JP7009877B2 - New carbazole compounds and their uses - Google Patents

Description

The present invention relates to a carbazole compound having an ortho-substituted structure having a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group at a specific position, and an organic EL device using the carbazole compound.

Organic EL elements featuring self-luminous light can be made thinner because they do not require the backlight used in liquid crystal panels, and because they have the advantage of flexible performance that allows the screen to be curved, they are next-generation thin. Research has been actively pursued in recent years as displays and lighting, and it has 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 for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter referred to as "biphenyl") is used. (Abbreviated as NPD) is known, but it cannot be said that the drive voltage, light emission efficiency and durability of the element using NPD for the hole transport layer are sufficient. Further, the development of an organic EL device using a phosphorescent light emitting material for the light emitting layer is also in progress, and a hole transporting material having a high triplet level is required for the device using phosphorescent light emitting. NPD is not sufficient in terms of triplet level, and it has been reported that, for example, an organic EL device in which a phosphorescent material having green light emission and NPD are combined has a reduced luminous efficiency (for example, non-patented). See Document 1). Against this background, carbazole compounds have been reported (see, for example, Patent Documents 1 and 2). However, since the aromatic fused rings of the pyrene ring and the anthracene ring described in Patent Documents 1 and 2 have a low triplet level, it is known that it is difficult to obtain high luminous efficiency with an element using a green phosphorescent material. Has been done. Recently, a carbazole compound having a naphthylphenyl group has been reported (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2008-078362 Japanese Unexamined Patent Publication No. 2008-195841 JP-A-2015-0751815

Journal of Applied Physics, 2004, Vol. 95, p. 7798

Many of the NPD and carbazole compounds shown in the background art have a high melting point, and it has been found that they are easily crystallized in the chamber in the vacuum deposition step at the time of manufacturing an organic EL element. In addition, since compounds containing aromatic fused rings or heterocycles tend to have a high sublimation temperature as the molecular weight increases, there is a growing concern about thermal deterioration of materials during the manufacture of organic EL devices, which has the problem of affecting productivity. It has happened. Therefore, an amorphous material and a material having a low sublimation temperature that suppresses crystallization of the material at the time of manufacturing an organic EL device is desired. Further, it is desired to develop a hole transport material that enables a low drive voltage, a high luminous efficiency, and a long life of an organic EL element.

That is, an object of the present invention is to provide a compound having low crystallinity and a low sublimation temperature.

As a result of diligent studies, the present inventors have found that a carbazole compound represented by the following general formula (1), which is characterized by a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group at a specific position, solves the above-mentioned problems. The invention of the present application has been completed.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a group represented by the following general formula (2), and at least one of R ¹ and R ² represents the following general formula (2). ). R ³ represents a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group [these groups may independently have a methyl group or a methoxy group]. )

(In the formula, Ar ¹ and Ar ² may be independently linked or condensed with 6 to 30 carbon atoms, or may be linked or condensed with 3 to 20 carbon atoms. Good heteroaromatic groups [These groups may each independently have one or more substituents selected from the group consisting of a methyl group, a 9-carbazolyl group, a dibenzothienyl group, and a dibenzofuranyl group. Good].)

The carbazole compound of the present invention has two aspects of the molecular structure with the carbazole ring based on the constitutional requirement that the carbazole compound has a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group at a specific position as shown in the general formula (1). The angular strain or steric strain becomes large, and as a result, the sublimated product of the compound becomes amorphous (glassy), which has the effect of lowering the sublimation temperature of the compound. The carbazole compound of the present invention, which exhibits the effect of amorphization and low sublimation temperature, can improve the yield at the time of manufacturing an organic EL device and suppress crystallization as compared with the conventionally known carbazole compound, so that the inside of the organic EL device manufacturing chamber can be suppressed. It has the effect of improving productivity because the crystal deposition of amorphous material is suppressed. Moreover, the carbazole compound of the present invention has the effects of being excellent in hole transportability and excited triplet state. Therefore, the organic EL element using the carbazole compound of the present invention has an effect of being excellent in luminous efficiency and life as compared with the organic EL element using a conventionally known carbazole compound.

Hereinafter, the present invention will be described in detail.

In the carbazole compound represented by the above general formula (1), R ³ is a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group [even if each of these groups independently has a methyl group or a methoxy group. Good].

In the carbazole compound represented by the above general formula (1), R ³ has a phenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-naphthyl group and 2 in terms of easy availability of raw materials. It is preferably a naphthyl group or a 9-phenanthryl group [these groups may each independently have a methyl group or a methoxy group], preferably a phenyl group, a 2-biphenylyl group, or a 3-biphenylyl group. A group, 4-biphenylyl group, 1-naphthyl group, 2-naphthyl group, or 9-phenanthryl group is more preferable, and a phenyl group, 3-biphenylyl group, 4-biphenylyl group, 2-naphthyl group, or 9- More preferably, it is a phenanthryl group.

In the carbazole compound represented by the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a group represented by the above general formula (2), and are of R ¹ and R ² . At least one of them is a group represented by the above general formula (2). In terms of hole transport characteristics and availability of raw materials, one of R ¹ and R ² is a group represented by the above general formula (2) (inevitably, the other is a hydrogen atom). Is preferable, and it is more preferable that R ¹ is a group represented by the above general formula (2) and R ² is a hydrogen atom.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are independently linked or condensed aromatic hydrocarbon groups having 6 to 30 carbon atoms, or have 3 carbon atoms. Heteroaromatic groups of up to 20 which may be linked or condensed [These groups are each independently substituted substituted from the group consisting of a methyl group, a 9-carbazolyl group, a dibenzothienyl group, and a dibenzofuranyl group. It may have one or more groups].

The aromatic hydrocarbon group represented by Ar ¹ and Ar ² which may be linked or condensed with 6 to 30 carbon atoms is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a turphenylyl group, and a naphthyl. Examples thereof include a group, a fluorenyl group, a phenanthryl group, a benzofluorenyl group, a triphenylenyl group and the like. As described above, the groups shown here may independently have a methyl group, a 9-carbazolyl group, a dibenzothienyl group, or a dibenzofranyl group, and the number of substituents is the same. Not particularly limited.

The heteroaromatic group which may be linked or condensed with 3 to 20 carbon atoms in Ar ¹ and Ar ² is not particularly limited, and contains, for example, at least one oxygen atom, nitrogen atom, or sulfur atom. Examples thereof include heteroaromatic groups having 3 to 20 carbon atoms which may be linked or condensed, and more preferably, at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom is aromatic. Examples thereof include a heteroaromatic group having 3 to 20 carbon atoms contained on the ring, which may be linked or condensed, and is not particularly limited, and for example, a pyrrolyl group, a thienyl group, a frill group, and an imidazolyl group. , Pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isooxazolyl group, pyridyl group, pyrimidyl group, pyrazil group, 1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzoimidazolyl group, indazolyl group, Benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxaziazolyl group, quinolyl group, isoquinolyl Examples thereof include a group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxadinyl group, a phenothiazine group, a phenazine group, a thianthrenyl group and the like. As described above, each of these groups may independently have a methyl group, a 9-carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group, and the number of substituents is particularly limited. Not done.

Specific examples of Ar ¹ and Ar ² include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3, 4-Dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl Group, 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 2-methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2 '-Methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl-1,1'-biphenyl -4-Il group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2', 3'- Dimethyl-1,1'-biphenyl-4-yl group, 2', 4'-dimethyl-1,1'-biphenyl-4-yl group, 2', 5'-dimethyl-1,1'-biphenyl-4 -Il group, 2', 6'-dimethyl-1,1'-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalene -1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalene-2-yl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1) -Naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 3-methyl-4- (1-naphthyl) phenyl group, 3-methyl-4- (2-naphthyl) phenyl group, 4- (2-methyl) Naphthalene-1-yl) phenyl group, 3- (2-methylnaphthalen-1-yl) phenyl group, 4-phenylnaphthalen-1-yl group, 4- (2-methylphenyl) naphthalene-1-yl group, 4 -(3-Methylphenyl) naphthalene-1-yl group, 4- (4-methylphenyl) naphthalene-1-yl group, 6-phenylnaphthalen-2-yl group, 4- (2-methylphenyl) naphthalene-2 -Il group, 4- (3-methylphenyl) naphthalene-2-yl group, 4- (4-methylphenyl) naphthalene -2-yl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthril group, 11,11'-dimethyl Benzo [a] fluoren-9-yl group, 11,11'-dimethylbenzo [a] fluoren-3-yl group, 11,11'-dimethylbenzo [b] fluoren-9-yl group, 11,11'- Dimethylbenzo [b] fluoren-3-yl group, 11,11'-dimethylbenzo [c] fluoren-9-yl group, 11,11'-dimethylbenzo [c] fluoren-2-yl group, 3-fluorane Tenyl group, 8-fluoranthenyl group, 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1- Imidazolyl group, 2- (2-naphthyl) -3,4-dimethyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1-Ethyl-2-imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl- 4,5-Diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dibiphenylyl -2-imidazolyl group, 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl-5-pyrazolyl group , 1-Phenyl-5-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-Oxazolyl group, 3-isoxazolyl group, 4-isooxazolyl group, 5-isooxazolyl group, 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl Group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2'-bipyridine-3-yl group, 2,2 '-Bipylene-4-yl group, 2,2'-bipyridine-5-yl group, 2,3'-bipyridine-3 -Il group, 2,3'-bipyridine-4-yl group, 2,3'-bipyridine-5-yl group, 5-pyrimidyl group, pyrazil group, 1,3,5-triazyl group, 4,6-diphenyl -1,3,5-triazine-2-yl group, 1-benzoimidazolyl group, 2-methyl-1-benzoimidazolyl group, 2-phenyl-1-benzoimidazolyl group, 1-methyl-2-benzoimidazolyl group, 1-phenyl- 2-Benzoimidazolyl group, 1-methyl-5-benzoimidazolyl group, 1,2-dimethyl-5-benzoimidazolyl group, 1-methyl-2-phenyl-5-benzoimidazolyl group, 1-phenyl-5-benzoimidazolyl group, 1, 2 -Diphenyl-5-benzoimidazolyl group, 1-methyl-6-benzoimidazolyl group, 1,2-dimethyl-6-benzoimidazolyl group, 1-methyl-2-phenyl-6-benzoimidazolyl group, 1-phenyl-6-benzoimidazolyl group, 1,2-Diphenyl-6-benzoimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7 -Benzothiozolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group, 7-benzoisothiazolyl group, 2,1,3- Benzothiazol-4-yl group, 2,1,3-benzothiazol-5-yl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group, 6-benzoxa Zoryl group, 7-benzoxazolyl group, 3-benzoisoxazolyl group, 4-benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7- Benzoisooxazolyl group, 2,1,3-benzoxadiazolyl-4-yl group, 2,1,3-benzoxadiazolyl-5-yl group, 2-quinolyl group, 3-quinolyl group, 5 -Kinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6 -Kinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthroline-3-yl group, 1 , 10-Phenyltroline-5-yl group, 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-furanyl group, 3 -Phenyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 9-methylcarbazole-2-yl group, 9-methylcarbazole-3-yl group, 9- Methylcarbazole-4-yl group, 9-phenylcarbazole-2-yl group, 9-phenylcarbazole-3-yl group, 9-phenylcarbazole-4-yl group, 9-biphenylcarbazole-2-yl group, 9- Biphenylcarbazole-3-yl group, 9-biphenylcarbazole-4-yl group, 2-thiantolyl group, 10-phenylphenothiazine-3-yl group, 10-phenylphenothiazine-2-yl group, 10-phenylphenoxazine-3 -Il group, 10-Phenylphenoxazine-2-yl group, 1-methylindole-2-yl group, 1-phenylindole-2-yl group, 9-Phenylcarbazole-4-yl group, 1-methylindole- 2-yl group, 1-phenylindole-2-yl group, 4- (2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3- (2-yl) Pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (2-phenylimidazol-1-yl) phenyl group, 4- (1-phenylimidazol-2-yl) Phenyl group, 4- (2,3,4-triphenylimidazol-1-yl) phenyl group, 4- (1-methyl-4,5-diphenylimidazol-2-yl) phenyl group, 4- (2) -Methylbenzoimidazole-1-yl) phenyl group, 4- (2-phenylbenzoimidazole-1-yl) phenyl group, 4- (1-methylbenzoimidazole-2-yl) phenyl group, 4- (2-phenyl) Phenylbenzoimidazole-1-yl) phenyl group, 3- (2-methylbenzoimidazole-1-yl) phenyl group, 3- (2-phenylbenzoimidazole-1-yl) phenyl group, 3- (1-methylbenzoimidazole) -2-Il) Phenyl group, 3- (2-Phenylbenzoimidazole-1-yl) phenyl group, 4- (3,5-diphenyltriazine-1-yl) phenyl group, 4- (2-thienyl) phenyl group , 4- ( 2-Phenyl) Phenyl Group, 5-Phenylthiophen-2-yl Group, 5-Phenylfuran-2-yl Group, 4- (5-Phenylthiophen-2-yl) Phenyl Group, 4- (5-Phenylfuran-) 2-yl) phenyl group, 3- (5-phenylthiophen-2-yl) phenyl group, 3- (5-phenylfuran-2-yl) phenyl group, 4- (2-benzothienyl) phenyl group, 4- (3-benzothienyl) phenyl group, 3- (2-benzothienyl) phenyl group, 3- (3-benzothienyl) phenyl group, 4- (2-dibenzothienyl) phenyl group, 4- (4-dibenzothienyl) Phenyl group, 3- (2-dibenzothienyl) phenyl group, 3- (4-dibenzothienyl) phenyl group, 4- (2-dibenzofuranyl) phenyl group, 4- (4-dibenzofuranyl) phenyl group, 3 -(2-Dibenzofuranyl) phenyl group, 3- (4-dibenzofuranyl) phenyl group, 5-phenylpyridine-2-yl group, 4-phenylpyridine-2-yl group, 5-phenylpyridine-3- Il group, 4- (9-carbazolyl) phenyl group, 3- (9-carbazolyl) phenyl group and the like can be exemplified, but the present invention is not limited thereto.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are independently phenyl group, biphenylyl group, terphenylyl group, naphthyl group and fluorenyl group, respectively, in that they are excellent in hole transportability. Alternatively, a phenanthryl group [each of these groups may independently have one or more substituents selected from the group consisting of a methyl group, a 9-carbazolyl group, a dibenzothienyl group, and a dibenzofuranyl group]. Is preferable.

Further, in the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are independently methyl group, 9-carbazolyl group, dibenzothienyl group or dibenzo in that they are excellent in hole transportability. It has a phenyl group which may have a substituent selected from the group consisting of a furanyl group, a biphenylyl group which may have a methyl group, a terphenylyl group which may have a methyl group, and a methyl group. More preferably, it is a naphthyl group which may be present, a fluorenyl group which may have a methyl group, or a phenanthryl group which may have a methyl group.

Further, in the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are independently phenyl group, 4-methylphenyl group and 4- (9) in that they are excellent in hole transportability. -Carbazolyl) phenyl group, 4- (4-dibenzothienyl) phenyl group, 4- (4-dibenzofuranyl) phenyl group, biphenylyl group, terphenylyl group, naphthyl group, 9,9-dimethyl-2-fluorenyl group, or It is more preferably a phenyl group.

The compound represented by the general formula (1) can be represented by the following general formula (1 ′) or general formula (1 ″).

(In the equation, R ³ , Ar ¹ and Ar ² have the same definition as the general equation (1).)
The preferred range of each substituent in the general formula (1') and the general formula (1 ″) is the same as that in the general formula (1).

Hereinafter, preferred compounds are exemplified for the carbazole compound represented by the general formula (1), but the present invention is not limited to these compounds.

The carbazole compound represented by the general formula (1) can be synthesized by a known method (Tetrahedron Letters, 1998, Vol. 39, p. 2376) using a halogenated 9H-carbazole compound as a raw material. For example, when a 9H-carbazole compound in which the 2-position of the carbazole ring is halogenated is used, it can be synthesized by the following route.

A 9H-carbazole compound in which the 2-position represented by the general formula (3) is halogenated and an aryl compound having a halogen atom represented by the general formula (4) are mixed with copper, if necessary, in the presence of a base. The reaction is carried out using a catalyst or a palladium catalyst to obtain a 2-halogenated-9-substituted carbazole compound represented by the general formula (5). Further, the obtained 2-halogenated-9-substituted carbazole compound represented by the general formula (5) and the secondary amine compound represented by the general formula (6) are subjected to a copper catalyst or a copper catalyst in the presence of a base. The reaction is carried out using a palladium catalyst.

[In the formula, R ¹ to R ⁵ , Ar ¹ and Ar ² represent the same definition as the general formula (1). A and B each independently represent a halogen atom (iodine, bromine, chlorine, or fluorine). ]
The compounds represented by the general formulas (3), (4) and (6) can be synthesized by a generally known method, or commercially available compounds can be used.

The carbazole compound represented by the general formula (1) of the present invention can be used as a material for an organic EL device, and more specifically, a light emitting layer, a hole transport layer or a hole injection of the organic EL device. Can be used as a layer. The carbazole compound represented by the general formula (1) is preferably highly pure in terms of hole transport characteristics and device life. Specifically, impurities such as halogen atoms and transition metal elements and impurities such as manufacturing raw materials and by-products are preferable.

When the carbazole compound represented by the general formula (1) is used as a hole injection layer or a hole transport layer of an organic EL element, a conventionally known fluorescent or phosphorescent material is used as the light emitting layer. 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 made of the carbazole compound represented by the general formula (1), two or more kinds of materials may be contained or laminated, if necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexa. A known electron-accepting material such as azatriphenylene may be contained or laminated.

Further, the carbazole 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 carbazole compound represented by the general formula (1) is used as a light emitting layer of an organic EL device, the carbazole compound is used alone, is doped with a known light emitting host material, or a known light emitting dopant is used. It can be doped and used.

As a method for forming the hole injection layer, the hole transport layer or the light emitting layer containing the carbazole compound represented by the general formula (1), for example, a vacuum vapor deposition method, a spin coating method, a casting method and the like are known. The method can be applied.

The basic structure of the organic EL device to which the effect 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. By applying an electric potential between the anode and the cathode, the organic EL element operates and emits light.

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 the substrate in such a case. The substrate may have a composite structure including multiple material layers.

When electroluminescence emission is confirmed through an 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 seleniums 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.

In the organic EL device of the present invention, the hole transport layer and / or the hole injection layer contains the carbazole compound represented by the general formula (1).

For the hole transport layer and / or the hole injection layer, an arbitrary one is selected from known hole transport materials and / or hole injection materials together with the carbazole compound represented by the general formula (1). Can be used in combination.

Known hole injecting materials and hole transporting materials include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted calcon derivatives, and the like. Examples thereof include oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stylben derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, especially thiophene oligomers. As the hole injecting material and the hole transporting material, the above-mentioned ones can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds may be used. preferable.

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-diphenylaminostillbenzene, 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).

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 different compositions.

The light emitting layer of the organic EL device contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.

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 color.

Examples of the host material of the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl 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, thiopyran 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 carbostylyl compounds.

Examples of phosphorescent dopants include organic metal complexes of transition metals such as iridium, platinum, palladium and osmium.

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

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 transport 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- (phenylphenanthroline) aluminum), bis (10-hydroxybenzo [h] quinolinate) beryllium) and the like can be mentioned.

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 improving 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, anthron and the like. Can be mentioned. In addition, the above-mentioned 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, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and 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.

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: Varian Gemini200
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measurement method: FD-MS analysis [Emission characteristics of organic EL element]
Measuring device: LUMINANCEMETER (BM-9) manufactured by TOPCON
Synthesis Example 1 Synthesis of 2-chloro-9- (2-biphenylyl) carbazole

In a 1000 mL three-necked flask under a nitrogen stream, 15.1 g (75.0 mmol) of 2-chloro-9H-carbazole, 15.5 g (90.0 mmol) of 2-fluorobiphenyl, 48.9 g (150.0 mmol) of cesium carbonate, And 280 mL of dimethyl sulfoxide were added, and the mixture was stirred at 180 ° C. for 24 hours. After cooling to room temperature, 200 mL of pure water and 200 mL of toluene were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 16.2 g (45.7 mmol) of a light brown powder of 2-chloro-9- (2-biphenylyl) carbazole was isolated (yield 61%, HPLC purity 98). .8%).

Compounds were identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.

FDMS (m / z); 353 (M +)
^{1 1} H-NMR (CDCl ₃ ); 7.99 (d, 1H), 7.92 (d, 1H), 7.68-7.54 (m, 4H), 7.49 (d, 1H), 7 .29 (d, 1H), 7.19 (t, 1H), 7.13 (d, 1H), 7.08-7.00 (m, 6H)
¹³ C-NMR (CDCl ₃ ); 141.63, 141.49, 141.05, 138.35, 134.18, 131.64, 131.38, 129.57, 129.12, 128.87, 128 .13, 127.70, 127.39, 125.94, 122.44, 121.63, 120.89, 120.00, 119.98, 119.96, 110.16, 110.08
Synthesis Example 2 2-Chloro-9- [1,1': 3'1''-terphenyl-6-yl] -synthesis of carbazole

12.9 g (64.0 mmol) of 2-chloro-9H-carbazole, 6-fluoro-1,1': 3'1''-terphenyl 19.1 g (76.8 mmol) in a 1000 mL three-necked flask under a nitrogen stream. ), 41.7 g (128.0 mmol) of cesium carbonate, and 250 mL of dimethyl sulfoxide were added, and the mixture was stirred at 180 ° C. for 20 hours. After cooling to room temperature, 50 mL of pure water and 50 mL of toluene were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 16.9 g (39) of a light brown powder of 2-chloro-9- [1,1': 3'1''-terphenyl-6-yl] -carbazole. 0.0 mmol) isolated (yield 61%, HPLC purity 99.3%).

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.00 (d, 1H), 7.91 (d, 1H), 7.71-7.59 (m, 4H), 7.31 (t, 1H), 7 .23-7.06 (m, 11H), 6.89 (d, 2H)
¹³ C-NMR (CDCl ₃ ); 141.78, 141.72, 141.31, 140.80, 140.51, 138.62, 134.24, 131.48, 129.80, 129.29, 129 .03, 128.59, 128.48, 127.07, 126.89, 126.64, 126.54, 126.14, 126.09, 122.44, 121.56, 120.90, 120.06 , 120.03, 120.00, 110.16, 110.09
Synthesis Example 3 2-Chloro-9- [1,1': 4'1''-terphenyl-6-yl] -synthesis of carbazole

In a 1000 mL three-necked flask under a nitrogen stream, 15.1 g (75.0 mmol) of 2-chloro-9H-carbazole, 6-fluoro-1,1': 4'1''-terphenyl 22.3 g (96.0 mmol). ), 48.9 g (150.0 mmol) of cesium carbonate, and 280 mL of dimethyl sulfoxide were added, and the mixture was stirred at 180 ° C. for 24 hours. After cooling to room temperature, 300 mL of pure water was added and stirred, and the product precipitated on the organic layer was collected by filtration and washed with water and methanol. Further recrystallization (toluene) resulted in 14.9 g (34.5 mmol) of a white powder of 2-chloro-9- [1,1': 4'1''-terphenyl-6-yl] -carbazole. Separated (yield 46%, HPLC purity 99.0%).

Compounds were identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 7.99 (d, 1H), 7.93 (d, 1H), 773-7.55 (m, 4H), 7.49 (d, 1H), 7 .41-7.29 (m, 5H), 7.23-7.07 (m, 8H)
¹³ C-NMR (CDCl ₃ ); 141.69, 141.57, 140.67, 140.28, 139.96, 137.35, 134.24, 131.60, 131.44, 129.67, 129 .17, 128.93, 128.60, 128.11, 127.22, 126.84, 126.80, 126.02, 122.51, 121.69, 120.93, 120.05, 110.17 , 110.09
FDMS (m / z); 429 (M +)
Synthesis Example 4 Synthesis of 2-chloro-9- (2- (2-naphthyl) phenyl) carbazole

18.9 g (94.0 mmol) of 2-chloro-9H-carbazole, 25.1 g (112.8 mmol) of 2- (2-fluorophenyl) naphthalene, 61.3 g of cesium carbonate (112.8 mmol) in a 1000 mL three-necked flask under a nitrogen stream. 188.0 mmol) and 350 mL of dimethyl sulfoxide were added, and the mixture was stirred at 180 ° C. for 24 hours. After cooling to room temperature, 200 mL of pure water and 200 mL of toluene were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 23.3 g (57.3 mmol) of a white powder of 2-chloro-9- (2- (2-naphthyl) phenyl) carbazole was isolated (yield 61%). , HPLC purity 98.7%).

Compounds were identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.

FDMS (m / z); 403 (M +)
^{1 1} H-NMR (CDCl ₃ ); 7.95 (d, 1H), 7.89 (d, 1H), 7.78 (d, 1H), 7.68-7.49 (m, 6H), 7 .40-7.22 (m, 4H), 7.17-7.09 (m, 4H), 7.02 (d, 1H)
¹³ C-NMR (CDCl ₃ ); 141.80, 141.61, 141.07, 136.01, 134.42, 133.14, 132.35, 132.00, 131.42, 129.75, 129 .23, 129.02, 127.96, 127.70, 127.37, 127.03, 126.00, 125.88, 125.59, 122.47, 121.70, 120.92, 120.05 , 120.03, 120.00, 110.19, 110.02
Synthesis Example 5 Synthesis of 2-chloro-9- (2- (9-phenanthryl) phenyl) carbazole

In a 200 mL three-necked flask under a nitrogen stream, 3.0 g (14.9 mmol) of 2-chloro-9H-carbazole, 6.1 g (122.3 mmol) of 9- (2-fluorophenyl) phenanthrene, and tripotassium phosphate 6. 3 g (29.8 mmol) and 30 mL of dimethyl sulfoxide were added, and the mixture was stirred at 180 ° C. for 30 hours. After cooling to room temperature, 50 mL of pure water was added and stirred, and the product precipitated on the organic layer was collected by filtration and washed with water and methanol. By recrystallizing the residue (toluene / butanol), 2.3 g (5.1 mmol) of a brown powder of 2-chloro-9- (2- (9-phenanthril) phenyl) carbazole was isolated (yield 34%). , HPLC purity 99.0%).

Compound identification was performed by FDMS.

FDMS (m / z); 453 (M +)
Synthesis Example 6 Synthesis of 4-chloro-9- (2-biphenylyl) carbazole

In a 300 mL three-necked flask under a nitrogen stream, 5.0 g (24.8 mmol) of 4-chloro-9H-carbazole, 5.1 g (29.8 mmol) of 2-fluorobiphenyl, 16.2 g (49.6 mmol) of cesium carbonate, And 100 mL of dimethyl sulfoxide was added, and the mixture was stirred at 180 ° C. for 48 hours. After cooling to room temperature, 100 mL of pure water was added and stirred, and the product precipitated on the organic layer was collected by filtration and washed with water and methanol. Further recrystallization (toluene / butanol) isolated 4.6 g (12.9 mmol) of a white powder of 4-chloro-9- (2-biphenylyl) carbazole (yield 54%, HPLC purity 99.0). %).

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.56 (d, 1H), 7.69-7.53 (m, 4H), 7.46 (d, 1H), 7.34 (t, 1H), 7 .26-7.08 (m, 3H), 7.00-6.94 (m, 6H)
¹³ C-NMR (CDCl ₃ ); 142.18, 141.33, 141.21, 138.32, 134.31, 131.61, 129.77, 129.15, 128.83, 128.40, 128 .16, 127.69, 127.39, 126.22, 125.84, 122.83, 122.00, 120.31, 119.89, 109.78, 108.35
Example 1 (Synthesis of compound (A13))

In a 100 mL three-necked flask under a nitrogen stream, 3.2 g (9.0 mmol) of 2-chloro-9- (2-biphenylyl) carbazole obtained in Synthesis Example 1, N- (4-biphenyl) -4-p-ter Add 3.6 g (9.0 mmol) of phenylamine, 1.2 g (12.6 mmol) of sodium-tert-butoxide, and 25 mL of o-xylene, and 10.1 mg (0.) of palladium acetate in the obtained slurry reaction solution. 045 mmol) and 109.0 mg (0.135 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The product precipitated on the organic layer was collected by filtration and washed with water and methanol. Further recrystallization (toluene / butanol) isolated 5.6 g (2.8 mmol) of a grayish white powder of compound (A13) (yield 88%, HPLC purity 99.4%). It was confirmed that the sublimation temperature of A13 was 315 ° C. and that the sublimated product A13 was glassy.

Compounds were identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.02 (d, 1H), 7.93 (d, 1H), 7.66-7.40 (m, 20H), 7.38-7.17 (m, 5H), 7.11-6.92 (m, 10H), 6.78 (s, 1H)
¹³ C-NMR (CDCl ₃ ); 147.32, 147.19, 145.25, 142.23, 141.79, 140.91, 140.72, 140.67, 139.58, 139.52, 138 .57, 134.74, 134.42, 134.04, 131.64, 129.73, 128.92, 128.79, 128.75, 128.17, 127.78, 127.63, 127.49 , 127.45, 127.24, 127.18, 126.96, 126.89, 126.76, 126.60, 125.37, 123.45, 123.33, 123.00, 120.87, 119. .85, 119.77, 119.69, 118.78, 109.80, 107.53
FDMS (m / z); 714 (M +)
Example 2 (Synthesis of compound (A20))

In a 100 mL three-necked flask under a nitrogen stream, 4.3 g (12.2 mmol) of 2-chloro-9- (2-biphenylyl) carbazole obtained in Synthesis Example 1, N- [4- (carbazole-9-yl) phenyl. ] -4-Biphenylamine 5.0 g (12.2 mmol), sodium-tert-butoxide 1.6 g (17.1 mmol), and o-xylene 25 mL were added, and palladium acetate 13. 7 mg (0.061 mmol) and 37.0 mg (0.183 mmol) of tri-tert-butylphosphine were added, and the mixture was stirred at 140 ° C. for 8 hours. After cooling to room temperature, 30 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / hexane), 6.2 g (8.5 mmol) of a white powder of compound (A20) was isolated (yield 69%, HPLC purity 99.7%). It was confirmed that the sublimation temperature of A20 was 300 ° C. and that the sublimated product A20 was glassy.

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.14 (d, 2H), 8.03 (d, 1H), 7.97 (d, 1H), 7.59 (d, 4H), 7.55-7 .47 (m, 4H), 7.42 (d, 6H), 7.36-7.19 (m, 8H), 7.10 (dd, 4H), 7.10-6.94 (m, 6H) ), 6.81 (d, 1H)
¹³ C-NMR (CDCl ₃ ); 147.21, 147.01, 145.13, 142.27, 141.81, 141.14, 140.95, 140.61, 138.52, 135.23, 134 .44, 131.65, 131.04, 129.79, 128.97, 128.77, 128.20, 127.79, 127.77, 127.75, 127.21, 126.87, 126.65 , 125.82, 125.50, 123.76, 123.62, 123.18, 122.96, 121.02,120.27,119.93,119.84,119.70,118.78,109 .84, 109.80, 107.66
Example 3 (Synthesis of compound (A71))

In a 50 mL three-necked flask under a nitrogen stream, 3.9 g (9.0 mmol) of 2-chloro-9- [1,1': 4'1''-terphenyl-6-yl] -carbazole obtained in Synthesis Example 3 was placed. ), N, N-bisbiphenylamine 2.9 g (9.0 mmol), sodium-tert-butoxide 1.2 g (12.6 mmol), and o-xylene 25 mL were added, and acetic acid was added to the obtained slurry reaction solution. 10.1 mg (0.045 mmol) of palladium and 109.0 mg (0.135 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. The product precipitated on the organic layer was collected by filtration and washed with water and methanol. Further, by recrystallization (toluene), 4.7 g (6.6 mmol) of a white powder of compound (A71) was isolated (yield 73%, HPLC purity 99.6%). It was confirmed that the sublimation temperature of A71 was 295 ° C., and that the sublimated product A71 was glassy.

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.05 (d, 1H), 7.93 (d, 1H), 7.61 (d, 1H), 7.52-7.45 (m, 9H), 7 .40-7.23 (m, 18H), 6.99-6.88 (m, 7H), 6.73 (d, 1H)
¹³ C-NMR (CDCl ₃ ); 147.18, 145.19, 142.23, 141.46, 140.50, 140.24, 140.08, 139.68, 137.62, 134.44, 134 .35, 131.58, 129.73, 128.90, 128.79, 128.67, 128.18, 127.48, 127.35, 126.88, 126.82, 126.66, 126.48 , 125.50, 123.08, 120.90, 120.00, 119.89, 119.85, 119.19, 109.82, 108.16
Example 6 (Synthesis of compound (A75))

In a 50 mL three-necked flask under a nitrogen stream, 1.3 g (3.0 mmol) of 2-chloro-9- [1,1': 4'1''-terphenyl-6-yl] -carbazole obtained in Synthesis Example 3 ), 2- (4-biphenylyl) amino-9,9-dimethylfluorene 1.1 g (3.0 mmol), sodium-tert-butoxide 0.40 g (4.2 mmol), and o-xylene 12 mL. 7 mg (0.03 mmol) of palladium acetate and 18 mg (0.09 mmol) of tri-tert-butylphosphine were added to the slurry-like reaction solution, and the mixture was stirred at 140 ° C. for 24 hours. After cooling to room temperature, 12 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By purifying the residue by silica gel column chromatography (toluene / hexane volume ratio = 1/1), 1.4 g (1.8 mmol) of white powder of compound (A75) was isolated (yield 60%, HPLC). Purity 99.6%). It was confirmed that the sublimation temperature of A75 was 285 ° C. and that the sublimated product A75 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 754 (M +)
Example 7 (Synthesis of compound (A76))

Use 0.89 g (3.0 mmol) of N-phenyl-4- (1-naphthyl) phenylamine instead of 1.1 g (3.0 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene. The same procedure as in Example 6 was carried out except that 1.2 g (1.7 mmol) of the white powder of compound (A76) was isolated (yield 58%, HPLC purity 99.3%). The sublimation temperature of A76 was 295 ° C., and it was confirmed that the sublimated product A76 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 688 (M +)
Example 8 (Synthesis of compound (A311))

Example 6 except that 0.83 g (3.0 mmol) of 2-anilinodibenzothiophene was used instead of 1.1 g (3.0 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene. The same procedure was carried out to isolate 1.1 g (1.6 mmol) of a white powder of compound (A311) (yield 53%, HPLC purity 99.2%). It was confirmed that the sublimation temperature of A311 was 290 ° C. and that the sublimated product A311 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 668 (M +)
Example 9 (Synthesis of compound (A318))

Instead of 1.1 g (3.0 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene, 1.0 g (3.0 mmol) of N-phenyl-4- (4-dibenzofuranyl) phenylamine The same procedure as in Example 6 was carried out except that 1.3 g (1.8 mmol) of the white powder of compound (A318) was isolated (yield 60%, HPLC purity 99.4%). It was confirmed that the sublimation temperature of A318 was 300 ° C. and that the sublimated product A318 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 728 (M +)
Example 10 (Synthesis of compound (A19))

In a 100 mL three-necked flask under a nitrogen stream, 3.5 g (10.0 mmol) of 2-chloro-9- (2-biphenylyl) carbazole obtained in Synthesis Example 1 and 4'-(carbazole-9-yl) -N- The obtained slurry form was obtained by adding 4.1 g (10.0 mmol) of phenyl- [1,1'-biphenyl] -4-amine, 1.3 g (13.0 mmol) of sodium-tert-butoxide, and 30 mL of o-xylene. 11.2 mg (0.050 mmol) of palladium acetate and 30.3 mg (0.150 mmol) of tri-tert-butylphosphine were added to the reaction solution, and the mixture was stirred at 140 ° C. for 10 hours. After cooling to room temperature, 30 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 7.0 g (9.6 mmol) of a white powder of compound (A19) was isolated (yield 96%, HPLC purity 99.8%). It was confirmed that the sublimation temperature of A19 was 310 ° C. and that the sublimated product A19 was glassy.

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.16 (d, 2H), 8.01 (d, 1H), 7.93 (d, 1H), 7.78 (d, 2H), 7.62-7 .39 (m, 12H), 7.36-7.17 (m, 7H), 7.14-6.91 (m, 11H), 6.76 (d, 1H)
¹³ C-NMR (CDCl ₃ ); 147.84, 147.78, 145.38, 142.21, 141.81, 140.96, 140.90, 139.84, 138.57, 136.22, 134 .46, 133.19, 131.62, 129.74, 129.13, 128.90, 128.76, 128.16, 127.81, 127.79, 127.54, 127.30, 127.18 , 125.92, 125.34, 123.87, 123.39, 123.00, 122.90, 122.50, 120.84, 120.29, 119.90, 119.85, 119.75, 119. .61, 118.70, 109.84, 109.79, 107.43
Example 11 (Synthesis of compound (A51))

In a 100 mL three-necked flask under a nitrogen stream, 3.9 g (9.0 mmol) of 2-chloro-9- [1,1': 3'1''-terphenyl-6-yl] -carbazole obtained in Synthesis Example 2 was placed. ), N, N-bisbiphenylamine 2.9 g (9.0 mmol), sodium-tert-butoxide 1.2 g (12.6 mmol), and o-xylene 25 mL were added, and acetic acid was added to the obtained slurry reaction solution. 10.1 mg (0.045 mmol) of palladium and 109.0 mg (0.135 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 6.1 g (8.5 mmol) of white powder of compound (A51) was isolated (yield 95%, HPLC purity 99.8%). It was confirmed that the sublimation temperature of A51 was 290 ° C. and that the sublimated product A51 was glassy.

The compounds were identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
^{1 1} H-NMR (CDCl ₃ ); 8.04 (d, 1H), 7.95 (d, 1H), 7.65-7.52 (m, 8H), 7.43-7.16 (m, 18H), 7.08-6.84 (m, 10H)
¹³ C-NMR (CDCl ₃ ); 147.20, 145.54, 142.35, 142.13, 141.15, 140.74, 140.64, 140.56, 138.81, 134.70, 134 .45, 131.49, 130.02, 129.13, 128.96, 128.71, 128.53, 127.58, 127.08, 126.97, 126.72, 126.64, 126.59 , 125.93, 125.51, 123.42, 122.96, 120.94, 119.87, 119.75, 119.59, 118.78, 109.84, 107.17
Example 12 (Synthesis of compound (A103))

2-Chloro-9- (2- (2-naphthyl) phenyl) carbazole 1.2 g (3.0 mmol) and 9-anilinophenanthrene 0.81 g obtained in Synthesis Example 4 in a 50 mL three-necked flask under a nitrogen stream. (3.0 mmol), 0.40 g (4.2 mmol) of sodium-tert-butoxide, and 12 mL of o-xylene were added, and 7 mg (0.03 mmol) of palladium acetate and tri-tert were added to the obtained slurry reaction solution. -Butyl phosphine 18 mg (0.09 mmol) was added and stirred at 140 ° C. for 24 hours. After cooling to room temperature, 12 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By purifying the residue by silica gel column chromatography (toluene / hexane volume ratio = 1/1), 1.2 g (1.9 mmol) of white powder of compound (A103) was isolated (yield 63%, HPLC). Purity 99.6%). It was confirmed that the sublimation temperature of A103 was 300 ° C. and that the sublimated product A103 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 636 (M +)
Example 13 (Synthesis of compound (A109))

The same operation as in Example 12 was carried out except that 0.89 g (3.0 mmol) of N- (4-biphenylyl) -1-naphthylamine was used instead of 0.81 g (3.0 mmol) of 9-anilinophenanthrene. Then, 1.4 g (2.1 mmol) of a white powder of compound (A109) was isolated (yield 70%, HPLC purity 99.4%). It was confirmed that the sublimation temperature of A109 was 300 ° C. and that the sublimated product A109 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 662 (M +)
Example 14 (Synthesis of compound (A112))

Examples except that 4-anilino-1,1': 4', 1''-terphenyl 0.96 g (3.0 mmol) was used instead of 0.81 g (3.0 mmol) of 9-anilinophenanthrene. The same procedure as in No. 12 was carried out to isolate 1.4 g (2.1 mmol) of a white powder of compound (A112) (yield 70%, HPLC purity 99.5%). It was confirmed that the sublimation temperature of A112 was 305 ° C. and that the sublimated product A112 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 688 (M +)
Example 15 (Synthesis of compound (A337))

Same as Example 12 except that 1.1 g (3.0 mmol) of N-phenyl-4- (4-dibenzothienyl) phenylamine was used instead of 0.81 g (3.0 mmol) of 9-anilinophenanthrene. The procedure was carried out to isolate 1.1 g (1.6 mmol) of white powder of compound (A337) (yield 52%, HPLC purity 99.5%). It was confirmed that the sublimation temperature of A337 was 305 ° C. and that the sublimated product A337 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 718 (M +)
Example 16 (Synthesis of compound (A126))

In a 50 mL three-necked flask under a nitrogen stream, 1.4 g (3.0 mmol) of 2-chloro-9- (2- (9-phenanthril) phenyl) carbazole obtained in Synthesis Example 5, N-phenyl-4-biphenylyl 0.74 g (3.0 mmol) of amine, 0.40 g (4.2 mmol) of sodium-tert-butoxide, and 12 mL of o-xylene were added, and 7 mg (0.03 mmol) of palladium acetate was added to the obtained slurry reaction solution. And 18 mg (0.09 mmol) of tri-tert-butylphosphine were added, and the mixture was stirred at 140 ° C. for 24 hours. After cooling to room temperature, 12 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By purifying the residue by silica gel column chromatography (toluene / hexane volume ratio = 1/1), 1.5 g (2.3 mmol) of white powder of compound (A126) was isolated (yield 76%, HPLC). Purity 99.3%). It was confirmed that the sublimation temperature of A126 was 305 ° C. and that the sublimated product A126 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 662 (M +)
Example 17 (Synthesis of compound (A160))

In a 50 mL three-necked flask under a nitrogen stream, 1.1 g (3.0 mmol) of 4-chloro-9- (2-biphenylyl) carbazole obtained in Synthesis Example 6 and N- [4- (carbazole-9-yl) phenyl) were placed. ] -4-Biphenylamine 1.2 g (3.0 mmol), sodium-tert-butoxide 0.40 g (4.2 mmol), and o-xylene 12 mL were added, and 7 mg of palladium acetate (7 mg) (palladium acetate) was added to the obtained slurry reaction solution. 0.03 mmol) and 18 mg (0.09 mmol) of tri-tert-butylphosphine were added, and the mixture was stirred at 140 ° C. for 24 hours. After cooling to room temperature, 12 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By purifying the residue by silica gel column chromatography (toluene / hexane volume ratio = 1/1), 1.6 g (2.2 mmol) of white powder of compound (A160) was isolated (yield 73%, HPLC). Purity 99.6%). It was confirmed that the sublimation temperature of A160 was 290 ° C. and that the sublimated product A160 was glassy.

Compound identification was performed by FDMS.

FDMS (m / z); 727 (M +)
Example 4 (Evaluation of element of compound (A20))
A glass substrate on which an ITO transparent electrode (anolyde) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, after cleaning with ultraviolet rays / ozone and installing in a vacuum vapor deposition apparatus, the air was 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 then compound (A20) 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 .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 a 5 nm exciton block layer, and then Alq ₃ (Tris) was further deposited. (8-Kinolinolat) aluminum) was 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 100 nm at a vapor deposition rate of 0.25 nm / sec 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 manufactured, and the drive voltage and current efficiency were measured. Further, a current of 6.25 mA / cm ² was applied to the element and the change with time of the luminance was measured, and the time (luminance half-life) at which the luminance became half of the initial value was investigated. The luminance half-life was evaluated as the device life. The results are shown in Table 1. The element life is expressed as a relative value with the element life (luminance half-life) of Comparative Example 1 described later as 100.

Example 5 (Evaluation of element of compound (A71))
An organic EL device was produced by the same method as in Example 4 except that the compound (A71) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 18 (Evaluation of element of compound (A13))
An organic EL device was produced by the same method as in Example 4 except that the compound (A13) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 19 (Evaluation of element of compound (A75))
An organic EL device was produced by the same method as in Example 4 except that the compound (A75) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 20 (Evaluation of element of compound (A76))
An organic EL device was produced by the same method as in Example 4 except that the compound (A76) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 21 (Evaluation of element of compound (A311))
An organic EL device was produced by the same method as in Example 4 except that the compound (A311) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 22 (Evaluation of element of compound (A318))
An organic EL device was produced by the same method as in Example 4 except that the compound (A318) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 23 (Evaluation of element of compound (A19))
An organic EL device was produced by the same method as in Example 4 except that the compound (A19) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 24 (Evaluation of element of compound (A51))
An organic EL device was produced by the same method as in Example 4 except that the compound (A51) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 25 (Evaluation of element of compound (A103))
An organic EL device was produced by the same method as in Example 4 except that the compound (A103) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 26 (Evaluation of element of compound (A109))
An organic EL device was produced by the same method as in Example 4 except that the compound (A109) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 27 (Evaluation of element of compound (A112))
An organic EL device was produced by the same method as in Example 4 except that the compound (A112) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 28 (Evaluation of element of compound (A337))
An organic EL device was produced by the same method as in Example 4 except that the compound (A337) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 29 (Evaluation of element of compound (A126))
An organic EL device was produced by the same method as in Example 4 except that the compound (A126) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Example 30 (Evaluation of element of compound (A160))
An organic EL device was produced by the same method as in Example 4 except that the compound (A160) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

Comparative Example 1 (Evaluation of NPD element)
A commercially available NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was sublimated and purified. The sublimation temperature of the NPD was 290 ° C., and it was confirmed that the NPD of the sublimated product was in the form of a crystalline powder.

An organic EL device was produced by the same method as in Example 4 except that NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was used instead of the compound (A20). .. Table 1 shows the drive voltage, current efficiency, and element life of the organic EL element measured by the same method as in Example 7.

Reference Example 1 (Evaluation of element of compound (a))
The following compound (a) was synthesized and sublimated and purified based on the description in International Publication No. 2011-049123. It was confirmed that the sublimation temperature of the compound (a) was 335 ° C., and the sublimated compound (a) was in the form of a crystalline powder.

An organic EL device was produced by the same method as in Example 4 except that the following compound (a) was used instead of the compound (A20). Table 1 shows the drive voltage, current efficiency, and device life of the organic EL device measured by the same method as in Example 4.

The carbazole compound of the present invention can be used as a material for an organic EL device, for example, as a hole injection material, a hole transport material, or a host material for a light emitting layer, and is compared with an organic EL device using a conventionally known material. Excellent in element efficiency and life. Further, 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 photoconducting material such as a photoelectric conversion element, a solar cell, or an image sensor. It can be applied.

Claims (6)

A carbazole compound represented by the general formula (1).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a group represented by the following general formula (2), and at least one of R ¹ and R ² represents the following general formula (2). ). R ³ represents a phenyl group, a biphenylyl group, a naphthyl group or a phenanthryl group [these groups may independently have a methyl group or a methoxy group]. )

(In the formula, Ar ¹ and Ar ² may be independently linked or condensed with 6 to 30 carbon atoms, or may be linked or condensed with 3 to 20 carbon atoms. Good heteroaromatic groups [These groups may each independently have one or more substituents selected from the group consisting of a methyl group, a 9-carbazolyl group, a dibenzothienyl group, and a dibenzofuranyl group. Good].)
However, the following compounds are excluded.

R ³ is a phenyl group, 2-biphenylyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group or 9-phenanthryl group [These groups are independently methyl group or methoxy group. The carbazole compound according to claim 1, which may have a group. R ¹ is a group represented by the general formula (2) and R ² is a hydrogen atom, or R ² is a group represented by the general formula (2) and R ¹ is a hydrogen atom. The carbazole compound according to claim 1 or 2, wherein the carbazole compound is characterized by being. Ar ¹ and Ar ² independently have a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, or a phenanthryl group [these groups are independently a methyl group, a 9-carbazolyl group, and a dibenzo group, respectively. The carbazole compound according to claim 1, wherein it may have one or more substituents selected from the group consisting of a thienyl group and a dibenzofuranyl group. Ar ¹ and Ar ² independently have a phenyl group, a 4-methylphenyl group, a 4- (9-carbazolyl) phenyl group, a 4- (4-dibenzothienyl) phenyl group, and a 4- (4-dibenzofuranyl) group. ) The carbazole compound according to claim 1, which is a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a 9,9-dimethyl-2-fluorenyl group, or a phenanthryl group. A material for an organic EL device, which comprises the carbazole compound according to any one of claims 1 to 5.