JP2002235075A - Azepine derivative, light emission element material and light emission element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a light emission element material which can be used for obtaining light emission elements capable of emitting light in high brightness and having excellent durability, to provide the light emission element using the same, and to obtain a new azepine derivative which can be used as a raw material for the light emission elements. SOLUTION: The material for the light emission elements comprises a compound represented by formula (1) [Ar11 is a monovalent or polyvalent aromatic hydrocarbon group having a ring-condensed structure of three or more rings, a monovalent or polyvalent aromatic heterocyclic group having a ring-condensed structure of three or more rings, or a group comprising a combination of the monovalent or polyvalent aromatic hydrocarbon group or the monovalent or polyvalent aromatic heterocyclic group with one or more aryl groups, arylene groups, heteroaryl groups and/or heteroarylene groups; R11, R12 and R13 are each a substituent; n11, n12, and n13 are each an integer of 0 to 4; m11 is an integer of >=1. The light emission element has a light emission layer or a plurality of organic compound layers containing the light emission layer between a pair of electrodes, wherein at least one layer of the light emission layer or the organic compound layers contains the light emission element material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-emitting device which emits light by converting electric energy into light, and more particularly to a display device, a display, a backlight, an electrophotograph, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, The present invention relates to a light emitting element that can be suitably used for a signboard, an interior, an optical communication device, and the like. Further, the present invention relates to a light emitting device material used for the light emitting device and a novel azepine derivative which can be used as the light emitting device material.

[0002]

2. Description of the Related Art At present, research and development on various display elements are being actively conducted, and among them, an organic electroluminescent (EL) element has attracted attention because it can emit light with high luminance at a low voltage. For example, a light emitting device having an organic thin film formed by vapor deposition of an organic compound is known (Applied Physics Letters, 51, 913, 1987). This light-emitting device has a structure in which an electron transport material (tris (8-hydroxyquinolinato) aluminum complex (Alq)) and a hole transport material (amine compound) are stacked, and is significantly improved compared to a single-layer device. This shows the light emission characteristics.

In recent years, the application of organic EL elements to full-color displays has been actively studied, but in order to develop high-performance full-color displays, blue, green, and
It is necessary to improve the characteristics of each red light emitting element. For example, in the case of blue light-emitting devices, distyryl arylene compounds (DPVBi) described on page 38 of “Organic EL devices and the forefront of industrialization” (NTS Corporation) have been widely studied, However, there are problems in durability, light emission luminance and efficiency, and improvement is desired. Also, JP-A-10-219
The 241 uses an azepine derivative as a light emitting element material, but has a problem in light emission luminance and in that an organic film becomes cloudy.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light emitting device material used for obtaining a light emitting device capable of emitting light of high luminance and having excellent durability, a light emitting device using the same, and a material for the light emitting device. Medical use, optical brightener,
An object of the present invention is to provide a novel azepine derivative that can be applied to photographic materials, UV absorbing materials, laser dyes, dyes for color filters, color conversion filters, recording materials, and the like.

[0005]

As a result of intensive studies in view of the above-mentioned object, the present inventors have found that a light-emitting element using an azepine derivative having a specific structure as a light-emitting element material can emit high-luminance light and is durable. Discover that it is excellent
The present invention has been made.

The light emitting device material of the present invention has the following general formula (1)
Characterized by comprising a compound represented by the formula:

Embedded image In the general formula (1), Ar ¹¹ is a monovalent or polyvalent aromatic hydrocarbon group having a condensed ring structure of three or more rings or a monovalent or polyvalent aromatic heterocyclic ring having a condensed ring structure of three or more rings. A group consisting of a group or a combination thereof with an aryl group, an arylene group, a heteroaryl group and / or a heteroarylene group; R ¹¹ , R ¹² and R ¹³ each represent a substituent;
1, n12 and n13 each represent an integer of 0 to 4, and m11 is 1
Represents the above integer.

The light-emitting element of the present invention has a light-emitting layer or a plurality of organic compound layers including a light-emitting layer between a pair of electrodes, and at least one of the light-emitting layer and the plurality of organic compound layers is formed of the light-emitting element material. It is characterized by containing. The layer containing the light emitting element material is particularly preferably formed by a coating process.

Further, the azepine derivative of the present invention is characterized by being represented by the following general formula (2).

Embedded image In the general formula (2), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a substituent, n21, n22, n23 and n24 each represent an integer of 0 to 4, and n25 represents 0 to 9 Represents an integer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Light-Emitting Device Material The light-emitting device material of the present invention comprises a compound represented by the following general formula (1).

Embedded image

In the general formula (1), Ar ¹¹ is a monovalent or polyvalent aromatic hydrocarbon group having a condensed ring structure of three or more rings or a monovalent or polyvalent aromatic group having a condensed ring structure of three or more rings. A heterocyclic group, or a group composed of an aryl group, an arylene group, a heteroaryl group, and / or a heteroarylene group. Ar ¹¹ is preferably an aryl group or an arylene group having three or more condensed ring structures. Ar ¹¹ may have a substituent.

The condensed ring structure of three or more rings constituting the aromatic hydrocarbon group is not particularly limited, and examples thereof include an anthracene structure, a phenanthrene structure, a pyrene structure, a perylene structure, and condensed structures of these structures (chrysene). Structure, benzoanthracene structure, benzopyrene structure, etc.). Among them, an anthracene structure, a pyrene structure and a perylene structure are preferred.

The condensed ring structure of three or more rings constituting the aromatic heterocyclic group is not particularly limited, but is preferably a nitrogen-containing heteroaryl structure. Specifically, benzoquinoline structure, benzoquinoxaline structure, benzoquinazoline structure,
Benzonaphthyridine structure, acridine structure, phenanthridine structure, phthalazine structure, phenanthroline structure,
Phenazine structure and the like, among which acridine structure,
Phenanthridine and phenanthroline structures are preferred.

R ¹¹ , R ¹² and R ¹³ each represent a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example, a methyl group, an ethyl group,
Isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc., alkenyl group (preferably having 2 to 30 carbon atoms, more preferably carbon 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc., alkynyl group (preferably 2 to 30 carbon atoms, more preferably carbon Number 2
-20, particularly preferably 2-10 carbon atoms, for example, a propargyl group, a 3-pentynyl group and the like, an aryl group (preferably 6-30 carbon atoms, more preferably 6-20 carbon atoms, particularly preferably carbon number 6-12, for example, a phenyl group, p-
A methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc.), an amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, An amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a ditolylamino group, etc., an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably Has 1 to 10 carbon atoms, for example, methoxy, ethoxy, butoxy, 2-
An ethylhexyloxy group and the like, an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, a phenyloxy group, a 1-naphthyloxy group, 2-naphthyloxy group, etc., heteroaryloxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms)
For example, pyridyloxy group, pyrazyloxy group,
A pyrimidyloxy group, a quinolyloxy group, etc.), an acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 3 carbon atoms)
20, particularly preferably having 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.),
An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 2 carbon atoms)
12; for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms, and Oxycarbonyl group), acyloxy group (preferably having 2 carbon atoms)
-30, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, for example, an acetoxy group, a benzoyloxy group, etc., an acylamino group (preferably 2-3 carbon atoms).
0, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetylamino group, benzoylamino group and the like, and alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably 2 to 20, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 12 carbon atoms)
20, particularly preferably having 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group, etc., and a sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 1 carbon atoms).
20, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably carbon Number 0
12, for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably having 1 to 1 carbon atoms).
30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group and the like, and an alkylthio group (preferably 1 to 3 carbon atoms).
0, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, a methylthio group, an ethylthio group, etc., an arylthio group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms) Particularly preferably 6 to 12 carbon atoms
And a heteroarylthio group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, for example, a pyridylthio group, 2-benziimi A zolylthio group, a 2-benzoxazolylthio group, a 2-benzothiazolylthio group, etc., a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). And a sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms), for example, a methanesulfinyl group and a benzenesulfinyl group. Group), a ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, for example, a ureide group, a methylureide group, a phenylureide group and the like, a phosphoric amide group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably Having 1 to 12 carbon atoms, such as a diethylphosphoramide group and a phenylphosphoramide group, a hydroxy group, a mercapto group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a 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 30 carbon atoms, more preferably having 1 to 12 carbon atoms, containing a nitrogen atom, an oxygen atom, a sulfur atom, or the like as a hetero atom, and may be an aliphatic heterocyclic group; It may be a heteroaryl group, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, carbazolyl group, azepinyl group, etc. A silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms,
Particularly preferably, it has 3 to 24 carbon atoms, such as a trimethylsilyl group and a triphenylsilyl group, and a phosphino group (preferably 2 to 30 carbon atoms, more preferably 2 to 3 carbon atoms).
12, for example, a dimethylphosphino group, a diphenylphosphino group, etc.). These substituents may be further substituted, and the substituents may combine with each other to form a ring structure.

Each of R ¹¹ , R ¹² and R ¹³ is preferably an alkyl group or an aryl group, more preferably an alkyl group.

N11, n12 and n13 each represent an integer of 0-4. n11, n12, n13 plurality of R ¹¹ when 2 or more, R
¹² and R ¹³ may be the same or different. n11, n12 and n13 are each preferably 0 or 1.

M11 represents an integer of 1 or more. m11 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1. When m11 is 2 or more, a plurality of azepinyl groups may be the same or different.

The compound represented by the formula (1) is preferably represented by the following formula (3), more preferably the following formula:
It is represented by (2).

[0018]

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[0019]

Embedded image

In the general formula (3), R ³¹ , R ³² , R ³³ and R ³⁴ have the same meanings as R ¹¹ described above, and the preferred range is also the same. n31,
n32 and n33 have the same meaning as n11 described above, and the preferred range is also the same. n34 represents an integer of 0 to 4, preferably 0 to
It is an integer of 2 and more preferably 0. When n34 is 2 or more, plural R ³⁴ may be different even in the same. n35 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 1. When n35 is plural, plural phenylene groups may be the same or different. Ar ³¹ represents a condensed aryl group having three or more rings, and examples thereof include an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, and condensed forms thereof. Among them, an anthryl group and a pyrenyl group are preferred.

In the general formula (2), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵
Has the same meaning as above R ^11, and preferred ranges are also the same. n
21, n22, n23 and n24 have the same meanings as n11 described above, and the preferred ranges are also the same. n25 represents an integer of 0 to 9, and preferably an integer of 0 to 2.

The compound represented by the general formula (1) used in the present invention is preferably a low molecular compound, but may be a so-called oligomer or polymer compound having a repeating unit. When it is an oligomer or a polymer, its mass average molecular weight (in terms of polystyrene) is preferably from 1,000 to 50.
00000, more preferably 2000-100000, particularly preferably
3000 to 100,000. Here, the polymer may be a homopolymer or a copolymer with another monomer,
When it is a copolymer, it may be a random copolymer or a block copolymer.

The light emitting device material of the present invention comprising the compound represented by the general formula (1) functions as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and the like. It may have a plurality of functions.
The light emitting device material of the present invention is preferably used as a light emitting material or a charge transport material. Hereinafter, specific examples of the compound represented by Formula (1) are shown, but they do not limit the present invention.

[0024]

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[0025]

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[0026]

[Formula 10]

The compound represented by the general formula (1) can be synthesized by various methods. For example, it can be obtained by reacting a metal catalyst (such as a copper derivative or a palladium derivative) with an azepine derivative and an aryl halide derivative and mixing them at room temperature or lower or while heating. If necessary, a solvent (a halogen-based solvent, an amide-based solvent, an ether-based solvent, a hydrocarbon-based solvent (toluene, xylene, or the like), or the like) or a base (an inorganic base or an organic base may be used. Sodium methoxide, potassium t-butoxide, triethylamine, potassium carbonate, etc.) may be used.

[2] Light Emitting Element The light emitting element of the present invention has a light emitting layer or a plurality of organic compound layers including the light emitting layer between a pair of electrodes (anode and cathode). At least one of the light emitting layer and the plurality of organic compound layers contains the light emitting device material of the present invention described above.
There is no particular limitation on the system, driving method, utilization form, and the like of the light emitting device of the present invention, but it is preferable that the light emitting device material of the present invention is used as a light emitting material or a charge transport material.
As a typical light emitting element, an organic EL (electroluminescence) element can be cited.

The method for forming the layer containing the light emitting device material of the present invention is not particularly limited, and includes a resistance heating evaporation method, an electron beam method, a sputtering method, a molecular lamination method, a coating method, and the like.
Methods such as an ink jet method, a printing method, and a transfer method can be used. Among them, the resistance heating vapor deposition method and the coating method are preferable from the viewpoint of the characteristics of the device and the production. The layer containing the light emitting element material is particularly preferably formed by a coating process.

The light emitting device of the present invention may include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like, in addition to the light emitting layer. May be provided. As described above, the light emitting device material of the present invention may be contained in any of these layers, and is preferably contained in the light emitting layer or the charge transport layer. Hereinafter, each layer will be described in detail.

(A) Anode The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer and the like. Materials for forming the anode include metals,
An alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4 eV or more is preferably used. Specific examples include metals (gold, silver, chromium, nickel, etc.) and conductive metal oxides (tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO)
Etc.), mixtures or laminates of these metals and conductive metal oxides, inorganic conductive substances (copper iodide, copper sulfide, etc.), organic conductive materials (polyaniline, polythiophene, polypyrrole, etc.) Laminates and the like can be mentioned. The anode is preferably made of a conductive metal oxide, and the productivity,
ITO is particularly preferred from the viewpoint of high conductivity, transparency and the like.

The method for forming the anode may be appropriately selected according to the material used. 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 indium tin oxide A method such as application of a dispersion can be used. By performing a treatment such as washing on the anode, the driving voltage of the light-emitting element can be reduced or the luminous efficiency can be increased. For example, in the case of an anode made of ITO, UV-ozone treatment, plasma treatment and the like are effective. The sheet resistance of the anode is preferably several hundreds Ω / □ or less. The thickness of the anode can be appropriately selected according to the material, but is usually preferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm.
More preferably, it is particularly preferably 100 to 500 nm.

The anode is usually formed on a substrate made of soda lime glass, non-alkali glass, transparent resin or the like. In the case of a glass substrate, it is preferable to use an alkali-free glass in order to reduce ions eluted from the glass. When a soda lime glass substrate is used, it is preferable to previously form a barrier coat such as silica on the surface thereof. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain mechanical strength, but in the case of a glass substrate, it is usually 0.2 mm or more, preferably 0.7 mm or more.
mm or more.

(B) Cathode The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer and the like. As the material of the cathode, metals, alloys, metal halides, metal oxides, electrically conductive compounds, mixtures thereof, and the like can be used. Adhesion with an adjacent layer such as a light emitting layer, ionization potential, and stability can be used. Etc. may be selected in consideration. Specific examples include alkali metals (Li, Na, K, etc.) and their fluorides and oxides, alkaline earth metals (Mg, Ca, etc.) and their fluorides and oxides, gold,
Alloys and mixed metals containing silver, lead, aluminum, sodium and potassium, alloys and mixed metals containing lithium and aluminum, alloys and mixed metals containing magnesium and silver, rare earth metals (such as indium and ytterbium), and mixtures thereof No. The cathode is preferably made of a material having a work function of 4 eV or less; aluminum, an alloy or a mixed metal containing lithium and aluminum,
Alternatively, it is more preferable to use an alloy or a mixed metal containing magnesium and silver.

The cathode may have a single-layer structure made of the above-described material, or may have a laminated structure including a layer made of the above-described material. For example, aluminum / lithium fluoride,
A laminated structure of aluminum / lithium oxide or the like is preferred.
The cathode can be formed by an electron beam method, a sputtering method, a resistance heating evaporation method, a coating method, or the like. In the case of a vapor deposition method, a material can be vapor-deposited alone or two or more materials can be vapor-deposited simultaneously. When an alloy electrode is formed, a plurality of metals can be formed by simultaneous evaporation, or an alloy prepared in advance may be evaporated. The sheet resistance of the cathode is preferably several hundreds Ω / □ or less.
The thickness of the cathode can be appropriately selected according to the material,
It is preferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm, particularly preferably from 100 nm to 1 μm.

(C) Hole Injection Layer and Hole Transport Layer The materials used for the hole injection layer and the hole transport layer have a function of injecting holes from the anode, a function of transporting holes, and a material injected from the cathode. Any function that has any of the functions of blocking electrons may be used. Specific examples thereof include carbazole, triazole, oxazole, oxadiazole,
Imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin -Based compounds, polysilane-based compounds, poly (N-vinylcarbazole), aniline-based copolymers, conductive polymer oligomers such as thiophene oligomers and polythiophenes, organic silanes, derivatives thereof, carbon films, light-emitting device materials of the present invention, etc. Is mentioned.

The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-mentioned materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good. As a method for forming the hole injection layer and the hole transport layer, a vacuum evaporation method, an LB method, a method in which the above material is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, etc.), An ink jet method, a printing method, a transfer method and the like are used. In the case of the coating method,
A coating solution may be prepared by dissolving or dispersing the above materials together with a resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, and polybutadiene. , Poly (N-vinylcarbazole), hydrocarbon resin,
Ketone resin, phenoxy resin, polyamide, ethyl cellulose, polyvinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin,
Epoxy resin, silicon resin and the like can be used. The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually 1
It is preferably from 5 nm to 5 μm, more preferably from 5 nm to 1 μm, and particularly preferably from 10 to 500 nm.

(D) Light Emitting Layer When an electric field is applied to the light emitting device, holes injected from an anode, a hole injection layer or a hole transporting layer, a cathode,
The electrons injected from the electron injection layer or the electron transport layer are recombined to emit light. The material forming the light emitting layer has a function of receiving holes from an anode or the like when an electric field is applied, a function of receiving electrons from a cathode or the like, a function of transferring electric charges, and a function of emitting light by providing a field for recombination of holes and electrons. Is not particularly limited as long as it can form a layer having The material of the light-emitting layer may emit light from either a singlet exciton or a triplet exciton, and examples thereof include benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, and naphthalene. Phthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyrazine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compound, metal complex (8-quinolinol Derivative metal complexes, rare earth complexes, etc.), polymer light emitting materials (polythiophene, polyphenylene, polyphenylene vinylene, etc.), organic silanes, derivatives thereof, light emitting device materials of the present invention, etc. are used. Kill.

The method for forming the light-emitting layer is not particularly limited, and includes a resistance heating evaporation method, an electron beam method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method,
Dip coating method), inkjet method, printing method, LB
Method, transfer method and the like can be used. Among them, the resistance heating evaporation method and the coating method are preferred. The thickness of the light emitting layer is not particularly limited, and is usually preferably 1 nm to 5 μm, and preferably 5 nm.
The thickness is more preferably from 1 to 1 μm, and particularly preferably from 10 to 500 nm.

(E) Electron injection layer and electron transport layer The material forming the electron injection layer and the electron transport layer has a function of injecting electrons from the cathode, a function of transporting electrons, and a barrier against holes injected from the anode. What is necessary is just to have any of the functions. Specific examples include aromatic rings such as triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene and perylene. Anhydrides, phthalocyanines, metal complexes (metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as ligands), organic silanes, derivatives thereof of the present invention Light-emitting element materials and the like can be mentioned.

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 evaporation method, an LB method, a method of dissolving or dispersing the above materials in a solvent and coating (a spin coating method, a casting method, a dip coating method, etc.), and an ink jet method. , A printing method, a transfer method and the like are used. In the case of the coating method,
The coating material may be prepared by dissolving or dispersing the above materials together with the resin component. As the resin component, the same one as in the case of the hole injection layer and the hole transport layer described above can be used.
The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 to 500 nm.

(F) Protective Layer The protective layer has a function of preventing moisture, oxygen, and the like that promotes device deterioration from entering the device. Metals (In, Sn, Pb, Au, Cu, Ag, Al, Ti, Ni
Etc.), metal oxides (MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, Ni
O, CaO, BaO, Fe ₂ O ₃ , Y ₂ O ₃ , TiO ₂ etc.), metal fluorides (MgF ₂ , LiF, AlF ₃ , CaF ₂ etc.), nitrides (SiN, SiN _x O)
_y, etc.), polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene A copolymer obtained by copolymerizing a monomer mixture containing at least one comonomer, a fluorinated copolymer having a cyclic structure in a copolymer main chain,
A water-absorbing substance having a water absorption of 1% or more and a moisture-proof substance having a water absorption of 0.1% or less can be used.

The method for forming the protective layer is not particularly limited, and may be a vacuum deposition method, a sputtering method, a reactive sputtering method,
MBE (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, Printing method, transfer method and the like can be applied.

[0044]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Comparative Example 1 A cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD (N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine) was vapor-deposited to a thickness of 40 nm. A distyryl compound a was evaporated to a thickness of 20 nm, and an azole compound b shown below was evaporated to a thickness of 40 nm to form an organic thin film. Next, on the obtained organic thin film, a light emitting area of 4
A mask patterned to a size of mm × 5 mm is installed, and magnesium and silver (magnesium:
(Silver = 10: 1 (mass ratio)) is co-deposited at 50 nm, and silver is further deposited at 50 nm.
The light emitting device of Comparative Example 1 was formed by vapor deposition. The resulting light-emitting element was fitted with “Source Measure Unit 24” manufactured by Toyo Technica.
A constant DC voltage was applied using the “00 type” to emit light, and the emission luminance was measured using a Topcon “Brightness meter BM-8” and the emission wavelength using a Hamamatsu Photonics company “Spectrum analyzer PMA-11”. . As a result, blue-green light was obtained, and the maximum luminance was 1130 cd / m ² . When the light-emitting element was left at room temperature in a nitrogen atmosphere for one day, cloudiness of the film surface was observed.

[0046]

[Formula 11]

Comparative Example 2 40 mg of poly (N-vinylcarbazole) and 12 mg of PBD (2- (4-
Biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole) and 1 mg of distyryl compound a were dissolved in 2.5 ml of dichloroethane, and the resulting solution was placed on a washed substrate. An organic layer was formed by spin coating (1500 rpm, 20 sec). The thickness of the obtained organic layer was 100 nm. Next, a mask patterned so as to have a light emitting area of 4 mm × 5 mm was set on the obtained organic layer, and magnesium and silver (magnesium: silver = 10: 1 (mass ratio)) were deposited in a vapor deposition apparatus.
nm was co-evaporated, and silver was further evaporated to 50 nm to produce a light emitting device of Comparative Example 2. As a result of measuring the light emission luminance and the light emission wavelength of the obtained light emitting device in the same manner as in Comparative Example 1, light blue light was obtained, and the highest luminance was 1100 cd / m ² . The light-emitting element was allowed to stand at room temperature for one day in a nitrogen atmosphere and measured again. As a result, the highest luminance was 500 cd / m ² .

Comparative Example 3 A cleaned ITO substrate was put into a vapor deposition apparatus, and the following compound c (exemplified compound 2 described in JP-A-10-219241) was vapor-deposited to a thickness of 40 nm, and Alq (trisquinolinato aluminum complex) was deposited thereon for 60 nm.
m was deposited. A cathode was formed thereon in the same manner as in Comparative Example 1, and a light emitting device of Comparative Example 3 was formed. The emission luminance and emission wavelength of the obtained light-emitting element were measured in the same manner as in Comparative Example 1 above. As a result, green light was emitted and the maximum luminance was 8,800 cd / m ² . When the light-emitting element was left at room temperature under a nitrogen atmosphere for one day, cloudiness of the organic film was observed.

[0049]

Embedded image

Example 1 Compound (1-1) was synthesized as follows.

Embedded image 38.3 g of 1,4-dibromobenzene 2 was added to 300 ml of diethyl ether, cooled to -78 ° C under a nitrogen atmosphere, and 101.4 ml of n-
BuLi (1.6 M / Hexane) was added dropwise over 10 minutes. This 3
The temperature was raised to room temperature over 0 minutes, and 30 g of Anthrone 3 was added over 5 minutes. After refluxing this solution for 8 hours, 400 m
One liter of 1M aqueous hydrochloric acid was slowly added, the solution was transferred to a separatory funnel, the organic layer was separated and concentrated to give a single yellow solid. This solid was subjected to column chromatography (developing solvent: hexane →
Purification by hexane / ethyl acetate = 10/1 (vol / vol) → chloroform) and 21 g of bromophenylanthracene 1
Was obtained as a white solid. 1 g of bromophenylanthracene 1 was dissolved in 50 ml of xylene and 0.73 g of benzazepine 4 was added. 0.35 g of t-BuONa, 0.02 g of P
d (OAc) ₂ and 0.1g of P and (tC ₄ H _{9) 3} was added and stirred under a nitrogen stream. After stirring for 3 hours, 100 ml of 1M hydrochloric acid and 100 ml of ethyl acetate were added to the reaction solution, which was transferred to a separating funnel, and the organic layer was washed with 100 ml of saturated saline. This was purified by column chromatography (developing solvent: hexane / ethyl acetate = 10/1 (vol / vol) → chloroform) to obtain a single yellow solid. This solid was recrystallized from a chloroform / acetonitrile system to obtain 0.5 g of the compound (1-1) as a pale yellow solid. The structure of the compound (1-1) was confirmed by NMR. The fluorescence lambda _max of the deposited film of the compound (1-1) is 458 nm, a melting point of 308 ° C..

A light emitting device of Example 1 was prepared in the same manner as in Comparative Example 1 except that the compound (1-1) obtained as described above was used instead of the distyryl compound a. As a result of measuring the light emission luminance and the light emission wavelength of the obtained light emitting device in the same manner as in Comparative Example 1, blue light emission was obtained, and the maximum luminance was 4700 cd / m ² . When the light-emitting element was left at room temperature in a nitrogen atmosphere for one day, no cloudiness on the film surface was observed.

[0052] Like the above Comparative Example 2 except for using the compound in place of Example 2 distyryl compound a (1-10), and a light-emitting element of Example 2. As a result of measuring the light emission luminance and the light emission wavelength of the obtained light emitting device in the same manner as in Comparative Example 1, light blue light emission was obtained,
The highest luminance was 3600 cd / m ² . The light-emitting element was allowed to stand at room temperature under a nitrogen atmosphere for one day, and was measured again. As a result, the highest luminance was 2900 cd / m ² .

[0053] Similar to the above Comparative Example 3 except for using compound instead of Example 3 Compound c (1-1), and a light-emitting element of Example 3. The emission luminance and emission wavelength of the obtained light-emitting element were measured in the same manner as in Comparative Example 1 above. As a result, green light was emitted and the maximum luminance was 12
It was 100 cd / m ² . When the light-emitting element was left at room temperature under a nitrogen atmosphere for one day, no opacity of the organic film was observed and the organic film was transparent.

[0054] Like the above Comparative Example 2 except for using the compound in place of Example 4 distyryl compound a (1-21), and a light-emitting element of Example 4. As a result of measuring the light emission luminance and the light emission wavelength of the obtained light emitting device in the same manner as in Comparative Example 1, blue light emission was obtained,
The maximum brightness was 3300 cd / m ² .

[0055] Like the above Comparative Example 2 except for using the compound in place of the Example 5 distyryl compound a (1-28), and a light-emitting element of Example 5. As a result of measuring the light emission luminance and the light emission wavelength of the obtained light emitting device in the same manner as in Comparative Example 1, blue light emission was obtained,
The maximum brightness was 3000 cd / m ² .

[0056]

As described in detail above, the light emitting device using the light emitting device material of the present invention can emit light with high luminance and has excellent durability. Therefore, the light emitting device of the present invention is a display device, a display, a backlight, an electrophotograph, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a sign,
It can be suitably used for interiors, optical communication devices, and the like. Further, the compound represented by the general formula (1) constituting the light emitting device material of the present invention, medical use, optical brightener, photographic material, UV absorbing material, laser dye, color filter dye, color conversion filter, It is applicable to recording materials and the like.

Claims (4)

[Claims] 1. A light emitting device material comprising a compound represented by the following general formula (1). Embedded image In the general formula (1), Ar ¹¹ is a monovalent or polyvalent aromatic hydrocarbon group having a condensed ring structure of three or more rings or a monovalent or polyvalent aromatic heterocyclic ring having a condensed ring structure of three or more rings. A group consisting of a group or a combination thereof with an aryl group, an arylene group, a heteroaryl group and / or a heteroarylene group; R ¹¹ , R ¹² and R ¹³ each represent a substituent;
1, n12 and n13 each represent an integer of 0 to 4, and m11 is 1
Represents the above integer. 2. A light-emitting element having a light-emitting layer or a plurality of organic compound layers including a light-emitting layer between a pair of electrodes, wherein at least one of the light-emitting layer and the plurality of organic compound layers is according to claim 1. A light-emitting device comprising the light-emitting device material of claim 1. 3. The light emitting device according to claim 2, wherein the layer containing the light emitting device material is a layer formed by a coating process. 4. An azepine derivative represented by the following general formula (2). Embedded image In the general formula (2), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a substituent, n21, n22, n23 and n24 each represent an integer of 0 to 4, and n25 represents 0 to 9 Represents an integer.