JP2017218446A - Carbazole compound having disubstituted benzene and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a specific carbazole compound that contributes to increases in the luminous efficiency and life of an organic EL element by causing dihedral-angle distortion or steric distortion in a molecular structure to reduce the crystallinity of a molecule.SOLUTION: The present invention provides a carbazole compound represented by formula (1), and an organic EL element that is prepared therewith and achieves increases in luminous efficiency and life (two of R-Ris a phenyl group and the others are H; R-Rare H or at least one -N(Ar)(Ar); Arand Arare aryl or heteroaryl).SELECTED DRAWING: None

Description

  The present invention relates to a carbazole compound having a specific disubstituted benzene 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, in recent years, organic EL elements using a phosphorescent material for a light emitting layer have been developed, and a hole transport material having a high triplet level is required for an element using phosphorescent light emission. 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 recently been reported (see, for example, Patent Documents 1 and 2). However, since the aromatic condensed ring of pyrene ring and anthracene ring described in Patent Documents 1 and 2 has a low triplet level and has an electron accepting property, a device using a green phosphorescent material has high luminous efficiency. Difficult to get.

  In addition, NPD and carbazole compounds have many compounds having a high melting point, and have a property of being easily crystallized in a chamber in a vacuum vapor deposition process at the time of manufacturing an organic EL element. Crystal deposition in the chamber has an effect on the yield of organic EL device manufacturing, and there is a problem that workability is not good. Therefore, an amorphous material that suppresses crystallization of the material at the time of manufacturing the organic EL element is desired, and further, a hole transport material that can reduce the driving voltage, increase the light emission efficiency, and extend the life of the organic EL element. Development is desired.

JP 2008-078362 A JP 2008-195841 A

Journal of Applied Physics, 2004, 95, 7798.

  An object of the present invention is to provide a compound in which the crystallinity of a molecule is lowered by causing dihedral angle distortion or steric distortion of the molecular structure as compared with conventionally known NPD and carbazole compounds. The object is to suppress crystal deposition inside the EL device manufacturing chamber. It is another object of the present invention to provide a specific carbazole compound that contributes to high light emission efficiency and long life of an organic EL device.

  As a result of intensive studies, the present inventors have found a carbazole compound represented by the following general formula (1) characterized by having a specific di-substituted benzene at the 9-position of the carbazole ring, thereby completing the present invention. It came.

(In the formula, any two of R ^{1 to} R ⁵ are phenyl groups [these groups may each independently have a methyl group, a methoxy group, or a cyano group], and the rest R ^{6 to} R ⁹ each independently represents a hydrogen atom or a group represented by the following general formula (2), and at least one of R ^{6 to} R ⁹ is represented by the following general formula ( 2).

(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].)

  The carbazole compound of the present invention has a disubstituted benzene at a specific position as shown in the general formula (1), and the dihedral benzene strain itself or the dihedral strain of the molecular structure of the disubstituted benzene and the carbazole ring or By producing steric strain, the material is made amorphous (glassy). Due to the effect of the amorphization, the carbazole compound of the present invention can suppress the crystallization during the production of the organic EL device as compared with the conventionally known carbazole compounds, and the productivity of the crystal deposition inside the organic EL device production chamber is suppressed. And the yield 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 above general formula (1), any two of R ^{1 to} R ⁵ are phenyl groups [these groups each independently have a methyl group, a methoxy group, or a cyano group. The remaining represents a hydrogen atom. The substituent that R ^{1 to} R ⁵ can take is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group, a cyanophenyl group, and a hydrogen atom. . In addition, from the point of the luminous efficiency of an organic EL element, it is preferable that any two of R < ¹ > -R < ⁵ > are the phenyl groups which may have a methyl group, and the remainder is a hydrogen atom.

In the carbazole compound represented by the general formula (1), R ^{6 to} R ⁹ each independently represent a hydrogen atom or a group represented by the general formula (2), and R ^{6 to} R ⁹ At least one of them is a group represented by the general formula (2). In addition, from the viewpoint of hole transport characteristics and availability of raw materials, it is preferable that one or two of R ^{6 to} R ⁹ is a group represented by the above general formula (2), and R ⁶ or R ⁷ Is more preferably a group represented by the general formula (2), R ⁶ is a group represented by the general formula (2), and R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms. Or R ⁷ is a group represented by the general formula (2), and R ⁶ , R ⁸ , and R ⁹ are more preferably a hydrogen atom, and R ⁶ is the general formula (2). More preferably, R ⁷ , R ⁸ , and R ⁹ are each 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, triphenylenyl group, dibenzothienyl group, dibenzofuranyl group 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 not particularly limited.

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 not particularly limited.

Specific examples of Ar ¹ and Ar ² are each independently a 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-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-1,1′-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4 -Methylnaphthalen-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-fluoreni 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- ( -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-pi Lazolyl 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 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, , 3′-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group, 1-benzimidazolyl 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-benzoimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2-dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzoy Dazolyl 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-benzoisothiazolyl group, 4-benzisothiazolyl group, 5-benzisothiazolyl group, 6-benzoisothiazolyl group, 7- Benzoisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl, 3-benzisoxa Zolyl group, 4-benzisoxazolyl group, 5-benzisoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2,1,3-benzoxazodiazolyl- 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, 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-thie Group, 3-thienyl 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-dibenzofuranyl group, 4-dibenzofuranyl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazole 2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazole -4-yl group, 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothi Gin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 9 -Phenylcarbazol-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-Diphenylimidazol-2-yl) phenyl group, 4- (2-methylbenzimidazol-1-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 4- (1- Methylbenzoimidazol-2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazol-1-yl) phenyl group, 3- (2-phenylbenzo) Imidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzoimidazol-1-yl) phenyl group, 4- (3,5-diphenyltriazine) -1-yl) phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) phenyl group, 5-phenylthiophene 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-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4- (9- Examples thereof include, but are not limited to, a carbazolyl) phenyl group or a 3- (9-carbazolyl) phenyl group.

In the arylamine compound represented by the general formula (1), Ar ¹ and Ar ² are each independently a phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, phenanthryl group, dibenzothienyl group, or Dibenzofuranyl 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. ] Is preferable.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently selected from the group consisting of a methyl group, a 9-carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group. Phenyl group which may have a substituent, biphenylyl group which may have a methyl group, terphenylyl group which may have a methyl group, naphthyl group which may have a methyl group, methyl group It is more preferably a fluorenyl group which may have a phenanthryl group, a dibenzothienyl group or a dibenzofuranyl 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, a 4- (9-carbazolyl) phenyl group, a 4- ( 4-dibenzothienyl) phenyl group, 4- (4-dibenzofuranyl) phenyl group, biphenylyl group, terphenylyl group, naphthyl group, 9,9-dimethyl-2-fluorenyl group, phenanthryl group, dibenzothienyl group, or dibenzofuran More preferably, it is a nyl group.

  That is, the carbazole compound represented by the general formula (1) is preferably a compound represented by any one of the following general formulas (1a) to (1f).

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a methyl group, a methoxy group, or a cyano group. R ^{6 to} R ⁷ are each independently a hydrogen atom or the above general formula. (It is group represented by (2), and at least one is group represented by the said General formula (2).)
Furthermore, the carbazole compound represented by the general formula (1) is preferably a compound represented by any one of the following general formulas (1g) to (1r).

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a methyl group, a methoxy group, or a cyano group. R ⁶ is each independently represented by the general formula (2). Group.)

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a methyl group, a methoxy group, or a cyano group. R ⁷ is each independently represented by the above general formula (2). Group.)
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- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole

  In a 200 mL three-necked flask under a nitrogen stream, 5.0 g (24.8 mmol) of 2-chloro-9H-carbazole, 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene, 16.2 g of cesium carbonate. (49.6 mmol) and 75 mL of dimethyl sulfoxide were added and stirred at 150 ° 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 (butanol) to give 6.9 g (16.16 g) of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole white powder. 1 mmol) isolated (yield 65%, HPLC purity 99.8%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.99 (d, 1H), 7.92 (d, 1H), 7.88 (s, 1H), 7.78-7.71 (m, 3H), 7 .55-7.39 (m, 4H), 7.32-7.00 (m, 10H)
¹³ C-NMR (CDCl ₃ ); 142.05, 141.63, 141.47, 141.26, 140.00, 138.37, 133.29, 131.42, 130.34, 129.90, 128 .99, 128.19, 127.91, 127.73, 127.51, 127.46, 127.24, 125.97, 122.50, 121.68, 120.91, 120.01, 110.22 , 110.13
Synthesis Example 2 Synthesis of 2-chloro-9- [1,1 ′: 2 ′, 1 ″ -terphenyl] -4′-yl-carbazole

  The same as Synthesis Example 1 except that 7.4 g (29.8 mmol) of 1,2-diphenyl-4-fluorobenzene was used instead of 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene Thus, 5.0 g (11.7 mmol) of a white powder of 2-chloro-9- [1,1 ′: 2 ′, 1 ″ -terphenyl] -4′-yl-carbazole was isolated (yield) 47%, HPLC purity 99.5%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.10 (d, 1H), 8.04 (d, 1H), 7.66-7.50 (m, 5H), 7.44 (t, 1H), 7 .33-7.18 (m, 12H)
¹³ C-NMR (CDCl ₃ ); 142.41, 141.43, 141.23, 140.58, 140.37, 140.12, 136.32, 132.26, 131.76, 129.89, 129 79, 128.77, 128.08, 127.02, 126.89, 126.27, 125.79, 122.83, 122.00, 121.68, 120.50, 120.46, 120.27 , 110.10, 110.00
Synthesis Example 3 Synthesis of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl-carbazole

  In a 200 mL three-necked flask under a nitrogen stream, 5.0 g (24.8 mmol) of 2-chloro-9H-carbazole, 9.7 g (27.3 mmol) of 1-bromo-3,5-diphenylbenzene, tripotassium phosphate 7 9.9 g (37.2 mmol) and o-xylene 40 mL were added, and 56 mg (0.25 mmol) of palladium acetate and 176 mg (0.87 mmol) of tri-tert-butylphosphine were added to the resulting slurry reaction solution. And stirred at 140 ° C. for 10 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. The residue was purified by silica gel column chromatography (toluene / hexane volume ratio = 1/3) to give 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-. 10.0 g (23.3 mmol) of yl-carbazole white powder was isolated (yield 94%, HPLC purity 99.5%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 429 (M +)
¹ H-NMR (CDCl ₃ ); 8.13 (d, 1H), 8.06 (d, 1H), 7.94 (s, 1H), 7.74-7.69 (m, 6H), 7 .53-7.39 (m, 9H), 7.34-7.16 (m, 2H)
Synthesis Example 4 Synthesis of 2-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole

  The same as Synthesis Example 1 except that 7.4 g (29.8 mmol) of 1,4-diphenyl-2-fluorobenzene was used instead of 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene 8.4 g (19.6 mmol) of white powder of 2-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole was isolated (yield) 79%, HPLC purity 99.8%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.00 (d, 1H), 7.92 (d, 1H), 7.84 (d, 1H), 7.43 (d, 2H), 7.66 (d , 2H), 7.48-7.35 (m, 3H), 7.32-7.02 (m, 10H)
¹³ C-NMR (CDCl ₃ ); 142.01, 141.57, 141.50, 139.66, 139.39, 138.02, 134.61, 132.07, 131.45, 129.00, 128 .20, 127.96, 127.68, 127.61, 127.47, 127.04, 126.03, 122.52, 121.66, 120.92, 120.05, 110.20, 110.12
Synthesis Example 5 Synthesis of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -2′-yl-carbazole

  The same as Synthesis Example 1 except that 7.4 g (29.8 mmol) of 1,3-diphenyl-2-fluorobenzene was used instead of 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene 6.9 g (16.1 mmol) of white powder of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -2′-yl-carbazole was isolated (yield) 65%, HPLC purity 99.7%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.82 (d, 1H), 7.75 (d, 1H), 7.71-7.60 (m, 3H), 7.16 (t, 1H), 7 .08-6.87 (m, 14H)
¹³ C-NMR (CDCl ₃ ); 142.63, 141.44, 141.37, 138.60, 131.42, 131.00, 130.67, 129.28, 127.85, 127.70, 127 .25, 125.64, 122.07, 121.30, 120.63, 119.75, 119.59, 110.34, 110.21
Synthesis Example 6 Synthesis of 4-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole

  Under a nitrogen stream, in a 200 mL three-necked flask, 5.0 g (24.8 mmol) of 4-chloro-9H-carbazole, 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene, 16.2 g of cesium carbonate (49.6 mmol) and 75 mL of dimethyl sulfoxide were added and stirred at 150 ° 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 purified by silica gel column chromatography (volume ratio of toluene / hexane = 1/3) to give 4-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′- 6.2 g (14.4 mmol) of yl-carbazole white powder was isolated (yield 58%, HPLC purity 99.8%).

  The compound was identified by FDMS.

FDMS (m / z); 429 (M +)
Synthesis Example 7 Synthesis of 4-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole

  The same as Synthesis Example 6 except that 7.4 g (29.8 mmol) of 1,4-diphenyl-2-fluorobenzene was used instead of 7.4 g (29.8 mmol) of 1,3-diphenyl-4-fluorobenzene Was performed to isolate 7.9 g (18.5 mmol) of 4-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole white powder. (Yield 62%, HPLC purity 99.8%).

  The compound was identified by FDMS.

FDMS (m / z); 429 (M +)
Example 1 (Synthesis of Compound (A42))

  In a 100 mL three-necked flask under a nitrogen stream, 3.8 g (9 of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole obtained in Synthesis Example 1). 0.0 mmol), 2.9 g (9.1 mmol) of N, N-bisbiphenylamine, 1.2 g (12.6 mmol) of sodium-tert-butoxide, and 30 mL of o-xylene, and the resulting slurry reaction solution To the mixture, 20 mg (0.09 mmol) of palladium acetate and 65 mg (0.32 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 product precipitated in the organic layer was collected by filtration and washed with water and methanol to isolate 6.0 g (8.4 mmol) of a white powder of compound (A42) (yield 93%, HPLC purity 99. 9%). It was confirmed that the sublimation A42 was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.02 (d, 1H), 7.93 (d, 1H), 7.77 (d, 1H), 7.27-7.65 (m, 3H), 7 .58-7.54 (m, 5H), 7.48-7.37 (m, 11H), 7.31-7.22 (m, 5H), 7.14-6.93 (m, 10H) , 6.84 (s, 1H)
¹³ C-NMR (CDCl ₃ ); 147.23, 145.31, 142.23, 141.80, 141.77, 141.11, 140.66, 140.01, 138.60, 134.68, 133 57, 130.37, 130.06, 128.91, 128.73, 128.23, 127.81, 127.63, 127.38, 127.29, 127.21, 126.74, 126.60 125.39, 123.37, 123.07, 120.89, 119.91, 119.79, 119.73, 118.84, 109.88, 107.62.
Example 2 (Synthesis of Compound (A74))

  In a 100 mL three-necked flask under a nitrogen stream, 2.5 g of 5-chloro-9- [1,1 ′: 2 ′, 1 ″ -terphenyl] -4′-yl-carbazole obtained in Synthesis Example 2 (5 8 mmol), 1.9 g (5.9 mmol) of N, N-bisbiphenylamine, 0.78 g (8.1 mmol) of sodium-tert-butoxide, and 20 mL of o-xylene, and the resulting slurry reaction solution To the mixture, 13 mg (0.06 mmol) of palladium acetate and 20 mg (0.20 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 8 hours. After cooling to room temperature, 20 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 to isolate 4.0 g (5.6 mmol) of a white powder of compound (A74) (yield 96%, HPLC purity 99. 8%). It was confirmed that the sublimated A74 was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.06 (t, 2H), 7.58-7.52 (m, 8H), 7.49-7.36 (m, 10H), 7.30 (t, 3H), 7.24-7.11 (m, 11H), 7.04 (s, 4H)
¹³ C-NMR (CDCl ₃ ); 147.30, 146.04, 142.19, 141.72, 141.23, 140.57, 140.39, 139.45, 136.69, 135.08, 132 .08,129.82,129.65,128.73,128.48,127.95,127.72,126.81,126.71,126.65,125.41,125.34,123.82 , 123.45, 121.11, 120.31, 119.83, 119.76, 118.64, 109.82, 106.57, 99.92.
Example 3 (Synthesis of Compound (A111))

  In a 100 mL three-necked flask under a nitrogen stream, 3.7 g (8 of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl-carbazole) obtained in Synthesis Example 3 was obtained. 0.5 mmol), 2.5 g (8.6 mmol) 2-anilino-9,9-dimethylfluorene, 1.1 g (11.1 mmol) sodium-tert-butoxide, and 40 mL o-xylene, and the resulting slurry To the reaction solution, 19 mg (0.09 mmol) of palladium acetate and 61 mg (0.30 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 20 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 3.9 g (5.7 mmol) of a white powder of compound (A111) (yield 68%, HPLC (Purity 99.6%). It was confirmed that A111 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 678 (M +)
Example 4 (Synthesis of Compound (A115))

  Except for using 2.9 g (8.6 mmol) of N- [4- (carbazol-9-yl) phenyl] phenylamine instead of 2.5 g (8.6 mmol) of 2-anilino-9,9-dimethylfluorene. The same operation as in Example 3 was performed to isolate 3.8 g (5.3 mmol) of a white powder of compound (A115) (yield 62%, HPLC purity 99.3%). It was confirmed that A115 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 727 (M +)
Example 5 (Synthesis of Compound (A138))

  In a 100 mL three-necked flask under a nitrogen stream, 1.0 g of 2-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole obtained in Synthesis Example 4 (2 3 mmol), 0.75 g (2.3 mmol) of N, N-bisbiphenylamine, 0.31 g (3.3 mmol) of sodium-tert-butoxide, and 8 mL of o-xylene, and the resulting slurry-like reaction solution To the mixture, 5 mg (0.02 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 8 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 (1.7 mmol) of white powder of compound (A138) (yield 73%, HPLC). (Purity 99.2%). It was confirmed that the sublimated A138 was glassy.

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.02 (d, 1H), 7.94 (d, 1H), 7.75 (d, 2H), 7.65-7.54 (m, 7H), 7 .44-7.21 (m, 16H), 7.11-6.88 (m, 11H)
¹³ C-NMR (CDCl ₃ ); 147.20, 145.42, 142.01, 141.81, 141.79, 140.69, 139.46, 139.38, 138.25, 134.86, 134 .76, 132.06, 128.91, 128.72, 128.25, 128.12, 127.82, 127.76, 127.64, 127.35, 127.24, 126.98, 126.75 126.61, 125.35, 123.49, 123.08, 120.88, 119.90, 119.75, 119.63, 118.63, 109.87, 107.28.
Example 6 (Synthesis of Compound (A170))

  In a 100 mL three-necked flask under a nitrogen stream, 3.4 g (8 of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -2′-yl-carbazole obtained in Synthesis Example 5) 0.0 mmol), N, N-bisbiphenylamine 2.6 g (8.1 mmol), sodium tert-butoxide 1.1 g (11.2 mmol), and o-xylene 30 mL were added, and the resulting slurry reaction solution To the mixture, 18 mg (0.08 mmol) of palladium acetate and 57 mg (0.28 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 10 hours. After cooling to room temperature, 30 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. By recrystallizing the obtained solid (toluene / butanol), 4.8 g (6.7 mmol) of a white powder of the compound (A170) was isolated (yield 84%, HPLC purity 99.9%). It was confirmed that the sublimated A170 was glassy.

The compound was identified by FDMS, ¹ H-NMR measurement, and ¹³ C-NMR measurement.
FDMS (m / z); 714 (M +)
¹ H-NMR (CDCl ₃ ); 7.82 (d, 2H), 7.60-7.39 (m, 14H), 7.33-7.23 (m, 3H), 7.15 (t, 2H), 7.08-6.82 (m, 17H)
¹³ C-NMR (CDCl ₃ ); 147.24, 145.05, 142.71, 142.21, 141.79, 140.70, 138.80, 134.60, 131.67, 130.69, 129 .14, 129.02, 128.74, 128.21, 127.83, 127.60, 127.13, 126.74, 126.60, 124.99, 123.16, 122.49, 120.88 119.67, 119.45, 119.40, 118.70, 110.04, 107.76.
Example 12 (Synthesis of Compound (A53))

  In a 100 mL three-necked flask under a nitrogen stream, 1.0 g of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole obtained in Synthesis Example 1 (2 .3 mmol), 0.63 g (2.3 mmol) of 2-anilinodibenzothiophene, 0.31 g (3.3 mmol) of sodium-tert-butoxide, and 8 mL of o-xylene were added to the resulting slurry reaction solution. 5 mg (0.02 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 24 hours. After cooling to room temperature, 8 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 1.0 g (1.6 mmol) of white powder of compound (A53) (yield 68%, HPLC (Purity 99.7%). It was confirmed that the sublimated A53 was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 668 (M +)
Example 13 (Synthesis of Compound (A54))

  Compound (A54) was prepared in the same manner as in Example 12, except that 0.60 g (2.3 mmol) of 2-anilinodibenzobenzofuran was used instead of 0.63 g (2.3 mmol) of 2-anilinodibenzothiophene. ) Was isolated as a white powder (yield 65%, HPLC purity 99.5%). It was confirmed that A54 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 652 (M +)
Example 14 (Synthesis of Compound (A35))

  Compound (A35) was prepared in the same manner as in Example 12, except that 0.62 g (2.3 mmol) of 9-anilinophenanthrene was used instead of 0.63 g (2.3 mmol) of 2-anilinodibenzothiophene. ) Was isolated as a white powder (yield 64%, HPLC purity 99.5%). It was confirmed that A35 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 662 (M +)
Example 15 (Synthesis of Compound (A44))

  Implemented except that 0.74 g (2.3 mmol) of 4-anilino-1,1 ′: 4 ′, 1 ″ -terphenyl was used instead of 0.63 g (2.3 mmol) of 2-anilinodibenzothiophene. In the same manner as in Example 12, 1.13 g (1.6 mmol) of a pale yellow powder of compound (A44) was isolated (yield 69%, HPLC purity 99.7%). It was confirmed that A44 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 714 (M +)
Example 16 (Synthesis of Compound (A123))

  In a 100 mL three-necked flask under a nitrogen stream, 1.0 g of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl-carbazole obtained in Synthesis Example 3 (2 .3 mmol), 0.81 g (2.3 mmol) of N- [4- (dibenzothienyl-4-yl) phenyl] phenylamine, 0.31 g (3.3 mmol) of sodium tert-butoxide, and 8 mL of o-xylene. In addition, 5 mg (0.02 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, and the mixture was stirred at 140 ° C. for 24 hours. After cooling to room temperature, 8 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 1.1 g (1.5 mmol) of white powder of compound (A123) (yield: 64%, HPLC (Purity 99.7%). It was confirmed that the sublimated A123 was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 744 (M +)
Example 17 (Synthesis of Compound (B42))

  In a 100 mL three-necked flask under a nitrogen stream, 1.0 g of 2-chloro-9- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4′-yl-carbazole obtained in Synthesis Example 6 (2 3 mmol), 0.74 g (2.3 mmol) of N, N-bisbiphenylamine, 0.31 g (3.3 mmol) of sodium tert-butoxide, and 8 mL of o-xylene, and the resulting slurry-like reaction solution To the mixture, 5 mg (0.02 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 8 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 (1.7 mmol) of white powder of compound (B42) (yield 74%, HPLC). (Purity 99.7%). It was confirmed that B42 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 714 (M +)
Example 18 (Synthesis of Compound (B48))

  Example 17 except that 0.83 g (2.3 mmol) of 2- (4-biphenylyl) amino-9,9-dimethylfluorene was used instead of 0.74 g (2.3 mmol) of N, N-bisbiphenylamine. In the same manner, 0.90 g (1.2 mmol) of a white powder of compound (B48) was isolated (yield 52%, HPLC purity 99.4%). It was confirmed that B48 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 754 (M +)
Example 19 (Synthesis of Compound (B133))

  In a 100 mL three-necked flask under a nitrogen stream, 1.0 g of 2-chloro-9- [1,1 ′: 4 ′, 1 ″ -terphenyl] -2′-yl-carbazole obtained in Synthesis Example 7 (2 3 mmol), 0.56 g (2.3 mmol) of N-phenyl-4-biphenylylamine, 0.31 g (3.3 mmol) of sodium-tert-butoxide, and 8 mL of o-xylene were added, and the resulting slurry was To the reaction solution, 5 mg (0.02 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 8 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 1.1 g (1.8 mmol) of white powder of compound (B133) (yield 77%, HPLC). (Purity 99.8%). It was confirmed that B133 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 638 (M +)
Example 20 (Synthesis of Compound (B138))

  The same operation as in Example 19 was performed, except that 0.74 g (2.3 mmol) of N, N-bisbiphenylamine was used instead of 0.56 g (2.3 mmol) of N-phenyl-4-biphenylylamine. Thus, 1.1 g (1.6 mmol) of a white powder of the compound (B138) was isolated (yield 70%, HPLC purity 99.8%). It was confirmed that B138 of the sublimation product was glassy.

  The compound was identified by FDMS.

FDMS (m / z); 714 (M +)
Example 7 (Element evaluation of compound (A42))
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 (A42) is deposited at a deposition rate of 0.3 nm / second to 30 nm to form holes. 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 8 (Element evaluation of compound (A74))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A74) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 9 (Element Evaluation of Compound (A111))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A111) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 10 (Device evaluation of compound (A138))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A138) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 11 (Element evaluation of compound (A170))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A170) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 21 (Element evaluation of compound (A53))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A53) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 22 (Element evaluation of compound (A54))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A54) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 23 (Element evaluation of compound (A35))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A35) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 24 (Element Evaluation of Compound (A44))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A44) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 25 (Element Evaluation of Compound (A123))
An organic EL device was produced in the same manner as in Example 7 except that the compound (A123) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 26 (Element evaluation of compound (B42))
An organic EL device was produced in the same manner as in Example 7 except that the compound (B42) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 27 (Element evaluation of compound (B48))
An organic EL device was produced in the same manner as in Example 7 except that the compound (B48) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 28 (Element Evaluation of Compound (B133))
An organic EL device was produced in the same manner as in Example 7 except that the compound (B133) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 29 (Element Evaluation of Compound (B138))
An organic EL device was produced in the same manner as in Example 7 except that the compound (B138) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Comparative Example 1 (NPD element evaluation)
Commercially available NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was purified by sublimation. It was confirmed that the NPD of the sublimated product was a crystalline powder.

An organic EL device was produced in the same manner as in Example 7 except that NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was used instead of the compound (A42). . Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Reference Example 1 (Device evaluation of compound (a))
The following compound (a) was synthesized and sublimated and purified based on the description in WO 2011/049123 pamphlet. 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 7 except that the following compound (a) was used instead of the compound (A42). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

  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 (5)

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

(In the formula, any two of R ^{1 to} R ⁵ are phenyl groups, each of which may independently have a methyl group, a methoxy group, or a cyano group), and the rest R ^{6 to} R ⁹ each independently represents a hydrogen atom or a group represented by the following general formula (2), and at least one of R ^{6 to} R ⁹ is represented by the following general formula ( 2).

(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 ⁶ is a group represented by the general formula (2), and R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or R ⁷ is a group represented by the general formula (2). The carbazole compound according to claim 1, wherein R ⁶ , R ⁸ , and R ⁹ are hydrogen atoms. Ar ¹ and Ar ² are each independently a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a dibenzothienyl group, or a dibenzofuranyl group [these groups are each independently It may 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]. Compound. 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 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, a phenanthryl group, a dibenzothienyl group, or a dibenzofuranyl group. Compound. An organic EL element material comprising the carbazole compound according to any one of claims 1 to 4.