JP2020152655A - Benzoheterophenanthrene compound having condensed ring group and use thereof - Google Patents

Abstract

To provide an organic EL material which exhibits higher efficiency than conventional materials.SOLUTION: A 2-aminocarbazole compound represented by general formula (1) (where X represents an oxygen atom or a sulfur atom; R1 and R2 each independently represent a hydrogen atom or a specific arylamino group; and at least one of R1 and R2 is the arylamino group) is used for one or more of a light-emitting layer, a hole transport layer, and a hole injection layer of an organic EL element.SELECTED DRAWING: None

Description

The present invention relates to a novel arylamine compound having a fused aromatic substituent and an organic EL device using the same.

The organic EL element characterized by self-luminous light can be made thinner because it does not require the backlight used in the liquid crystal panel, and it has the advantage of flexible performance that allows the screen to be curved, so it is the next-generation thin. Research has been actively pursued in recent years as displays and lighting, and they have already been put into practical use in mobile phone displays and televisions.

Generally, an organic EL element has a structure in which a hole transport material, a light emitting material, and an electron transport material are laminated between an anode and a cathode, but at present, in order to achieve low power consumption and long life. , A multi-layer laminated structure in which a hole injection material, an electron injection material, a hole blocking material, etc. are inserted is the mainstream. As the hole transport material, an amine compound having an appropriate ionization potential and hole transport ability is used, and as a standard material, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] Biphenyl (hereinafter abbreviated as NPD) is known (for example, Non-Patent Document 1).

However, NPD has a problem in device life because the glass transition temperature is not sufficiently high. In addition, the drive voltage and luminous efficiency of the device using the NPD for the hole transport layer were not sufficient to satisfy the market requirements.

Against this background, the development of an arylamine compound having a condensed ring that can secure a high glass transition temperature and has excellent hole transportability is being promoted.

As one of the fused rings that can secure a high glass transition temperature, a structure in which a benzothiophene ring or a benzofuran ring is fused to a phenanthrene ring is known, and a hole transport material using such a fused ring has also been reported. (See, for example, Patent Documents 1, 2 and 3).

Special Table 2013-544776 International Publication No. 2013-055132 JP-A-2015-96484

Applied Physics Letters, 1996, Vol. 69, p. 2160

For the compounds disclosed in Patent Documents 1, 2 and 3, improvement in device life is required.

As a result of diligent studies, the present inventors have the following general formula having a benzo [b] phenanthreno [9,10-d] thiophene ring or a benzo [b] phenanthreno [9,10-d] furan ring in the molecule. It has been found that the arylamine compound represented by (1) is superior in the device life of the organic EL element as compared with the conventionally known compound, and the present invention has been completed.

(In the formula, X represents an oxygen atom or a sulfur atom. R ¹ and R ² each independently represent a hydrogen atom or a group represented by the following general formula (2), and R ¹ and R ^{2 respectively.} At least one of them is a group represented by the following general formula (2).)

(In the formula, m and n represent 0 or 1. A and B may form a benzene ring.)

Since the arylamine compound of the present invention has an excellent life of the organic EL device as compared with the conventionally known material, it has an effect that a device equipped with the organic EL device having a long life can be provided.

It is presumed that the arylamine compound of the present invention has an effect of excellent redox stability, and based on the effect, has an effect of extending the life of the organic EL device.

Since the arylamine compound of the present invention is excellent in heat-resistant decomposition property, it has an effect of contributing to improvement of continuous productivity and yield of organic EL device.

Further, when the arylamine compound of the present invention is used as a hole transport layer or a hole injection layer of an organic EL device, it exhibits higher luminous efficiency than conventionally known materials and reduces power consumption of equipment. It has the effect of contributing to.

Such an effect is derived from the characteristic chemical structure of the arylamine compound of the present invention, which is characterized by the structure of the diarylamino group and its bonding position.

Hereinafter, the present invention will be described in detail.

In the arylamine compound represented by the general formula (1), X represents an oxygen atom or a sulfur atom. R ¹ and R ² each independently represent a hydrogen atom or a group represented by the above general formula (2), and at least one of R ¹ and R ² is represented by the above general formula (2). Is the basis for being.

In the above general formula (2), m and n represent 0 or 1. A and B may form a benzene ring.

When A and B form a benzene ring, a phenanthrenyl group is formed as a result, and when A and B do not form a benzene ring, a naphthalenyl group is formed for the portion.

When m or n is 0, the benzene ring (phenylene group) of the relevant portion does not exist, and the naphthalenyl group or the phenanthrenyl group is bonded to the amino group.

When m or n is 1, a benzene ring (phenylene group) is present in the portion, but the bond of the phenylene group at this time is not particularly limited, and the o-phenylene group and m It may be either a −phenylene group or a p-phenylene group.

The general formula (2) is not particularly limited, but as a part thereof, for example, N, N-bis (1-naphthalenyl) amino group, N, N-bis (2-naphthalenyl) amino group, and the like. N- (1-naphthalenyl) -N- (2-naphthalenyl) amino group, N, N-bis (9-phenanthrenyl) amino group, N- (1-naphthalenyl) -N- (9-phenanthrenyl) amino group, N -(2-Naphthalenyl) -N- (9-phenanthrenyl) amino group, N, N-bis [4- (1-naphthalenyl) phenyl] amino group, N, N-bis [4- (2-naphthalenyl) phenyl] Amino group, N- [4- (1-naphthalenyl) phenyl] -N- [4- (2-naphthalenyl) phenyl] amino group, N, N-bis [4- (9-phenanthrenyl) phenyl] amino group, N -[4- (1-naphthalenyl) phenyl] -N- [4- (9-phenanthrenyl) phenyl] amino group, or N- [4- (2-naphthalenyl) phenyl] -N- [4- (9-phenanthrenyl) phenyl] ) Phenyl] Amino groups and the like can be mentioned, and other examples including these groups will be shown later using structural formulas.

Regarding the arylamine compound represented by the general formula (1), ^one of R ¹ and R ² is represented by the above general formula (2) in terms of device life and easy availability of raw materials. It is preferable that the group is a hydrogen atom and the other is a hydrogen atom, and it is more preferable that R ¹ is a hydrogen atom and R ² is a group represented by the above general formula (2).

Regarding the arylamine compound represented by the general formula (1), it is preferable that X is an oxygen atom in terms of excellent device life.

Further, the group represented by the above general formula (2) is preferably a group represented by the following general formula (2') in terms of excellent device life.

(In the formula, m and n represent 0 or 1.)
Hereinafter, preferred compounds are specifically exemplified with respect to the carbazole compound represented by the general formula (1), but the present invention is not limited to these compounds.

Among these arylamine compounds, the formulas (A4), (A25), (A31), (A49), (A70), (A76), (A94), (A115), and (A121) are excellent in device life. ), (A139), (A160), or (A166) is preferable.

The arylamine compound represented by the general formula (1) of the present application is not particularly limited, but is preferably used as, for example, a light emitting host material for an organic EL device, a hole transport material, and / or a hole injection material. can do. Since the arylamine compound represented by the general formula (1) of the present application is excellent in hole transporting ability, the life of the organic EL device can be extended when used as a hole transporting layer and / or a hole injecting layer. can do.

Conventionally, it has been used as a light emitting material in a light emitting layer when the arylamine compound represented by the general formula (1) is used as a light emitting layer, a hole injection layer, and / or a hole transporting layer of an organic EL device. Known fluorescent or phosphorescent materials can be used. The light emitting layer may be formed of only one kind of light emitting material, or may be doped with one or more kinds of light emitting materials in the host material.

When forming the hole injection layer and / or the hole transport layer containing the arylamine compound represented by the general formula (1), the arylamine compound can be used alone, or if necessary. Two or more materials may be contained or laminated, for example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7, Known electron-accepting materials such as 7,8,8-tetracyanoquinodimethane and hexacyanohexazatriphenylene may be contained or laminated.

Further, the arylamine compound represented by the general formula (1) of the present invention can also be used as a light emitting layer of an organic EL device. When the arylamine compound represented by the general formula (1) is used as a light emitting layer of an organic EL device, the arylamine compound is used alone, doped with a known light emitting host material, or known light emission. It can be used by doping with a dopant.

Known methods for forming the hole injection layer, hole transport layer, or light emitting layer containing the arylamine compound represented by the general formula (1) include, for example, a vacuum deposition method, a spin coating method, and a casting method. Method can be applied.

The basic structure of the organic EL device from which the effects of the present invention can be obtained preferably includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, and some of them are included. Layers may be omitted or vice versa.

The anode and cathode of the organic EL element are connected to the power supply via an electric conductor. The organic EL element operates by applying an electric potential between the anode and the cathode.

Holes are injected into the organic EL device from the anode, and electrons are injected into the organic EL device at the cathode.

The organic EL element is typically overlaid on the substrate and the anode or cathode can be in contact with the substrate. The electrodes that come into contact with the substrate are called lower electrodes for convenience. Generally, the lower electrode is an anode, but the organic EL device of the present invention is not limited to such a form.

The substrate may be light transmissive or opaque, depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is adopted as a substrate in such a case. The substrate may have a composite structure including multiple material layers.

When the electroluminescence emission is confirmed through the anode, the anode is formed by passing or substantially passing the emission.

The general transparent anode material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. .. Other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

The anode can be modified with plasma-deposited fluorocarbons. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not important and any transparent, opaque or reflective conductive material can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

A plurality of hole-transporting layers such as a hole-injecting layer and a hole-transporting layer can be provided between the anode and the light-emitting layer. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer, and by interposing these layers between the anode and the light emitting layer, many holes are generated at a lower electric field. Holes can be injected into the light emitting layer.

The organic EL device of the present invention contains an arylamine compound represented by the general formula (1) in a light emitting layer, a hole transport layer, and / or a hole injection layer.

An arylamine compound represented by the general formula (1) can be used for the hole transport layer and / or the hole injection layer, and together with the arylamine compound, a known hole transport material and / or hole Any material can be selected from the injection materials and used in combination.

Known hole injection materials and hole transport materials include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and the like. Examples thereof include oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers (for example, thiophene oligomers). As the hole injection material and the hole transport material, the above-mentioned materials can be used, and examples thereof include porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, and in particular, aromatic tertiary amine compounds. Is preferably used.

Typical examples of the above aromatic tertiary amine compound and styrylamine compound are N, N, N', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p-) Trillaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4'-[4- (di-p-tolylamino) styryl] stilben, 4-N, N- Diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostylbenzene, N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenyl Examples thereof include amino] biphenyl (NPD), 4,4', 4''-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) and the like.

Inorganic compounds such as p-type-Si and p-type-SiC can also be used as hole injection materials and hole transport materials. The hole injection layer and the hole transport layer may have a one-layer structure composed of one or more of the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or a different composition.

The light emitting layer of the organic EL element preferably contains a phosphorescent material or a fluorescent material, and emits light as a result of the recombination of electron / hole pairs in this region. As one component, the general formula (1) is used. It may contain the represented arylamine compound.

The light emitting layer may consist of a single material containing both small molecules and polymers, but more generally it consists of a host material doped with a guest compound, the emission of which originates primarily from dopants and is optional. Can have a color.

Examples of the host material of the light emitting layer include an arylamine compound represented by the general formula (1), a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and a compound having an anthranil group. .. For example, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazobinylene) 1,1'-biphenyl. ), TBADN (2-talshalbutyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis (carbazole-9) -Il) biphenyl), CDBP (4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that assists (supports) hole / electron recombination, or a combination of these materials. Good.

Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyrane compound, thiopyrene compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifrantene derivative, indenoperylene. Examples thereof include derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

Examples of phosphorescent dopants include organometallic complexes of transition metals such as iridium, platinum, palladium, or osmium.

Examples of dopants are Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4'-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples thereof include tris (2-phenylpyridine) iridium (III) and FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)).

Examples of the electron transporting material include an alkali metal complex, an alkaline earth metal complex, and an earth metal complex. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinate) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinate) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, Bis (10-hydroxybenzo [h] quinolinate) berylium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) ( Examples thereof include o-cresolate) gallium, bis (2-methyl-8-quinolinate) -1-naphtholate aluminum, and bis (2-methyl-8-quinolinate) -2-naphtholate gallium.

A hole blocking layer may be provided between the light emitting layer and the electron transporting layer for the purpose of improving the carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphenyl (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2). −Methyl-8-quinolinolate) -4- (phenylphenolate) aluminum), bis (10-hydroxybenzo [h] quinolinate) berylium) and the like.

In the organic EL device of the present invention, an electron injection layer may be provided for the purpose of improving the electron injection property and the device characteristics (for example, luminous efficiency, constant voltage drive, or high durability).

Desirable compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fleolenilidenemethane, anthraquinodimethane, or anthron. And so on. In addition, the metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, as described above, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, or C, nitrides, and inorganic compounds such as oxide nitrides can also be used.

The cathode used in the present invention can be formed from any conductive material if the emission is confirmed only through the anode. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium. , Lithium / aluminum mixture, rare earth metals and the like.

Represents a cyclic voltammogram of compound (A76).

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not construed as being limited to these Examples.

The analytical instruments and measurement methods used in this example are listed below.

[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh Multi-Station LC-8020
Measurement conditions: Column Inertsil ODS-3V (4.6 mmΦ x 250 mm)
Detector UV detection (wavelength 254 nm)
Eluent Methanol / tetrahydrofuran = 9/1 (v / v ratio)
[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measurement method: FD-MS analysis

Example 1 (Synthesis of compound (A25))
In a nitrogen atmosphere, 0.93 g (3.06 mmol) of the above compound (3) and 1.23 g (2.92 mmol) of N, N-bis [4- (1-naphthalenyl) phenyl] amine were placed in a 100 mL four-necked flask. , O-Xylene 14 mL, palladium acetate 3.3 mg (0.015 mmol), tri-tert-butylphosphine 8.9 mg (0.044 mmol), and tert-butoxysodium 0.39 g (4.09 mmol) were added at 140 ° C. Heated to. After 5 hours, heating was terminated and the mixture was allowed to cool to room temperature. 30 mL of pure water was added to this reaction solution, and the precipitated crystals were collected by filtration and washed with pure water and methanol. The obtained white powder was recrystallized from toluene to obtain 1.83 g of the white powder of compound (A25) (yield 91%, purity 99.9%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A25).

Mass spectrometry (FD-MS): 687 (M +).

Example 2 (Synthesis of compound (A31))
In Example 1, instead of 1.23 g of N, N-bis [4- (1-naphthalenyl) phenyl] amine, 1.23 g (2) of N, N-bis [4- (2-naphthalenyl) phenyl] amine was used. The same experimental procedure as in Example 1 was carried out except that .92 mmol) was used to obtain 1.75 g of white powder (yield 87%, purity 99.7%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A31).

Mass spectrometry (FD-MS): 687 (M +).

Example 3 (Synthesis of compound (A4))
In Example 1, 1.01 g (2.93 mmol) of N,4-bis (1-naphthalenyl) aniline was used instead of 1.23 g of N, N-bis [4- (1-naphthalenyl) phenyl] amine. Except for the above, the same experimental procedure as in Example 1 was carried out to obtain 1.51 g of white powder (yield 84%, purity 99.9%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A4).

Mass spectrometry (FD-MS): 611 (M +).

Example 4 (Synthesis of compound (A70))
In Example 1, 1.91 g of white powder was obtained by performing the same experimental operation as in Example 1 except that 0.93 g of the above compound (4) was used instead of 0.93 g of the compound (3). (Yield 95%, purity 99.2%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A70).

Mass spectrometry (FD-MS): 687 (M +).

Example 5 (Synthesis of compound (A76))
In Example 1, 0.93 g of the above compound (4) was used instead of 0.93 g of compound (3), and 1.23 g of N, N-bis [4- (1-naphthalenyl) phenyl] amine was further used. In addition, 1.21 g (2.92 mmol) of N, N-bis [4- (2-naphthalenyl) phenyl] amine was used, and the same experimental procedure as in Example 1 was carried out to obtain 1.61 g of white powder. Obtained (yield 80%, purity 99.8%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A76).

Mass spectrometry (FD-MS): 687 (M +).

Example 6 (Synthesis of compound (A49))
In Example 1, 0.93 g (3.06 mmol) of the above compound (4) was used instead of 0.93 g of the compound (3), and N, N-bis [4- (1-naphthalenyl) phenyl] amine 1. The same experimental procedure as in Example 1 was carried out except that 1.01 g (2.93 mmol) of N,4-bis (1-naphthalenyl) aniline was used instead of 23 g to obtain 1.77 g of white powder. (Yield 99%, Purity 99.4%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A49).

Mass spectrometry (FD-MS): 611 (M +).

Example 7 (Synthesis of compound (A115))
In Example 1, the same experimental procedure as in Example 1 was carried out except that 0.98 g (3.06 mmol) of the above compound (5) was used instead of 0.93 g of the compound (3) to obtain a white powder. 1.85 g was obtained (yield 90%, purity 99.0%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A115).

Mass spectrometry (FD-MS): 703 (M +).

Example 8 (Synthesis of compound (A121))
In Example 1, 0.98 g (3.06 mmol) of the above compound (5) was used instead of 0.93 g of the compound (3), and N, N-bis [4- (1-naphthalenyl) phenyl] amine 1. The same experimental procedure as in Example 1 was carried out to obtain a white powder, except that 1.23 g (2.92 mmol) of N, N-bis [4- (2-naphthalenyl) phenyl] amine was used instead of 23 g. 1.77 g was obtained (yield 86%, purity 99.5%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A121).

Mass spectrometry (FD-MS): 703 (M +).

Example 9 (Synthesis of compound (A94))
In Example 1, 0.98 g (3.06 mmol) of the above compound (5) was used instead of 0.93 g of the compound (3), and N, N-bis [4- (1-naphthalenyl) phenyl] amine 1. The same experimental procedure as in Example 1 was carried out except that 1.01 g (2.93 mmol) of N,4-bis (1-naphthalenyl) aniline was used instead of 23 g to obtain 1.47 g of white powder. (Yield 80%, purity 99.8%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A94).

Mass spectrometry (FD-MS): 627 (M +).

Example 10 (Synthesis of compound (A160))
In Example 1, the same experimental procedure as in Example 1 was carried out except that 0.98 g (3.06 mmol) of the above compound (6) was used instead of 0.93 g of the compound (3) to obtain a white powder. 1.83 g was obtained (yield 89%, purity 99.3%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A160).

Mass spectrometry (FD-MS): 703 (M +).

Example 11 (Synthesis of compound (A166))
In Example 1, 0.98 g (3.06 mmol) of the above compound (6) was used instead of 0.93 g of the compound (3), and N, N-bis [4- (1-naphthalenyl) phenyl] amine 1. The same experimental procedure as in Example 1 was carried out to obtain a white powder, except that 1.23 g (2.92 mmol) of N, N-bis [4- (2-naphthalenyl) phenyl] amine was used instead of 23 g. 1.60 g was obtained (yield 78%, purity 99.3%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A166).

Mass spectrometry (FD-MS): 703 (M +).

Example 12 (Synthesis of compound (A139))
In Example 1, 0.98 g (3.06 mmol) of the above compound (6) was used instead of 0.93 g of the compound (3), and N, N-bis [4- (1-naphthalenyl) phenyl] amine 1. The same experimental procedure as in Example 1 was carried out except that 1.01 g (2.93 mmol) of N,4-bis (1-naphthalenyl) aniline was used instead of 23 g to obtain 1.58 g of white powder. (Yield 86%, purity 99.2%). From mass spectrometry (FD-MS), it was confirmed that the obtained white powder was the target compound (A139).

Mass spectrometry (FD-MS): 627 (M +).

Example 13 (Evaluation of element of compound (A25))
A glass substrate on which an ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, it was washed with ultraviolet rays / ozone, installed in a vacuum vapor deposition apparatus, and exhausted with a vacuum pump until it became 1 × 10 ^-4 Pa. First, copper phthalocyanine was vapor-deposited on an ITO transparent electrode at a vapor deposition rate of 0.1 nm / sec to form a hole injection layer of 10 nm, and subsequently, compound (A25) was vapor-deposited at a vapor deposition rate of 0.3 nm / sec at 30 nm to form holes. It was used as a transport layer. Subsequently, the phosphorescent dopant material tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) and the host material 4,4'-bis (N-carbazolyl) biphenyl (CBP) have a weight ratio of 1:11. Co-deposited at a vapor deposition rate of 0.25 nm / sec so as to be 0.5 to obtain a light emitting layer of 30 nm. Next, BAlq (bis (2-methyl-8-quinolinolat) (p-phenylphenolate) aluminum) was vapor-deposited at a vapor deposition rate of 0.3 nm / sec to form an exciton block layer of 5 nm, and then Alq ₃ (Tris) was further deposited. (8-Kinolinolato) aluminum) was vapor-deposited at 0.3 nm / sec to form a 45 nm electron transport layer. Subsequently, lithium boiled lithium was deposited at a vapor deposition rate of 0.01 nm / sec for 1 nm as an electron injection layer, and aluminum was further deposited at a vapor deposition rate of 0.25 nm / sec for 100 nm to form a cathode. Under a nitrogen atmosphere, a glass plate for sealing was adhered with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm ² was applied to the device thus produced, and the drive voltage and current efficiency were measured. Further, a current of 6.25 mA / cm ² was applied to the element to measure the change with time of the brightness, and the time (brightness half-life) at which the brightness became half of the initial value was examined. The brightness half-life was evaluated as the device life. The results are shown in Table 1. The element life was expressed as a relative value with the element life (luminance half-life) of Comparative Example 1 described later as 100.

Example 14 (Device evaluation of compound (A31))
An organic EL device was produced by the same method as in Example 13 except that compound (A31) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 15 (Device evaluation of compound (A4))
An organic EL device was produced by the same method as in Example 13 except that compound (A4) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 16 (Device evaluation of compound (A70))
An organic EL device was produced by the same method as in Example 13 except that compound (A70) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 17 (Device evaluation of compound (A76))
An organic EL device was produced in the same manner as in Example 13 except that compound (A76) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 18 (Device evaluation of compound (A49))
An organic EL device was produced in the same manner as in Example 13 except that compound (A49) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 19 (Device evaluation of compound (A115))
An organic EL device was produced by the same method as in Example 13 except that compound (A115) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 20 (Evaluation of element of compound (A121))
An organic EL device was produced by the same method as in Example 13 except that compound (A121) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 21 (Device evaluation of compound (A94))
An organic EL device was produced in the same manner as in Example 13 except that compound (A94) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 22 (Device evaluation of compound (A160))
An organic EL device was produced by the same method as in Example 13 except that compound (A160) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 23 (Device evaluation of compound (A166))
An organic EL device was produced by the same method as in Example 13 except that compound (A166) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 24 (Device Evaluation of Compound (A139))
An organic EL device was produced by the same method as in Example 13 except that compound (A139) was used instead of compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Comparative Example 1 (NPD element evaluation)
In the same manner as in Example 13 except that NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) obtained by sublimating and purifying a commercially available product was used instead of compound (A25). An organic EL element was manufactured. Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Reference Example 1 (Evaluation of element of compound (a))
An organic EL device was produced by the same method as in Example 13 except that the following compound (a) was used instead of the compound (A25). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 13.

Example 25 (Evaluation of Redox Stability of Compound (A76))
The redox stability of compound (A76) was evaluated by cyclic voltammetry. Compound (A76) was dissolved in an anhydrous dichloromethane solution having a concentration of tetrabutylammonium perchlorate of 0.1 mol / L at a concentration of 0.001 mol / L, glassy carbon on the working electrode, platinum wire on the counter electrode, and reference electrode. using a silver wire immersed in acetonitrile AgNO _3, to obtain a cyclic voltammogram of the compound (A76) (Fig. 1). Compound (A76) showed a reversible redox wave, and no change in waveform was observed even after repeating the redox cycle 50 times, and the compound (A76) was stable to redox.

The arylamine compound of the present invention can be used as a hole injection material, a hole transport material, or a host material for a light emitting layer of an organic EL device, and has excellent device life characteristics and a low voltage material more than conventional materials. It is expected. Furthermore, not only as a hole injection material, a hole transport material or a light emitting material for an organic EL element or an electrophotographic photosensitive member, but also in the field of an organic photoconductive material such as a photoelectric conversion element, a solar cell, or an image sensor. It can be applied.

Claims (7)

An arylamine compound represented by the general formula (1).
(In the formula, X represents an oxygen atom or a sulfur atom. R ¹ and R ² each independently represent a hydrogen atom or a group represented by the following general formula (2), and R ¹ and R ^{2 respectively.} At least one of them is a group represented by the following general formula (2).)
(In the formula, m and n represent 0 or 1. A and B may form a benzene ring.) The arylamine compound according to claim 1, wherein one of R ¹ and R ² is a group represented by the above general formula (2), and the other is a hydrogen atom. The arylamine compound according to claim 1 or 2, wherein R ¹ is a hydrogen atom and R ² is a group represented by the above general formula (2). The arylamine compound according to any one of claims 1 to 3, wherein X is an oxygen atom. The arylamine compound according to any one of claims 1 to 4, wherein the group represented by the general formula (2) is a group represented by the following general formula (2').
(In the formula, m and n represent 0 or 1.) The arylamine compound according to any one of claims 1 to 5, which is represented by any of the following formulas.
A material for an organic EL device, which comprises the arylamine compound according to any one of claims 1 to 6.