JP2000344780A - New benzopyran compound, light emission element material and light emission element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material capable of highly luminant and highly efficient light emission by low-voltage drive, excellent in stability when repeatedly used, and capable of uniform planar light emission by including a specific benzopyran compound. SOLUTION: This material is obtained by incorporating a compound of formula I [R1 to R8 are each H or a substitutent; X is O, S or a group NR; R is H, an aliphatic hydrocarbon or the like; Y is O, S, or a group CQ1(Q2); Q1 and Q2 are each H or a substitutent, and at least one of them is an electron attractive group or they form a ring by being bound to each other; Z is a group OM or the like; M is a heterocyclic ring, cation or the like] (e.g. a compound of formula II). The compound of formula I is obtained, for instance, by formylation of a compound of formula III followed by reaction of the product with a compound of formula IV (e.g. 2-benzimidazolyl acetonitrile) in the presence of a base such as piperidine to be cyclized, and then by reacting the product with a compound of formula V (L1 and L2 are each an eliminable group) (e.g. phenyl chloroformate) in the presence of a base such as pyridine to be cyclized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in filter dyes, color conversion filters, photographic light-sensitive materials, sensitizing dyes, pulp dyeing dyes, laser dyes, medical diagnostic fluorescent agents, and light emitting devices. The present invention relates to compounds, and particularly to a light emitting device using them.

[0002]

2. Description of the Related Art Light-emitting elements using organic substances are expected to be used as inexpensive large-area, full-color display elements of the solid-state light-emitting type, and many developments have been made. In general, a light emitting element includes a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. Light emission occurs when an electric field is applied between both electrodes.
Electrons are injected from the cathode, and holes are injected from the anode.
Further, the electrons and holes are recombined in the light emitting layer, and the energy is emitted as light when the energy level returns from the conduction band to the valence band.

[0003] Conventional light-emitting elements have a high driving voltage and low light emission luminance and light emission efficiency. In recent years, an organic light-emitting device in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported (Applied Physics Letters, vol. 51, p. 913, 19).
1987). This method uses a metal chelate complex as an electron transporting layer, a fluorescent band layer as a light emitting layer, and an amine compound as a hole transporting layer to obtain high-luminance green light emission. Further, in consideration of use as a full-color display and a light source, it is necessary to emit three primary colors or white in practical use, and an element which emits a desired color by doping a fluorescent dye has been reported (Journal of Japan). Applied Physics, 65, 3610, 1989
Year). This method is particularly effective for red light emission in which concentration quenching is large and it is difficult to use a fluorescent dye alone as a light emitting layer, and achieves good color purity and high luminance. However, in the case of producing a device doped with a dye by vapor deposition, a host material and a trace amount of a fluorescent dye are co-deposited, so that there is a problem that the operation is complicated and the performance tends to vary. Therefore, from the viewpoint of simplification of the manufacturing process and stabilization of the performance of the element, a light-emitting material having good color purity and capable of using a dye alone as a light-emitting layer, and particularly good even when used alone as a light-emitting layer There has been a demand for a non-doped luminescent material that achieves an excellent chromaticity and luminance.

On the other hand, a light emitting element which achieves high-luminance light emission is an element in which an organic substance is laminated by vacuum deposition. However, the light emitting element is coated from the viewpoint of simplification of a manufacturing process, workability, and a large area. It is desirable to produce the element by a method. However, a device manufactured by a conventional coating method is inferior to a device manufactured by a vapor deposition method in terms of luminous luminance and luminous efficiency, and high luminance and highly efficient luminescence have been major issues.
Further, in a device in which an organic low-molecular compound is dispersed and applied in an organic polymer medium, there is a problem that it is difficult to emit uniform planar light due to aggregation of the organic low-molecular compound when light is emitted for a long time.

[0005] In recent years, there have been various types of fluorescent materials such as filter dyes, color conversion filters, photographic light-sensitive material dyes, sensitizing dyes, pulp dyes, laser dyes, fluorescent materials for medical diagnosis, and materials for light-emitting devices. Although it is used and its demand is increasing, there are not many compounds having high color purity of fluorescent light and strong intensity, and development of new materials has been desired.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to emit light with high luminance and high efficiency by driving at a low voltage, having excellent stability in repeated use, and capable of emitting uniform planar light. An object of the present invention is to provide an element material and a light-emitting element using the same.
A second object of the present invention is to provide a compound having high fluorescence intensity and high color purity. A third object of the present invention is to provide a light emitting device material capable of emitting light with high luminance and high efficiency even in an undoped type, and a light emitting device using the same.

[0007]

This object has been achieved by the following means. (1) A light-emitting element material, which is a compound represented by the following general formula (I). General formula (I)

[0008]

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(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent. X represents O,
Represents S or NR (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group). Y is O,
S or _{CQ 1 (Q 2) (Q} 1, Q 2 represents a hydrogen atom or a substituent, at least one of them either represents an electron withdrawing group. The Q _1, Q ₂ are connected to each other to form a ring May be formed.). Z is represented by the following general formula (II). General formula (II)

[0010]

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(Wherein, R _a and R _b each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group. _Ra and R _b , and / or _Ra and R ₁ , and / or Or
R _b and R ₂ may be linked together to form a ring. M represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or a cation. )

(2) A compound represented by the following general formula (Ia). General formula (Ia)

[0013]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent. X represents O,
Represents S or NR (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group). Ar _a and Ar _b each represent an aryl group or an aromatic heterocyclic group. Ar _a and Ar _b , and / or Ar _a and R ₁ , and / or
Ar _b and R ₂ may be linked to each other to form a ring. Y is O
Or represents S. )

(3) A light emitting device material characterized by being a compound represented by the general formula (Ia). (4) A compound represented by the following general formula (III).

[0016]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ₂₁ represents a hydrogen atom or a substituent, X represents O, S or NR
(R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.) Ar _a and Ar _b each represent an aryl group or an aromatic heterocyclic group. Ar _a
And Ar _b , and / or Ar _a and R ₁ , and / or Ar _b and R ₂ may be linked to each other to form a ring. (5) A light emitting device material characterized by being a compound represented by the general formula (III).

(6) In a light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer formed between a pair of electrodes, at least one of the light-emitting elements has the general formula described in (1), (2) or (4). A light-emitting element comprising a layer containing at least one of the compounds represented by (I), (Ia) or (III). (7) In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, at least one of the light-emitting elements has the general formula (I) described in (1), (2), or (4). A light-emitting device comprising a layer in which at least one compound represented by formula (Ia) or (III) is dispersed in a polymer.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by formula (I) of the present invention will be described in detail. R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent. As the substituent represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms) To 12, 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. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, for example, propargyl,
3-pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 2 carbon atoms)
0, particularly preferably 6 to 12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 12 carbon atoms, and particularly preferably having 0 to 6 carbon atoms).
And examples thereof include amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino and the like. ), 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, for example, methoxy, ethoxy, butoxy, etc.), and an aryloxy group ( It preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyloxy, 2-naphthyloxy and the like.), Acyl group (preferably carbon number) 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl), and an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 carbon atoms
-16, particularly preferably 2-10 carbon atoms, such as acetoxy and benzoyloxy. ),
Acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms)
And include, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms)
6, particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 2 carbon atoms)
0, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino 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, methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl) Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.) ), And
Alkylthio 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 methylthio, ethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms,
More preferably, it has 6 to 16 carbon atoms, 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 16 carbon atoms, and particularly preferably having 1 carbon atoms.
To 12, for example, mesyl, tosyl and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), Ureido 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, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoramide and phenylphosphoramide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms
And examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, and benzothiazolyl. Is mentioned. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably having 3 to 24 carbon atoms,
For example, trimethylsilyl, triphenylsilyl and the like can be mentioned. ). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. When possible, they may be connected to each other to form a ring.

R ₁ , R ₂ and R ₃ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a lower alkyl group, and particularly preferably a hydrogen atom. R ₄ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a lower alkyl group, and particularly preferably a hydrogen atom or a methyl group. R _5, R _6, R ₇ and R ₈ are preferably those in which a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a cyano group, a sulfonyl group, a heterocyclic group and a substituent are connected to form a benzene ring. , More preferably a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, n
-Propyl group, iso-propyl group, t-butyl group, trifluoromethyl group and the like. ) And aryl groups (for example, phenyl group, p-methylphenyl group, naphthyl group, etc.). More preferably, they are a hydrogen atom, a chlorine atom, and a cyano group.

X is O, S or NR (R is a hydrogen atom,
Represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ). The aliphatic hydrocarbon group represented by R is a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
-30, more preferably 1-20 carbon atoms, even more preferably 1-12 carbon atoms, for example, methyl, ethyl, is
o-propyl, tert-butyl, n-octyl, n-
Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, still more preferably having 2 to 12 carbon atoms,
For example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like can be mentioned. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, still more preferably having 2 to 12 carbon atoms, for example, propargyl, 3
-Pentynyl and the like. ), Preferably an alkyl group or an alkenyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, or an allyl group.

The aryl group represented by R is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, etc.).
More preferably, it is a phenyl group having 6 to 20 carbon atoms, and further preferably, a phenyl group having 6 to 12 carbon atoms.

The heterocyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one N, O or S atom, which may be a single ring, Further, a condensed ring may be formed with another ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. 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,
Examples thereof include tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine,
Pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole benzimidazole, benzoxazole, benzothiazole, and more preferably benzotriazole. Imidazole, pyridine, quinoline, thiazole,
Oxazole, benzimidazole, benzoxazole, benzothiazole and benzotriazole, more preferably pyridine and quinoline.

The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R may have a substituent, and the substituents described above as the substituents of R ₁ to R ₈ can be applied. R is preferably an alkyl group, an alkenyl group, or an aryl group, and more preferably an alkyl group or a phenyl group. X is preferably O, NR, and more preferably O.

Y represents O, S or CQ ₁ (Q ₂ ) (wherein at least _one of Q ₁ and Q ₂ represents an electron-withdrawing group). As the substituents represented by Q ₁ and Q ₂ , the substituents listed for R _{1 to} R ₈ are applied. The electron-withdrawing groups represented by Q ₁ and Q ₂ are groups having a Hammett's σp value of 0 or more. Preferably cyano group, carbonyl group, thiocarbonyl group, aryl group, aromatic heterocyclic group, sulfonyl group,
A carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a halogen atom and the like. More preferred are a cyano group, a carbonyl group, a sulfonyl group and a trifluoromethyl group, and further preferred are a cyano group and a carbonyl group.

Q ₁ and Q ₂ may form a ring together with the carbon atom to which they are bonded, preferably a 1-indanone nucleus,
1,3-dicarbonyl nucleus, pyrazolinone nucleus, 2,4,6
A triketohexahydropyrimidine nucleus (including a thioketone body), a 2-thio-2,4-thiazolidinedione nucleus,
-Thio-2,4-oxazolidinedione nucleus, 2-thio-
A 2,5-thiazolidinedione nucleus, a 2,4-thiazolidinedione nucleus, a 2,4-imidazolidinedione nucleus, a 2-thio-2,4-imidazolidinedione nucleus, and a 2-imidazolin-5-one nucleus; Preferred are a 1-indanone nucleus, a 1,3-dicarbonyl nucleus, and a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), and particularly preferred are a 3-aryl-1-indanone nucleus,
Cyclic 1,3-dicarbonyl nucleus, barbituric acid derivative, 2
-A thiobarbituric acid derivative. Preferably as Y
O 1, S 2, CQ _1a (Q _2a ) (Q _1a and Q _2a each represent a substituent (as the substituent, those mentioned as the substituents of R _{1 to} R ₈ can be applied), and at least one of them is A cyano group, a carbonyl group) or a cyclic 1,3-dicarbonyl nucleus, more preferably O 2 and S 3, and particularly preferably O 2.

Z is -NR _a (R _b ) or a group represented by -OM, and R _a and R _b may be the same or different and each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a hetero group. Represents a ring group. If possible, _Ra and R
_b and / or R _a and R ₁ and / or R _b and R ₂ may be linked to each other to form a ring. M represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or a cation.

The aliphatic hydrocarbon group represented by R _a or R _b is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably Formulas 1 to 12, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and still more preferably having 2 carbon atoms).
-12, for example, vinyl, allyl, 2-butenyl,
3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 carbon atoms)
-20, more preferably 2-12 carbon atoms, such as propargyl and 3-pentynyl. ), Preferably an alkyl group or an alkenyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, an allyl group, R _a and R _b are bonded to a benzene ring to form a condensed ring (for example, a urolidine ring) Etc.).

The aryl group represented by R _a and R _b is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, etc.), and more preferably. A phenyl group having 6 to 20 carbon atoms, more preferably a phenyl group having 6 to 12 carbon atoms.

The heterocyclic group represented by R _a and R _b is N,
A 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one O or S atom, which may be a single ring or may form a condensed ring with another ring. The heterocyclic group is preferably a 3- to 10-membered aromatic heterocyclic group containing at least one N, O or S atom, more preferably a 5- to 6-membered aromatic heterocyclic group, still more preferably It is a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. 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 and the like. Preferred as the hetero ring are thiophene, triazole, oxazole, piperidine, triazine and quinoline, and more preferred are thiophene, piperidine, triazine and quinoline. More preferably, it is thiophene.

An aliphatic hydrocarbon group represented by R _a or R _b ,
The aryl group and the heterocyclic group may have a substituent, and as the substituent, those exemplified as the substituents for R ₁ to R ₈ can be applied.

R _a and R _b are preferably a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group. When used as the undoped light emitting material, R _a, preferably an aryl group as R _b, an aromatic heterocyclic group, more preferably an aryl group (preferably monocyclic or bicyclic aryl group having 6 to 30 carbon atoms And more preferably a phenyl group having 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms.
Is a phenyl group. ), And when used as a doped light emitting material, R _a and R _b are preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and still more preferably an alkyl group having 1 to 8 carbon atoms. ,
Particularly preferred are a methyl group and an ethyl group. The aliphatic hydrocarbon group, aryl group and hetero ring represented by M have the same meaning as the aliphatic hydrocarbon group, aryl group and hetero ring represented by R in the formula (I).

Examples of the cation represented by M include metal cations (eg, lithium cation, sodium cation, potassium cation, cesium cation, magnesium cation, calcium cation, aluminum cation, europium cation) and quaternary ammonium ions (preferably Has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms, such as tetrabutylammonium ion. The metal cation may have a ligand.

M is preferably a hydrogen atom, an alkyl group, an aryl group, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a zinc ion, a europium ion, or a quaternary ammonium ion, and more preferably a hydrogen atom, an alkyl group. , An aryl group, and more preferably a hydrogen atom or a methyl group. Preferably hard NR _a R _b as Z.

Of the compounds represented by the general formula (I), a compound represented by the general formula (Ia) is preferred. General formula (Ia)

[0036]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R _6, R ₇ , R _8, X and Y are each represented by the general formula (I)
And the preferred range is also the same. Ar _a and Ar _b represent an aryl group or an aromatic heterocyclic group, and R _a and R _a in the general formula (I), respectively.
It has the same meaning as the aryl group and the aromatic heterocyclic group represented by R _b . Ar _a and Ar _b are preferably an aryl group, more preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms, still more preferably a phenyl group having 6 to 20 carbon atoms, particularly preferably carbon atom. It is a phenyl group of the number 6 to 12.

Among the compounds represented by the general formula (I), more preferred are the compounds represented by the general formula (Ib). General formula (Ib)

[0039]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ have the same meanings as those in formula (I), and the preferred ranges are also the same.
Ar _a and Ar _b represent an aryl group or an aromatic heterocyclic group, each having the same meaning as those in formula (I-a), and the preferred ranges are also the same. )

Next, the compound represented by formula (III) will be described in detail. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent, each has the same meaning as those in formula (I), and the preferred range is also the same. X represents O, S, or N—R (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group), and has the same meaning as those in formula (I), and is also preferable. The same applies to the range. Ar _a and Ar _b
Represents an aryl group or an aromatic heterocyclic group, has the same meaning as those in formula (Ia), and the preferred range is also the same. R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, and has the same meaning as R in formula (1). R ₁₁ is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, further preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably. Is a hydrogen atom. R ₂₁ represents a hydrogen atom or a substituent, and has the same meaning as R _{1 to} R ₈ in formula (I). R ₂₁ is preferably a hydrogen atom, an alkyl group,
Aryl group, acyl group, carbonylamino group, sulfonylamino group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, and heterocyclic group. More preferably a hydrogen atom, an aryl group, an acyl group, a carbonylamino group, a sulfonylamino group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, an aromatic heterocyclic group, still more preferably a hydrogen atom, An acyl group, a carbonylamino group, a sulfonylamino group, a cyano group, a carboxyl group, a nitro group, an aromatic heterocyclic group, particularly preferably a cyano group or an aromatic heterocyclic group, and most preferably an aromatic heterocyclic ring Group.

Among the compounds represented by the general formula (III), a compound represented by the general formula (III-a) is preferable.

[0043]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ ,
X 1, Ar _a and Ar _b have the same meanings as those in formula (III), and the preferred ranges are also the same. Q
₁₁ represents an atomic group necessary for forming an aromatic hetero ring. The aromatic heterocyclic group represented by Q ₁₁ is a 3- to 10-membered aromatic heterocyclic group containing at least one of N, O and S atoms, which may be monocyclic, It may form a condensed ring with another ring. The aromatic heterocyclic group is preferably an aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. Specific examples of the aromatic hetero ring include, for example, furan, thiophene, pyran, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, oxazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, Tetrazole, quinoline,
Examples include benzimidazole, benzoxazole, benzothiazole, benzotriazole and the like. Aromatic hetero ring represented by Q ₁₁ may further form a condensed ring, and may have a substituent. As the substituent, those exemplified as the substituents of R _{1 to} R ₈ in the general formula (I) can be applied. )

Of the compounds represented by formula (III), more preferred are compounds represented by formula (III-b).

[0046]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ ,
Ar _a and Ar _b have the same meanings as those in formula (III-a), and the preferred ranges are also the same. Q
₁₂ represents a group of atoms necessary for forming a nitrogen-containing aromatic hetero ring. The nitrogen-containing aromatic hetero ring formed by Q ₁₂ may further form a condensed ring, and may have a substituent.
As the substituent, those exemplified as the substituents of R _{1 to} R ₈ in formula (I) can be applied. The ring formed by Q ₁₂ is preferably a 5- or 6-membered nitrogen-containing aromatic hetero ring, and more preferably a 5-membered nitrogen-containing aromatic hetero ring. Specific examples of the nitrogen-containing aromatic hetero ring include, for example, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, oxazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, tetrazole, quinoline, Benzimidazole, benzoxazole, benzothiazole, benzotriazole, more preferably as a nitrogen-containing aromatic heterocycle, thiazole, oxazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, tetrazole, benzimidazole, benz Oxazole and benzothiazole. )

Among the compounds represented by the general formula (III), more preferred are the compounds represented by the general formula (III-c).

[0049]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ ,
Ar _a and Ar _b have the same meanings as those in formula (III-a), and the preferred ranges are also the same.
Q ₁₃ represents an atomic group necessary for forming an aromatic hetero ring or an aromatic hydrocarbon ring. The aromatic hetero ring or aromatic hydrocarbon ring formed by Q ₁₃ may further form a condensed ring, and may have a substituent. As the substituent, those exemplified as the substituents of R _{1 to} R ₈ in the general formula (I) can be applied. Z is O, S or NR ₃₁ (R ₃₁
Represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, and has the same meaning as R in formula (I). ). )

The aromatic hetero ring formed by Q ₁₃ is preferably those described as specific examples of the aromatic hetero ring in formula (III-a), and more preferably pyridine and pyrazine. The preferred aromatic hydrocarbon ring formed by Q ₁₃ is an aromatic hydrocarbon ring monocyclic or bicyclic ring having from 6 to 30 carbon atoms, more preferably having a carbon number of 6 to 2
0 aromatic hydrocarbon ring, more preferably 6 to 12 carbon atoms
Is an aromatic hydrocarbon ring. Q ₁₃ preferably has the general formula The ring formed by (III -a) those noted as specific examples of the aromatic heterocyclic ring in, or a benzene ring having 6 to 12 carbon atoms, more preferably pyridine, pyrazine, Benzene, more preferably benzene.

Z represents O, S or NR ₃₁ (R ₃₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group and has the same meaning as R in the formula (I)). . R ₃₁ is preferably a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, even more preferably a hydrogen atom, alkyl having 1 to 8 carbon atoms, A phenyl group having 6 to 12 carbon atoms, particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Preferably as Z
O, S or N-R ₃₂ (R _32, a hydrogen atom, a methyl group,
Represents an ethyl group or a phenyl group. ), More preferably N-R _32. In addition, general formulas (I), (Ia), (I
-B), (III), (III-a), (III-b) and (III-c)
May be a low molecular weight compound or a high molecular weight compound having a residue connected to the polymer main chain (preferably a weight average molecular weight of 1,000 to 5,000,000, more preferably 5,000 to 2,000,000, further preferably 10 to 20,000,000).
000-1,000,000) or a high molecular weight compound having the compound of the present invention in the main chain (preferably, a weight average molecular weight of 1,000 to 5,000,000, more preferably 5,000 to 5,000).
2,000,000, more preferably 10,000-100
0000). In the case of a high molecular weight compound, it may be a homopolymer, or may be a copolymer with another polymer.If it is a copolymer, it may be a random copolymer or a block copolymer. There may be. The compound used in the present invention is preferably a low molecular weight compound. Further, in the above general formula, the compound is represented by an extreme structure for convenience, but may be a tautomer thereof.

Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

[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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Specific examples of the compound represented by formula (III) are shown below, but the present invention is not limited thereto.

[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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The above compound examples may be their tautomers. Next, a method for synthesizing the compound represented by the general formula (I) of the present invention will be described below. Scheme 1 shows a typical synthesis method.
Shown in Scheme 1

[0073]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ , X, Y, and Z are the same as those in formula (I). L ₁ and L ₂ represent a leaving group, for example, a halogen atom, an alkoxy group or an azole group. The synthesis method from (A) to (B) in Scheme 1 is a formylation reaction to a phenyl group.
4, can be synthesized by the method described in pages 683 to 705 (Maruzen), and specifically, dimethylformamide (preferably,
(A) 1 to 100 equivalents, more preferably 1 to 5 equivalents
Use 0 equivalents. ) And phosphorus oxychloride (preferably (A)
1 to 5 equivalents, more preferably 1 to 2 equivalents are used. ), There is a Vilsmeier reaction, etc.
In the synthesis method of (B) to (D), a base (preferably an organic base, more preferably an organic amine (for example, piperidine etc.) is preferably used), and preferably 0.00 to (B).
1 to 10 equivalents, more preferably 0.01 to 2 equivalents, and still more preferably 0.1 to 2 equivalents of a base). (E.g., benzene, toluene, xylene, etc.), nitriles (e.g., acetonitrile, etc.), and alcohols (e.g., methanol, ethanol)
, Isopropanol and butanol. ), D
Ters (eg, tetrahydrofuran, 1,4-dioxane, diethyl ether, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.) are preferable, and the reaction temperature is preferably 0 to 15;
0 ° C, more preferably 15 to 120 ° C. (D)
From (F) to compound (E) having two leaving groups (for example, phosgene, triphosgene, ethyl orthoformate, phenyl orthoformate, carbonyldiimidazole, phenylchlorothioforme). And the like,
It is preferably used in an amount of 1 to 10 equivalents, more preferably 1 to 5 equivalents, and still more preferably 1 to 2 equivalents to (D). )
And a base (preferably organic amines, more preferably azoles or tertiary amines, and specific examples thereof include pyridine and triethylamine.
This is a synthesis method based on cyclization using preferably 1 to 100 equivalents, more preferably 1 to 50 equivalents. Examples of the solvent include organic halides (for example, chloroform, dichloroethane, dichloromethane, etc.),
Benzene, toluene, xylene, acetonitrile, alcohols (for example, methanol, ethanol, isopropanol, butanol, etc.), pyridine and lutidine are preferable, and pyridine and lutidine are more preferable.
The reaction temperature is preferably from 0 to 150C, more preferably from 15 to 120C.

Next, a method for synthesizing the compound represented by formula (III) of the present invention will be described below. A representative synthetic method is shown in Scheme 2.

[0076]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₂₁ , Ar _a , Ar
_b and X are respectively the same as those in the general formula (III). )

In the synthesis method of (G) to (J), a base (preferably an organic base, more preferably an organic amine (for example, piperidine etc.) is preferably used), 10 equivalents, more preferably 0.01 to
Two equivalents, more preferably 0.1 to 2 equivalents of base are used. ) Is a synthesis method based on the method of cyclization in the presence,
Examples of the solvent include hydrocarbons (eg, benzene, toluene, xylene, etc.), nitriles (eg, acetonitrile, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, etc.), and ether. (Eg, tetrahydrofuran,
There are 1,4-dioxane, diethyl ether and the like. ),
Amides (for example, dimethylformamide, dimethylacetamide, etc.) are preferable, and the reaction temperature is preferably 0 to 150 ° C, more preferably 15 to 120 ° C.
It is.

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. , 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, one having 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 and the adjacent layer 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.

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 contains the compound of the present invention, but other light-emitting materials of the compound 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, aldazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, Pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivatives and rare earth complexes, polythiophene, polyphenylene, polyphenylenevinylene, etc. And polymer compounds. The thickness of the light emitting layer is not particularly limited, but is 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 500 nm. The method for forming the light-emitting layer is not particularly limited, but resistance heating evaporation, electron beam, sputtering, molecular lamination,
A coating method (such as a spin coating method, a casting method, or a dip coating method) or an LB method is used, and resistance heating evaporation and a coating method are preferable.

The material of the hole injection layer and the hole transport layer has any one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Anything should do. 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, 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, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene perylene, and phthalocyanine derivatives And various metal complexes typified by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxazole 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 5 μm.
m, more preferably 5 nm to 1
μm, and more preferably 10 nm to 500 nm. 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. As the resin component, for example, those exemplified 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 and 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 , metal oxides 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, a 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,
BE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method Applicable.

[0087]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 Synthesis method of compound (1)

[0088]

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4-Diethylaminosalicylaldehyde 2
5.0 g, 2-benzimidazolylacetonitrile
2 g, ethanol 500 mL, piperidine 12.7 mL
After heating under reflux for 7 hours, the temperature was returned to room temperature, and the precipitated crystals were separated by filtration, washed with ethanol and dried to obtain the compound (a
) Was obtained in an amount of 39.1 g (yield: 91%). Compound (a)
5.0 g of pyridine, 500 ml of triethylamine 2
Add 2 mL of ethyl chloroformate at room temperature under a nitrogen atmosphere.
mL was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux for 12 hours, the reaction solution was returned to room temperature, and the precipitated crystals were separated by filtration, washed with ethanol and dried to obtain 3.1 g of compound (1) (yield: 60%). The analysis results of this compound were as follows. Absorption spectrum: maximum absorption wavelength 518 nm (in dichloroethane solvent) Fluorescence spectrum: maximum fluorescence wavelength 548 nm (in dichloroethane solvent) Elemental analysis (C ₂₁ H ₁₈ O ₂ N ₄ ) Calculated value C: 70.38% H: 5.06% N: 15.63% Found C: 70.77% H: 5.04% N: 15.79%

Example 2 Method for synthesizing compound (3)

[0091]

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In the same manner, instead of 4-diethylaminosalicylaldehyde, 4.3 g of compound (b), 3.1 g of 2-benzimidazolylacetonitrile, and 40 g of ethanol
4.9 g (yield: 69%) of compound (c) was obtained using 2.0 mL of piperidine. Compound (c) was 2.0
g, pyridine 50 mL, triethylamine 0.8 mL,
Compound (3) was prepared using 1.2 mL of ethyl chloroformate in 1.2 mL.
g (57% yield). The analysis results of this compound were as follows. Absorption spectrum: maximum absorption wavelength 536 nm (in dichloroethane) Fluorescence spectrum: maximum fluorescence wavelength 557 nm (in dichloroethane) Elemental analysis (C ₂₃ H ₁₈ O ₂ N ₄ ) Calculated value C: 72.24% H: 4.74% N: 14.65% Found C: 72.20% H: 4.80% N: 14.87%

Example 3 Synthesis of Compounds (21) and (A-1)

[0094]

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Synthesis of Compound (e) 5.5 g of 3-methoxyphenyl-diphenylamine was dissolved in 25 mL of dichloroethane, cooled to 0 ° C., and BBr ₃
5.6 mL is slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours.
Extract with aqueous sodium hydroxide solution, concentrate the organic phase,
The purification operation was performed by silica gel column chromatography (hexane / ethyl acetate = 19: 1 (v / v)).
4.2 g (81%) of compound (e) was obtained. Synthesis of Compound (f) 100 mL of dimethylformamide was cooled to 0 ° C., and 18 mL of phosphorus oxychloride was added dropwise.
After stirring for 3 minutes, a solution prepared by dissolving 34.0 g of compound (e) in 100 mL of dimethylformamide was added dropwise.
Stir for hours. Next, the reaction solution is dropped into water, extracted with chloroform and an aqueous sodium hydroxide solution, the organic phase is concentrated, and purified by silica gel column chromatography (hexane / chloroform = 8: 2 (v / v)). Performed to obtain 22.5 g (60%) of compound (f). Synthesis of Compound (A-1) 2.89 g of compound (f), 1.57 g of 2-benzimidazolylacetonitrile, 50 mL of ethanol and 0.2 mL of piperidine were added, and the mixture was heated under reflux for 7 hours, returned to room temperature, and the precipitated crystals were filtered. Separately, wash with ethanol, dry,
3.4 g (yield 79%) of compound (A-1) was obtained. The analysis results of this compound were as follows. Absorption spectrum: absorption maximum wavelength 434 nm (in chloroform). Fluorescence spectrum: maximum fluorescence wavelength 548 nm (in chloroform). Synthesis of Compound (21) To 3.0 g of Compound (g), 50 mL of pyridine was added, and 1.3 mL of phenyl chloroformate was added dropwise at room temperature under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated under reflux for 6 hours, the reaction solution was returned to room temperature, and the precipitated crystals were separated by filtration, washed with ethanol and dried to obtain 1.9 g of Compound (21) (yield: 60%).
Obtained. The analysis results of this compound were as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm) = 6.95
(M, 2H), 7.20 to 7.58 (m, 13H), 7.8
2 (1H, d), 7.48 (1H, d), 8.87 (1
H, s)

Example 4 Production and Evaluation of Light-Emitting Element Example 4-1 IT on a 25 mm × 25 mm × 0.7 mm glass substrate
O was formed to a thickness of 150 nm to obtain a transparent support substrate. After etching and washing this transparent support substrate, 40 mg of poly (N-vinylcarbazole) and PBD (2-
(4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) 12 m
g, 0.5 mg of the compound shown in Table 1 was dissolved in 1,2-dichloroethane (3 ml) and spin-coated on a washed ITO substrate. The thickness of the generated organic thin film was about 120 nm. A mask (a mask having a light emitting area of 5 mm × 5 mm) patterned on an organic thin film is provided, and magnesium: silver = 10: 1 is co-deposited at 50 nm in a vapor deposition apparatus, and then 50 nm of silver is vapor deposited to produce a light emitting element. did. Using Toyo Technica Source Measure Unit Model 2400,
A constant DC voltage was applied to the light emitting element to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength and chromaticity coordinates were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. In addition, the fabricated device was kept at 60 ° C. and 20%
After allowing to stand for 3 hours under the condition of RH (driving voltage: 15 V), the presence or absence of a dark spot on the light emitting surface was evaluated. Table 1 shows the results.

[0097]

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As is clear from the results shown in Table 1, the device using the compound of the present invention can be driven at a low voltage and emits light at a high luminance, and generates less dark spots over time, as compared with the comparative compound. It exhibited excellent properties in terms of homogeneous planar light emission and durability. In particular, good light-emitting characteristics were obtained by a coating method with low light emission luminance.

[0099]

[Table 1]

Example 4-2 An ITO substrate was etched and washed in the same manner as in Example 4-1 to obtain TPD (N, N'-bis (3-methylphenyl)-
N, N'-diphenylbenzidine) about 40 nm, the compound shown in Table 2 about 20 nm, 2,5-bis (1-naphthyl)
About 1,3,4-oxadiazole about 40 nm in order
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of ^-5 to 10 ^-6 Torr. Next, a cathode was vapor-deposited in the same manner as in Example 4-1 to produce a light-emitting element, which was evaluated. Table 2 shows the results.
As is clear from the results in Table 2, the device using the compound of the present invention emitted light with higher luminance even in the vapor deposition method than the comparative compound.

[0101]

[Table 2]

Example 4-3 An ITO substrate was etched and washed in the same manner as in Example 4-1. After depositing TPD to a thickness of about 40 nm, the compound shown in Table 3 and Alq (tris (8-hydroxyquinolinato) aluminum) were added. Each deposition rate 0.04Å / sec, 4Å /
Co-evaporation was performed to a film thickness of about 60 nm in seconds. Next, a cathode was deposited in the same manner as in Example 4-1 to produce a light-emitting element.
An evaluation was performed. Table 3 shows the results. As is clear from the results in Table 3, the device using the compound of the present invention emitted light with higher luminance than the comparative compound even in the vapor-doped system.

[0103]

[Table 3]

Example 4-4 An ITO substrate was etched and washed in the same manner as in Example 4-1. After the TPD was deposited to a thickness of about 40 nm, the compounds shown in Table 4 were deposited to a thickness of about 40 nm, and then Alq (Tris (8- Hydroxyquinolinato) aluminum) was deposited to a thickness of about 20 nm. Next, a cathode was vapor-deposited in the same manner as in Example 4-1 to produce a light-emitting element, which was evaluated. Table 4 shows the results.

[0105]

[Table 4]

As is evident from these results, the device using the compound of the present invention exhibited high-luminance emission even in the non-doped type by the vapor deposition method.

Example 4-5 An ITO substrate was etched and washed in the same manner as in Example 4-1. Thereafter, a compound shown in Table 5 was deposited to a thickness of about 60 nm.
lq (tris (8-hydroxyquinolinato) aluminum) was deposited to a thickness of about 40 nm. Next, a cathode was vapor-deposited in the same manner as in Example 4-1 to produce a light-emitting element, which was evaluated. Table 5 shows the results.

[0108]

[Table 5]

As is apparent from these results, it was found that the compound of the present invention was also effective as a hole-injecting / transporting and light-emitting agent, and exhibited high-luminance emission. .

[0110]

According to the present invention, it is possible to obtain an organic light-emitting device having a lower driving voltage, a higher luminance and a longer life than those of the prior art. In the device using the compound of the present invention, high efficiency and high luminance light emission became possible even in a non-doped device. 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.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tatsuya Igarashi 210 Nakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film F-term (reference) 3K007 AB00 AB02 AB03 AB06 AB13 AB18 BB00 CA01 CA05 CB01 DA00 DB03 EB00 FA01

Claims (7)

[Claims] 1. A light emitting device material, which is a compound represented by the following general formula (I). General formula (I) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent. X represents O, S or N—
R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Y is O, S or CQ _{1
(Q 2) (Q 1,} Q 2 represents a hydrogen atom or a substituent, at least one of them either represents an electron withdrawing group. Also Q ₁
And Q ₂ may be linked together to form a ring. ).
Z is represented by the following general formula (II). General formula (II) (Wherein, R _a and R _b are each a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or, .R represents a heterocyclic group _a
And R _b , and / or _Ra and R ₁ , and / or R _b and R ₂ may be linked to each other to form a ring. M represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or a cation. ) 2. A compound represented by the following general formula (Ia). Formula (I-a) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent. X represents O, S or N—
R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Ar _a and Ar _b each represent an aryl group or an aromatic heterocyclic group. Ar _a
And Ar _b , and / or Ar _a and R ₁ , and / or Ar _b and R ₂ may be linked to each other to form a ring. Y represents O or S. ) 3. A light emitting device material characterized by being a compound represented by the general formula (Ia). 4. A compound represented by the following general formula (III). Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. R ₂₁ represents a hydrogen atom or a substituent. X represents O, S or NR (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group). Ar _a and Ar _b each represent an aryl group or an aromatic heterocyclic group. Ar _a and Ar _b , and / or Ar _a and R ₁ , and / or Ar _b and R ₂ may be linked to each other to form a ring. ) 5. A light emitting device material characterized by being a compound represented by the general formula (III). 6. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes,
5. A light-emitting device comprising at least one layer containing at least one compound represented by formula (I), (Ia) or (III) according to claim 1, 2 or 4. . 7. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes,
At least one layer is a layer in which at least one compound represented by the general formula (I), (Ia) or (III) according to claim 1, 2, or 3 is dispersed in a polymer. Light emitting element.