JP5609256B2 - 2-Aminocarbazole compounds and uses thereof - Google Patents

Description

  The present invention relates to a novel 2-aminocarbazole compound and an organic EL device using the same.

  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, some practical applications such as mobile phone displays have begun. An organic EL element is an element that utilizes light emitted when holes injected from an anode and electrons injected from a cathode are recombined in a light emitting layer, and has a structure of a hole transport layer, a light emitting layer A multi-layer laminate type in which an electron transport layer and the like are laminated 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 is very important for 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. For example, 4,4′-bis [N- (1-naphthyl) -N-phenyl] biphenyl (hereinafter referred to as NPD). Is abbreviated). However, the driving voltage, light emission efficiency and durability of an element using NPD for the hole transport layer are not sufficient, and development of new materials is required. Furthermore, in recent years, an organic EL element using a phosphorescent material for a light emitting layer has been developed, and a hole transport material having a high triplet level is required for an element using phosphorescent light emission. NPD is not sufficient from the point of triplet level, and for example, it has been reported that the organic EL element in which a phosphorescent material having green light emission and NPD are combined reduces the luminous efficiency (for example, non-patent Reference 1).

  Against this background, recently, amine compounds having a carbazole ring introduced in the molecule have been reported. An amine compound having a carbazole ring introduced is a useful molecular skeleton because it has a higher triplet level than NPD and is excellent in hole transportability, but many of the compounds reported so far are A 3-aminocarbazole compound in which an amino group is introduced at the 3-position of the carbazole ring (see, for example, Patent Documents 1 and 2). Since the 3-position of the carbazole ring is the para-position of the nitrogen atom that is an electron donor property, the amino group substituted at the 3-position is activated by the nitrogen atom of the carbazole ring. That is, the ionization potential of the 3-aminocarbazole compound is lower than that of a normal amine compound. Therefore, when the 3-aminocarbazole compounds reported so far are used for the hole transport layer, there is a problem that the hole injection barrier to the light emitting layer is increased and the driving voltage of the organic EL element is increased. . From such a background, there is a possibility that the amino group has an appropriate ionization potential when bonded to the 2-position of the carbazole ring. So far, regarding 2-aminocarbazole compounds, 2-ditolylaminocarbazoles have been exemplified as charge transport materials in electrophotographic photoreceptors (see, for example, Patent Document 3). However, the exemplified compounds have a low glass transition temperature, and when used in an organic EL device, there is a problem in durability at high temperature driving. In addition, 7-phenyl-2-aminocarbazole compounds are also disclosed as materials for organic electronic devices (see, for example, Patent Document 4). However, in the compound described in Patent Document 4 in which a phenyl group is substituted at the 7-position of the carbazole ring, which is the para-position of the amino group, the conjugation of pi electrons is widened, so the molecular energy gap is small and the electron affinity is also high. Become. Therefore, when used as a hole transport layer of an organic EL device, the effect of confining the energy of electrons injected into the light emitting layer and the exciton generated in the light emitting layer is insufficient, and the light emission efficiency is lowered. In addition, since the triplet level is also low, an element combined with a phosphorescent material having green light emission cannot obtain sufficient light emission efficiency.

JP 2006-28176 A JP 2006-298898 A JP 2003-316035 A International Publication 2006/108497 Pamphlet

Journal of Applied Physics, 2004, 95, 7798.

  An object of the present invention is to provide a 2-aminocarbazole compound suitable for a hole transport material of an organic EL device, and further to provide an organic EL device having high luminous efficiency and excellent durability.

  As a result of intensive studies, the present inventors have found that a 2-aminocarbazole compound represented by the following general formula (1) has excellent hole transport properties, and an organic EL device using the compound for a hole transport layer has a driving voltage. It was found to be low and further excellent in luminous efficiency and durability, and the present invention was completed. That is, the present invention relates to the general formula (1)

（式中、Ａｒ^１及びＡｒ^２は各々独立して置換基を有していてもよい炭素数６〜５０のアリール基、又は置換基を有していてもよい炭素数４〜５０のヘテロアリール基を表し［但し、Ａｒ^１とＡｒ^２が各々独立して無置換のフェニル基、アルキル基若しくはアルコキシ基で置換されたフェニル基、又は置換基を有していてもよいカルバゾリル基から選ばれる置換基で構成される場合を除く。］、Ｒ^１は炭素数１〜１８の直鎖、分岐若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜５０のアリール基、又は置換基を有していてもよい炭素数４〜５０のヘテロアリール基を表し、Ｒ^２及びＲ^３は各々独立して水素原子、ハロゲン原子、炭素数１〜１８の直鎖、分岐若しくは環状のアルキル基、炭素数１〜１８の直鎖、分岐若しくは環状のアルコキシ基、置換基を有していてもよい炭素数６〜５０のアリール基、又は置換基を有していてもよい炭素数４〜５０のヘテロアリール基を表し、Ｒ^４は水素原子、ハロゲン原子、炭素数１〜１８の直鎖、分岐若しくは環状のアルキル基、又は炭素数１〜１８の直鎖、分岐若しくは環状のアルコキシ基を表す。）
で表される２−アミノカルバゾール化合物及びその用途に関するものである。

(In the formula, Ar ¹ and Ar ² are each independently an aryl group having 6 to 50 carbon atoms which may have a substituent, or a heteroaryl having 4 to 50 carbon atoms which may have a substituent) [Wherein Ar ¹ and Ar ² are each independently a substituted phenyl group substituted with an unsubstituted phenyl group, an alkyl group or an alkoxy group, or a carbazolyl group optionally having a substituent] R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 50 carbon atoms which may have a substituent, or a substituent. Represents an optionally substituted heteroaryl group having 4 to 50 carbon atoms, wherein R ² and R ³ each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Group, straight chain with 1 to 18 carbon atoms, branched Or a cyclic alkoxy group, an optionally substituted aryl group having 6 to 50 carbon atoms, or an optionally substituted heteroaryl group having 4 to 50 carbon atoms, wherein R ⁴ represents A hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms.)
The 2-aminocarbazole compound represented by these and its use.

  Hereinafter, the present invention will be described in detail.

In the 2-aminocarbazole compound represented by the general formula (1) of the present invention, Ar ¹ and Ar ² are each independently an aryl group having 6 to 50 carbon atoms which may have a substituent, or a substituent. Represents a heteroaryl group having 4 to 50 carbon atoms which may have

Examples of the aryl group having 6 to 50 carbon atoms which may have a substituent represented by Ar ¹ and Ar ² include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a benzofluorene group. Examples thereof include, but are not limited to, a nyl group, a dibenzofluorenyl group, a fluoranthenyl group, a pyrenyl group, a chrycenyl group, a perylenyl group, and a picenyl group.

In addition, examples of the substituent for the aryl group having 6 to 50 carbon atoms represented by Ar ¹ and Ar ² include a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, an aryloxy group, and a trialkyl. A silyl group, a triarylsilyl group, and a halogen atom can be exemplified, but the substitution position and the number of substitutions are not particularly limited.

  Examples of linear, branched or cyclic alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and stearyl. Examples thereof include, but are not limited to, a group, a trichloromethyl group, a trifluoromethyl group, a cyclopropyl group, and a cyclohexyl group.

  Linear, branched or cyclic alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, stearyloxy Examples of the group include, but are not limited to, groups.

  Examples of the aryloxy group include a phenoxy group, a 4-methylphenyloxy group, a 3-methylphenyloxy group, a 4-biphenyloxy group, a 3-biphenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. However, it is not limited to these.

  Examples of the trialkylsilyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and a tributylsilyl group.

  As triarylsilyl group, triphenylsilyl group, tri (4-methylphenyl) silyl group, tri (3-methylphenyl) silyl group, tri (4-methylphenyl) silyl group, tri (4-biphenyl) silyl group However, the present invention is not limited to these examples.

  Examples of the halogen atom include fluorine, chlorine, bromine, or iodine atom.

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, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group , 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxy Phenyl 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-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5 -Difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 4- (1- Butyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1 -Naphthyl group, 6-methyl-2-naphthyl group, 4-phenyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 2-anthryl group, 9-anthryl group, 10-phenyl-9-anthryl 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, benzofluorenyl group, dibe Zofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, p-terphenyl group, m-terphenyl group, o-ter A phenyl group etc. can be illustrated, but it is not limited to these. However, when the glass transition temperature is low, Ar ¹ and Ar ² are each independently composed of an unsubstituted phenyl group, or a substituent selected from a phenyl group substituted with an alkyl group or an alkoxy group. It is not preferable.

As the heteroaryl group of Ar ¹ and Ar ² carbon atoms which may have a substituent represented by 4-50 aromatic containing at least one hetero atom of oxygen atom, nitrogen atom and sulfur atom For example, 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl Group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, benzothiophenyl group, benzoimidazolyl group, dibenzothiophenyl group and the like can be exemplified, but not limited thereto. However, Ar ¹ or Ar ² does not constitute a carbazolyl group.

Since the 2-aminocarbazole compound represented by the general formula (1) has a high glass transition temperature and a high triplet level as compared with a phosphorescent material having green emission, at least ^one of Ar ¹ and Ar ² One is preferably an optionally substituted 4-biphenylyl group, 3-biphenylyl group, m-terphenyl group, or 2-fluorenyl group.

In the 2-aminocarbazole compound represented by the general formula (1), R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and optionally having 6 to 50 carbon atoms. An aryl group or a heteroaryl group having 4 to 50 carbon atoms which may have a substituent is represented.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R ¹ include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert- Examples thereof include, but are not limited to, butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group and the like. .

Examples of the aryl group having 6 to 50 carbon atoms which may have a substituent represented by R ¹ and the heteroaryl group having 4 to 50 carbon atoms which may have a substituent include the Ar ¹ And the substituents exemplified for Ar ² .

Since the 2-aminocarbazole compound represented by the general formula (1) has a high glass transition temperature, R ¹ may have a phenyl group, a 4-biphenylyl group, a 3-biphenylyl group, which may have a substituent, A p-terphenyl group, an m-terphenyl group, or a 2-fluorenyl group is preferred.

In the 2-aminocarbazole compound represented by the general formula (1), R ² and R ³ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a carbon number. 1-18 linear, branched or cyclic alkoxy groups, aryl groups having 6 to 50 carbon atoms which may have substituents, or heteroaryls having 4 to 50 carbon atoms which may have substituents Represents a group.

Examples of the halogen atom represented by R ² and R ³ include a fluorine, chlorine, bromine, or iodine atom.

Examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R ² and R ³ include the substituents exemplified for R ¹ .

Specific examples of the linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms represented by R ² and R ³ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, sec -Butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group and the like can be exemplified, but are not limited thereto.

Examples of the aryl group having 6 to 50 carbon atoms which may have a substituent represented by R ² and R ³ , and the heteroaryl group having 4 to 50 carbon atoms which may have a substituent include the Ar Examples include the substituents exemplified for ¹ and Ar ² .

In the 2-aminocarbazole compound represented by the general formula (1), R ⁴ is a hydrogen atom, a halogen atom, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or a straight chain having 1 to 18 carbon atoms. Represents a branched or cyclic alkoxy group.

Examples of the halogen atom represented by R ⁴ , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms include the above R ¹ , R ² and Examples of the substituent include those exemplified for R ³ .

  Preferred compounds are illustrated below, but are not limited to these compounds.

前記一般式（１）で表される２−アミノカルバゾール化合物は、例えば、公知の方法（Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，１９９８年，第３９巻，２３６７頁）によって合成することができる。具体的には、２位がハロゲン化されたカルバゾール化合物と２級アミン化合物又は１級アミン化合物とを塩基の存在下、銅触媒又はパラジウム触媒を用いて反応させ、合成することができる。

The 2-aminocarbazole compound represented by the general formula (1) can be synthesized, for example, by a known method (Tetrahedron Letters, 1998, Vol. 39, page 2367). Specifically, it can be synthesized by reacting a carbazole compound halogenated at the 2-position with a secondary amine compound or a primary amine compound using a copper catalyst or a palladium catalyst in the presence of a base.

  The 2-aminocarbazole compound represented by the general formula (1) 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, since the 2-aminocarbazole compound represented by the general formula (1) is excellent in hole transport ability, when used as a hole transport layer and / or a hole injection layer, the organic EL element has a low A drive voltage, high luminous efficiency, and improved durability can be realized. Further, since the 2-aminocarbazole compound represented by the general formula (1) has a triplet level higher than that of a conventional material, an element using not only a fluorescent light emitting material but also a phosphorescent light emitting material for a light emitting layer. In this case, high luminous efficiency can be obtained.

  In the light-emitting layer when the 2-aminocarbazole compound represented by the general formula (1) is used as a hole injection layer and / or a hole transport layer of an organic EL device, a known fluorescence that has been conventionally used is used. Alternatively, a phosphorescent material can be used. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  When the 2-aminocarbazole compound represented by the general formula (1) is used as a hole transport layer of an organic EL device, a high luminous efficiency is obtained as a phosphorescent material used for the light emitting layer. A material having an emission wavelength longer than 480 nm is preferable.

  When forming a hole injection layer and / or a hole transport layer made of a 2-aminocarbazole compound, two or more kinds of materials may be contained or laminated as necessary. For example, oxidation of molybdenum oxide or the like , Known electrons such as 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexaazatriphenylene A receptive material may be contained or laminated.

  When the 2-aminocarbazole compound represented by the general formula (1) is used as a light emitting layer of an organic EL device, the 2-aminocarbazole compound is used alone, used by doping a known light emitting host material, Alternatively, it can be used by doping a known light-emitting dopant.

  Examples of a method for forming a hole injection layer, a hole transport layer, or a light emitting layer containing the 2-aminocarbazole compound represented by the general formula (1) include a vacuum deposition method, a spin coating method, and a casting method. The known methods can be applied.

  The 2-aminocarbazole compound represented by the general formula (1) according to the present invention has a higher hole transport capability and a higher glass transition temperature than those of conventional materials. Durability can be improved.

  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.

  The FDMS measurement was performed using Hitachi M-80B.

  The glass transition temperature was measured using DSC-3100 manufactured by Mac Science under a temperature rising condition of 10 ° C./min.

  The ionization potential was evaluated by cyclic voltammetry using HA-501 and HB-104 manufactured by Hokuto Denko.

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

Synthesis Example 1 (Synthesis of 2- (4-chlorophenyl) nitrobenzene [see the following formula (2)])
Under a nitrogen stream, in a 500 ml three-necked flask, 25.0 g (123.0 mmol) of o-bromonitrobenzene, 21.1 g (135.3 mmol) of p-chlorophenylboronic acid, 0.71 g of tetrakis (triphenylphosphine) palladium (0. 61 mmol), 100 ml of tetrahydrofuran and 162 g (307.5 mmol) of a 20 wt% aqueous potassium carbonate solution were added, and the mixture was heated to reflux for 8 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene), and 27.2 g of 2- (4-chlorophenyl) nitrobenzene was isolated (94% yield).

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

¹ H-NMR (CDCl ₃ ); 7.87 (d, 1H), 7.36-7.66 (m, 5H), 7.21-7.27 (m, 2H)
¹³ C-NMR (CDCl ₃ ); 148.98, 135.85, 135.12, 134.37, 132.45, 131.79, 129.23, 128.84, 128.53, 124.21
Synthesis Example 2 (Synthesis of 2-chlorocarbazole [see the following formula (2)])
Under a nitrogen stream, 10.0 g (42.7 mmol) of 2- (4-chlorophenyl) nitrobenzene obtained in Synthesis Example 1 was charged into a 200 ml eggplant-shaped flask, 50 ml of triethyl phosphite was added, and then 24 ° C. at 24 ° C. Stir for hours. Triethyl phosphite was distilled off under reduced pressure, and 5.1 g (25.6 mmol) of 2-chlorocarbazole white powder was isolated by adding o-xylene to the residue and recrystallizing (yield 60%). ).

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

¹ H-NMR (Acetone-d ₆ ); 10.46 (br-s, 1H), 8.10 (d, 2H), 7.37-7.55 (m, 3H), 7.15-7. 24 (m, 2H)
¹³ C-NMR (Acetone-d ₆ ); 141.35, 141.15, 131.33, 126.70, 123.17, 122.64, 121.92, 120.84, 120.09, 119.78 , 111.81, 111.43

合成例３ （２−クロロ−Ｎ−フェニルカルバゾールの合成）
窒素気流下、５０ｍｌの三口フラスコに、合成例２で得た２−クロロカルバゾール ４．０ｇ（１９．８ｍｍｏｌ）、ブロモベンゼン １５．４ｇ（９９．４ｍｍｏｌ）、炭酸カリウム ３．８ｇ（２７．７ｍｍｏｌ）、ｏ−キシレン １０ｍｌを加え、スラリー状の反応液に酢酸パラジウム ４４ｍｇ（０．１９ｍｍｏｌ）、トリ（ｔｅｒｔ−ブチル）ホスフィン ０．１４ｇ（０．６９ｍｍｏｌ）を添加して１３０℃で２４時間攪拌した。室温まで冷却後、水 １０ｍｌを加え、有機層を分離した。有機層を水、飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー（トルエンとヘキサンの混合溶媒）で精製し、無色オイル状の２−クロロ−Ｎ−フェニルカルバゾールを４．５ｇ（１６．２ｍｍｏｌ）単離した（収率８１％）。

Synthesis Example 3 (Synthesis of 2-chloro-N-phenylcarbazole)
In a 50 ml three-necked flask under a nitrogen stream, 4.0 g (19.8 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2, 15.4 g (99.4 mmol) of bromobenzene, 3.8 g (27.7 mmol) of potassium carbonate Then, 10 ml of o-xylene was added, 44 mg (0.19 mmol) of palladium acetate and 0.14 g (0.69 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution, and the mixture was stirred at 130 ° C. for 24 hours. After cooling to room temperature, 10 ml of water was added and the organic layer was separated. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane) to isolate 4.5 g (16.2 mmol) of colorless oily 2-chloro-N-phenylcarbazole (yield 81%).

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

¹ H-NMR (CDCl ₃ ); 8.08 (d, 1H), 8.01 (d, 1H), 7.16-7.64 (m, 10H)
¹³ C-NMR (CDCl ₃ ); 141.40, 141.20, 137.04, 131.66, 130.01, 127.85, 127.06, 126.19, 122.72, 121.88, 121 .11, 120.36, 120.23, 109.94, 109.87
Synthesis Example 4 (Synthesis of 2-chloro-N- (4-biphenylyl) carbazole)
Under a nitrogen stream, in a 50 ml three-necked flask, 4.0 g (19.8 mmol) of 2-chlorocarbazole obtained in Synthesis Example 2, 5.5 g (23.7 mmol) of 4-bromobiphenyl, 3.83 g of potassium carbonate (27. 7 mmol) and 20 ml of o-xylene were added, and 44 mg (0.19 mmol) of palladium acetate and 0.14 g (0.69 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution, followed by stirring at 130 ° C. for 24 hours. did. After cooling to room temperature, the deposited precipitate was collected by filtration, and the resulting solid was washed with water and methanol. After drying under reduced pressure, recrystallization from n-butanol isolated 4.9 g (13.8 mmol) of white powder of 2-chloro-N- (4-biphenylyl) carbazole (yield 69%).

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

¹ H-NMR (CDCl ₃ ); 8.07 (d, 1H), 8.00 (d, 1H), 7.77 (d, 2H), 7.65 (d, 2H), 7.54 (d , 2H), 7.21-7.41 (m, 8H)
¹³ C-NMR (CDCl ₃ ); 141.38, 141.18, 140.72, 140.08, 136.17, 131.75, 128.99, 128.66, 127.74, 127.27, 127 .16, 126.23, 122.82, 121.99, 121.19, 120.47, 120.29, 110.05, 109.98
Synthesis Example 5 (Synthesis of 2-chloro-6-phenyl-N-phenylcarbazole)
Under a nitrogen stream, 8.0 g (28.8 mmol) of 2-chloro-N-phenylcarbazole obtained in Synthesis Example 3 was charged into a 200 ml three-necked flask, 160 ml of dichloromethane, and 4.1 g (23.0 mmol) of N-bromosuccinimide. Was added. The mixture was stirred at room temperature for 2 hours, 100 ml of water was added, and the organic layer was separated. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained oily product was a mixture of raw materials 2-chloro-N-phenylcarbazole and 2-chloro-6-bromo-N-phenylcarbazole (2-chloro-6-bromo-N- The purity of phenylcarbazole is 75%). Under a nitrogen stream, 10 g of the above mixture was charged into a 100 ml three-necked flask, 3.4 g (27.8 mmol) of phenylboronic acid, 0.32 g (0.28 mmol) of tetrakis (triphenylphosphine) palladium, 50 ml of tetrahydrofuran, 20 wt% carbonic acid. 37 g (70.0 mmol) of an aqueous potassium solution was added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate and concentrating under reduced pressure, the residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane) to give 6.5 g of white crystals of 2-chloro-6-phenyl-N-phenylcarbazole. (18.4 mmol) was isolated (yield 63%).

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

¹ H-NMR (CDCl ₃ ); 8.28 (s, 1H), 8.06 (d, 1H), 7.23-7.71 (m, 14H)
¹³ C-NMR (CDCl ₃ ); 141.82, 141.71, 140.65, 137.01, 133.97, 131.88, 130.07, 128.79, 127.93, 127.30, 126 .99, 126.68, 125.75, 123.26, 122.01, 121.17, 120.55, 118.73, 110.20, 110.03
Synthesis Example 6 (Synthesis of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine)
Under a nitrogen stream, in a 100 ml three-necked flask, 9.5 g (26.8 mmol) of 2-chloro-N- (4-biphenylyl) carbazole obtained in Synthesis Example 4, 3.7 g (40.2 mmol) of aniline, sodium- Add 3.6 g (37.5 mmol) of tert-butoxide and 60 ml of o-xylene, and add 60 mg (0.26 mmol) of palladium acetate and 189 mg (0.93 mmol) of tri (tert-butyl) phosphine to the slurry reaction solution. And stirred at 130 ° C. for 10 hours. After cooling to room temperature, 35 ml of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the organic layer was washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a brown solid. Recrystallized from o-xylene, 8.0 g (19.4 mmol) of white powder of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine was isolated (yield 72%) .

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

¹ H-NMR (CDCl ₃ ); 7.95-8.04 (m, 2H), 7.74 (d, 2H), 7.18-7.66 (m, 12H), 6.99-7. 12 (m, 4H), 5.77 (br, 1H)
¹³ C-NMR (CDCl ₃ ); 143.62, 142.19, 141.73, 141.02, 140.21, 136.79, 129.37, 128.95, 128.49, 127.63, 127 .23, 127.14, 124.79, 123.77, 121.11, 120.71, 120.12, 119.45, 118.00, 117.27, 112.38, 109.63, 99.03
Example 1 (Synthesis of Compound (A1) and Evaluation of Thin Film Stability)
In a 50 ml three-necked flask under a nitrogen stream, 1.0 g (3.6 mmol) of 2-chloro-N-phenylcarbazole obtained in Synthesis Example 3 and 1.1 g of N, N-bis (4-biphenylyl) amine (3. 6 mmol), 484 mg (5.0 mmol) of sodium-tert-butoxide, 10 ml of o-xylene, and 8 mg (0.03 mmol) of palladium acetate and 25 mg (0.12 mmol) of tri (tert-butyl) phosphine in the slurry reaction solution. And stirred at 130 ° C. for 24 hours. After cooling to room temperature, the deposited precipitate was collected by filtration, and the resulting solid was washed with water and ethanol. After drying under reduced pressure, it was recrystallized from o-xylene to isolate 1.7 g (3.0 mmol) of white powder of compound (A1) (yield 85%).

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

FDMS; 562
¹ H-NMR (CDCl ₃ ); 8.05 (d, 1H), 8.02 (d, 1H), 7.07-7.57 (m, 28H)
¹³ C-NMR (CDCl ₃ ); 147.30, 145.93, 141.84, 141.38, 140.62, 137.45, 134.96, 129.88, 128.77, 127.72, 127 41, 126.86, 126.81, 126.62, 125.43, 123.64, 123.31, 121.15, 120.23, 119.87, 118.90, 109.72, 106.88
The thin film formed on the glass plate by the vacuum deposition method did not show white turbidity (aggregation and crystallization) even when allowed to stand at room temperature for 1 month. Moreover, the glass transition temperature was 96 degreeC, and even if the thin film on a glass plate was heated to 90 degreeC, it did not become cloudy.

Example 2 (Synthesis of Compound (A8) and Evaluation of Thin Film Stability)
In a 50 ml three-necked flask under a nitrogen stream, 1.2 g (3.6 mmol) of 2-chloro-N- (4-biphenylyl) carbazole obtained in Synthesis Example 4 and N, N-bis (4-biphenylyl) amine were obtained. 1 g (3.6 mmol), 484 mg (5.0 mmol) of sodium-tert-butoxide and 10 ml of o-xylene were added, and 8 mg (0.03 mmol) of palladium acetate and 25 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. 0.12 mmol) was added and the mixture was stirred at 130 ° C. for 24 hours. After cooling to room temperature, 10 ml of water was added and the organic layer was separated. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 1.6 g (2.5 mmol) of a glassy solid of compound (A8) was isolated (yield 72%).

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

FDMS; 638
¹ H-NMR (CDCl ₃ ); 8.08 (d, 1H), 8.04 (d, 1H), 7.71 (d, 2H), 7.10-7.62 (m, 30H)
¹³ C-NMR (CDCl ₃ ); 147.30, 145.94, 141.81, 141.33, 140.58, 140.18, 140.10, 136.57, 134.94, 128.86, 128 73, 128.51, 127.71, 127.56, 127.08, 127.01, 126.77, 126.61, 125.45, 123.62, 123.37, 121.15, 120.29 119.94, 119.87, 118.99, 109.80, 106.99.
When a thin film was formed on a glass plate by the same method as in Example 1, no cloudiness (aggregation and crystallization) was observed even when allowed to stand at room temperature for 1 month. Moreover, the glass transition temperature was 119 degreeC, and even if it heated the thin film on a glass plate to 90 degreeC, it did not become cloudy.

Example 3 (Synthesis of Compound (A11) and Evaluation of Thin Film Stability)
In a 50 ml three-necked flask under a nitrogen stream, 1.7 g (4.1 mmol) of N-phenyl-N- (2- (N- (4-biphenylyl)) carbazolyl) amine obtained in Synthesis Example 6 and 2-bromo- 1.1 g (4.1 mmol) of 9,9-dimethylfluorene, 556 mg (5.7 mmol) of sodium-tert-butoxide and 15 ml of o-xylene were added, and 9 mg (0.04 mmol) of palladium acetate was added to the slurry reaction solution. 29 mg (0.14 mmol) of (tert-butyl) phosphine was added and stirred at 130 ° C. for 3 hours. After cooling to room temperature, 10 ml of water was added and the organic layer was separated. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 2.1 g (3.5 mmol) of a glassy solid of compound (A11) was isolated (yield 85%).

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

FDMS; 602
¹ H-NMR (CDCl ₃ ); 7.99-8.08 (m, 2H), 7.49-7.68 (m, 8H), 7.14-7.45 (m, 15H), 6. 99-7.08 (m, 3H), 1.39 (s, 6H)
¹³ C-NMR (CDCl ₃ ); 154.82, 153.38, 148.21, 147.63, 146.55, 141.75, 141.26, 140.14, 140.10, 139.04, 136 .59, 133.60, 129.13, 128.84, 128.44, 127.54, 127.06, 126.97, 126.30, 125.25, 124.02, 123.44, 122.54 , 122.43, 120.95, 120.51, 120.22, 119.72, 119.32, 118.31, 117.73, 109.72, 105.91, 46.86, 27.17.
The thin film formed on the glass plate by the vacuum deposition method did not show white turbidity (aggregation and crystallization) even when allowed to stand at room temperature for 1 month. The glass transition temperature was 108 ° C., and even when the thin film on the glass plate was heated to 90 ° C., it did not become cloudy.

Example 4 (Synthesis of Compound (A33) and Evaluation of Thin Film Stability)
In a 50 ml three-necked flask under a nitrogen stream, 3.0 g (8.4 mmol) of 2-chloro-6-phenyl-N-phenylcarbazole obtained in Synthesis Example 5 and 2.0 g of N-phenyl-N-biphenylamine (8 .4 mmol), 1.1 g (11.8 mmol) of sodium-tert-butoxide, and 30 ml of o-xylene, and 19 mg (0.08 mmol) of palladium acetate and 60 mg (0) of tri (tert-butyl) phosphine were added to the slurry reaction solution. .29 mmol) was added and stirred at 130 ° C. for 10 hours. After cooling to room temperature, 15 ml of water was added and the organic layer was separated. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane), and 3.7 g (6.7 mmol) of a glassy solid of compound (A33) was isolated (yield 79%).

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

FDMS; 562
¹ H-NMR (CDCl ₃ ); 8.26 (s, 1H), 8.05 (d, 1H), 7.70 (d, 2H), 6.96-7.62 (m, 26H)
¹³ C-NMR (CDCl ₃ ); 147.90, 147.41, 146.31, 142.24, 141.93, 140.80, 140.62, 137.39, 134.71, 133.66, 129 87, 129.15, 128.75, 128.71, 127.63, 127.41, 127.27, 126.73, 126.57, 124.83, 123.95, 123.86, 123.40 122.63, 121.06, 119.67, 118.75, 118.26, 109.89, 106.63.
The thin film formed on the glass plate by the vacuum deposition method did not show white turbidity (aggregation and crystallization) even when allowed to stand at room temperature for 1 month. Moreover, the glass transition temperature was 95 degreeC, and even if it heated the thin film on a glass plate to 90 degreeC, it did not become cloudy.

Comparative Example 1 (Evaluation of Thin Film Stability of Comparative Compound (a))
When a thin film of the comparative compound (a) shown below was formed on a glass plate in the same manner as in Example 1, cloudiness was observed after one month at room temperature. Further, the glass transition temperature was 90 ° C. or less, and when it was heated to 90 ° C., it became cloudy.

実施例５ （化合物（Ａ１）のイオン化ポテンシャルの評価）
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（Ａ１）を０．００１ｍｏｌ／ｌの濃度で溶解させ、サイクリックボルタンメトリーでイオン化ポテンシャルを測定した。作用電極には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た。標準物質としてフェロセンを用い、フェロセンの酸化還元電位を基準とした際の化合物（Ａ１）のイオン化ポテンシャルは０．３５Ｖ ｖｓ．Ｆｃ／Ｆｃ^＋であった。この値は、従来から正孔輸送材料として知られているＮＰＤのイオン化ポテンシャル（０．３１Ｖ ｖｓ．Ｆｃ／Ｆｃ^＋）と同等であった。

Example 5 (Evaluation of ionization potential of compound (A1))
Compound (A1) was dissolved at a concentration of 0.001 mol / l in an anhydrous dichloromethane solution having a concentration of tetrabutylammonium perchlorate of 0.1 mol / l, and the ionization potential was measured by cyclic voltammetry. Glassy carbon was used for the working electrode, platinum wire was used for the counter electrode, and silver wire immersed in an acetonitrile solution of AgNO ₃ was used for the reference electrode. Ferrocene is used as the standard substance, and the ionization potential of the compound (A1) based on the oxidation-reduction potential of ferrocene is 0.35 V vs. Fc / Fc ⁺ . This value was equivalent to the ionization potential (0.31 V vs. Fc / Fc ⁺ ) of NPD which has been conventionally known as a hole transport material.

Example 6 (Evaluation of ionization potential of compound (A8))
When the ionization potential of the compound (A8) was evaluated in the same manner as in Example 5, it was 0.34 V vs. Fc / Fc ⁺ , which was equivalent to the ionization potential (0.31 V vs. Fc / Fc ⁺ ) of NPD, which has been conventionally known as a hole transport material.

Example 7 (Evaluation of ionization potential of compound (A11))
When the ionization potential of the compound (A11) was evaluated in the same manner as in Example 5, it was 0.28 V vs. Fc / Fc ⁺ , which was equivalent to the ionization potential (0.31 V vs. Fc / Fc ⁺ ) of NPD, which has been conventionally known as a hole transport material.

Example 8 (Evaluation of ionization potential of compound (A33))
When the ionization potential of the compound (A33) was evaluated in the same manner as in Example 5, it was 0.35 V vs. Fc / Fc ⁺ , which was equivalent to the ionization potential (0.31 V vs. Fc / Fc ⁺ ) of NPD, which has been conventionally known as a hole transport material.

Comparative Example 2 (Evaluation of ionization potential of comparative compound (b))
When the ionization potential of the following comparative compound (b) was evaluated in the same manner as in Example 5, it was 0.13 V vs. Fc / Fc ⁺ , which was lower than the ionization potential (0.31 V vs. Fc / Fc ⁺ ) of NPD, which has been conventionally known as a hole transport material.

実施例９ （化合物（Ａ１）の素子評価）
厚さ２００ｎｍのＩＴＯ透明電極（陽極）を積層したガラス基板を、アセトン及び純水による超音波洗浄、イソプロピルアルコールによる沸騰洗浄を行なった。さらに、紫外線オゾン洗浄を行ない、真空蒸着装置へ設置後、１×１０^−４Ｐａになるまで真空ポンプにて排気した。まず、ＩＴＯ透明電極上に銅フタロシアニンを蒸着速度０．１ｎｍ／秒で蒸着し、２５ｎｍの正孔注入層とした。引続き、化合物（Ａ１）を蒸着速度０．３ｎｍ／秒で４０ｎｍ蒸着した後、トリス（８−キノリノラート）アルミニウム（以下、Ａｌｑ_３と略す）を蒸着速度０．３ｎｍ／秒で６０ｎｍ蒸着して発光層とした。引続き、電子注入層として沸化リチウムを蒸着速度０．０１ｎｍ／秒で０．５ｎｍ蒸着し、さらにアルミニウムを蒸着速度０．２５ｎｍ／秒で１００ｎｍ蒸着して陰極を形成した。窒素雰囲気下、封止用のガラス板をＵＶ硬化樹脂で接着し、評価用の有機ＥＬ素子とした。このように作製した素子に２０ｍＡ／ｃｍ^２の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表１に示す。

Example 9 (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. Furthermore, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 25 nm hole injection layer. Subsequently, after depositing compound (A1) at 40 nm at a deposition rate of 0.3 nm / second, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq ₃ ) is deposited at 60 nm at a deposition rate of 0.3 nm / second to form a light emitting layer. It was. 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 external quantum efficiency were measured. The results are shown in Table 1.

Example 10 (Device evaluation of compound (A8))
An organic EL device was produced in the same manner as in Example 9 except that the compound (A1) was changed to the compound (A8). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 11 (Element evaluation of compound (A11))
An organic EL device was produced in the same manner as in Example 9 except that the compound (A1) was changed to the compound (A11). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Example 12 (Element evaluation of compound (A33))
An organic EL device was produced in the same manner as in Example 9 except that the compound (A1) was changed to the compound (A33). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Comparative Example 3
An organic EL device was produced in the same manner as in Example 9 except that the compound (A1) was changed to NPD. Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

Comparative Example 4
An organic EL device was produced in the same manner as in Example 9 except that the compound (A1) was changed to the comparative compound (b). Table 1 shows the driving voltage and the external quantum efficiency when a current of 20 mA / cm ² is applied.

実施例１３ （化合物（Ａ１）の素子評価）
厚さ２００ｎｍのＩＴＯ透明電極（陽極）を積層したガラス基板を、アセトン及び純水による超音波洗浄、イソプロピルアルコールによる沸騰洗浄を行なった。さらに、紫外線オゾン洗浄を行ない、真空蒸着装置へ設置後、１×１０^−４Ｐａになるまで真空ポンプにて排気した。まず、ＩＴＯ透明電極上にＮＰＤを蒸着速度０．３ｎｍ／秒で蒸着し、２０ｎｍの正孔注入層とした。引続き、化合物（Ａ１）を蒸着速度０．３ｎｍ／秒で３０ｎｍ蒸着した後、燐光ドーパント材料であるトリス（２−フェニルピリジン）イリジウム（Ｉｒ（ｐｐｙ）_３）とホスト材料である４，４’−ビス（Ｎ−カルバゾリル）ビフェニル（ＣＢＰ）を重量比が１：１１．５になるように蒸着速度０．２５ｎｍ／秒で共蒸着し、２０ｎｍの発光層とした。次に、２，９−ジメチル−４，７−ジフェニル−１，１０−フェナントロリン（ＢＣＰ）を蒸着速度０．３ｎｍ／秒で蒸着し、１０ｎｍのエキシトンブロック層とした後、さらに、Ａｌｑ_３を０．３ｎｍ／秒で蒸着し、３０ｎｍの電子輸送層とした。引続き、電子注入層として沸化リチウムを蒸着速度０．０１ｎｍ／秒で０．５ｎｍ蒸着し、さらに、アルミニウムを蒸着速度０．２５ｎｍ／秒で１００ｎｍ蒸着して陰極を形成した。窒素雰囲気下、封止用のガラス板をＵＶ硬化樹脂で接着し、評価用の有機ＥＬ素子とした。このように作製した素子に２０ｍＡ／ｃｍ^２の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表２に示す。

Example 13 (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. Furthermore, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, NPD was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 20 nm hole injection layer. Subsequently, after depositing compound (A1) at a deposition rate of 0.3 nm / second for 30 nm, phosphorous dopant material tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) and host material 4,4′- Bis (N-carbazolyl) biphenyl (CBP) was co-evaporated at a deposition rate of 0.25 nm / second so that the weight ratio was 1: 11.5 to obtain a 20 nm light emitting layer. Next, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was deposited at a deposition rate of 0.3 nm / sec, after the 10nm of exciton blocking layer, further, the Alq ₃ 0 The film was deposited at a rate of 3 nm / second to form a 30 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 external quantum efficiency were measured. The results are shown in Table 2.

Example 14 (Device evaluation of compound (A8))
An organic EL device was produced in the same manner as in Example 13 except that the compound (A1) was changed to the compound (A8). Table 2 shows the drive voltage and external quantum efficiency when a current of 20 mA / cm ² was applied.

Example 15 (Element Evaluation of Compound (A11))
An organic EL device was produced in the same manner as in Example 13 except that the compound (A1) was changed to the compound (A11). Table 2 shows the drive voltage and external quantum efficiency when a current of 20 mA / cm ² was applied.

Example 16 (Element evaluation of compound (A33))
An organic EL device was produced in the same manner as in Example 13 except that the compound (A1) was changed to the compound (A33). Table 2 shows the drive voltage and external quantum efficiency when a current of 20 mA / cm ² was applied.

Comparative Example 5
An organic EL device was produced in the same manner as in Example 13 except that the compound (A1) was changed to NPD. Table 2 shows the drive voltage and external quantum efficiency when a current of 20 mA / cm ² was applied.

Comparative Example 6
An organic EL device was produced in the same manner as in Example 13 except that the compound (A1) was changed to the comparative compound (c) shown below. Table 2 shows the drive voltage and external quantum efficiency when a current of 20 mA / cm ² was applied.

Claims (3)

General formula (1)

(In the formula, Ar ¹ is a substituent selected from the group consisting of a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, an aryloxy group, a trialkylsilyl group, and a triarylsilyl group. C 6-50 biphenylyl group, terphenyl group, naphthyl group, fluorenyl group, phenanthryl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group, a perylenyl group, or a picenyl group, Ar ² is an aryl group of carbon atoms which may 6-50 substituted or may have a substituent group heteroaryl having a carbon number of 4 to 50 group (provided that have a substituent except for good carbazolyl group) to display the, R ¹ is a straight-chain having 1 to 18 carbon atoms, branched or cyclic alkyl group, a linear Branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, an aryloxy group, a trialkylsilyl group, and carbon atoms, which may have a substituent group selected from the group 6 consisting of triarylsilyl group 50 phenyl groups, biphenylyl groups, terphenyl groups, naphthyl groups, fluorenyl groups, phenanthryl groups, benzofluorenyl groups, dibenzofluorenyl groups, or fluoranthenyl groups, or an optionally substituted carbon R ⁴ and R ³ each independently represents a hydrogen atom, a halogen atom, a straight chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a straight chain having 1 to 18 carbon atoms. A chain, branched or cyclic alkoxy group, an aryl group having 6 to 50 carbon atoms which may have a substituent, or carbon which may have a substituent The number represents a heteroaryl group 4 to 50, R ⁴ is a hydrogen atom, a halogen atom, a straight chain of 1 to 18 carbon atoms, branched or cyclic alkyl group, or a straight-chain having 1 to 18 carbon atoms, branched or cyclic Represents an alkoxy group.)
The 2-aminocarbazole compound represented by these. In the general formula (1), Ar ¹ is selected from the group consisting of a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, an aryloxy group, a trialkylsilyl group, and a triarylsilyl group. A biphenylyl group having 6 to 50 carbon atoms, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or a benzofluorenyl group, which may have a selected substituent. The 2-aminocarbazole compound described. An organic EL device, wherein the 2-aminocarbazole compound according to claim 1 or 2 is used for any one of a light emitting layer, a hole transport layer, and a hole injection layer.