JP2018062505A - Novel carbazole compound and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having low crystallinity and a low sublimation temperature.SOLUTION: The present invention provides a carbazole compound represented by the general formula (1). (Rand Rare each independently H or an amino group substituted with two aryl groups, where at least one of Rand Ris the amino group substituted with two aryl groups; and Ris a phenyl group, biphenyl group, naphthyl group or phenanthryl group, which may be substituted with a methyl group or methoxy group.)SELECTED DRAWING: None

Description

  The present invention relates to a carbazole compound characterized by 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 same.

  Organic EL devices featuring self-light emission can be thinned because they do not require a backlight used in liquid crystal panels, and have the advantage of flexible performance that can make the screen curved. In recent years, research has been actively conducted as a display and lighting, and it has already been put into practical use for a mobile phone display, a television, and the like.

  In general, 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. However, in order to achieve low power consumption and long life at present. A multilayer laminated structure in which a hole injection material, an electron injection material, a hole blocking material, and the like are inserted has become the mainstream. As the hole transport material, an amine compound having an appropriate ionization potential and hole transport ability is used. For example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter, NPD is abbreviated as NPD), but it is difficult to say that the driving voltage, luminous efficiency, and durability of an element using NPD for the hole transport layer are sufficient. Furthermore, the development of organic EL devices using a phosphorescent material for the light emitting layer is also underway, and a device using phosphorescent light emission requires a hole transport material having a high triplet level. NPD is not sufficient from the point of triplet level, and for example, it has been reported that the organic EL element in which a phosphorescent material having green light emission and NPD are combined reduces the luminous efficiency (for example, non-patent Reference 1). Against this background, carbazole compounds have been reported (see, for example, Patent Documents 1 and 2). However, the pyrene ring and the anthracene aromatic condensed ring described in Patent Documents 1 and 2 have low triplet levels, so it is known that it is difficult to obtain high luminous efficiency in a device using a green phosphorescent material. It has been. Recently, a carbazole compound having a naphthylphenyl group has been reported (for example, see Patent Document 3).

JP 2008-078362 A JP 2008-195841 A JP2015-078158 A1

Journal of Applied Physics, 2004, 95, 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 a chamber in a vacuum vapor deposition process when manufacturing an organic EL device. In addition, since compounds containing an aromatic condensed ring or a heterocyclic ring are likely to have a high sublimation temperature as the molecular weight increases, there is a concern that heat deterioration of the material at the time of manufacturing an organic EL element increases, which affects productivity. It has occurred. Therefore, an amorphous material and a material having a low sublimation temperature that suppress crystallization of the material at the time of manufacturing the organic EL element are desired. Furthermore, it is desired to develop a hole transport material that can reduce the driving voltage, increase the light emission efficiency, and extend the life of the 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 intensive studies, the present inventors have found that a carbazole compound represented by the following general formula (1) characterized by a phenyl group, a biphenylyl group, a naphthyl group, or a phenanthryl group at a specific position solves the above problem, The present invention 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 is represented by the following general formula (2 R ³ represents a phenyl group, a biphenylyl group, a naphthyl group, or a phenanthryl group [these groups may each independently have a methyl group or a methoxy group]. )

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group which may be linked or condensed with 6 to 30 carbon atoms, or a linked or condensed group with 3 to 20 carbon atoms. Good heteroaromatic group [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. Represents good].)

  As shown in the general formula (1), the carbazole compound of the present invention is based on the structural requirement that it has a phenyl group, a biphenylyl group, a naphthyl group, or a phenanthryl group at a specific position. Angular strain or steric strain becomes large, and as a result, the sublimate of the compound becomes amorphous (glassy), and the sublimation temperature of the compound can be lowered. The carbazole compound of the present invention, which has the effect of amorphization and low sublimation temperature, improves the yield during the manufacture of the organic EL device and suppresses crystallization, compared with the conventionally known carbazole compound, thereby suppressing the inside of the organic EL device manufacturing chamber. As a result, the productivity is improved. In addition, the carbazole compound of the present invention has an effect of being excellent in hole transport property and excited triplet state. For this reason, the organic EL element using the carbazole compound of the present invention has an effect of being excellent in luminous efficiency and lifetime as compared with an 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 general formula (1), R ³ represents a phenyl group, a biphenylyl group, a naphthyl group, or a phenanthryl group [these groups may each independently have a methyl group or a methoxy group. Good].

In the carbazole compound represented by the general formula (1), R ³ is a phenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-naphthyl group, 2 in terms of easy availability of raw materials. 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. More preferably a group, a 4-biphenylyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-phenanthryl group, a phenyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 2-naphthyl group, or a 9- More preferred 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 general formula (2), and R ¹ and R ² At least one of them is a group represented by the general formula (2). In addition, 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) (the other is necessarily a hydrogen atom) R ¹ is more preferably a group represented by the above general formula (2), and R ² is more preferably a hydrogen atom.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked or condensed, or 3 carbon atoms. -20 heteroaromatic groups which may be linked or condensed [These groups are each independently selected 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 linking or fused which may be an aromatic hydrocarbon group having 6 to 30 carbon atoms represented by Ar ¹ and Ar ^2, is not particularly limited, for example, a phenyl group, biphenylyl group, terphenylyl group, a naphthyl Group, fluorenyl group, phenanthryl group, benzofluorenyl group, or triphenylenyl group. In addition, about the group shown here, as above-mentioned, it may have a methyl group, 9-carbazolyl group, dibenzothienyl group, or dibenzofuranyl group each independently, About the number of substituents There is no particular limitation.

The heteroaromatic group that may be linked or condensed with 3 to 20 carbon atoms in Ar ¹ and Ar ² is not particularly limited, but includes, for example, at least one oxygen atom, nitrogen atom, or sulfur atom A heteroaromatic group having 3 to 20 carbon atoms which may be linked or condensed, more preferably at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. Examples of the heteroaromatic group which may be linked or condensed with 3 to 20 carbon atoms contained on the ring include, but are not particularly limited to, for example, pyrrolyl group, thienyl group, furyl group, imidazolyl group , Pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazi Group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group Group, 2,1,3-benzooxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, or thiantenyl Groups and the like. As described above, these groups may each 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.

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'-bifu Nyl-4-yl group, 2,2′-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, 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-yl group, 2 ′, 6′-dimethyl group -1,1'-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalene- 1-yl group, 6-methylnaphthalen-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-methylnaphthalen-1-yl) phenyl group, 3- (2-methylnaphthalen-1-yl) phenyl group, 4-phenylnaphthalen-1-yl group, 4- (2-methylphenyl) Naphthalen-1-yl group, 4- (3-methylphenyl) naphthalen-1-yl group, 4- (4-methylphenyl) naphthalen-1-yl group, 6-phenylnaphthalen-2-yl group, 4- ( 2-methylphenyl) naphthalen-2-yl group, 4- (3-methylphenyl) naphthalen-2-yl group, 4- (4-methylphenyl) naphthalen-2-yl group, 2-fluorenyl group, 9,9 Dimethyl-2-fluorenyl group, 9,9′-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11′-dimethylbenzo [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-fluoranthenyl 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-isoxazolyl group, 5-isoxazolyl 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′-bipyridin-3-yl group, 2,2 ′ -Bipyridin-4-yl group, 2,2'-bipyridin-5-yl group, 2,3'-bipyridin-3-yl group, 2,3'-bipyridin-4-yl group, 2,3'-bi group Pi Gin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group, 1-benzoimidazolyl group, 2- Methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzoimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5-benzimidazolyl group, 1,2-dimethyl-5 -Benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2- Dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5- Benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group, 7-benzoisothiazolyl group Ryl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzo Oxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzisoxazolyl group, 4 -Benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2,1,3-benzoxoxadiazolyl-4-yl group 2,1,3-benzooxadiazolyl-5-yl group, 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group Group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl 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-phenanthroline-5-yl group, 2-thienyl group, 3- Enyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzo Furanyl group, 4-dibenzofuranyl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazine-2- Group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 9-phenylcarbazole- 4-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 4- (2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4- Pyridyl) phenyl group, 3- (2-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-diphenyl) Nylimidazol-2-yl) phenyl group, 4- (2-methylbenzimidazol-1-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 4- (1-methylbenzimidazole) 2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazol-1-yl) phenyl group, 3- (2-phenylbenzimidazole-1) -Yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 4- (3,5-diphenyltriazine-1- Yl) phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) phenyl group, 5-phenylthiophen-2-yl 5-phenylfuran-2-yl group, 4- (5-phenylthiophen-2-yl) phenyl group, 4- (5-phenylfuran-2-yl) phenyl group, 3- (5-phenylthiophene-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-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4- (9-carbazolyl) phenyl Group, 3- (9-carbazolyl) phenyl group and the like can be exemplified, but are not limited thereto.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, in terms of excellent hole transportability. Or a phenanthryl group [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] It is preferable that

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently a methyl group, a 9-carbazolyl group, a dibenzothienyl group, or a dibenzo, because of excellent hole transportability. 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 It is more preferably 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.

Furthermore, in the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently a phenyl group, a 4-methylphenyl group, and 4- (9) in terms of excellent 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 More preferably, it is a phenanthryl group.

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

(In the formula, R ³ , Ar ¹ and Ar ² have the same definition as in the general formula (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 of the carbazole compound represented by the general formula (1) are exemplified, 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, page 2367) 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 can be synthesized by the following route.

  A 9H-carbazole compound halogenated at the 2-position represented by the general formula (3) and an aryl compound having a halogen atom represented by the general formula (4) are optionally mixed with copper 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 mixed with a copper catalyst or The reaction is carried out using a palladium catalyst.

[Wherein R ^{1 to} R ⁵ , Ar ¹ and Ar ² represent the same definition as in 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 based on a generally known method, or commercially available compounds can also 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. In addition, it is preferable that the carbazole compound represented by the general formula (1) has high purity in terms of hole transport characteristics and device lifetime. Specifically, those having as few impurities as possible, such as impurities due to halogen atoms and transition metal elements, and manufacturing raw materials and by-products, are preferable.

  For the light emitting layer 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 device, a conventionally known fluorescent or phosphorescent light emitting material is used. Can be used. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  When forming the hole injection layer and / or 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 as necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexahexa A known electron-accepting material such as azatriphenylene may be contained or laminated.

  Moreover, 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 the light emitting layer of the organic EL device, the carbazole compound is used alone, doped into a known light emitting host material, or a known light emitting dopant is used. Can be used by doping.

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

  As a basic structure of the organic EL device that can obtain the effects of the present invention, those including a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are preferable. Layers may be omitted, or vice versa.

  The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. By applying a potential between the anode and the cathode, the organic EL element operates and emits light.

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

  The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element 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 used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.

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

  The general transparent anode (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 fluorocarbon. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective 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 injection layer and a hole transport 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. By interposing these layers between the anode and the light emitting layer, the hole injection layer and the hole transport layer are often used in 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 a carbazole compound represented by the general formula (1).

  For the hole transport layer and / or hole injection layer, any one of well-known hole transport materials and / or hole injection materials is selected together with the carbazole compound represented by the general formula (1). Can be 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, Examples thereof include oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material and the hole transporting material, those described above can be used, and porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, particularly aromatic tertiary amine compounds can be used. preferable.

  Representative examples of the aromatic tertiary amine compound and styrylamine compound include 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- Tolylaminophenyl) -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) quadri Phenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4′-bis [N- (1-naphthyl) -N-phenylamino ] Biphenyl (NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) and the like. That.

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

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

  The emissive layer may consist of a single material that includes both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, where the emission occurs primarily from the dopant, Can have a color.

  Examples of the host material for 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-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-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 supports hole / electron recombination (support), or a combination of these materials. Good.

  Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium or thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indenoperylene. Derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyryl compounds and the like can be mentioned.

  As an example of the phosphorescent dopant, an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-p-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples 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 alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolinate) 1-naphthyl Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

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

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above-described 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, and inorganic compounds such as nitride and oxynitride can also be used.

If light emission is confirmed only through the anode, the cathode used in the present invention can be formed from any conductive material. 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 mixtures, rare earth metals and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples at all, and is interpreted.

  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 × 250 mm)
Detector UV detection (wavelength 254nm)
Eluent Methanol / Tetrahydrofuran = 9/1 (v / v ratio)
[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measuring 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

  Under a nitrogen stream, in a 1000 mL three-necked flask, 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 was 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was recrystallized (toluene / butanol) to isolate 16.2 g (45.7 mmol) of 2-chloro-9- (2-biphenylyl) carbazole as a light brown powder (yield 61%, HPLC purity 98 .8%).

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.

FDMS (m / z); 353 (M +)
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 Synthesis of 2-chloro-9- [1,1 ′: 3′1 ″ -terphenyl-6-yl] -carbazole

  Under a nitrogen stream, in a 1000 mL three-necked flask, 12.9 g (64.0 mmol) of 2-chloro-9H-carbazole, 19.1 g (76.8 mmol) of 6-fluoro-1,1 ′: 3′1 ″ -terphenyl ), 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was recrystallized (toluene / butanol) to give 16.9 g (39 of 2-chloro-9- [1,1 ′: 3′1 ″ -terphenyl-6-yl] -carbazole pale brown powder. 0.0 mmol) isolated (yield 61%, HPLC purity 99.3%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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 Synthesis of 2-chloro-9- [1,1 ′: 4′1 ″ -terphenyl-6-yl] -carbazole

  Under a nitrogen stream, in a 1000 mL three-necked flask, 15.1 g (75.0 mmol) of 2-chloro-9H-carbazole, 22.3 g (96.0 mmol) of 6-fluoro-1,1 ′: 4′1 ″ -terphenyl ), 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 in the organic layer was collected by filtration and washed with water and methanol. By further recrystallization (toluene), 14.9 g (34.5 mmol) of 2-chloro-9- [1,1 ′: 4′1 ″ -terphenyl-6-yl] -carbazole white powder was obtained. (Yield 46%, HPLC purity 99.0%).

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.99 (d, 1H), 7.93 (d, 1H), 7.73-7.55 (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

  Under a nitrogen stream, in a 1000 mL three-necked flask, 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 ( 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 23.3 g (57.3 mmol) of white powder of 2-chloro-9- (2- (2-naphthyl) phenyl) carbazole was isolated (yield 61%). HPLC purity 98.7%).

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.

FDMS (m / z); 403 (M +)
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, 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 in 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 2-chloro-9- (2- (9-phenanthryl) phenyl) carbazole brown powder was isolated (yield 34%). HPLC purity 99.0%).

  The compound was identified by FDMS.

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

  Under a nitrogen stream, in a 300 mL three-necked flask, 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 it stirred at 180 degreeC for 48 hours. After cooling to room temperature, 100 mL of pure water was added and stirred, and the product precipitated in the organic layer was collected by filtration and washed with water and methanol. Furthermore, 4.6 g (12.9 mmol) of white powder of 4-chloro-9- (2-biphenylyl) carbazole was isolated by recrystallization (toluene / butanol) (yield 54%, HPLC purity 99.0). %).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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 and N- (4-biphenyl) -4-p-ter Phenylamine (3.6 g, 9.0 mmol), sodium-tert-butoxide (1.2 g, 12.6 mmol), and o-xylene (25 mL) were added. To the resulting slurry reaction solution, 10.1 mg (0.0. 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 in the organic layer was collected by filtration and washed with water and methanol. Further, 5.6 g (2.8 mmol) of an off-white powder of the compound (A13) was isolated by recrystallization (toluene / butanol) (yield 88%, HPLC purity 99.4%). The sublimation temperature of A13 was 315 ° C., and it was confirmed that A13 of the sublimation product was glassy.

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.
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 and N- [4- (carbazol-9-yl) phenyl were obtained. ] 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 was added to the resulting slurry reaction solution. 7 mg (0.061 mmol) and 37.0 mg (0.183 mmol) of tri-tert-butylphosphine were added and 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / hexane), 6.2 g (8.5 mmol) of white powder of compound (A20) was isolated (yield 69%, HPLC purity 99.7%). The sublimation temperature of A20 was 300 ° C., and it was confirmed that A20 of the sublimation product was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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))

  Under a nitrogen stream, in a 50 mL three-necked flask, 3.9 g (9.0 mmol) of 2-chloro-9- [1,1 ′: 4′1 ″ -terphenyl-6-yl] -carbazole obtained in Synthesis Example 3 was obtained. ), N, N-bisbiphenylamine 2.9 g (9.0 mmol), sodium tert-butoxide 1.2 g (12.6 mmol), and o-xylene 25 mL, and acetic acid was added to the resulting slurry reaction solution. Palladium 10.1 mg (0.045 mmol) and tri-tert-butylphosphine 109.0 mg (0.135 mmol) 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 in the organic layer was collected by filtration and washed with water and methanol. Further, 4.7 g (6.6 mmol) of a white powder of compound (A71) was isolated by recrystallization (toluene) (yield 73%, HPLC purity 99.6%). The sublimation temperature of A71 was 295 ° C., and it was confirmed that A71 of the sublimation product was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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 was obtained. ), 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 are obtained. To the slurry-like reaction solution, 7 mg (0.03 mmol) of palladium acetate and 18 mg (0.09 mmol) of tri-tert-butylphosphine were 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene / hexane volume ratio = 1/1) to isolate 1.4 g (1.8 mmol) of white powder of compound (A75) (yield 60%, HPLC (Purity 99.6%). The sublimation temperature of A75 was 285 ° C., and it was confirmed that A75 of the sublimation product was glassy.

  The compound was identified by FDMS.

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

  Instead of 1.1 g (3.0 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene, 0.89 g (3.0 mmol) of N-phenyl-4- (1-naphthyl) phenylamine was used. The white powder of the compound (A76) was isolated in an amount of 1.2 g (1.7 mmol) (yield 58%, HPLC purity 99.3%). The sublimation temperature of A76 was 295 ° C., and it was confirmed that A76 of the sublimated product was glassy.

  The compound was identified 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-anilinodibenzobenzophene was used instead of 1.1 g (3.0 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene The same operation was performed to isolate 1.1 g (1.6 mmol) of a white powder of compound (A311) (yield 53%, HPLC purity 99.2%). The sublimation temperature of A311 was 290 ° C., and it was confirmed that A311 of the sublimation product was glassy.

  The compound was identified 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 white powder of the compound (A318) was isolated in an amount of 1.3 g (1.8 mmol) (yield 60%, HPLC purity 99.4%). The sublimation temperature of A318 was 300 ° C., and it was confirmed that the sublimated A318 was glassy.

  The compound was identified 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 ′-(carbazol-9-yl) -N— were obtained. Phenyl- [1,1′-biphenyl] -4-amine (4.1 g, 10.0 mmol), sodium-tert-butoxide (1.3 g, 13.0 mmol), and o-xylene (30 mL) were added, and the resulting slurry was obtained. 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 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 a saturated aqueous sodium chloride solution, further 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 the compound (A19) was isolated (yield 96%, HPLC purity 99.8%). The sublimation temperature of A19 was 310 ° C., and it was confirmed that A19 of the sublimation product was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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))

  Under a nitrogen stream, in a 100 mL three-necked flask, 3.9 g (9.0 mmol) of 2-chloro-9- [1,1 ′: 3′1 ″ -terphenyl-6-yl] -carbazole obtained in Synthesis Example 2 was obtained. ), N, N-bisbiphenylamine 2.9 g (9.0 mmol), sodium tert-butoxide 1.2 g (12.6 mmol), and o-xylene 25 mL, and acetic acid was added to the resulting slurry reaction solution. Palladium 10.1 mg (0.045 mmol) and tri-tert-butylphosphine 109.0 mg (0.135 mmol) 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / butanol), 6.1 g (8.5 mmol) of a white powder of compound (A51) was isolated (yield 95%, HPLC purity 99.8%). The sublimation temperature of A51 was 290 ° C., and it was confirmed that A51 of the sublimation product was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
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))

  In a 50 mL three-necked flask under a nitrogen stream, 1.2 g (3.0 mmol) of 2-chloro-9- (2- (2-naphthyl) phenyl) carbazole obtained in Synthesis Example 4 and 0.81 g of 9-anilinophenanthrene were obtained. (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 resulting slurry reaction solution. -18 mg (0.09 mmol) of butylphosphine 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene / hexane volume ratio = 1/1) to isolate 1.2 g (1.9 mmol) of white powder of compound (A103) (yield 63%, HPLC). (Purity 99.6%). The sublimation temperature of A103 was 300 ° C., and it was confirmed that the sublimated A103 was glassy.

  The compound was identified 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. Thus, 1.4 g (2.1 mmol) of a white powder of the compound (A109) was isolated (yield 70%, HPLC purity 99.4%). The sublimation temperature of A109 was 300 ° C., and it was confirmed that the sublimated A109 was glassy.

  The compound was identified by FDMS.

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

  Example except that 0.96 g (3.0 mmol) of 4-anilino-1,1 ′: 4 ′, 1 ″ -terphenyl was used instead of 0.81 g (3.0 mmol) of 9-anilinophenanthrene The white powder of the compound (A112) was isolated in an amount of 1.4 g (2.1 mmol) (yield 70%, HPLC purity 99.5%). The sublimation temperature of A112 was 305 ° C., and it was confirmed that the sublimated A112 was glassy.

  The compound was identified by FDMS.

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

  9-anilinophenanthrene The 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). The operation was performed to isolate 1.1 g (1.6 mmol) of a white powder of the compound (A337) (yield 52%, HPLC purity 99.5%). The sublimation temperature of A337 was 305 ° C., and it was confirmed that the sublimated A337 was glassy.

  The compound was identified 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-phenanthryl) phenyl) carbazole obtained in Synthesis Example 5 and N-phenyl-4-biphenylyl were synthesized. 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 resulting slurry reaction solution. Then, 18 mg (0.09 mmol) of tri-tert-butylphosphine 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene / hexane volume ratio = 1/1) to isolate 1.5 g (2.3 mmol) of white powder of compound (A126) (yield 76%, HPLC). (Purity 99.3%). The sublimation temperature of A126 was 305 ° C., and it was confirmed that A126 of the sublimation product was glassy.

  The compound was identified 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- (carbazol-9-yl) phenyl ] 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 palladium acetate 7 mg ( 0.03 mmol) and 18 mg (0.09 mmol) of tri-tert-butylphosphine were 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 a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene / hexane volume ratio = 1/1) to isolate 1.6 g (2.2 mmol) of a white powder of compound (A160) (yield 73%, HPLC (Purity 99.6%). The sublimation temperature of A160 was 290 ° C., and it was confirmed that the sublimated A160 was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 727 (M +)
Example 4 (Element Evaluation of Compound (A20))
The glass substrate on which the 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. Furthermore, ultraviolet / ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, copper phthalocyanine is deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Subsequently, the compound (A20) is deposited to a thickness of 30 nm at a deposition rate of 0.3 nm / second. It was set as the transport layer. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer. Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer by 1 nm at a deposition rate of 0.01 nm / second, and aluminum was deposited by 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded 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 fabricated, and driving voltage and current efficiency were measured. In addition, a current of 6.25 mA / cm ² was applied to the device to measure a change in luminance with time, and a time during which the luminance was half of the initial value (luminance half-life) was examined. The luminance half-life was evaluated as the device lifetime. The results are shown in Table 1. In addition, about the element lifetime, it represented with the relative value which set the element lifetime (luminance half-life) of the comparative example 1 mentioned later to 100.

Example 5 (Element evaluation of compound (A71))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 18 (Element evaluation of compound (A13))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 19 (Element evaluation of compound (A75))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 20 (Device evaluation of compound (A76))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 21 (Element evaluation of compound (A311))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 22 (Element evaluation of compound (A318))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 23 (Element evaluation of compound (A19))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 24 (Element Evaluation of Compound (A51))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 25 (Element Evaluation of Compound (A103))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 26 (Element evaluation of compound (A109))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 27 (Element evaluation of compound (A112))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 28 (Element Evaluation of Compound (A337))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 29 (Device Evaluation of Compound (A126))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Example 30 (Element evaluation of compound (A160))
An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element by the same method as in Example 4.

Comparative Example 1 (NPD element evaluation)
Commercially available NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was purified by sublimation. The sublimation temperature of NPD was 290 ° C., and it was confirmed that NPD of the sublimation product was in the form of crystalline powder.

  An organic EL device was produced in the same manner 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 lifetime measured for the organic EL element by the same method as in Example 7.

Reference Example 1 (Device evaluation of compound (a))
Based on the description in WO 2011-049123 pamphlet, the following compound (a) was synthesized and purified by sublimation. The sublimation temperature of the compound (a) was 335 ° C., and it was confirmed that the sublimated compound (a) was in the form of crystalline powder.

  An organic EL device was produced in the same manner 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 element lifetime measured for the organic EL element 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 compared with an organic EL device using a conventionally known material. Excellent device efficiency and lifetime. Furthermore, not only as a hole injection material, a hole transport material or a light emitting material of an organic EL element or an electrophotographic photosensitive member, but also in a field to an organic photoconductive material such as a photoelectric conversion element, a solar cell, or an image sensor. Applicable.

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 is represented by the following general formula (2 R ³ represents a phenyl group, a biphenylyl group, a naphthyl group, or a phenanthryl group [these groups may each independently have a methyl group or a methoxy group]. )

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group which may be linked or condensed with 6 to 30 carbon atoms, or a linked or condensed group with 3 to 20 carbon atoms. Good heteroaromatic group [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. Represents good].) R ³ represents a phenyl group, a 2-biphenylyl group, a 3-biphenyl group, a 4-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-phenanthryl group [these groups are each independently a methyl group or a 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, characterized in that Ar ¹ and Ar ² are each independently a phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, or phenanthryl group [these groups are each independently a methyl group, a 9-carbazolyl group, a dibenzo group, The carbazole compound according to claim 1, which may have one or more substituents selected from the group consisting of a thienyl group and a dibenzofuranyl group. Ar ¹ and Ar ² are each independently a phenyl group, 4-methylphenyl group, 4- (9-carbazolyl) phenyl group, 4- (4-dibenzothienyl) phenyl group, 4- (4-dibenzofuranyl) 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. An organic EL element material comprising the carbazole compound according to any one of claims 1 to 5.