1-ethyl-4-phenylimidazole, 1-phenylimidazole, etc.), benzimidazole nucleus (for example, 1-ethylbenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-propyl-
5,6-dichlorobenzimidazole, 1-ethyl-5
-Methoxybenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-butyl-6-chloro-5-cyanobenzimidazole , 1-ethyl-6-chloro-5
-Trifluoromethylbenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-allyl-5,6
-Dichlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-phenyl-5-methoxybenzimidazole, 1-phenyl-5-cyano Benzimidazole,
Etc.), a naphthoimidazole nucleus (for example, 1-ethylnaphtho [1,2-d] imidazole, 1-phenylnaphtho [1,2-d] imidazole, etc.), a pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl) -2-pyridine, 3-methyl-4-pyridine and the like, quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro -2-quinoline, 8-fluoro-2-quinoline, 6
-Methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-
Ethoxy-4-quinoline, 6-nitro-4-quinoline,
8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, etc., isoquinoline nucleus (for example, isoquinoline, 6
-Nitro-1-isoquinoline, 3,4-dihydro-1-
Isoquinoline, 6-nitro-3-isoquinoline, etc.), imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-
Diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus,
Examples include a triazole nucleus, a tetrazole nucleus, a pyrimidine nucleus, and a pyrazole nucleus.

Z ₁ , Z ₂₁ , Z ₂₂ , Z ₃ , Z ₄ , Z ₅₁ , Z
_61, a preferably ring containing _{Z 62, Z 71, Z 72} , a thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
Thiazoline nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, isoxazole nucleus, oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus,
Naphthelenazole nucleus, tellurazole nucleus, indolenine nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, more preferably benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphtho Oxazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, indolenine nucleus, benzimidazole nucleus, naphthymidazole nucleus, pyridine nucleus, quinoline nucleus, more preferably benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole Nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, indolenine nucleus, benzimidazole nucleus, naphthoimidazole nucleus.

[0023] Preferably the ring containing Z _52, rhodanine ring, hydantoin ring, 2-thiohydantoin ring, oxazolidine-2,4-dione ring, a 2-thio-2,4-dione ring, 2- Chioserenazo Lysine-2,
4-dione ring, 5-pyrazolone ring, indandione ring,
5 (4H) -isoxazolone ring, 2,4-chromandione ring, 4,6- (1H, 5H) pyridinedione ring, barbituric acid ring, 2-thiobarbituric acid ring, 1,3-
Dioxane-4,6-dione ring, 3,5-pyrazolidinedione ring, more preferably rhodanine ring, hydantoin ring, 2-thiohydantoin ring, barbituric acid ring, 2-thiobarbituric acid ring .

L ₁ , L ₂ , L ₂₁ , L ₂₂ , L ₃ , L ₄ , L
₅ , L ₅₁ , L ₅₂ , L ₆ , L ₆₁ , L ₆₂ , L ₇ , L ₇₁ and L ₇₂ each represent a methine group. The methine group may have a substituent, and examples of the substituent include R ₁₁ , R ₂₁ , R ₂₂ ,
The substituents mentioned for R ₃₁ , R ₄₁ , R ₅₁ , R ₆₁ , R ₆₂ , R ₇₁ and R ₇₂ can be applied. As the substituent, preferably an alkyl group (eg, methyl, ethyl, propyl, etc.), an aryl group (eg, phenyl, 2-carboxyphenyl,
4-methylphenyl, 2-chlorophenyl, etc.), an aralkyl group (eg, benzyl), a halogen atom (eg, chlorine atom, bromine atom, etc.), and an alkoxy group (eg, methoxy, ethoxy, etc.), and more preferably an alkyl group. .

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ is R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ , R ₅₁ , R ₆₁ ,
It may _combine with R ₇₁ to form a 5- or 6-membered ring. Further, L ₂₁ and L _22, L ₅₁ and L _52, L ₆₁ and L _62, L ₇₁ and L ₇₂
May be linked to form a 5- or 6-membered ring.

N ₁ , n ₂₁ , n ₂₂ , n ₃ , n ₄ , n ₅ , n
₆₁ , _n62 , _n71 and _n72 each represent 0 or 1, and preferably 0. m ₁ , m ₃ and m ₄ each represent 0, 1 or 2, and preferably 0 or 1.
q ₂ , q ₅ , q ₆ and q ₇ represent 0, 1, 2 or 3, respectively, preferably 0, 1, 2 and more preferably 0, 1.

X₁, X_Two, X_Three, X_Four, X₆And X₇
Represents an anion. Organic or inorganic anions
These anions may be used, for example, halide ions (eg,
Cl ^-, Br^-, I^-Etc.), sulfonate ions (eg
Trifluoromethanesulfonate, paratoluenesulfur
Hornate, benzenesulfonate, parachlorobenzene
Sulfonate, etc.), sulfato ion (for example, methyls
Lulfate, ethyl sulfate, etc.), park roller
G, tetrafluoroborate, hexafluorophosphate
And the like. p₁, P_Two, P_Three, P_Four, P₆You
And p₇Represents 0 or 1, and the compound forms an inner salt
If so, it is 0.

The compounds represented by the general formulas (I) to (VII) may be multimeric or linked to a polymer chain. Further, the general formulas (I) to (VII) are represented by the limit structural formula for convenience, but may be tautomers thereof. Among the compounds represented by formulas (I) to (VII), compounds represented by formulas (Ia) to (VII-a) are preferable.

[0029]

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[0030]

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Where R₁₁, R_{twenty one}, R_{twenty two}, R₃₁, R₄₁,
R₅₁, R₆₁, R₆₂, R₇₁, R₇₂, R_a1, R_a2, R_a3, R
_a4, R_a5, R_a6, R₆₃, R₇₃, R '₃₂, R '₃₃,
R '₃₄, R '₃₅, R '₄₂, R '₄₃, R '₄₄,
R '₄₅, R '₅₂, R '₅₃, R '₅₄, R '₅₅,
R '₆₂, R '₆₃, R '₆₄, R '₆₅, R '₇₂,
R '₇₃, R '₇₄, R '₇₅, Z₁, Z_{twenty one}, Z_{twenty two}, Z
_Three, Z_Four, Z₅₁, Z₅₂, Z ₆₁, Z₆₂, Z₇₁, L₁,
L_Two, L_{twenty one}, L_{twenty two}, L_Three, L_Four, L_Five, L₅₁, L₅₂, L
₆, L₆₁, L₆₂, L₇, L₇₁, N₁, N_{twenty one}, N_{twenty two},
n_Three, N_Four, N_Five, N₆₁, N ₆₂, N₇₁, N₇₂, M₁, M
_Three, M_Four, Q_Two, Q_Five, Q₆, Q₇, X₁, X_Two,
X _Three, X_Four, X₆, X₇, P₁, P_Two, P_Three, P_Four, P
₆, P₇Are represented by the general formulas (I) to (VII) and the general formula a, respectively.
And the preferred range is also the same.
is there. Specific examples of the compounds represented by the following general formulas (I) to (VII)
However, the present invention is not limited to these.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0080]

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[0081]

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[0083]

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[0084]

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[0085]

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[0087]

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The above compound examples may be tautomers thereof. The compounds represented by the general formulas (I) to (VII) can be synthesized by various synthesis methods.
No. 45630, No. 6-895, No. 6-17989
No. 5-28815, No. 5-60868, No. 5-
No. 83587, No. 5-83588, No. 4-5069
No. 4-53304, JP-A-63-136554
No. 63-89388, No. 63-89389, No. 62-2681, No. 62-35342, No. 62-3
No. 5343, No. 62-56953, No. 62-5695
No. 4, 62-186205 and 62-294204
Nos. 62-294205 and 61-113542
Nos. 61-113543 and 61-133942
Nos. 61-134755 and 61-137148
Nos. 61-138251 and 61-138948
Nos. 61-167940 and 61-169832
No. 61-187301, No. 61-215541
No. 61-223835 and the like.

The use of the compounds represented by formulas (I) to (VII) of the present invention as an EL device material is not particularly limited, but is preferably used as a light emitting material. The method for forming the layer containing the compounds represented by the general formulas (I) to (VII) of the present invention is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination,
A method such as a coating method is used, and resistance heating evaporation and a coating method are preferable in terms of characteristics and production.

The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound thin films including the light-emitting layer is formed between a pair of anode and cathode electrodes.
It may have a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like, and may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda lime glass, a non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for manufacturing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a dispersion of indium tin oxide are used. The film is formed by a method such as coating. The anode can be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment or the like is effective.

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer and the like. The cathode has good adhesion and ionization potential between the negative electrode such as the electron injecting layer, the electron transporting layer and the light emitting layer. It is selected in consideration of stability and the like. As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used, and specific examples thereof include an alkali metal (eg, Li, Na, K, etc.) or a fluoride thereof, and an alkaline earth metal. Metals such as Mg, Ca
Etc.) or its fluorides, gold, silver, lead, aluminum,
Sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, preferably having a work function of 4 eV or less. The material is more preferably aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm. The cathode is manufactured by a method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method (e.g., metal can be evaporated alone or two or more components can be evaporated at the same time. It is also possible to form an alloy electrode by vapor-depositing the metal at the same time, or to deposit an alloy prepared in advance.The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less. .

The material of the light emitting layer is capable of injecting holes from an anode, a hole injection layer, or a hole transport layer and applying electrons from a cathode, an electron injection layer, or an electron transport layer when an electric field is applied. Any material can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons to emit light. Preferably, the light emitting layer has the general formula (I) of the present invention.
It contains the compounds represented by formulas (VII) to (VII), but other luminescent materials of the compounds represented by formulas (I) to (VII) of the present invention can also be used. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, oxadiazole Azole derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives,
Pyrrolopyridine derivatives, thiadiazolopyridine derivatives,
Polymer compounds such as polythiophene, polyphenylene, polyphenylenevinylene, etc., such as cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivatives and rare earth complexes, and the like. The thickness of the light emitting layer is not particularly limited, but is preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm.
And more preferably 10 nm to 500 nm.
The method of forming the light emitting layer is not particularly limited,
Methods such as resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.) and LB are used.
Preferred are resistance heating evaporation and coating methods.

The material of the hole injection layer and the hole transport layer has a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Should be fine. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 5 μm.
00 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Etc.) are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, or a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic anhydrides such as fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbidiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, and naphthaleneperylene, phthalocyanines And various metal complexes represented by metal complexes of derivatives, 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxadiazole or benzothiazole as ligands. The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually 1 nm to
It is preferably in the range of 5 μm, more preferably 5 nm
１1 μm, more preferably 10 nm to 500 nm.
It is. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injection layer and the electron transport layer include a vacuum deposition method, an LB method, and a method in which the electron injection and transport agent is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, and the like). Is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component.
What was illustrated in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing a substance which promotes element deterioration such as moisture or oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ Al ₂ O ₃ ,
GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O
_3, a metal oxide such as TiO _2, MgF _2, LiF, Al
F ₃ , metal fluoride such as CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide,
Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer Copolymer obtained, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more,
A moisture-proof substance having a water absorption of 0.1% or less can be used. There is no particular limitation on the method for forming the protective layer. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method,
A BE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a plasma CVD method, a laser CVD method, a thermal CVD method, and a gas source CVD method can be applied.

[0098]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 A transparent support substrate was prepared by depositing ITO to a thickness of 150 nm on a glass substrate of 1.25 mm × 25 mm × 0.7 mm by a vapor deposition method (manufactured by Tokyo Sanyo Vacuum Co., Ltd.).
After etching and washing the transparent support substrate, 40 mg of poly (N-vinylcarbazole), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,
12 mg of 3,4-oxadiazole and 3.0 × 10 ⁻⁶ mol of the compound described in Table 1 were dissolved in 1,2-dichloroethane, and spin-coated at 3000 rpm. Next, as a cathode, magnesium and silver are 10 ^-5 to 10: 1.
Co-evaporation was performed at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. A light emitting characteristic was evaluated by applying a DC voltage to the device in the atmosphere using an ITO electrode as an anode and an Al electrode as a cathode. The luminescence was measured by a spectroscope. The luminescence intensity after aging was 100% at the maximum luminescence wavelength immediately after device fabrication.
In this case, the emission intensity after 7 days has been expressed as a relative value. Table 1 shows the evaluation results.

[0099]

[Table 1]

[0100]

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As is clear from the results shown in Table 1, the compounds of the present invention are effective for electroluminescence in the near infrared. In addition, it can be seen that the organic electroluminescent device using the compound of the present invention can be driven at a lower voltage and has excellent durability as compared with the organic electroluminescent device using the comparative compound. In particular, good light-emitting characteristics can be obtained even in a coating method with low light emission luminance, and an element can be produced which is advantageous in terms of manufacturing cost and the like.

Example 2.25 mm × 25 mm × 0.7 m
A glass substrate having a thickness of 150 nm was formed on a glass substrate having a thickness of 150 nm by a vapor deposition method (manufactured by Tokyo Sanyo Vacuum Co., Ltd.) as a transparent support substrate. After etching and washing the transparent support substrate, 40 mg of poly (N-vinylcarbazole) and 3.0 × 10 ⁻⁶ mol of the compound shown in Table 2 were dissolved in 1,2-dichloroethane, and spin-coated at 5000 rpm. Next, the following compounds x and y are sequentially deposited under a vacuum of 10 ^-5 to 10 ^-6 Torr at a substrate temperature of room temperature so that the film thicknesses become 10 nm and 40 nm, respectively, on which magnesium and silver are used as cathodes. 10 ^-5 to 10 ^-6 To so as to be 10: 1
Co-evaporation was performed at a substrate temperature of room temperature in a vacuum of rr. A light emitting characteristic was evaluated in the same manner as in Example 1 by applying a DC voltage to this device in the atmosphere using an ITO electrode as an anode and a Mg: Ag electrode as a cathode. Table 2 shows the evaluation results.

[0103]

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[0104]

[Table 2]

As is evident from the results in Table 2, it can be seen that the compounds of the present invention are effective for electroluminescence in the near-infrared to infrared region even in an organic layer laminated system. In addition, it can be seen that the organic electroluminescent device using the compound of the present invention can be driven at a lower voltage and has excellent durability as compared with the organic electroluminescent device using the comparative compound.

[0106]

According to the present invention, an organic EL device driven at a lower voltage and having a longer life than the conventional one can be obtained. In particular, good light-emitting characteristics can be obtained even in a coating method with low light emission luminance, and an element can be produced which is advantageous in terms of manufacturing cost and the like.

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[Procedure amendment]

[Submission date] December 11, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

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Embedded image _{(Wherein, R ll, R 21, R} 22, R 31, R 4l, R
₅₁ , R ₆₁ , R ₆₂ , R ₇₁ and R ₇₂ each represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₁₂ , R ₃₂ and R ₄₂ each represent an aryl group or an aromatic heterocyclic group. R ₆₃ and R ₇₃
Represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group, respectively. _{R '11, R' 12,} R '
_{21, R '22, R'} 31, R '32, R' 33, R '
_{34, R '35, R'} 41, R '42, R' 43, R '
_{44, R '45, R'} 51, R '52, R' 53, R '
_{54, R '55, R'} 61, R '62, R' 63, R '
_{64, R '65, R'} 71, R '72, R' 73, R '
₇₄ and _R'75 each represent a hydrogen atom or a substituent. Z ₁ , Z ₂₁ , Z ₂₂ , Z ₃ , Z ₄ , Z ₅₁ , Z
₅₂ , Z ₆₁ , Z ₆₂ , Z ₇₁ and Z ₇₂ each represent an atomic group necessary for forming a 5- or 6-membered ring.
L ₁ , L ₂ , L ₂₁ , L ₂₂ , L ₃ , L ₄ , L ₅ , L
_{51, L 52, L 6,} L 61, L 62, L 7, L 71 and _{L 72} each represents a methine group. n _l , n ₂₁ ,
_{n 22, n 3, n 4} , n 5, n 61, n 62, n 71 and _{n 72} each represents 0 or 1. m ₁ , m ₃ and m ₄ each represent 0, 1 or 2. q ₂ ,
q ₅ , q ₆ and q ₇ represent 0, 1, 2 or 3, respectively. X ₁ , X ₂ , X ₃ , X ₄ , X ₆ and X ₇ represent anions. p ₁ , p ₂ , p ₃ , p ₄ , p ₆ and p ₇
Represents 0 or 1, and is 0 when the compound forms an inner salt. )

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006]

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[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

[0020] _{R '11, R' 12,} R '21,
_{R '22, R' 31,} R '41, R' 51, R '61,
R ′ ₇₁ is preferably a hydrogen atom.
R ′ ₃₂ , R ′ ₄₅ , R ₅₂ , R ₆₂ , and R ′ ₇₅ are preferably a hydrogen atom and a lower alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, etc.)
And more preferably a hydrogen atom. _R'33 ,
_{R '35, R' 42,} R '44, R' 53, R '55,
_{R '63, R' 65,} R is preferably a hydrogen atom _'72, R' _74, a lower alkyl group having 1 to 6 carbon atoms (e.g. methyl, ethyl, isopropyl, butyl, etc.).
_{R '34, R' 43,} R '54, R' 64, preferably a hydrogen atom R _'73, a lower alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), unsubstituted or substituted An amino group (eg, amino,
In addition to methylamino, dimethylamino, diethylamino and the like, those formed by bonding to a benzene ring of a benzopyrylium nucleus are also preferable. ), A hydroxy group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction contents]

[0075]

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[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0082]

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[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 008

[Correction method] Change

[Correction contents]

[0086]

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[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction contents]

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer and the like. The cathode has good adhesion and ionization potential between the negative electrode such as the electron injecting layer, the electron transporting layer and the light emitting layer. It is selected in consideration of stability and the like. As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used, and specific examples thereof include an alkali metal (eg, Li, Na, K, etc.) or a fluoride thereof, and an alkaline earth metal. Metals such as Mg, Ca
Etc.) or its fluorides, gold, silver, lead, aluminum,
Sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, preferably having a work function of 4 eV or less. The material is more preferably aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

Claims (3)

[Claims] 1. A compound represented by the following general formulas (I) to (VII):
An organic electroluminescent device material, which is a compound. Embedded imageEmbedded image(Where R₁₁, R_{twenty one}, R_{twenty two}, R₃₁, R₄₁, R₅₁, R₆₁,
R₆₂, R₇₁And R₇₂Is an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. R₁₂, R₃₂and
R₄₂Represents an aryl group or an aromatic heterocyclic group, respectively.
Represent. R₆₃And R₇₃Are hydrogen atom and aliphatic carbon, respectively.
Represents a hydride group, an aryl group or a heterocyclic group. R '
₁₁, R '₁₂, R '₂₁, R '₂₂, R '₃₁, R '
₃₂, R '₃₃ , R '₃₄, R '₃₅, R '₄₁, R '
₄₂, R '₄₃, R '₄₄, R '₄₅, R '₅₁, R '
₅₂, R '₅₃, R '₅₄, R '₅₅, R '₆₁, R '
₆₂, R '₆₃, R '₆₄, R '₆₅, R '₇₁, R '
₇₂, R '₇₃, R '₇₄And R '₇₅Are each
Represents a hydrogen atom or a substituent. Z₁, Z_{twenty one}, Z_{twenty two},
Z_Three, Z_Four, Z₅₁, Z₅₂, Z₆₁, Z₆₂, Z₇₁And Z₇₂
Is an atom required to form a 5- or 6-membered ring, respectively.
Represents a group. L₁, L_Two, L_{twenty one}, L_{twenty two}, L_Three, L_Four,
L_Five, L₅₁, L₅₂, L₆, L₆₁, L₆₂, L₇, L₇₁And
And L₇₂Each represents a methine group. n₁, N_{twenty one}, N_{twenty two},
n_Three, N_Four, N_Five, N₆₁, N₆₂, N₇₁And n₇₂Is it
Represents 0 or 1, respectively. m₁, M_ThreeAnd m_FourEach
Represents 0, 1 or 2. q_Two, Q_Five, Q₆And q₇
Represents 0, 1, 2 or 3, respectively. X₁, X_Two, X
_Three, X_Four, X₆And X₇Represents an anion. p₁, P
_Two, P_Three, P_Four, P₆And p₇Represents 0 or 1,
0 if the compound forms an inner salt. ) 2. An organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, at least one of which is represented by the general formulas (I) to (VII) according to claim 1. An organic electroluminescent device comprising a layer containing at least one of the organic electroluminescent device materials to be produced. 3. An organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, at least one of which is represented by the general formulas (I) to (VII) according to claim 1. An organic electroluminescent device characterized in that the organic electroluminescent device material is a layer in which a material of the organic electroluminescent device is dispersed in a polymer.