JP2000229966A - Azole derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a material for organic luminescent materials having high color purity, capable of obtaining luminescence having high brightness and high efficiency in driving at low voltage and excellent in stability in repeated use. SOLUTION: This compound has a partial structure of formula I [Q is an atomic group necessary for forming a 5-6 membered ring; X is the group C-Ra or N; R11 to R16 and Ra are each H or a substituent group; Y is the group CO, SO or SO2; and (m) is 0 or 1], and is e.g. a compound of formula II. The compound of formula I is obtained by dissolving 2-methylquinoline, 1,8- naphthalimide and zinc chloride into N,N-dimethylaniline, heating and stirring the solution, adding aqueous hydrochloric acid solution thereto and heating and stirring the solution to afford a compound of formula III, dissolving the compound of formula III into methanol, adding sodium methoxide-methanol solution thereto, dropping methanol solution of zinc acetate dihydrate thereto and heating the solution under reflux.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye for a filter, a color conversion filter, a dye for a photographic light-sensitive material, a sensitizing dye, a dye for pulp dyeing, a laser dye, a fluorescent agent for medical diagnosis, a material for an organic light emitting device, and the like. The present invention relates to a novel azole compound suitable for use and an organic light emitting device using the same.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active. Among them, organic light-emitting elements have attracted attention as promising display elements because they can obtain high-luminance light emission at a low voltage. For example, a light emitting device that forms an organic thin film by vapor deposition of an organic compound is known (Applied
Physics Letters, 51, 913, 1987
Year). The organic light emitting device described in this document uses a tris (8-hydroxyquinolinato) aluminum complex (Alq) as an electron transporting material, and a hole transporting material (amine compound).
By stacking them, the light emission characteristics are greatly improved as compared with the conventional single-layer type device.

As a means for further improving the luminous efficiency of the stacked type light emitting device, a method of doping a fluorescent dye is known. For example, Journal of Applied
The luminous efficiency of the organic light-emitting device doped with a coumarin dye described in Physics, Vol. 65, p. 3610, 1989 is greatly improved as compared with the non-doped device. In this case, it is possible to extract light of a desired wavelength by changing the type of the fluorescent compound to be used. However, when Alq is used as the electron transporting material, when the driving voltage is increased to obtain high luminance, the doping is prevented. Since green emission of Alq is observed in addition to the emission of the fluorescent compound, the reduction in color purity is a problem when emitting blue or red light, and the development of a host material that does not reduce color purity is desired. I have. In addition, conventional devices with good color purity and high luminous efficiency are those in which a small amount of fluorescent dye is doped into the charge transporting material, making it difficult to achieve reproducibility of device characteristics in manufacturing and the durability of the dye. Therefore, when used for a long time, there are problems such as a decrease in luminance and a change in color. As a means to solve this, the development of a material that has both a charge transport function and a light emitting function is desired.However, in the materials developed so far, if a fluorescent dye is used at a high concentration as a charge transport material, concentration quenching and the like will occur. There was a problem that high-luminance light emission was difficult.

Although the organic light-emitting devices that have been developed have been improved in light emission intensity, durability and the like by improving the device structure and materials, they are still insufficient for various applications. Does not have good performance. For example, A
Conventional metal complexes such as lq are chemically unstable during electroluminescence, have poor adhesion to the cathode, and do not solve the problem of device deterioration. Further, Alq is a complex using oxine as a ligand, and its material safety is also concerned. Therefore, development of an electron transporting material for an organic light-emitting device having no safety problem has been demanded. Under such circumstances, research on fluorescent or luminescent dyes intended for use in organic light-emitting devices and the like has been actively conducted. As a compound having fluorescence, the following compound a (Chem. Ber., Vol. 10)
0,2261 (1967)) and zinc complexes thereof (JP-A-10-226691).

[0005]

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[0006] However, these compounds emit fluorescence in the green to yellow portions and are not suitable for obtaining red light emission.
Further, even when a red light-emitting dye was used as a host material, red light with good color purity could not be obtained. On the other hand, organic light-emitting devices that achieve high-luminance light emission are devices in which organic substances are stacked by vacuum deposition. However, in view of simplification of the manufacturing process, workability, enlargement of the area, etc., the coating method is used. Device fabrication is desirable. 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.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorescent compound having high color purity.
A second object of the present invention is to provide an organic light emitting device material and an organic light emitting device which have high color purity, can emit light with high luminance and high efficiency at low voltage driving, and have excellent stability when used repeatedly. It is in. A third object of the present invention is to provide a red light emitting material necessary for realizing white light emission and an organic light emitting device using the same. A fourth object of the present invention is to provide a compound useful for a dye for a filter, a color conversion filter, a dye for a photographic material, a sensitizing dye, a pulp dye, a laser dye, a fluorescent agent for medical diagnosis and the like. is there.

[0008]

This object has been achieved by the following means. (1) A compound having a partial structure represented by the following general formula (I) or a tautomer thereof.

[0009]

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(Wherein, Q represents an atomic group necessary for forming a 5- or 6-membered ring; X represents C— _Ra or N.
_{11, R 12, R 13,} R 14, R 15, R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, S
Represents O or SO _2. m represents 0 or 1. (2) A compound having a partial structure represented by the following general formula (Ia) or a tautomer thereof.

[0011]

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(Wherein Q represents an atomic group necessary for forming a 5- or 6-membered ring; X represents C— _Ra or N.
_{11, R 12, R 13,} R 14, R 15, R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, S
Represents O or SO _2. m represents 0 or 1. (3) A metal complex having a compound having a partial structure represented by the general formula (I) in (1) or a tautomer thereof as a ligand. (4) The compound in (1) or (3) is represented by the following general formula (K)
-I) or a metal complex represented as tautomer thereof.

[0013]

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(Wherein Q represents an atomic group necessary for forming a 5- or 6-membered ring; X represents C— _Ra or N.
_{11, R 12, R 13,} R 14, R 15, R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, S
Represents O or SO _2. m represents 0 or 1. M represents a metal ion. n represents an integer of 1 to 4. (5) The compound in (1) or (3) is represented by the following general formula (K)
-II) or a metal complex represented as a tautomer thereof.

[0015]

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(Wherein Q represents an atom group necessary for forming a 5- or 6-membered ring; X represents C— _Ra or N; R
_{11, R 12, R 13,} R 14, R 15, R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, S
Represents O or SO _2. m represents 0 or 1. M represents a metal ion. X ₁ and X ₂ each independently represent a bridging ligand. (6) A metal complex according to (3) to (5), wherein the metal ion of the metal complex is a zinc ion. (7) An organic light-emitting device material, which is a compound according to (1) to (6). (8) In an organic light emitting device having a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of electrodes, at least one layer is a layer containing the compound described in (1) to (6). Organic light-emitting device. (9) In an organic light-emitting element having a light-emitting layer or a plurality of organic compound thin films including the light-emitting layer formed between a pair of electrodes, at least one layer is a layer in which the compound according to (1) to (6) is dispersed in a polymer. An organic light-emitting device comprising:

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, general formula (I) will be described. Q represents an atom group necessary for forming a 5- or 6-membered ring. These 5- or 6-membered rings may further be condensed with a benzene ring, a naphthalene ring or the like. Examples of the 5- or 6-membered ring formed by Q include imidazoline, imidazole, benzimidazole, naphthimidazole, thiazolidine, thiazole, benzothiazole, naphthothiazole, isothiazole, oxazoline, oxazole, benzoxazole, naphthoxazole, isoxazole, Selenazole, benzselenazole, naphthoselenazole,
Pyridine, quinoline, isoquinoline, indole, indolenine, pyrazole, pyrazine, pyrimidine, pyridazine, indazole, purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine, phenanthroline, perimidine, carbolin, tetrazaindene, oxa Diazole, thiadiazole, triazole, triazine and the like, preferably imidazole, benzimidazole, naphthymidazole, thiazole, benzthiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, indolenine, pyridine,
Quinoline, isoquinoline, oxadiazole, thiadiazole, triazole, more preferably benzimidazole, naphthymidazole, benzthiazole,
Naphthothiazole, benzoxazole, naphthoxazole, pyridine, quinoline, isoquinoline, oxadiazole, thiadiazole, and triazole, more preferably benzimidazole, benzothiazole, benzoxazole, pyridine, quinoline, and isoquinoline.

The 5- or 6-membered ring formed with Q (also with respect to the above-mentioned condensed ring such as a benzene ring) may have a substituent, for example, an alkyl group (preferably having 1 to carbon atoms). 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, i
so-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,
For example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like can be mentioned. ), 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,
Pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having 0 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 1 carbon atoms).
6, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, N-phenyl-N-naphthylamino, N-phenyl-N- (3-methylphenyl), N, N-di ( 3-methylphenyl) and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
-12, particularly preferably 1-8 carbon atoms, for example, methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, and particularly preferably having 6 to 12 carbon atoms.
And examples thereof include phenyloxy and 2-naphthyloxy. ), Acyl group (preferably having 1 to 1 carbon atoms)
20, 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 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 12 carbon atoms.
And examples thereof include methoxycarbonyl, ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), and an acylamino group (preferably 2 to 2 carbon atoms
It has 0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and includes, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like), aryloxycarbonylamino Group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), and a sulfonylamino group (preferably having a carbon number of 7). 1 to 20, 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 0 to 20 carbon atoms, More preferably 0 to 1 carbon atoms
6, particularly preferably having 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, 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 having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Number 6-20, more preferably carbon number 6-16,
Particularly preferably, it has 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, particularly preferably having 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl). A number of 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.),
A ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like), and a phosphoric amide group (Preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide, etc.), hydroxy group, mercapto Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group,
An imino group, a heterocyclic group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, imidazolyl, pyridyl, Furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, etc.),
And a silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, and particularly preferably having 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to form a ring.

The substituent of the ring formed by Q is preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group,
A carbonylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a cyano group, a nitro group, a halogen atom, a heterocyclic group, and more preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group , A substituted amino group, a halogen atom, and an aromatic heterocyclic group.

X represents C— _Ra or N. R ₁₁ ,
_{R 12, R 13, R 14} , R 15, R 16 and R _a each independently represent a hydrogen atom or a substituent. R ₁₁ , R ₁₂ ,
Examples of the substituent represented by _{R 13, R 14, R 15} , R 16, R a, can be applied for example those mentioned as the substituent of 5 or 6-membered ring formed by Q. _Ra is preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, or an aromatic heterocyclic group, more preferably a hydrogen atom, an alkyl group, or a cyano group, and still more preferably a hydrogen atom.
X is preferably C—R _a , more preferably CH.

R _{11 to} R ₁₆ are preferably a hydrogen atom,
Alkyl group, alkenyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, amino group, hydroxy group, cyano group, nitro group, halogen atom, aromatic heterocyclic group, more preferably hydrogen atom, alkyl group Alkenyl group, aryl group, alkoxy group, aryloxy group, substituted amino group, halogen atom, and aromatic heterocyclic group.

Y represents CO, SO or SO ₂ . Y is preferably CO or SO ₂ , more preferably C
O. m represents 0 or 1, and is preferably 1.

Among the compounds having the partial structure represented by the general formula (I), a metal complex having a ligand having the compound having the partial structure represented by the general formula (I) is more preferable. It is a metal complex represented by the following general formula (KI) or (K-II).

[0024]

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[0025]

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Where Q, X, R₁₁, R₁₂, R₁₃, R₁₄,
R₁₅, R₁₆, Y and m are each represented by the general formula (I)
It has the same meaning as the above, and the preferred range is also the same.
M represents a metal ion. 2-4 valent metal ions
Cations are preferred, more preferably divalent or trivalent
A cation, more preferably Be²⁺, Mg ²⁺, Al
³⁺, Ga³⁺, Zn²⁺And particularly preferably Al³⁺, Z
n²⁺And most preferably Zn²⁺It is. n is 1 to 4
Represents an integer. n is preferably represented by the general formula (KI)
The complex represented is an integer that becomes a neutral complex. And n is
In the case of two or more, the ligands of the metal complex are the same or different from each other.
May be.

X ₁ and X ₂ each independently represent a bridging ligand. Examples of the bridging ligand include, for example, halogen ions (eg, Cl ⁻ , Br ⁻ , I ^−, etc.), hydroxo, oxo, thiocyanato, isothiocyanato, nitro, nitrite, carbonato, carboxylate (eg, acetato,
Etc. oxalato), it is like alcoholate (such as phenolato), preferably a halogen ion, hydroxo, oxo, more preferably a halogen ion, particularly preferably Cl ^- is.

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

[0029]

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Wherein Q, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R _15, R _16, R _a are the same as those, respectively, in formula (I), the preferred range is also the same.
M and n have the same meanings as those in formula (KI), respectively, and their preferred ranges are also the same. General formula (K
Among the compounds represented by -I), a compound represented by the general formula (K-Ib) is more preferable.

[0031]

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Wherein Q, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ and R ₁₆ have the same meanings as those in formula (I), and the preferred ranges are also the same.

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

[0034]

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Wherein Q, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R _15, R _16, R _a are the same as those, respectively, in formula (I), the preferred range is also the same.
M, X ₁ and X ₂ have the same meanings as those in formula (K-II), respectively, and their preferable ranges are also the same. Among the compounds represented by the general formula (K-II), a compound represented by the general formula (K-IIb) is more preferable.

[0036]

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Wherein Q, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ and R ₁₆ have the same meanings as those in formula (I), and the preferred ranges are also the same. X _1b , X
_2b represents a halogen ion, preferably a chloro ion.

The compound having a partial structure represented by the general formula (I) may be a low molecular weight compound or a high molecular weight compound in which a residue represented by the general formula (I) is connected to a polymer main chain. Compound (preferably 1000 to 5,000,000 in weight average molecular weight (in terms of polystyrene), more preferably 50 to 50,000,000
00 to 2,000,000, more preferably 10,000 to 1
000000) or a high molecular weight compound having a skeleton of the general formula (I) in the main chain (preferably, a weight average molecular weight (polystyrene conversion) of 1,000 to 5,000,000, more preferably 5,000 to 2,000,000, further preferably 100
00 to 1,000,000). In the case of a high molecular weight compound, it may be a homopolymer or a copolymer with another monomer. In addition, the general formula (I)
Is represented by a limiting structural formula for convenience, but may be a tautomer thereof. When geometric isomers are present, any of them may be used.

Specific examples of the compound having a partial structure represented by formula (I) of the present invention are shown below, but the present invention is not limited to these.

[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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The compound having a partial structure represented by formula (I) of the present invention is described in, for example, JP-A-10-226691.
No., Liebigs Ann. Chem. , Vol. 3
15, 303 (1901), Chem. Ber. , V
ol. 100, 2261 (1967) and the like. In the synthesis of a metal complex having a compound having a partial structure represented by the general formula (I) as a ligand, a complex may be formed at the same time as the synthesis of the ligand, or the metal may be synthesized using the once isolated ligand. Alternatively, it can be synthesized by reaction with a metal salt. The metal salt is not particularly limited, but nitrate, halogen salt (for example, hydrochloride), sulfate, carboxylate (for example, acetate), phosphonate, sulfonate, hydroxide and the like are preferably used. And preferred are nitrates, hydrochlorides, sulfates and acetates. The molar ratio between the ligand and the metal salt used in synthesizing the metal complex is appropriately selected according to the complex to be synthesized, but the ligand is usually 0.1 to 10 moles, preferably 0 to 10 moles per mole of the metal ion. .5
The molar ratio is from 1 to 8 times, more preferably from 1 to 6 times. When synthesizing the metal complex, a solvent may be used. The solvent is not particularly limited, but water, alcohols (eg, methanol, ethanol, 2-propanol, etc.), esters (eg, ethyl acetate, etc.), ethers (eg, Diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), nitriles (eg, acetonitrile, etc.), ketones (eg, acetone, cyclohexanone, etc.), and hydrocarbons (eg, hexane, Benzene, toluene and the like), halogenated hydrocarbons (for example, dichloromethane, chloroform, 1,2-dichloroethane and the like), carboxylic acids (for example, acetic acid) and the like can be used. Further, these solvents may be mixed and used. As a solvent preferably alcohols, ethers,
Ketones, more preferably alcohols,
Particularly preferred are methanol, ethanol and 2-propanol. The reaction temperature at the time of synthesizing the metal complex is not particularly limited, but is preferably 10 to 150 ° C., and preferably 1 to 150 ° C.
The temperature is 0 to 100 ° C, more preferably 10 to 80 ° C.

Hereinafter, the synthesis of the compound of the present invention will be described with reference to specific examples. Synthesis Example 1 Synthesis of Exemplified Compound 8 14.3 g (0.100 mol) of 2-methylquinoline,
21.7 g (0.110 mol) of 1,8-naphthalimide and 31.3 g (0.230 mol) of zinc chloride were added to N, N
-Dissolved in 165 ml of dimethylaniline, and heated and stirred at 150 ° C for 22 hours in a nitrogen atmosphere. After cooling to room temperature, 800 ml of 3N hydrochloric acid was added, and the mixture was heated and stirred at 90 ° C. for 2 hours. After cooling to room temperature, the precipitated solid was collected by filtration and washed with water. After purification by silica gel column chromatography (developing solvent: chloroform), recrystallization from chloroform / ethyl acetate / n-hexane gave 19.3 g (0.059 mol) of Exemplified Compound 8. Yield 59% orange solid: melting point 232-234 ° C

Synthesis Example 2 Synthesis of Exemplified Compound 25 15.5 g of 7-chloro-2-methylquinoline (0.08
73 mol), 18.9 g of 1,8-naphthalimide (0.
0960 mol) and 27.6 g (0.202 mol) of zinc chloride were dissolved in 142 g of N, N-dimethylaniline, and the mixture was heated and stirred at 150 ° C. for 37 hours under a nitrogen atmosphere. After cooling to room temperature, 615 ml of 3N hydrochloric acid was added, and the mixture was heated and stirred at 95 ° C. for 3 hours. After cooling to room temperature, the precipitated solid was collected by filtration and washed with water. The compound is purified by silica gel column chromatography (developing solvent: chloroform) and then recrystallized from ethanol to give Exemplified Compound 2.
9.80 g (0.022 mol) of Compound 5 was obtained. Yield 25% orange solid: melting point 289-291 ° C

Synthesis Example 3 Synthesis of Exemplified Compound 33 3.22 g (0.010 mol) of Exemplified Compound 8 was dissolved (suspended) in methanol, and 2.05 ml (0.01 mol) of a 28% sodium methoxide-methanol solution was added. While stirring at room temperature, a solution of 1.10 g (0.005 mol) of zinc acetate dihydrate in 15 ml of methanol was added dropwise. After heating under reflux for 5 hours, the mixture was cooled to room temperature, and the solid was collected by filtration. The obtained solid was washed with methanol to give 3.30 g of Exemplified Compound 33 (4.6 g).
6 mmol). Yield 93% (Sublimation products are used for EL device production) Red solid: Melting point> 300 ° C

Synthesis Example 4 Synthesis of Exemplified Compound 36 3.57 g (0.010 mol) of Exemplified Compound 25 was dissolved (suspended) in methanol, and 2.05 ml (0.01 mol) of a 28% sodium methoxide-methanol solution was added. While stirring at room temperature, 1.10 g (0.005 mol) of zinc acetate dihydrate in 15 ml of methanol
The solution was added dropwise. After heating under reflux for 3 hours, the mixture was cooled to room temperature, and the solid was collected by filtration. The obtained solid was washed with methanol to give 3.80 g of Exemplified Compound 36 (4.8 g).
8 mmol). Yield 98% (Sublimation products are used for EL element production) Red-brown solid: melting point> 300 ° C

Next, an organic light emitting device containing the compound of the present invention will be described. The method for forming the organic layer of the organic light-emitting device containing the compound of the present invention is not particularly limited, and methods such as resistance heating evaporation, electron beam, sputtering, molecular lamination, and coating are used, In terms of surface and production, resistance heating evaporation and coating are preferred.

When the compound of the present invention is used as a material for an organic light emitting device, it may be used in any of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a light emitting layer. Alternatively, it is preferably used as a light emitting layer.

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 are 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, etc., 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, an alkali-free 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 producing 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 coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. 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 injection layer, the electron transport layer, the light emitting layer and the like. The cathode has good adhesion and ionization potential between the negative electrode and the adjacent layers such as the electron injection layer, the electron transport 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, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, Quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by metal complexes of 8-quinolinol derivatives and rare earth complexes, polythiophene, polyphenylene, polyphenylene And polymer compounds such as vinylene. Although the thickness of the light emitting layer is not particularly limited, it is usually 1n.
m to 5 μm, more preferably 5 to 5 μm.
nm to 1 μm, more preferably 10 nm to 500
nm. The method for forming the light-emitting layer is not particularly limited, but a method such as resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), and LB method And preferably a resistance heating evaporation and coating method.

The material of the hole injection layer and the hole transport layer has 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, and styryl anthracene derivatives , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds,
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, and a function of blocking holes injected from the anode. Good. Preferably, the compound of the present invention is contained in the electron injection layer and / or the electron transport layer, but other materials of the compound of the present invention can also be used. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, and distyryl derivatives. Pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, phthalocyanine derivatives, 8
-Metal complexes of quinolinol derivatives, metal phthalocyanines, and various metal complexes represented by metal complexes having benzoxazole or benzothiazole as ligands. The thickness of the electron injecting layer and the electron transporting 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 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 that 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
, TiO _{2 and} other metal oxides, 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,
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 Law can be applied.

[0068]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Embodiment 1 FIG. On a washed glass substrate with an ITO electrode, phthalocyanine was formed to a thickness of 5 nm, and bis [N- (1-naphthyl) -N-phenyl] benzidine was formed to a thickness of 50 nm.
The compound described was vacuum-deposited (8 ×
10 ^-6 to 1 × 10 ^-5 torr). A patterned mask (a mask having a light-emitting area of 5 mm × 5 mm) is set thereon, and magnesium: silver = 10: 1 is added at 250 n.
After co-evaporation, 300 nm of silver was evaporated (8 × 10 ^−6).
１1 × 10 ⁻⁵ Torr). Using Toyo Technica Source Measure Unit Model 2400, ITO was used as anode and Mg:
A constant DC voltage was applied to the EL element using Ag as a cathode to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength and chromaticity were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Table 1 shows the results.

[0069]

[Table 1]

[0070]

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From the results shown in Table 1, it can be seen that the use of the compound of the present invention enables low-voltage driving, and also enables the emission of red light with good color purity even with an undoped device.

Example 2 After cleaning the ITO substrate as in Example 1, copper phthalocyanine 5 nm, TPD (N, N-bis (3-methylphenyl) -N, N-diphenylbenzidine) 40 nm, red light emitting material R and The compounds described in Table 2 were co-evaporated at a deposition rate of 0.04 ° / sec and 4 ° / sec to a film thickness of 60 nm. Then, a film thickness of 2 was obtained at an Al: Li = 100: 2 ratio.
Co-evaporation was performed to a thickness of 00 nm. Drive voltage 8V and 15
Table 2 shows the results of measuring the luminance and chromaticity at V.

[0073]

[Table 2]

[0074]

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[0075]

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As is clear from the results in Table 2, it can be seen that the device using the compound of the present invention can emit light with high luminance even in a system doped with a fluorescent compound. In the device using the comparative compound as a host, the red purity decreases when the driving voltage is increased. On the other hand, in the device using the compound of the present invention as a host, little change in the color purity is observed, and the high purity of the color is high. It can be seen that luminance emission is possible.

Example 3 40 mg of poly (N-vinylcarbazole), 2.0 mg of blue luminescent material B, 0.5 mg of green luminescent material Alq, Table 3
2.0 mg of the compound described in 3 m of 1,2-dichloroethane
1 and spin-coated on a washed ITO substrate. The thickness of the generated organic thin film was about 110 nm. A mask patterned on the organic thin film (a mask having a light-emitting area of 5 mm × 5 mm) is provided, and magnesium: silver = 10: 1 is co-evaporated in a vapor deposition apparatus to a thickness of 50 nm.
150 nm of silver was deposited. This device was evaluated in the same manner as in Example 1. Table 3 shows the results.

[0078]

[Table 3]

[0079]

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[0080]

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As is evident from the results in Table 3, the device using the compound of the present invention can be driven at a low voltage and emit light with high luminance even in the coating method in which the light emission luminance is lower than that of the comparative compound. I understand. In addition, the comparative compound e (PB
In the device using D), generation of a dark spot was remarkably observed, whereas in the device of the present invention, good planar light emission was shown. Furthermore, it can be seen that good white light emission is possible when the compound of the present invention is used in combination with a blue light emitting material or a green light emitting material.

[0082]

According to the present invention, an organic light-emitting device capable of emitting high-luminance light even in an undoped type can be obtained. In particular, good light-emitting characteristics can be obtained even by a coating method with low luminance, and an element can be produced which is advantageous in terms of manufacturing cost. In addition, an organic light-emitting device having a small change in chromaticity due to a difference in driving voltage can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 401/14 C07D 401/14 403/06 209 403/06 209 413/06 221 413/06 221 413/14 221 413/14 221 417/06 215 417/06 215 221 221 471/04 112 471/04 112T 471/06 471/06 C09K 11/06 640 C09K 11/06 640 655 655 660 660 660 680 680 G03C 1/10 G03C 1/10 H05B 33/14 H05B 33/14 B 33/22 33/22 B // C07F 3/06 C07F 3/06 F term (reference) 2H023 FD01 3K007 AB04 AB06 AB18 CA01 CB01 DA01 DB03 EB00 4C063 AA01 AA03 AA05 BB01 BB03 CC14 CC17 CC25 CC26 CC29 CC34 CC52 CC58 CC62 CC64 CC67 CC92 DD08 DD12 DD14 DD15 DD17 DD52 EE10 4C065 AA04 AA07 AA19 BB09 CC09 DD02 EE02 HH02 HH05 JJ01 KK02 LL04 PP18 PP19 4H048 AA01 AB92 VA12 VA20 VA22 VA30 VA32 VA40 VA42 VA66 VB10

Claims (9)

[Claims] 1. A compound having a partial structure represented by the following general formula (I) or a tautomer thereof. Embedded image (In the formula, Q represents an atom group necessary to form a 5- or 6-membered ring. X represents C— _Ra or N. R ₁₁ , R ₁₂ , R
_{13, R 14, R 15,} R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, SO or SO
Represents ₂ . m represents 0 or 1. ) 2. A compound having a partial structure represented by the following general formula (Ia) or a tautomer thereof. Embedded image (In the formula, Q represents an atom group necessary to form a 5- or 6-membered ring. X represents C— _Ra or N. R ₁₁ , R ₁₂ , R
_{13, R 14, R 15,} R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, SO or SO
Represents ₂ . m represents 0 or 1. ) 3. A metal complex having a compound having a partial structure represented by the general formula (I) in claim 1 or a tautomer thereof as a ligand. 4. A metal complex, wherein the compound according to claim 1 or 3 is represented by the following general formula (KI) or a tautomer thereof. Embedded image (In the formula, Q represents an atom group necessary to form a 5- or 6-membered ring. X represents C— _Ra or N. R ₁₁ , R ₁₂ , R
_{13, R 14, R 15,} R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, SO or SO
Represents ₂ . m represents 0 or 1. M represents a metal ion. n represents an integer of 1 to 4. ) 5. A metal complex, wherein the compound according to claim 1 is represented by the following general formula (K-II) or a tautomer thereof. Embedded image (In the formula, Q represents an atom group necessary to form a 5- or 6-membered ring. X represents C— _Ra or N. R ₁₁ , R ₁₂ , R
_{13, R 14, R 15,} R 16 and R _a each independently represent a hydrogen atom or a substituent. Y is CO, SO or SO
Represents ₂ . m represents 0 or 1. M represents a metal ion. X ₁ and X ₂ each independently represent a bridging ligand. ) 6. A metal complex according to claim 3, wherein the metal ion of the metal complex according to claim 3 is a zinc ion. 7. An organic light-emitting device material comprising the compound according to claim 1. 8. An organic light-emitting device having a light-emitting layer or a plurality of organic compound thin films including the light-emitting layer formed between a pair of electrodes, wherein at least one layer is a layer containing the compound according to claim 1. Organic light-emitting device. 9. An organic light emitting device having a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of electrodes, wherein at least one layer is a layer in which the compound according to claim 1 is dispersed in a polymer. An organic light-emitting device comprising: