JP6281414B2 - 4-carbazolylamine compounds - Google Patents

Description

  The present invention relates to a novel 4-carbazolylamine compound.

  An organic EL element is a surface-emitting element in which an organic thin film is held between a pair of electrodes, and has features such as a thin and light weight, a high viewing angle, and a high-speed response, and is expected to be applied to various display elements. . Recently, practical use has begun for mobile phone displays and the like.

  The organic EL element uses light emitted when holes injected from the anode and electrons injected from the cathode are recombined in the light emitting layer, and the structure thereof is a hole transport layer, a light emitting layer, A multilayer stack type in which an electron transport layer and the like are stacked is the mainstream. Here, the charge transport layer such as the hole transport layer and the electron transport layer does not emit light by itself, but facilitates the injection of charges into the light emitting layer, and the charge injected into the light emitting layer or the light emitting layer. It plays the role of confining the energy of the generated excitons. Therefore, the charge transport layer plays a very important role in lowering the driving voltage and improving the light emission efficiency of the organic EL element.

  As the hole transport material, an amine compound having an appropriate ionization potential and hole transport ability is used, and 4,4′-bis [N- (1-naphthyl) -N-phenylamino] is used as such an amine compound. Biphenyl (hereinafter abbreviated as NPD) is well known. However, the driving voltage and luminous efficiency of an element using NPD for the hole transport layer are not sufficiently good, and development of a new material has been demanded.

  Recently, amine compounds having a carbazole ring have been reported for the above problems (see, for example, Patent Documents 1 to 5). However, according to the measurement by the inventors, the characteristics of the amine compound into which the carbazole ring is introduced greatly differ depending on the substitution position of the amino group with respect to the carbazole ring.

  For example, conventionally reported amine compounds having an amino group at the 3-position of the carbazole ring have a higher (shallow) HOMO than NPD (see, for example, Patent Documents 1 and 2). The HOMO of the material is an important physical property value that affects the characteristics of the organic EL element. In particular, when used for a hole transport layer adjacent to the light emitting layer, it greatly affects the light emission efficiency of the organic EL element. For example, when a material having a high (shallow) HOMO is used for the hole transport layer adjacent to the light emitting layer, the light emission efficiency of the organic EL element is reduced due to exciplex formation with the light emitting material (see, for example, Non-Patent Document 1). ). For this reason, in an organic EL device using an amine compound having an amino group at the 3-position of the carbazole ring for the hole transport layer, a sufficiently high luminous efficiency could not be obtained. Therefore, a hole transporting material having a HOMO comparable to that of NPD is desired.

  On the other hand, amine compounds having an amino group via a phenylene group at the 3-position of the carbazole ring have also been reported (see, for example, Patent Documents 3 and 4). Such an amine compound has an appropriate HOMO level equivalent to that of NPD due to the effect of the phenylene group, but the LUMO is low (deep) due to the spread of molecular conjugation, and high luminous efficiency cannot be obtained. .

  In addition, the amine compound having an amino group at the 4-position of the carbazole ring also has an appropriate HOMO comparable to that of NPD (see, for example, Patent Document 5). However, there was room for improvement in oxidation stability and LUMO height.

  That is, in the case of amine compounds having a carbazole ring, in order to obtain an organic EL device exhibiting higher luminous efficiency than before, development of a compound having a high (shallow) LUMO while having an appropriate HOMO equivalent to NPD is required. It was done.

JP 2006-028176 A JP 2006-298898 A KR2010-0033265 JP2013-075891A WO2013 / 062043

Journal of Physical Chemistry C, 2008, 112, 7735

  The present invention has been made in view of the above-described background art. The object of the present invention is an organic EL device having an appropriate HOMO, a LUMO higher than that of conventionally known compounds, and a high oxidation stability. An object of the present invention is to provide a compound having excellent luminous efficiency.

  As a result of intensive studies, the present inventors have found that a novel 4-carbazolylamine compound represented by the following general formula (1) has an appropriate HOMO, a LUMO higher than that of conventionally known compounds, and a high oxidation stability. It was found to have sex. Moreover, it discovered that this compound was excellent as a positive hole transport material of an organic EL element, and came to complete this invention.

（式中、Ａｒ^１及びＡｒ^２は、各々独立して、炭素数６〜１７の芳香族炭化水素基、又は炭素数３〜２０のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜１２のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、フッ素原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］を表す。
Ａｒ^３は、炭素数６〜２０の芳香族炭化水素基、又は炭素数３〜２０のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、フッ素原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］を表す。
Ｒ^１〜Ｒ^５は、各々独立して、炭素数６〜２０の芳香族炭化水素基、若しくは炭素数３〜２０のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、フッ素原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、若しくは環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、若しくは環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数６〜１８のアリールオキシ基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、フッ素原子、重水素原子、又は水素原子を表す。
ｎは０又は１の整数を表す。）
即ち本発明は、上記の一般式（１）で表される４−カルバゾリルアミン化合物に関するものである。

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 17 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently Methyl group, ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, C1-C1 3 halogenated alkyl groups, C 1-3 halogenated alkoxy groups, C 6-12 aryl groups, C 6-18 aryloxy groups, C 3-20 heteroaryl groups, C 3 May have one or more substituents selected from the group consisting of ˜18 trialkylsilyl groups, C18-40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms]. .
Ar ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, an ethyl group, or a C 3-18 carbon atom. Linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms Halogenated alkoxy groups, C6-C20 aryl groups, C6-C18 aryloxy groups, C3-C20 heteroaryl groups, C3-C18 trialkylsilyl groups, C18-C18 It may have one or more substituents selected from the group consisting of 40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms].
R ^{1 to} R ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , C3-C18 straight chain, branched Or a cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, A trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, a deuterium atom, or a hydrogen atom is represented.
n represents an integer of 0 or 1. )
That is, the present invention relates to a 4-carbazolylamine compound represented by the above general formula (1).

  The 4-carbazolylamine compound of the present invention has an appropriate HOMO and has a higher LUMO than the conventionally known compounds, and thus solves the problems of the conventionally known compounds. In addition, the 4-carbazolylamine compound of the present invention is excellent in durability because it has high oxidation-reduction resistance due to electrons and holes. In addition, the organic EL device using the 4-carbazolylamine compound of the present invention exhibits higher light emission efficiency (current efficiency) than when a conventionally known carbazolylamine compound is used, and suppresses the driving voltage to be low. did it.

  Therefore, according to the present invention, it is possible to provide a high-efficiency organic EL element with low voltage and high luminance.

  Hereinafter, the present invention will be described in detail.

In the 4-carbazolylamine compound represented by the general formula (1), Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 17 carbon atoms or a heterocarbon having 3 to 20 carbon atoms. Aromatic groups (these groups are each independently a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, or a straight chain having 3 to 18 carbon atoms. Chain, branched, or cyclic alkoxy group, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, aryl group having 6 to 12 carbon atoms, aryloxy group having 6 to 18 carbon atoms A substituent selected from the group consisting of a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and a deuterium atom One or more groups Representing the then may be).

The aromatic hydrocarbon group having 6 to 17 carbon atoms in Ar ¹ and Ar ² can be referred to as an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked or condensed, and as the substituent, Is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a phenanthryl group, and a fluoranthenyl group.

The C3-C20 heteroaromatic group in Ar < ¹ > and Ar < ² > can be rephrased as a C3-C20 heteroaromatic group which may be linked or condensed, and as the substituent, Although it does not specifically limit, For example, the C3-C20 heteroaromatic group containing an at least 1 oxygen atom, a nitrogen atom, or a sulfur atom can be raised, More preferably, an oxygen atom, a nitrogen atom And a heteroaromatic group having 3 to 20 carbon atoms containing at least one atom selected from the group consisting of sulfur atoms on the aromatic ring, which is not particularly limited, for example, a pyrrolyl group, Thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrazyl 1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzoimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group Group, benzoisoxazolyl group, 2,1,3-benzooxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group Group, a phenazine group, a thiantenyl group, or the like.

Although it does not specifically limit as a C3-C18 linear, branched or cyclic alkyl group in Ar < ¹ > and Ar < ² >, For example, a propyl group, isopropyl group, n-butyl group, sec-butyl group Tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, cyclopropyl group, cyclohexyl group and the like.

Although it does not specifically limit as a C3-C18 linear, branched, or cyclic alkoxy group in Ar < ¹ > and Ar < ² >, For example, a propoxy group, an isopropoxy group, n-butoxy group, sec-butoxy Group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group and the like.

Although it does not specifically limit as a C1-C3 halogenated alkyl group which Ar < ¹ > and Ar < ² > may have as a substituent, For example, a trifluoromethyl group, a trichloromethyl group, or 2- A fluoroethyl group etc. are mentioned.

Examples of the halogenated alkoxy group having 1 to 3 carbon atoms in Ar ¹ and Ar ^2, is not particularly limited, for example, a trifluoromethoxy group, trichloromethoxy group, or a 2-fluoroethoxy group and the like.

The aryl group having 6 to 12 carbon atoms in Ar ¹ and Ar ² can be restated as an aromatic hydrocarbon group which may have a substituent having 6 to 12 carbon atoms in total. Although not particularly limited, for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, Examples include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 3,4-dimethylphenyl group, 2,6-dimethylphenyl group, biphenyl group, or naphthyl group.

The aryloxy group having 6 to 18 carbon atoms in Ar ¹ and Ar ² can be rephrased as an aromatic hydrocarbon oxy group which may have a substituent having 6 to 18 carbon atoms in total. Although not particularly limited, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group Group, 2-cyanophenoxy group, 3-cyanophenoxy group, 4-cyanophenoxy group, 3,4-dimethylphenoxy group, 2,6-dimethylphenoxy group, biphenyloxy group, or naphthyloxy group.

The heteroaryl group having 3 to 20 carbon atoms in Ar ¹ and Ar ² can be paraphrased as a heteroaromatic hydrocarbon group which may have a substituent having a total carbon number of 3 to 20, preferably, A heteroaromatic hydrocarbon group which may have a substituent having 3 to 20 carbon atoms in total containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom on the aromatic ring; Examples of the substituent include, but are not limited to, for example, pyrrolyl group, 1-methylpyrrolyl group, 1-phenylpyrrolyl group, thienyl group, 2-methylthienyl group, 2-cyanothienyl group, 2 -Phenylthienyl group, furyl group, 2-phenylfuryl group, imidazolyl group, 1-methylimidazolyl group, 2-methylimidazolyl group, 1-phenylimidazolyl group, 2-phenyl -Imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 2,4-diphenyl-1,3,5-triazyl Group, indolyl group, benzothienyl group, benzofuranyl group, benzoimidazolyl group, 2-methylbenzoimidazolyl group, 2-phenylbenzoimidazolyl group, 1-methylbenzoimidazolyl group, 1-phenylbenzoimidazolyl group, 1,2-diphenylbenzimidazolyl group, indazolyl group, Benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzooxadiazolyl group, quinolyl group, isoquinolyl Group Noxalyl group, quinazolyl group, carbazolyl group, 9-methylcarbazolyl group, 9-ethylcarbazolyl group, 9-phenylcarbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, acridinyl Group, a phenanthroline group, a phenazine group, or a thiantenyl group.

The trialkylsilyl group having 3 to 18 carbon atoms in Ar ¹ and Ar ^2, is not particularly limited, for example, trimethylsilyl group, triethylsilyl group, or tributylsilyl group, and the like.

The triarylsilyl group having 18 to 40 carbon atoms in Ar ¹ and Ar ² is not particularly limited, and examples thereof include a triphenylsilyl group, a tri (2-methylphenyl) silyl group, and tri (3-methylphenyl). ) Silyl group, tri (4-methylphenyl) silyl group, or tri (4-biphenylyl) silyl group.

Specific examples of Ar ¹ and Ar ² include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-decylphenyl group, 4-n- Dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-tritylphenyl group, 3-tritium Phenyl group, 4-triphenylsilylphenyl group, 3-triphenylsilylphenyl 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-methoxyphenyl group, 3-methoxyphenyl group 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2- Isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphe Nyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxy Phenyl group, 2- (2-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl -4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-d 5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2 -Methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 3-cyanophenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6- Fluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl 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-phenyl Nylnaphthalen-1-yl group, 4- (2-methylphenyl) naphthalen-1-yl group, 4- (3-methylphenyl) naphthalen-1-yl group, 4- (4-methylphenyl) naphthalene-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-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group, 9,9-di-n-octyl-2-fluorenyl group, 9,9-diphenyl-2-fluorenyl group, 9,9′-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl 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′-bipyridine-3 -Yl group, 2,3'-bipyridin-4-yl group, 2,3'-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl -1,3, -Triazin-2-yl group, 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzoimidazolyl group, 1-methyl-2-benzimidazolyl group, 1-phenyl-2-benzoimidazolyl 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-benzoimidazolyl group, 1,2-diphenyl- 6-Benzimidazolyl group, 1-methyl-3-i Danazolyl 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-benzoisothiazolyl group Ryl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group, 7-benzisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazole- 5-yl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl, 3-benzoisoxa Zolyl group, 4-benzisoxazolyl group, 5-benzisoxazolyl group, 6-benzoisoxazolyl group, 7-benzoisoo Sazolyl group, 2,1,3-benzooxadiazolyl-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-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, -Furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 9-methylcarbazol-2-yl group, 9-methylcarbazole-3- Yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazole-2-yl Yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group, 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazin-2-yl group, 10- Phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylin Dole-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-triphenylimidazole- 1-yl) phenyl group, 4- (1-methyl-4,5-diphenylimidazol-2-yl) phenyl group, 4- (2-methylbenzimidazol-1-yl) phenyl group, 4- ( -Phenylbenzimidazol-1-yl) phenyl group, 4- (1-methylbenzimidazol-2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methyl) Benzimidazol-1-yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzimidazole) -1-yl) phenyl group, 4- (3,5-diphenyltriazin-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-phenyl) Furan-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-dibenzo Thienyl) 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 4-carbazolylamine compound represented by the general formula (1), Ar ¹ and Ar ² are each independently a phenyl group, a biphenyl group, a naphthyl group, from the viewpoint of excellent hole transport properties and durability. A phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, or a carbazolyl group (these groups are each independently a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms) Group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, C1-C3 halogenated alkyl group, C6-C12 aryl group, C6-C18 Aryloxy group, heteroaryl group having 3 to 20 carbon atoms, trialkylsilyl group having 3 to 18 carbon atoms, triarylsilyl group having 18 to 40 carbon atoms, cyano group, fluorine Child, and it is preferable that a substituent selected from the group consisting of heavy hydrogen atoms have one or more is also be).

  Among these, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, or a carbazolyl group (these groups are each independently a methyl group, a methoxy group, a cyano group, , Fluorine atom, deuterium atom, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, naphthyl group, carbazolyl group, dibenzothienyl group, and dibenzofuranyl group More preferably, it may have one or more substituents.

  Among these, a phenyl group, a fluorenyl group, or a carbazolyl group (the above groups are each independently a methyl group, a methoxy group, a cyano group, a fluorine atom, a deuterium atom, a phenyl group, a 2-methylphenyl group, 3 -It may have one or more substituents selected from the group consisting of methylphenyl group, 4-methylphenyl group, naphthyl group, carbazolyl group, dibenzothienyl group and dibenzofuranyl group), biphenyl group, naphthyl It is more preferably a group, a phenanthryl group, a dibenzothienyl group, or a dibenzofuranyl group.

  Among these, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 4- (4-dibenzothienyl) phenyl group, 4- (4-dibenzo) Furanyl) phenyl group, 3- (4-dibenzothienyl) phenyl group, 3- (4-dibenzofuranyl) phenyl group, 4- (9-carbazolyl) phenyl group, 4-biphenyl group, 3-biphenyl group, 1 -Naphtyl group, 2-naphthyl group, 9-phenanthryl group, 4- (1-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 9,9-dimethyl-2-fluorenyl group, 2-dibenzothienyl group , 2-dibenzofuranyl group, or 9-phenylcarbazol-3-yl group is more preferable.

In the 4-carbazolylamine compound represented by the general formula (1), Ar ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms (these are each independently A methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, carbon A halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, It may have one or more substituents selected from the group consisting of a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and a deuterium atom. ).

The aromatic hydrocarbon group having 6 to 20 carbon atoms in Ar ³ can be rephrased as an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, and the substituent is particularly For example, but not limited to, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, fluoranthenyl group, anthryl group, chrysenyl group , Pyrenyl group, triphenylene group, or perylenyl group.

The hetero aromatic group having 3 to 20 carbon atoms in Ar ^3, although not particularly limited, include the same substituents as heteroaromatic group having 3 to 20 carbon atoms shown in Ar ¹ and Ar ² of the It is done.

Ar ³ , a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, carbon A halogenated alkoxy group having 1 to 3 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, and a triaryl having 18 to 40 carbon atoms Examples of the silyl group include the same substituents as those described above for Ar ¹ and Ar ² .

  Note that an aryl group having 6 to 20 carbon atoms can be called an aromatic hydrocarbon group which may have a substituent having 6 to 20 carbon atoms in total, and the substituent is particularly limited. Although not a thing, for example, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-cyanophenyl Group, 3-cyanophenyl group, 4-cyanophenyl group, 3,4-dimethylphenyl group, 2,6-dimethylphenyl group, biphenyl group, terphenyl group, phenanthryl group, or naphthyl group.

Specific examples of Ar ³ include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n -Propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-n -Pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-tritylphenyl group, 3-tritylphenyl group 4-triphenylsilylphenyl group, 3-triphenylsilylphenyl 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-methoxyphenyl group, 3-methoxyphenyl group, 2 -Methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxy group Phenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4 n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxy Phenyl group, 2-cyclohexyloxyphenyl group, 4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl Group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5- Toxiphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3, 4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6 -Ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 3-cyanophenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl Group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl An phenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 4-biphenyl group, a 3-biphenyl group, a 2-biphenyl group, a 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, p-terphenyl group, m-terphenyl group, o-terphenyl 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-phenyl Lunaphthalen-1-yl group, 4- (2-methylphenyl) naphthalen-1-yl group, 4- (3-methylphenyl) naphthalen-1-yl group, 4- (4-methylphenyl) naphthalene-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-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group, 9,9-di-n-octyl-2-fluorenyl group, 9,9-diphenyl-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-pyrenyl group, 2-pyrenyl group, 9-anthryl group, 2-anthryl group, 2-triphenylene group, 3-chrysenyl group, 6-chrycenyl group 3-perylenyl 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-pyrazo 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'- Pyridin-4-yl group, 2,3′-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazine- 2-yl group, 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzoimidazolyl group, 1-methyl-2-benzimidazolyl group, 1-phenyl-2-benzoimidazolyl group, 1-methyl- 5-benzoimidazolyl 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-benzoisothiazolyl group, 4-benzisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group Group, 7-benzoisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group, 2-benzoxazolyl group, 4-benzooxa Zolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl Group, 3-benzoisoxazolyl group, 4-benzisoxazolyl group, 5-benzisoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2,1 , 3-Benzoxadiazolyl-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-phenanthrolol N-5-yl group, 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-furanyl group, 3-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-methylcarbazole- 4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazole- 3-yl group, 9-biphenylcarbazol-4-yl group, 2-thianthryl group, 10-phenylphenothiazin-3-yl group 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group 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-phenylimidazole-) 1-yl) phenyl group, 4- (1-phenylimidazol-2-yl) phenyl group, 4- (2,3,4-triphenylimidazol-1-yl) pheny Group, 4- (1-methyl-4,5-diphenyl-imidazol-2-yl) phenyl group, 4- (2-methyl-benzimidazol-1-yl) phenyl group, 4- (2-phenyl benzimidazole -
1-yl) phenyl group, 4- (1-methylbenzimidazol-2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazole-1- Yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) Phenyl group, 4- (3,5-diphenyltriazin-1-yl) phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) phenyl group, 5-phenylthiophen-2-yl group, 5-phenylfuran-2-yl group, 4- (5-phenylthiophen-2-yl) phenyl group, 4- (5-phenylfuran-2-yl) phenyl group, -(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- Group, 4- (9-carbazolyl) phenyl group, or a 3- (9-carbazolyl) can be exemplified a phenyl group, but is not limited thereto.

Ar ³ is a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, fluorenyl group, benzofluorenyl group, triphenylene group, dibenzothienyl group, dibenzofuranyl group, in terms of excellent hole transport properties. Or a carbazolyl group (these groups are each independently a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, or a straight chain having 3 to 18 carbon atoms. A chain, branched or cyclic alkoxy group, a halogenated alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, Selected from the group consisting of a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and a deuterium atom. It may have one or more substituents.

  Among these, phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, fluorenyl group, benzofluorenyl group, triphenylene group, dibenzothienyl group, dibenzofuranyl group, or carbazolyl group (these groups are Each independently a methyl, methoxy, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, naphthyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and 9- More preferably, it may have one or more substituents selected from the group consisting of phenylcarbazolyl groups.

  Among these, a phenyl group, a fluorenyl group, or a carbazolyl group (the above groups are each independently a methyl group, a methoxy group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group) , A naphthyl group, a dibenzothienyl group, a dibenzofuranyl group, a carbazolyl group, and a 9-phenylcarbazolyl group, which may have one or more substituents), a biphenyl group, a terphenyl group , A naphthyl group, a phenanthryl group, a benzofluorenyl group, a triphenylene group, a dibenzothienyl group, or a dibenzofuranyl group.

  Among these, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 4- (4-dibenzothienyl) phenyl group, 4- (4-dibenzo) Furanyl) phenyl group, 4- (9-carbazolyl) phenyl group, 4-biphenyl group, 3-biphenyl group, p-terphenyl group, m-terphenyl group, 1-naphthyl group, 2-naphthyl group, 9- Phenanthryl group, 4- (1-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 9,9-dimethyl-2-fluorenyl group, 2-dibenzothienyl group, 2-dibenzofuranyl group, 4- ( It is more preferably a 9-carbazolyl) phenyl group or a 9-phenylcarbazol-4-yl group.

In the 4-carbazolylamine compound represented by the general formula (1), R ^{1 to} R ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms. Group (These groups are each independently a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, a branched or cyclic alkyl group, a methoxy group, an ethoxy group, or a straight chain having 3 to 18 carbon atoms. A branched or cyclic alkoxy group, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, A substituent selected from the group consisting of a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and a deuterium atom Have one or more Or a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms. A halogenated alkyl group having 1 to 3 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, Denotes a deuterium atom or a hydrogen atom.

The aromatic hydrocarbon group having 6 to 20 carbon atoms in R ^{1 to} R ⁵ is not particularly limited, but is the same as the aromatic hydrocarbon group having 6 to 20 carbon atoms shown in Ar ³ .

The heteroaromatic group having 3 to 20 carbon atoms in R ^{1 to} R ⁵ is not particularly limited, but the heteroaromatic group having 3 to 20 carbon atoms shown in the aforementioned Ar ¹ , Ar ² , and Ar ³ . Is the same.

Linear 3 to 18 carbon atoms in R ¹ to R ^5, branched, or cyclic alkyl, straight chain 3 to 18 carbon atoms, branched, or cyclic alkoxy, halogenated alkyl having 1 to 3 carbon atoms, carbon atoms 1 to 3 halogenated alkoxy, 6 to 20 aryl, 6 to 18 aryloxy, 3 to 20 heteroaryl, 3 to 18 trialkylsilyl, and 18 to 40 carbon atoms The triarylsilyl group is the same as the substituents shown for Ar ¹ , Ar ² , and Ar ³ .

R ¹ , R ² , R ⁴ and R ⁵ are each independently a phenyl group, a biphenyl group, or a naphthyl group (these groups are each independently a methyl group from the viewpoint of excellent hole transport properties. , An ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a carbon number of 1 to 3 Halogenated alkyl group, C1-C3 halogenated alkoxy group, C6-C20 aryl group, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 A trialkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and a deuterium atom (which may have one or more substituents), a methyl group, Ethyl group, carbon A linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a cyano group, a deuterium atom, or a hydrogen atom. It is preferable.

  Of these, each independently a phenyl group, biphenyl group, or naphthyl group (these groups are each independently a methyl group, an ethyl group, a linear, branched, or cyclic group having 3 to 18 carbon atoms). Even if it has 1 or more types of substituents chosen from the group which consists of an alkyl group, a methoxy group, an ethoxy group, a C3-C18 linear, branched or cyclic alkoxy group, a cyano group, and a deuterium atom. Good), methyl group, ethyl group, linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, methoxy group, ethoxy group, linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, cyano It is more preferably a group, a deuterium atom, or a hydrogen atom.

  Of these, each independently is more preferably a phenyl group, a methyl group, a methoxy group, a cyano group, a deuterium atom, or a hydrogen atom.

  Of these, a hydrogen atom is more preferable.

R ³ is a phenyl group, a biphenyl group, or a naphthyl group (these groups are each independently a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, a branched group, from the viewpoint of excellent hole transport properties. Or a cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogenated alkoxy having 1 to 3 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 18 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, trialkylsilyl group having 3 to 18 carbon atoms, and triaryl having 18 to 40 carbon atoms A silyl group, a cyano group, a fluorine atom, and one or more substituents selected from the group consisting of deuterium atoms), a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, a branched chain, Or annular An alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a cyano group, a deuterium atom, or a hydrogen atom is preferable.

  Among these, a phenyl group, a biphenyl group, or a naphthyl group (these groups are each independently a methyl group, an ethyl group, a C3-C18 linear, branched, or cyclic alkyl group, a methoxy group, , An ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a cyano group, and one or more substituents selected from the group consisting of deuterium atoms), a methyl group , Ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, cyano group, deuterium atom Or a hydrogen atom.

  Of these, a phenyl group, a methyl group, a methoxy group, a cyano group, a deuterium atom, or a hydrogen atom is more preferable.

  Although the preferable compound is illustrated below about the 4-carbazolylamine compound of this invention, it is not limited to these compounds.

前記一般式（１）で表される４−カルバゾリルアミン化合物は、例えば、ハロゲン化されたカルバゾール中間体を公知の方法（Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，１９９８年，第３９巻，２３６７頁）でアミノ化することによって合成することができる。具体的には、下記のスキーム１に従って合成することができる。

For the 4-carbazolylamine compound represented by the general formula (1), for example, a halogenated carbazole intermediate is aminated by a known method (Tetrahedron Letters, 1998, Vol. 39, page 2367). Can be synthesized. Specifically, it can be synthesized according to the following scheme 1.

  Reaction of the carbazole compound halogenated at the 4-position represented by the general formula (2) and the primary amine compound represented by the general formula (3) using a copper catalyst or a palladium catalyst in the presence of a base. To obtain a secondary amine compound represented by the general formula (4). By reacting the obtained secondary amine compound represented by the general formula (4) and the halogen compound represented by the general formula (5) using a copper catalyst or a palladium catalyst in the presence of a base, the general formula The 4-carbazolylamine compound represented by (1) can be obtained.

  In addition, a carbazole compound halogenated at the 4-position represented by the general formula (2) and a secondary amine compound represented by the general formula (6) are reacted in the presence of a base using a copper catalyst or a palladium catalyst. Also, the 4-carbazolylamine compound represented by the general formula (1) can be obtained.

（式中、Ａｒ^１〜Ａｒ^３、Ｒ^１〜Ｒ^５、及びnは前記と同義であり、Ｘ及びＹは各々独立してハロゲン原子［ヨウ素原子、臭素原子、塩素原子、又はフッ素原子］を表す。）
一般式（１）で表される４−カルバゾリルアミン化合物の合成方法は、スキーム１に限定されるものでなく、他のルートによって合成することも可能である。

(In the formula, Ar ^{1 to} Ar ³ , R ^{1 to} R ⁵ , and n are as defined above, and X and Y are each independently a halogen atom [iodine atom, bromine atom, chlorine atom, or fluorine atom]. Represents.)
The method for synthesizing the 4-carbazolylamine compound represented by the general formula (1) is not limited to Scheme 1 and can be synthesized by other routes.

  The 4-carbazolylamine compound of the present invention can be used as a light emitting layer, a hole transport layer or a hole injection layer of an organic EL device.

  In particular, the 4-carbazolylamine compound represented by the general formula (1) is any of a hole injection layer, a hole transport layer, and a light emitting layer in an element using a fluorescent light emitting material or a phosphorescent light emitting material for a light emitting layer. It can be preferably used in more than one layer.

  For the light emitting layer when the 4-carbazolylamine compound of the present invention is used as a hole injection layer and / or a hole transport layer of an organic EL device, a conventionally known fluorescent or phosphorescent light emitting material is used. can do. 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.

  Further, when using the 4-carbazolylamine compound of the present invention as a hole injection layer and / or a hole transport layer of an organic EL device, an anode, a hole injection layer, a hole transport layer, an electron transport layer, Conventionally known materials can be used for the electron injection layer, the cathode, and the like.

  When forming the hole injection layer and / or hole transport layer comprising the 4-carbazolylamine compound of the present invention, two or more kinds of materials may be contained or laminated as necessary, for example, oxidation Oxides such as molybdenum, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexaazatriphenylene, etc. These known electron-accepting materials may be contained or laminated.

  Further, the 4-carbazolylamine compound of the present invention can also be used as a light emitting layer of an organic EL device. When the 4-carbazolylamine compound represented by the general formula (1) is used as the light emitting layer of the organic EL device, the 4-carbazolylamine compound is used alone, and doped into a known light emitting host material. It can be used or doped with a known luminescent dopant.

  As a method for forming a hole injection layer, a hole transport layer or a light emitting layer containing the 4-carbazolylamine compound of the present invention, for example, a known method such as a vacuum deposition method, a spin coating method, or a casting method is applied. can do.

  The basic structure of the organic EL device that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

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

  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 hole injection layer contains the 4-carbazolylamine compound of the present invention.

  For the hole transport layer and / or hole injection layer, together with the 4-carbazolylamine compound of the present invention, any one of known hole transport materials and / or hole injection materials may be selected and combined. Can be used.

  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, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

  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-para-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 further in detail based on an Example, this invention is not limited by these Examples.

¹ H-NMR and ¹³ C-NMR measurements were performed using Gemini 200 manufactured by Varian.

  FDMS measurement was performed using M-80B manufactured by Hitachi, Ltd.

HOMO was estimated from the oxidation potential (E _ox (V vs. Fc / Fc ⁺ )) obtained by cyclic voltammetry using HA-501 and HB-104 manufactured by Hokuto Denko (HOMO = −E _ox −4 .8)
LUMO was estimated from the energy gap value (E _g ) obtained by UV / Vis spectrum measurement using U-2010 manufactured by Hitachi, Ltd. (LUMO = HOMO + E _g ).

  The light emission characteristics of the organic EL element were evaluated by applying a direct current to the element produced using a source meter (2400) manufactured by Keithley Instruments and using a luminance meter of LUMINANCEMETER (BM-9) manufactured by TOPCON.

Synthesis Example 1 (Synthesis of 4-chloro-9-phenylcarbazole)
In a 100 mL three-necked flask under a nitrogen stream, 5.0 g (24.7 mmol) of 4-chlorocarbazole, 4.2 g (27.2 mmol) of bromobenzene, 4.7 g (34.7 mmol) of potassium carbonate, and 50 mL of o-xylene. Was added to the slurry reaction solution, and 55 mg (0.24 mmol) of palladium acetate and 174 mg (0.86 mmol) of tri (tert-butyl) phosphine were added and stirred at 140 ° C. for 16 hours. After cooling to room temperature, 30 mL of pure water was added, and the organic layer was separated. Next, the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Next, the residue was purified by silica gel column chromatography (hexane), and 4.5 g (16.5 mmol) of a colorless oil of 4-chloro-9-phenylcarbazole was isolated (yield 67%).

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

¹ H-NMR (CDCl ₃ ); 8.67 (d, 1H), 7.22-7.65 (m, 11H)
¹³ C-NMR (CDCl ₃ ); 142.04, 141.05, 137.15, 129.94, 128.73, 127.93, 127.39, 126.41, 126.06, 123.07, 122 21, 120.64, 120.51, 120.23, 109.56, 108.11
Synthesis Example 2 (Synthesis of 4-chloro-9- (4-biphenylyl) carbazole)
In a 100 mL three-necked flask under a nitrogen stream, 4.0 g (19.8 mmol) of 4-chlorocarbazole, 4.6 g (20.8 mmol) of 4-bromobiphenyl, 3.8 g (27.7 mmol) of potassium carbonate, and o-xylene 40 mL was added, and 44 mg (0.19 mmol) of palladium acetate and 139 mg (0.69 mmol) of tri (tert-butyl) phosphine were added to the slurry-like reaction solution, followed by stirring at 140 ° C. for 10 hours. Subsequently, after cooling to room temperature, 20 mL of pure water was added, and the organic layer was separated. Next, the organic layer was washed with pure water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained powder was washed with ethanol, and 5.1 g (14.6 mmol) of a light brown powder of 4-chloro-9- (4-biphenylyl) carbazole was isolated (yield 74%).

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

¹ H-NMR (CDCl ₃ ); 8.68 (d, 1H), 7.80 (d, 2H), 7.67 (d, 2H), 7.22-7.59 (m, 11H)
¹³ C-NMR (CDCl ₃ ); 142.04, 141.05, 140.83, 140.08, 136.29, 128.97, 128.79, 128.58, 127.74, 127.61, 127 .14, 126.48, 126.13, 123.13, 122.32, 120.75, 120.62, 120.33, 109.65, 108.20
Synthesis Example 3 (Synthesis of 4-chloro-9- (2-dibenzothienyl) carbazole)
In a 100 mL three-necked flask under a nitrogen stream, 7.8 g (38.7 mmol) of 4-chlorocarbazole, 10.2 g (38.7 mmol) of 2-bromodibenzothiophene, 10.5 g (77.7 mmol) of potassium carbonate, and o- 40 mL of xylene was added, and 87 mg (0.36 mmol) of palladium acetate and 273 mg (1.3 mmol) of tri (tert-butyl) phosphine were added to the slurry-like reaction solution, followed by stirring at 140 ° C. for 12 hours. After cooling to room temperature, 20 mL of pure water was added, and the organic layer was separated. Next, the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 2)), and 11.2 g of white powder of 4-chloro-9- (2-dibenzothienyl) carbazole ( 29.4 mmol) isolated (76% yield).

The compound was identified by ¹ H-NMR measurement.

¹ H-NMR (CDCl ₃ ); 8.71 (d, 1H), 8.27 (d, 1H), 8.04-8.16 (m, 3H), 7.83-7.94 (m, 2H), 7.25-7.61 (m, 7H)
Example 1 (Synthesis of Compound (A1))
In a 50 mL three-necked flask under a nitrogen stream, 1.6 g (5.8 mmol) of 4-chloro-9-phenylcarbazole obtained in Synthesis Example 1 and N-phenyl-N- (9-phenylcarbazol-3-yl) were obtained. Amine 1.9 g (5.8 mmol), sodium-tert-butoxide 0.74 g (7.4 mmol), o-xylene 15 mL, palladium acetate 12 mg (0.05 mmol), and tri (tert-butyl) phosphine 37 mg (0. 18 mmol) was added and stirred at 140 ° C. for 7 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 2.5 g (4.3 mmol) of a colorless glassy solid of compound (A1) was isolated. (Yield 75%).

  The compound was identified by FDMS.

FDMS: 575
Example 2 (Synthesis of Compound (A40))
Under a nitrogen stream, 0.98 g (2.8 mmol) of 4-chloro-9- (4-biphenyl) carbazole obtained in Synthesis Example 2 and N-phenyl-N- (9-phenylcarbazole-) were placed in a 50 mL three-necked flask. 3-yl) amine 0.93 g (2.8 mmol), sodium tert-butoxide 0.37 g (3.9 mmol), o-xylene 10 mL, palladium acetate 6 mg (0.03 mmol), and tri (tert-butyl) phosphine 21 mg (0.10 mmol) was added and stirred at 140 ° C. for 5 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 1.5 g (2.3 mmol) of a colorless glassy solid of the compound (A40) was isolated. (Yield 83%).

  The compound was identified by FDMS.

FDMS: 651
Example 3 (Synthesis of Compound (A72))
In a 50 mL three-necked flask under a nitrogen stream, 1.5 g (3.9 mmol) of 4-chloro-9- (2-dibenzothienyl) carbazole obtained in Synthesis Example 3 and N-phenyl-N- (9-phenylcarbazole) were obtained. -3-yl) amine 1.3 g (3.9 mmol), sodium-tert-butoxide 0.52 g (5.4 mmol), o-xylene 15 mL, palladium acetate 26 mg (0.11 mmol), and tri (tert-butyl) 77 mg (0.38 mmol) of phosphine was added and stirred at 140 ° C. for 14 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 2.0 g (3.0 mmol) of a colorless glassy solid of the compound (A72) was isolated. (Yield 78%).

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

FDMS: 681
¹ H-NMR (CDCl ₃ ); 8.43 (s, 1H), 7.94-8.19 (m, 6H), 6.93-7.75 (m, 24H)
¹³ C-NMR (CDCl ₃ ); 143.44, 141.58, 140.55, 138.98, 138.02, 137.38, 135.34, 134.75, 130.12, 129.40, 127 62, 127.25, 127.21, 126.53, 126.28, 125.95, 125.00, 122.51, 124.40, 123.59, 123.31, 122.18, 122.12 121.08, 120.82, 120.48, 120.37, 120.02, 119.79, 116.88, 116.82, 110.75, 110.09, 109.36, 106.81, 100 .22
Example 4 (Synthesis of Compound (B1))
In a 50 mL three-necked flask under a nitrogen stream, 2.4 g (8.7 mmol) of 4-chloro-9-phenylcarbazole obtained in Synthesis Example 1 and N-phenyl-N- [4- (9-phenylcarbazole-3) were obtained. -Yl) phenyl] amine 3.5 g (8.7 mmol), sodium-tert-butoxide 1.1 g (11.1 mmol), o-xylene 25 mL, palladium acetate 18 mg (0.07 mmol), and tri (tert-butyl) 55 mg (0.27 mmol) of phosphine was added and stirred at 140 ° C. for 7 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 3.9 g (6.0 mmol) of a colorless glassy solid of compound (B1) was isolated. (Yield 69%).

  The compound was identified by FDMS.

FDMS: 651
Example 5 (Synthesis of Compound (B29))
In a 50 mL three-necked flask under a nitrogen stream, 1.3 g (3.9 mmol) of 4-chloro-9- (4-biphenylyl) carbazole obtained in Synthesis Example 2 and N-phenyl-N- [4- (9- Phenylcarbazol-3-yl) phenyl] amine 1.6 g (3.9 mmol), sodium tert-butoxide 0.52 g (5.5 mmol), o-xylene 10 mL, palladium acetate 18 mg (0.07 mmol), and tri ( 55 mg (0.27 mmol) of tert-butyl) phosphine was added and stirred at 140 ° C. for 9 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 2.3 g (3.1 mmol) of a colorless glassy solid of the compound (B29) was isolated. (Yield 81%).

  The compound was identified by FDMS.

FDMS: 727
Example 6 (Synthesis of Compound (B56))
In a 50 mL three-necked flask under a nitrogen stream, 3.0 g (7.8 mmol) of 4-chloro-9- (2-dibenzothienyl) carbazole obtained in Synthesis Example 3 and N-phenyl-N- [4- (9 -Phenylcarbazol-3-yl) phenyl] amine 3.2 g (7.8 mmol), sodium-tert-butoxide 1.0 g (10.9 mmol), o-xylene 15 mL, palladium acetate 35 mg (0.15 mmol), and tri 110 mg (0.54 mmol) of (tert-butyl) phosphine was added and stirred at 140 ° C. for 14 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 2: 3)), and 4.5 g (5.9 mmol) of a colorless glassy solid of the compound (B56) was isolated. (Yield 75%).

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

FDMS: 757
¹ H-NMR (CDCl ₃ ); 8.32 (d, 2H), 8.03-8.15 (m, 3H), 7.89 (d, 2H), 7.23-7.66 (m, 25H), 6.96-7.10 (m, 3H)
¹³ C-NMR (CDCl ₃ ); 147.90, 146.66, 143.52, 141.75, 141.64, 141.59, 140.59, 140.35, 139.06, 138.02, 137 41, 135.74, 135.34, 134.68, 133.45, 130.17, 129.53, 128.22, 127.71, 127.33, 127.29, 126.50, 126.32 126.18, 125.42, 125.04, 124.45, 124.15, 123.82, 123.53, 123.34, 122.60, 122.20, 122.12, 121.98, 121. .52, 121.06, 120.91, 120.64, 120.53, 120.28, 118.53, 110.24, 110.17, 109.48, 10 .53
Example 7 (Evaluation of HOMO and LUMO of Compound (A1))
The oxidation potential (E _ox ) was measured by cyclic voltammetry. The measurement is performed by dissolving compound (A1) at a concentration of 0.001 mol / L in an anhydrous dichloromethane solution having a concentration of tetrabutylammonium perchlorate of 0.1 mol / L, a glassy carbon as a working electrode, a platinum wire as a counter electrode, A silver wire immersed in an acetonitrile solution of AgNO ₃ was used as a reference electrode. Using ferrocene as a standard substance, the E _ox of the compound (A1) based on the oxidation-reduction potential of ferrocene was 0.27 (V vs. Fc / Fc ⁺ ). Table 1 shows the HOMO of the compound (A1) estimated from E _ox .

The energy gap (E _g ) was estimated from the wavelength of the absorption edge of the UV / Vis spectrum. Tetrahydrofuran was dissolved the compound (A1) at a concentration of 1 × ¹⁰ -5 mol / L, were measured UV / Vis spectra, calculation of _{E g} the wavelength of the absorption edge was 3.21 eV. Table 1 shows the LUMO of the compound (A1) estimated from the E _g .

Example 8 (Evaluation of HOMO and LUMO of Compound (A40))
The oxidation potential and energy gap of the compound (A40) were measured by the same method as in Example 7. The results were 0.26 (V vs. Fc / Fc ⁺ ) and 3.20 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (A40) estimated from these values.

Example 9 (Evaluation of HOMO and LUMO of Compound (A72))
The oxidation potential and energy gap of the compound (A72) were measured by the same method as in Example 7. The result was 0.27 (V vs. Fc / Fc ⁺ ) and 3.19 eV, respectively. Table 1 shows HOMO and LUMO of the compound (A72) estimated from these values.

Example 10 (Evaluation of HOMO and LUMO of Compound (B1))
The oxidation potential and energy gap of the compound (B1) were measured by the same method as in Example 7. The results were 0.30 (V vs. Fc / Fc ⁺ ) and 3.32 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (B1) estimated from these values.

Example 11 (Evaluation of HOMO and LUMO of Compound (B29))
The oxidation potential and energy gap of the compound (B29) were measured by the same method as in Example 7. The results were 0.30 (V vs. Fc / Fc ⁺ ) and 3.31 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (B29) estimated from these values.

Example 12 (Evaluation of HOMO and LUMO of Compound (B56))
The oxidation potential and energy gap of the compound (B56) were measured by the same method as in Example 7. As a result, they were 0.29 (V vs. Fc / Fc ⁺ ) and 3.31 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (B56) estimated from these values.

比較例１ （化合物（ａ）のＨＯＭＯとＬＵＭＯの評価）
実施例７と同様の方法で化合物（ａ）の酸化電位とエネルギーギャップを測定したところ、それぞれ０．１２（Ｖ ｖｓ．Ｆｃ／Ｆｃ^＋）、３．０４ｅＶであった。これらの値から見積もった化合物（ａ）のＨＯＭＯとＬＵＭＯを表１に示す。

Comparative Example 1 (Evaluation of HOMO and LUMO of Compound (a))
The oxidation potential and energy gap of compound (a) were measured by the same method as in Example 7. The results were 0.12 (V vs. Fc / Fc ⁺ ) and 3.04 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (a) estimated from these values.

Comparative Example 2 (Evaluation of HOMO and LUMO of Compound (b))
The oxidation potential and energy gap of compound (b) were measured by the same method as in Example 7. The results were 0.29 (V vs. Fc / Fc ⁺ ) and 3.20 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (b) estimated from these values.

Comparative Example 3 (Evaluation of NPD HOMO and LUMO)
The oxidation potential and energy gap of NPD were measured by the same method as in Example 7. The results were 0.31 (V vs. Fc / Fc ⁺ ) and 3.09 eV, respectively. Table 1 shows the HOMO and LUMO of NPD estimated from these values.

Reference Example 1 (Evaluation of HOMO and LUMO of Compound (c))
The oxidation potential and energy gap of compound (c) were measured by the same method as in Example 7. The results were 0.44 (V vs. Fc / Fc ⁺ ) and 3.29 eV, respectively. Table 1 shows the HOMO and LUMO of the compound (c) estimated from these values.

  The HOMO of the 4-carbazolylamine compound of the present invention has a suitable HOMO as a hole transport material, and has a higher LUMO (shallow) than NPD, compound (b), and compound (c). The problem of the compound was solved.

実施例１３ （化合物（Ｂ１）の酸化還元安定性評価）
サイクリックボルタンメトリーで化合物（Ｂ１）の酸化還元安定性を評価した。過塩素酸テトラブチルアンモニウムの濃度が０．１ｍｏｌ／Ｌである無水ジクロロメタン溶液に化合物（Ｂ１）を０．００１ｍｏｌ／Ｌの濃度で溶解させ、作用電極にグラッシーカーボン、対極に白金線、参照電極にＡｇＮＯ_３のアセトニトリル溶液に浸した銀線を用いて、化合物（Ｂ１）のサイクリックボルタモグラムを得た（図１）。化合物（Ｂ１）は可逆な酸化還元波を示し、酸化還元に対して安定であった。

Example 13 (Evaluation of redox stability of compound (B1))
The redox stability of the compound (B1) was evaluated by cyclic voltammetry. Compound (B1) is dissolved in an anhydrous dichloromethane solution having a concentration of tetrabutylammonium perchlorate of 0.1 mol / L at a concentration of 0.001 mol / L. The working electrode is glassy carbon, the counter electrode is a platinum wire, and the reference electrode is a reference electrode. A cyclic voltammogram of compound (B1) was obtained using a silver wire immersed in an acetonitrile solution of AgNO ₃ (FIG. 1). Compound (B1) showed a reversible redox wave and was stable against redox.

Reference Example 2 (Evaluation of redox stability of compound (c))
The redox stability of the compound (c) was evaluated in the same manner as in Example 13. Compound (c) was irreversible in the second dioxide (FIG. 2) and unstable to two-electron oxidation.

Example 14 (Element Evaluation of Compound (A1))
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. Further, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until the pressure became 5 × 10 ⁻⁴ Pa or less after installation in a vacuum deposition apparatus. First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Thereafter, the compound (A1) was deposited to a thickness of 40 nm at a deposition rate of 0.3 nm / second to form a hole transport layer. Subsequently, DPAVBi (4,4′-bis [2- (4-diphenylaminophenyl) vinyl] biphenyl) which is a blue light emitting dopant material and ADN (9,10-di (2-naphthyl) anthracene) which is a host material Was vapor-deposited at a vapor deposition rate of 0.33 nm / second so that the weight ratio was 1: 32.3 to obtain a 40 nm light-emitting layer. Next, Alq ₃ (tris (8-quinolinolato) aluminum) was vapor-deposited at 0.3 nm / second to form a 20 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 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. The results are shown in Table 2.

Examples 15 to 19 (Element evaluation of compounds (A40), (A72), (B1), (B29), (B56))
An organic EL device was produced in the same manner as in Example 14 except that the compound (A1) was changed to (A40), (A72), (B1), (B29), or (B56). The driving voltage and current efficiency when a current of 20 mA / cm ² was applied to the device thus fabricated were measured. The results are shown in Table 2.

Comparative Examples 4 to 6 (Compound (a), Compound (b), Device Evaluation of NPD)
An organic EL device was produced in the same manner as in Example 14 except that the compound (A1) was changed to the compound (a), the compound (b), or NPD. The driving voltage and current efficiency when a current of 20 mA / cm ² was applied to the device thus fabricated were measured. The results are shown in Table 2.

Reference Example 3 (Device evaluation of compound (c))
An organic EL device was produced in the same manner as in Example 14 except that the compound (A1) was changed to the compound (c). The driving voltage and current efficiency when a current of 20 mA / cm ² was applied to the device thus fabricated were measured. The results are shown in Table 2.

  The 4-carbazolylamine compound of the present invention showed higher current efficiency (luminous efficiency) than conventionally known compounds, and the driving voltage of the organic EL device could be kept low.

4 is a cyclic voltammogram of the compound (B1) obtained in Example 13. 4 is a cyclic voltammogram of the compound (c) obtained in Reference Example 2.

  The 4-carbazolylamine compound of the present invention can be used as a light emitting material, a hole injection material, or a hole transport material of an organic EL device. In particular, the 4-carbazolylamine compound of the present invention is useful as a hole injection material or a hole transport material because of its excellent hole transport ability. Furthermore, the 4-carbazolylamine compound of the present invention is not only used as a hole injection material or a hole transport material for an organic EL device or an electrophotographic photoreceptor, but also an organic device such as an organic thin film solar cell, an organic transistor, or an image sensor. Application to is also possible.

Claims (5)

General formula (1)

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 17 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently Methyl group, ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, C1-C1 3 halogenated alkyl groups, C 1-3 halogenated alkoxy groups, C 6-12 aryl groups, C 6-18 aryloxy groups, C 3-20 heteroaryl groups, C 3 May have one or more substituents selected from the group consisting of ˜18 trialkylsilyl groups, C18-40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms]. .
Ar ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, an ethyl group, or a C 3-18 carbon atom. Linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms Halogenated alkoxy groups, C6-C20 aryl groups, C6-C18 aryloxy groups, C3-C20 heteroaryl groups, C3-C18 trialkylsilyl groups, C18-C18 It may have one or more substituents selected from the group consisting of 40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms].
R ^{1 to} R ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , C3-C18 straight chain, branched Or a cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, A trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, a deuterium atom, or a hydrogen atom is represented.
n represents an integer of 0 or 1. )
The 4-carbazolylamine compound represented by these. Ar ¹ and Ar ² are each independently a phenyl group, biphenyl group, naphthyl group, phenanthryl group, fluorenyl group, dibenzothienyl group, dibenzofuranyl group, naphthylphenyl group, dibenzothienylphenyl group, or dibenzofuranylphenyl. Group (these groups are each independently a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, a branched or cyclic alkyl group, a methoxy group, an ethoxy group, a straight chain of 3 to 18 carbon atoms, Branched or cyclic alkoxy group, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, aryl group having 6 to 12 carbon atoms, aryloxy group having 6 to 18 carbon atoms, carbon Heteroaryl group having 3 to 20 carbon atoms, trialkylsilyl group having 3 to 18 carbon atoms, triarylsilyl group having 18 to 40 carbon atoms, cyano group, fluorine Child, and wherein the optionally having a substituent selected from the group consisting of a deuterium atom 1 or more is also be), 4-carbazolyl amine compound according to claim 1. Ar ³ is a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, fluorenyl group, dibenzothienyl group, dibenzofuranyl group, naphthylphenyl group, dibenzothienylphenyl group, or dibenzofuranylphenyl group or 4- A carbazolyl group (these groups are each independently a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, or a linear chain having 3 to 18 carbon atoms) A branched or cyclic alkoxy group, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, A heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, 1 or 2, which may have one or more substituents selected from the group consisting of a hydrogen group, a fluorine atom, and a deuterium atom). The 4-carbazolylamine compound described. R ^{1 to} R ⁵ are each independently a phenyl group, a biphenyl group, or a naphthyl group (these groups are each independently a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, branched, or A cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, and a triarylsilyl group having 18 to 40 carbon atoms , May have one or more substituents selected from the group consisting of a cyano group, a fluorine atom, and a deuterium atom), a methyl group, an ethyl group, a linear, branched, or cyclic group having 3 to 18 carbon atoms An alkyl group of Any one of claims 1 to 3, which is a toxi group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a cyano group, a deuterium atom, or a hydrogen atom. The 4-carbazolylamine compound according to claim 1. General formula (1)

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 17 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently Methyl group, ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, C1-C1 3 halogenated alkyl groups, C 1-3 halogenated alkoxy groups, C 6-12 aryl groups, C 6-18 aryloxy groups, C 3-20 heteroaryl groups, C 3 May have one or more substituents selected from the group consisting of ˜18 trialkylsilyl groups, C18-40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms]. .
Ar ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, an ethyl group, or a C 3-18 carbon atom. Linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms Halogenated alkoxy groups, C6-C20 aryl groups, C6-C18 aryloxy groups, C3-C20 heteroaryl groups, C3-C18 trialkylsilyl groups, C18-C18 It may have one or more substituents selected from the group consisting of 40 triarylsilyl groups, cyano groups, fluorine atoms, and deuterium atoms].
R ^{1 to} R ⁵ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , C3-C18 straight chain, branched Or a cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, A trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a fluorine atom, a deuterium atom, or a hydrogen atom is represented.
n represents an integer of 0 or 1. )
A hole transport material, a hole injection material, or a light-emitting material containing a 4-carbazolylamine compound represented by:

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