WO2013088973A1 - Organic electroluminescent element - Google Patents

Organic electroluminescent element Download PDF

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WO2013088973A1
WO2013088973A1 PCT/JP2012/081059 JP2012081059W WO2013088973A1 WO 2013088973 A1 WO2013088973 A1 WO 2013088973A1 JP 2012081059 W JP2012081059 W JP 2012081059W WO 2013088973 A1 WO2013088973 A1 WO 2013088973A1
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瑠美 三宮
孝弘 甲斐
正樹 古森
山本　敏浩
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新日鉄住金化学株式会社
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Abstract

Provided is an organic electroluminescent element (EL element) which uses an indolocarbazole compound. An organic EL element wherein a positive electrode, a plurality of organic layers including a phosphorescent layer, and a negative electrode are laminated on a substrate and wherein an organic layer, which is selected from among the phosphorescent layer, a hole transport layer, an electron transport layer, a hole blocking layer and an electron blocking layer, contains an indolocarbazole compound that has a structure wherein one N-position of the indolocarbazole ring is substituted by a carbazolyl group and another N-position is substituted by at least one aromatic hydrocarbon group or aromatic heterocyclic group.

Description

有機電界発光素子Organic electroluminescence device
  本発明はインドロカルバゾール化合物を含有する有機電界発光素子に関するものであり、詳しくは、有機化合物からなる発光層に電界をかけて光を放出する薄膜型デバイスに関するものである。 The present invention relates to an organic electroluminescent device containing an indolocarbazole compound, and more particularly to a thin film device that emits light by applying an electric field to a light emitting layer made of an organic compound.
  一般に、有機電界発光素子（以下、有機ＥＬ素子という）は、その最も簡単な構造としては発光層及び該層を挟んだ一対の対向電極から構成されている。すなわち、有機ＥＬ素子では、両電極間に電界が印加されると、陰極から電子が注入され、陽極から正孔が注入され、これらが発光層において再結合し、光を放出する現象を利用する。 In general, an organic electroluminescence element (hereinafter referred to as an organic EL element) has a light emitting layer and a pair of counter electrodes sandwiching the layer as its simplest structure. That is, in an organic EL element, when an electric field is applied between both electrodes, electrons are injected from the cathode, holes are injected from the anode, and these are recombined in the light emitting layer to emit light. .
  近年、有機薄膜を用いた有機ＥＬ素子の開発が行われるようになった。特に、発光効率を高めるため、電極からキャリアー注入の効率向上を目的として電極の種類の最適化を行い、芳香族ジアミンからなる正孔輸送層と8-ヒドロキシキノリンアルミニウム錯体（以下、Alq3という）からなる発光層とを電極間に薄膜として設けた素子の開発により、従来のアントラセン等の単結晶を用いた素子と比較して大幅な発光効率の改善がなされたことから、自発光・高速応答性といった特徴を持つ高性能フラットパネルへの実用化を目指して進められてきた。 In recent years, organic EL elements using organic thin films have been developed. In particular, in order to increase luminous efficiency, the type of electrode was optimized for the purpose of improving the efficiency of carrier injection from the electrode. From the hole transport layer made of aromatic diamine and 8-hydroxyquinoline aluminum complex (hereinafter referred to as Alq3) As a result of the development of a device with a light emitting layer as a thin film between the electrodes, the luminous efficiency has been greatly improved compared to conventional devices using single crystals such as anthracene. It has been promoted with the aim of putting it into practical use for high-performance flat panels with these characteristics.
  また、素子の発光効率を上げる試みとして、蛍光ではなく燐光を用いることも検討されている。上記の芳香族ジアミンからなる正孔輸送層とAlq3からなる発光層とを設けた素子をはじめとした多くの素子が蛍光発光を利用したものであったが、燐光発光を用いる、すなわち、三重項励起状態からの発光を利用することにより、従来の蛍光（一重項）を用いた素子と比べて、３～４倍程度の効率向上が期待される。この目的のためにクマリン誘導体やベンゾフェノン誘導体を発光層とすることが検討されてきたが、極めて低い輝度しか得られなかった。また、三重項状態を利用する試みとして、ユーロピウム錯体を用いることが検討されてきたが、これも高効率の発光には至らなかった。近年では、特許文献１に挙げられるように発光の高効率化や長寿命化を目的にイリジウム錯体等の有機金属錯体を中心に燐光発光ドーパント材料の研究が多数行われている。 In addition, as an attempt to increase the luminous efficiency of the device, the use of phosphorescence instead of fluorescence has been studied. Many devices, including those provided with the hole transport layer composed of the above aromatic diamine and the light emitting layer composed of Alq3, used fluorescence emission, but use phosphorescence emission, that is, triplet. By using the light emitted from the excited state, the efficiency is expected to be improved by about 3 to 4 times compared to the conventional device using fluorescence (singlet). For this purpose, it has been studied to use a coumarin derivative or a benzophenone derivative as a light emitting layer, but only an extremely low luminance was obtained. Further, as an attempt to use the triplet state, use of a europium complex has been studied, but this has not led to highly efficient light emission. In recent years, as described in Patent Document 1, many studies on phosphorescent dopant materials have been conducted with a focus on organometallic complexes such as iridium complexes for the purpose of improving the efficiency of light emission and extending the lifetime.
特表2003-515897号公報Special Table 2003-515897 特開2001-313178号公報JP 2001-313178 A 特開平11-162650号公報Japanese Patent Laid-Open No. 11-162650 特開平11-176578号公報Japanese Patent Laid-Open No. 11-176578 WO2008/056746AWO2008 / 056746A WO2009/136595AWO2009 / 136595A WO2010/113755AWO2010 / 113755A
  高い発光効率を得るには、前記ドーパント材料と同時に、使用するホスト材料が重要になる。ホスト材料として提案されている代表的なものとして、特許文献２で紹介されているカルバゾール化合物の4,4'-ビス(9-カルバゾリル)ビフェニル（以下、CBPという）が挙げられる。CBPはトリス(2-フェニルピリジン)イリジウム錯体（以下、Ir(ppy)3という）に代表される緑色燐光発光材料のホスト材料として使用した場合、正孔を流し易く電子を流しにくい特性上、電荷注入バランスが崩れ、過剰の正孔は電子輸送層側に流出し、結果としてIr(ppy)3からの発光効率が低下する。 In order to obtain high luminous efficiency, the host material to be used is important simultaneously with the dopant material. A representative example of a host material proposed is 4,4′-bis (9-carbazolyl) biphenyl (hereinafter referred to as CBP), which is a carbazole compound introduced in Patent Document 2. When CBP is used as a host material of a green phosphorescent material typified by tris (2-phenylpyridine) iridium complex (hereinafter referred to as Ir (ppy) 3 ), it is easy to flow holes and charges. The injection balance is lost, and excess holes flow out to the electron transport layer side. As a result, the light emission efficiency from Ir (ppy) 3 decreases.
  前述のように、有機ＥＬ素子で高い発光効率を得るには、高い三重項励起エネルギーを有し、かつ両電荷（正孔・電子）注入輸送特性においてバランスがとれたホスト材料が必要である。更に、電気化学的に安定であり、高い耐熱性と共に優れたアモルファス安定性を備える化合物が望まれており、更なる改良が求められている。 As described above, in order to obtain high luminous efficiency in an organic EL element, a host material having high triplet excitation energy and balanced in both charge (hole / electron) injection and transport characteristics is required. Further, a compound that is electrochemically stable and has high heat resistance and excellent amorphous stability is desired, and further improvement is required.
  特許文献３においては、正孔輸送材料として以下に示すようなインドロカルバゾール化合物が開示されている。 In Patent Document 3, an indolocarbazole compound as shown below is disclosed as a hole transport material.
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
  特許文献４においては、正孔輸送材料として以下に示すようなインドロカルバゾール化合物が開示されている。
Figure JPOXMLDOC01-appb-I000006
In Patent Document 4, an indolocarbazole compound as shown below is disclosed as a hole transport material.
Figure JPOXMLDOC01-appb-I000006
  しかしながら、これらはインドロカルバゾール骨格を有する化合物を正孔輸送材料としての使用を推奨するものの、蛍光発光素子においての実施例のみであり、燐光発光素子用材料としての使用を開示するものではない。 However, although it is recommended to use a compound having an indolocarbazole skeleton as a hole transport material, these are only examples in a fluorescent light emitting device, and do not disclose use as a material for a phosphorescent light emitting device.
  特許文献５、特許文献６及び特許文献７には燐光ホスト材料として以下に示すようなインドロカルバゾール化合物が開示され、これを使用した有機ＥＬ素子は発光効率を改善し、高い駆動安定性を有するものとなることを開示する。また、特許文献６及び特許文献７は、インドロカルバゾールのN位にカルバゾール環が結合した化合物のいくつかを開示する。
Figure JPOXMLDOC01-appb-I000007
 Patent Document 5, Patent Document 6 and Patent Document 7 disclose indolocarbazole compounds as shown below as phosphorescent host materials, and organic EL devices using these compounds have improved luminous efficiency and high driving stability. Disclose what will happen. Patent Documents 6 and 7 disclose some compounds in which a carbazole ring is bonded to the N-position of indolocarbazole.
Figure JPOXMLDOC01-appb-I000007
  有機ＥＬ素子をフラットパネルディスプレイ等の表示素子に応用するためには、素子の発光効率を改善すると同時に駆動時の安定性を十分に確保する必要がある。本発明は、上記現状に鑑み、高効率かつ高い駆動安定性を有した実用上有用な有機ＥＬ素子及びそれに適する化合物を提供することを目的とする。 In order to apply the organic EL element to a display element such as a flat panel display, it is necessary to improve the light emission efficiency of the element and at the same time ensure the stability during driving. An object of this invention is to provide the practically useful organic EL element which has high efficiency and high drive stability in view of the said present condition, and a compound suitable for it.
  本発明者らは、鋭意検討した結果、特定構造のインドロカルバゾール骨格を有する化合物を有機ＥＬ素子として用いることで優れた特性を示すことを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that a compound having an indolocarbazole skeleton having a specific structure is used as an organic EL element, and have completed the present invention.
  本発明は、基板上に、陽極、燐光発光層を含む複数の有機層及び陰極が積層されてなる有機電界発光素子において、燐光発光層、正孔輸送層、電子輸送層正孔阻止層及び電子阻止層からなる群れから選ばれる少なくとも一つの有機層中に、一般式（１）で表されるインドロカルバゾール化合物を含有することを特徴とする有機電界発光素子に関する。 The present invention relates to an organic electroluminescent device in which a plurality of organic layers including a positive electrode, a phosphorescent light emitting layer, and a cathode are laminated on a substrate, the phosphorescent light emitting layer, the hole transport layer, the electron transport layer, the hole blocking layer, and the electron The present invention relates to an organic electroluminescent device comprising an indolocarbazole compound represented by the general formula (1) in at least one organic layer selected from the group consisting of blocking layers.
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
  一般式（１）中、環Ｉは隣接環と任意の位置で縮合する式（１ａ）で表される芳香族炭化水素環を示し、環IIは隣接環と任意の位置で縮合する式（１ｂ）で表される複素環を表す。一般式(１)中、Ａは炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を表し、一般式(１)及び式(１ａ)中、Ｒはそれぞれ独立に、炭素数１～１０の脂肪族炭化水素基、炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を示し、ｐはそれぞれ独立に０～４の整数、ｑは０～２の整数を表す。式(１ｂ)中、Ｘ1～Ｘ4はそれぞれ独立に炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基を示し、ｌ、ｍおよびｎは各々独立に０～５の整数を表す。ここで、ｌ、ｍまたはｎが２以上の場合、Ｘ2、Ｘ3およびＸ4はそれぞれ同一でも異なってもよい。 In general formula (1), ring I represents an aromatic hydrocarbon ring represented by formula (1a) that is condensed with an adjacent ring at an arbitrary position, and ring II is a formula (1b) that is condensed with an adjacent ring at an arbitrary position. ) Represents a heterocyclic ring represented by In general formula (1), A represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms. In general formulas (1) and (1a), R represents Independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 3 to 17 carbon atoms, and each p independently represents 0 to 4 carbon atoms. An integer, q represents an integer of 0-2. In the formula (1b), X 1 to X 4 each independently represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms, and each of l, m and n is independently An integer of 0 to 5 is represented. Here, when l, m or n is 2 or more, X 2 , X 3 and X 4 may be the same or different.
  上記一般式(１)で表されるインドロカルバゾール化合物としては、一般式(２)～(５)のいずれかで表されるインドロカルバゾール化合物がある。 イ ン ド The indolocarbazole compound represented by the general formula (1) includes an indolocarbazole compound represented by any one of the general formulas (2) to (5).
Figure JPOXMLDOC01-appb-I000009
(一般式(２)～(５)中、Ａ、Ｒ、Ｘ1～Ｘ4、p及びｑは一般式(１)と同意であり、ｌ、ｍ及びｎは０～３の整数を表す。ここで、ｌ、ｍまたはｎが２以上の場合、Ｘ2、Ｘ3およびＸ4は同一でも異なってもよい。)
Figure JPOXMLDOC01-appb-I000009
(In the general formulas (2) to (5), A, R, X 1 to X 4 , p and q are the same as those in the general formula (1), and l, m and n each represents an integer of 0 to 3. Here, when l, m or n is 2 or more, X 2 , X 3 and X 4 may be the same or different.)
  上記式(１ｂ)において、Ｘ1～Ｘ4の総数が４～７であることが好ましく、より好ましくは５～７である。また、Ｘ1～Ｘ4が、下記式（６）～(８)のいずれかで表される化合物から生じる芳香族炭化水素基または芳香族複素環基であることが好ましい。 In the above formula (1b), the total number of X 1 to X 4 is preferably 4 to 7, and more preferably 5 to 7. X 1 to X 4 are preferably an aromatic hydrocarbon group or an aromatic heterocyclic group generated from a compound represented by any of the following formulas (6) to (8).
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
（式(６)～(８)中、Ｙはそれぞれ独立してメチンまたは窒素を表し、Ｚは単結合、－Ｓ－、－Ｏ－または－Ｎ（Ａｒ）－のいずれかを表す。ここで、Ａｒは炭素数６～１８の芳香族炭化水素基または炭素数６～１７の芳香族複素環基を表す。)
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
(In the formulas (6) to (8), Y independently represents methine or nitrogen, and Z represents a single bond, —S—, —O— or —N (Ar) —). Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 6 to 17 carbon atoms.)
  式(６)～(８)のいずれかで表される化合物が、ベンゼン、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、ナフタリン、キノリン、イソキノリン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、カルバゾール、ジベンゾチオフェン、及びジベンゾフランから選ばれるいずれかであることが好ましい。 The compound represented by any one of formulas (6) to (8) is benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, naphthalene, quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline, carbazole, dibenzothiophene, and It is preferably any one selected from dibenzofuran.
  また、本発明の他の態様はインドロカルバゾール化合物を含む有機層が、燐光発光ドーパントを含有する発光層であることを特徴とする上記の有機電界発光素子である。 In another aspect of the present invention, the organic electroluminescent device is characterized in that the organic layer containing the indolocarbazole compound is a light emitting layer containing a phosphorescent dopant.
有機ＥＬ素子の一構造例を示す断面図である。It is sectional drawing which shows one structural example of an organic EL element. インドロカルバゾール化合物(B-27)の1Ｈ－ＮＭＲチャートを示す。 1 shows a 1 H-NMR chart of an indolocarbazole compound (B-27).
  本発明の有機電界発光素子は、前記一般式（１）で表されるインドロカルバゾール化合物（以下、一般式（１）で表される化合物又はインドロカルバゾール化合物ともいう）を含有する。 The organic electroluminescent device of the present invention contains an indolocarbazole compound represented by the general formula (1) (hereinafter also referred to as a compound represented by the general formula (1) or an indolocarbazole compound).
  一般式（１）において、環Iは隣接環と任意の位置で縮合する式（１ａ）で表される芳香族炭化水素環を示し、環IIは隣接環と任意の位置で縮合する式（１ｂ）で表される複素環を表す。 In general formula (1), ring I represents an aromatic hydrocarbon ring represented by formula (1a) that is condensed with an adjacent ring at an arbitrary position, and ring II is a formula (1b) that is condensed with an adjacent ring at an arbitrary position. ) Represents a heterocyclic ring represented by
  一般式（１）で表されるインドロカルバゾール骨格において、式（１ａ）で表される芳香族炭化水素環は２つの隣接環と任意の位置で縮合することができるが、構造的に縮合できない位置がある。式（１ａ）で表される芳香族炭化水素環は、６つの辺を有するが、隣接する２つの辺で２つの隣接環と縮合することはない。また、式（１ｂ）で表される複素環は２つの隣接環と任意の位置で縮合することができるが、構造的に縮合できない位置がある。すなわち、式（１ｂ）で表される複素環は、５つの辺を有するが、隣接する２つの辺で２つの隣接環と縮合することはなく、また、窒素原子を含む辺で隣接環と縮合することはない。したがって、インドロカルバゾール骨格の種類は限られる。具体的には、インドール骨格はカルバゾール骨格の２，３－位、３，４－位、４，５－位で縮合することができ、5種類の骨格の異性体が存在する。 In the indolocarbazole skeleton represented by the general formula (1), the aromatic hydrocarbon ring represented by the formula (1a) can be condensed with two adjacent rings at any position, but cannot be structurally condensed. There is a position. The aromatic hydrocarbon ring represented by the formula (1a) has six sides, but does not condense with two adjacent rings at two adjacent sides. In addition, the heterocyclic ring represented by the formula (1b) can be condensed with two adjacent rings at any position, but there is a position where it cannot be condensed structurally. That is, the heterocyclic ring represented by the formula (1b) has five sides, but does not condense with two adjacent rings at two adjacent sides, and also condenses with an adjacent ring at a side including a nitrogen atom. Never do. Therefore, the types of indolocarbazole skeleton are limited. Specifically, the indole skeleton can be condensed at the 2,3-position, 3,4-position, and 4,5-position of the carbazole skeleton, and there are five types of isomers of the skeleton.
  一般式（１）において、インドロカルバゾール骨格は以下の（IC-1）～（IC-4）の形態で表されるものが好ましい。この例から、インドロカルバゾール骨格中の芳香族炭化水素環及び複素環の好ましい縮合位置が理解される。 In general formula (1), the indolocarbazole skeleton is preferably represented by the following forms (IC-1) to (IC-4). From this example, the preferred condensation positions of the aromatic hydrocarbon ring and the heterocyclic ring in the indolocarbazole skeleton are understood.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
  一般式(１)中、Ａは炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を表す。 In general formula (1), A represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms.
  Ａが炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基である場合の具体例としては、ベンゼン、ペンタレン、インデン、ナフタレン、アントラセン、フェナントレン、ピロール、イミダゾール、ピラゾール、チアゾール、チオフェン、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、イソインドール、インダゾール、プリン、ベンゾイミダゾール、インドリジン、クロメン、ベンゾオキサゾール、イソベンゾフラン、キノリジン、イソキノリン、イミダゾール、ナフチリジン、フタラジン、キナゾリン、キノキサリン、シンノリン、キノリン、プテリジン、ペリミジン、フェナントロリン、フェナントリジン、アクリジン、フェナジン、フェノチアジン、フェノキサジン、シベンゾジオキシン、カルボリン、インドール、カルバゾール、フラン、ベンゾフラン、イソベンゾフラン、ベンゾチアゾール、オキサトレン、ジベンゾフラン、チオフェン、チオキサンテン、チアントレン、フェノキサチイン、チオナフテン、イソチアナフテン、チオフテン、チオファントレン、又はジベンゾチオフェンから水素を取って生じる基が挙げられる。 Specific examples when A is an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms include benzene, pentalene, indene, naphthalene, anthracene, phenanthrene, pyrrole, imidazole, Pyrazole, thiazole, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, isoindole, indazole, purine, benzimidazole, indolizine, chromene, benzoxazole, isobenzofuran, quinolidine, isoquinoline, imidazole, naphthyridine, phthalazine, quinazoline, quinoxaline , Cinnoline, quinoline, pteridine, perimidine, phenanthroline, phenanthridine, acridine, phenazine, phenothiazine, phenoxazine, cibenzodioxin, carbo Remove hydrogen from phosphorus, indole, carbazole, furan, benzofuran, isobenzofuran, benzothiazole, oxatolene, dibenzofuran, thiophene, thioxanthene, thianthrene, phenoxathiin, thionaphthene, isothianaphthene, thiobutene, thiophanthrene, or dibenzothiophene And the resulting group.
  一般式(１)及び式(１ａ)中、Ｒはそれぞれ独立に、炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を示す。好ましくは炭素数１～４のアルキル基、炭素数３～６のシクロアルキル基、フェニル基、ナフチル基、ピリジル基、ピリミジル基、トリアジル基、カルバゾリル基である。そして、より好ましくはフェニル基、カルバゾリル基である。 In the general formulas (1) and (1a), each R independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or carbon. An aromatic heterocyclic group of formula 3 to 17 is shown. Preferred are an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a triazyl group, and a carbazolyl group. And more preferably, they are a phenyl group and a carbazolyl group.
  一般式(１)及び式(１ａ)において、ｐは独立に０～４の整数、ｑは０～２の整数を表す。好ましくは、ｐ及びｑは０又は１であり、合計のＲの数は０～３の範囲が好ましい。 In general formulas (1) and (1a), p independently represents an integer of 0 to 4, and q represents an integer of 0 to 2. Preferably, p and q are 0 or 1, and the total number of R is preferably in the range of 0-3.
  式(１ｂ)中、Ｘ1～Ｘ4は炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基を示す。これらの芳香族炭化水素基または芳香族複素環基は単環であっても、縮合環であってもよいが、芳香族基が鎖状に連結する基であることはない。 In the formula (1b), X 1 to X 4 represent an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms. These aromatic hydrocarbon groups or aromatic heterocyclic groups may be monocyclic or condensed rings, but the aromatic groups are not groups linked in a chain.
  ここで、Ｘ2はＸ1に連結する基、Ｘ3はＸ2に連結する基、Ｘ4はＸ3に連結する基を表し、Ｘ1～Ｘ4が炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基である場合の具体例は、２価以上の基である場合があることを除き、上記Ａで説明したものと同様である。 Here, X 2 represents a group linked to X 1 , X 3 represents a group linked to X 2 , X 4 represents a group linked to X 3 , and X 1 to X 4 are aromatic carbon atoms having 6 to 18 carbon atoms. Specific examples in the case of a hydrogen group or an aromatic heterocyclic group having 3 to 17 carbon atoms are the same as those described in A above, except that it may be a divalent or higher valent group.
  式(１ｂ)において、l、ｍ、ｎはそれぞれ０～５の整数を表すが、好ましくは０～３の整数である。 In formula (1b), l, m and n each represents an integer of 0 to 5, preferably an integer of 0 to 3.
  また、式(１ｂ)において、Ｘ1～Ｘ4の総数は２～１０であることが良く、好ましくは４～７であり、より好ましくは５～７である。ｌ、ｍまたはｎが２以上の場合、Ｘ2、Ｘ3およびＸ4はそれぞれ同一でも異なってもよい。Ｘ1～Ｘ4の総数は１+ｎ+ｍｎ+ｍｎl＝１+ｎ（１+ｍ+ｍl）で計算される。したがって、Ｘ1～Ｘ4の総数が２～１０であるためには、ｎは１以上の整数となり、総数が５～７であるためには、ｎが１のときは、（ｍ+ｍl）は３～５となり、ｎが２のときは、（ｍ+ｍl）は１～２となる。 In the formula (1b), the total number of X 1 to X 4 is preferably 2 to 10, preferably 4 to 7, and more preferably 5 to 7. When l, m or n is 2 or more, X 2 , X 3 and X 4 may be the same or different. The total number of X 1 to X 4 is calculated as 1 + n + mn + mnl = 1 + n (1 + m + ml). Therefore, for the total number of X 1 to X 4 to be 2 to 10, n is an integer equal to or greater than 1. For the total number to be 5 to 7, when n is 1, (m + ml) Is 3 to 5, and when n is 2, (m + ml) is 1 to 2.
  X1-[X2-[X3-(X4)l]m]nにおいて、Ｘ1～Ｘ4の総数が複数である場合の例としては、下記式が挙げられる。 In the case where X 1- [X 2- [X 3- (X 4 ) l ] m ] n has a plurality of X 1 to X 4 in total, the following formula can be given.
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
  式（９）～（１１）中、Ｘ1～Ｘ4は、芳香族炭化水素基または芳香族複素環基を示すが、これらの一部又は全部は縮合環であってもよい。しかし、芳香族複素環基は５環以上の縮合複素環を含まず、芳香族複素環基中に縮合複素環を含む場合は、４環までの縮合芳香族複素環に限る。 In formulas (9) to (11), X 1 to X 4 each represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and a part or all of these may be a condensed ring. However, the aromatic heterocyclic group does not include five or more condensed heterocyclic rings, and when the aromatic heterocyclic group includes a condensed heterocyclic ring, the aromatic heterocyclic group is limited to four or more condensed aromatic heterocyclic rings.
  -X1-[X2-[X3-(X4)l]m]nで表わされる芳香環が複数連結されて生じる基の具体例としては、例えば以下のような１価の基が挙げられる。 Specific examples of the group formed by linking a plurality of aromatic rings represented by -X 1- [X 2- [X 3- (X 4 ) l ] m ] n include the following monovalent groups: It is done.
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
　ここで、Ｒ'は炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基を示す。炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基の具体例は、上記一般式（１）中のＡで説明したものと同様である。 Here, R ′ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms. Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 3 to 17 carbon atoms are the same as those described for A in the general formula (1).
  上記Ａ及びＲにおける芳香族炭化水素基又は芳香族複素環基は置換基を有しても良く、これらが置換基を有する場合、置換基としては、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～２のアルコキシ基、アセチル基、炭素数６～１８の２級アミノ基、炭素数６～１８の２級ホスファニル基、炭素数３～１８のシリル基、炭素数６～１８の芳香族炭化水素基、炭素数３～１７の芳香族複素環基である。好ましくは炭素数１～４のアルキル基、炭素数３～６のシクロアルキル基又は炭素数６～１５の２級アミノ基、炭素数６～１２の芳香族炭化水素基、炭素数３～１１の芳香族複素環基であり、芳香族炭化水素基および芳香族複素環基の具体例は、炭素数が異なる他は上記Ａで説明したものと同様である。 The aromatic hydrocarbon group or aromatic heterocyclic group in A and R may have a substituent. When these have a substituent, the substituent includes an alkyl group having 1 to 20 carbon atoms, a carbon number A cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, a secondary amino group having 6 to 18 carbon atoms, a secondary phosphanyl group having 6 to 18 carbon atoms, and a silyl group having 3 to 18 carbon atoms And an aromatic hydrocarbon group having 6 to 18 carbon atoms and an aromatic heterocyclic group having 3 to 17 carbon atoms. Preferably, it is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a secondary amino group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 3 to 11 carbon atoms. Specific examples of the aromatic heterocyclic group and the aromatic hydrocarbon group are the same as those described in A above except that the number of carbon atoms is different.
  Ｘ1～Ｘ4の好ましい例として、上記式（６）～(８)のいずれかで表される化合物から所定の数の水素を取って生じる芳香族炭化水素基または芳香族複素環基がある。一般式（６）～(８)において、Ｙはそれぞれ独立してメチン又は窒素を表す。 Preferable examples of X 1 to X 4 include an aromatic hydrocarbon group or an aromatic heterocyclic group generated by taking a predetermined number of hydrogens from the compound represented by any one of the above formulas (6) to (8). . In the general formulas (6) to (8), Y each independently represents methine or nitrogen.
  一般式(６)～(８)で表される化合物の中でも、ベンゼン、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、ナフタリン、キノリン、イソキノリン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、カルバゾール、ジベンゾチオフェン、又はジベンゾフランのいずれかであることが好ましい。 Among the compounds represented by the general formulas (6) to (8), benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, naphthalene, quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline, carbazole, dibenzothiophene, or dibenzofuran It is preferable that it is either.
  一般式（１）で表されるインドロカルバゾール化合物の好ましい例として、一般式（２）～（５）のいずれかで表されるインドロカルバゾール化合物がある。一般式（２）～（５）において、一般式（１）、式(１ａ)及び式(１ｂ)と共通の記号は同じ意味を有するが、ｌ、ｍ及びｎは０～３の整数である。 好 ま し い Preferable examples of the indolocarbazole compound represented by the general formula (1) include an indolocarbazole compound represented by any one of the general formulas (2) to (5). In general formulas (2) to (5), symbols common to general formula (1), formula (1a), and formula (1b) have the same meaning, but l, m, and n are integers of 0 to 3. .
  一般式（１）又は一般式（２）～（５）で表されるインドロカルバゾール化合物は、目的とする化合物の構造に応じて原料を選択し、公知の手法を用いて合成することができる。 The indolocarbazole compound represented by the general formula (1) or the general formulas (2) to (5) can be synthesized by selecting a raw material according to the structure of the target compound and using a known method. .
  例えば、一般式（２）で表されるインドロカルバゾール化合物を与える骨格（IC-1）は、Synlett，2005，No．1，p42-48に示される合成例を参考にして以下の反応式により合成することができる。 For example, the skeleton (IC-1) giving the indolocarbazole compound represented by the general formula (2) is described in Synlett, 2005, No. 1, can be synthesized by the following reaction formula with reference to the synthesis example shown in p42-48.
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000017
  また、一般式（４）で表されるインドロカルバゾール化合物を与える骨格（IC-3）は、Archiv der Pharmazie (Weinheim, Germany) 1987, 320(3), p280-2に示される合成例を参考にして以下の反応式により合成することができる。 The skeleton (IC-3) that gives the indolocarbazole compound represented by the general formula (4) is the synthesis example shown in Archiv der Pharmazie (Weinheim, Germany) 1987, 320 (3), p280-2 Can be synthesized according to the following reaction formula.
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000018
  一般式（１）で表されるインドロカルバゾール化合物の具体例を以下に示すが、本発明の有機電界発光素子用材料はこれらに限定されない。 Specific examples of the indolocarbazole compound represented by general formula (1) are shown below, but the organic electroluminescent element material of the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000026
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000026
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000031
Figure JPOXMLDOC01-appb-I000032
Figure JPOXMLDOC01-appb-I000033
Figure JPOXMLDOC01-appb-I000034
Figure JPOXMLDOC01-appb-I000035
Figure JPOXMLDOC01-appb-I000036
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000031
Figure JPOXMLDOC01-appb-I000032
Figure JPOXMLDOC01-appb-I000033
Figure JPOXMLDOC01-appb-I000034
Figure JPOXMLDOC01-appb-I000035
Figure JPOXMLDOC01-appb-I000036
Figure JPOXMLDOC01-appb-I000037
Figure JPOXMLDOC01-appb-I000038
Figure JPOXMLDOC01-appb-I000039
Figure JPOXMLDOC01-appb-I000040
Figure JPOXMLDOC01-appb-I000041
Figure JPOXMLDOC01-appb-I000042
Figure JPOXMLDOC01-appb-I000043
Figure JPOXMLDOC01-appb-I000044
Figure JPOXMLDOC01-appb-I000037
Figure JPOXMLDOC01-appb-I000038
Figure JPOXMLDOC01-appb-I000039
Figure JPOXMLDOC01-appb-I000040
Figure JPOXMLDOC01-appb-I000041
Figure JPOXMLDOC01-appb-I000042
Figure JPOXMLDOC01-appb-I000043
Figure JPOXMLDOC01-appb-I000044
Figure JPOXMLDOC01-appb-I000045
Figure JPOXMLDOC01-appb-I000046
Figure JPOXMLDOC01-appb-I000047
Figure JPOXMLDOC01-appb-I000048
Figure JPOXMLDOC01-appb-I000049
Figure JPOXMLDOC01-appb-I000050
Figure JPOXMLDOC01-appb-I000051
Figure JPOXMLDOC01-appb-I000045
Figure JPOXMLDOC01-appb-I000046
Figure JPOXMLDOC01-appb-I000047
Figure JPOXMLDOC01-appb-I000048
Figure JPOXMLDOC01-appb-I000049
Figure JPOXMLDOC01-appb-I000050
Figure JPOXMLDOC01-appb-I000051
Figure JPOXMLDOC01-appb-I000052
Figure JPOXMLDOC01-appb-I000053
Figure JPOXMLDOC01-appb-I000054
Figure JPOXMLDOC01-appb-I000055
Figure JPOXMLDOC01-appb-I000056
Figure JPOXMLDOC01-appb-I000057
Figure JPOXMLDOC01-appb-I000058
Figure JPOXMLDOC01-appb-I000052
Figure JPOXMLDOC01-appb-I000053
Figure JPOXMLDOC01-appb-I000054
Figure JPOXMLDOC01-appb-I000055
Figure JPOXMLDOC01-appb-I000056
Figure JPOXMLDOC01-appb-I000057
Figure JPOXMLDOC01-appb-I000058
Figure JPOXMLDOC01-appb-I000059
Figure JPOXMLDOC01-appb-I000060
Figure JPOXMLDOC01-appb-I000061
Figure JPOXMLDOC01-appb-I000062
Figure JPOXMLDOC01-appb-I000063
Figure JPOXMLDOC01-appb-I000064
Figure JPOXMLDOC01-appb-I000065
Figure JPOXMLDOC01-appb-I000059
Figure JPOXMLDOC01-appb-I000060
Figure JPOXMLDOC01-appb-I000061
Figure JPOXMLDOC01-appb-I000062
Figure JPOXMLDOC01-appb-I000063
Figure JPOXMLDOC01-appb-I000064
Figure JPOXMLDOC01-appb-I000065
Figure JPOXMLDOC01-appb-I000066
Figure JPOXMLDOC01-appb-I000067
Figure JPOXMLDOC01-appb-I000068
Figure JPOXMLDOC01-appb-I000069
Figure JPOXMLDOC01-appb-I000070
Figure JPOXMLDOC01-appb-I000066
Figure JPOXMLDOC01-appb-I000067
Figure JPOXMLDOC01-appb-I000068
Figure JPOXMLDOC01-appb-I000069
Figure JPOXMLDOC01-appb-I000070
Figure JPOXMLDOC01-appb-I000071
Figure JPOXMLDOC01-appb-I000072
Figure JPOXMLDOC01-appb-I000073
Figure JPOXMLDOC01-appb-I000074
Figure JPOXMLDOC01-appb-I000075
Figure JPOXMLDOC01-appb-I000071
Figure JPOXMLDOC01-appb-I000072
Figure JPOXMLDOC01-appb-I000073
Figure JPOXMLDOC01-appb-I000074
Figure JPOXMLDOC01-appb-I000075
Figure JPOXMLDOC01-appb-I000076
Figure JPOXMLDOC01-appb-I000077
Figure JPOXMLDOC01-appb-I000078
Figure JPOXMLDOC01-appb-I000079
Figure JPOXMLDOC01-appb-I000080
Figure JPOXMLDOC01-appb-I000076
Figure JPOXMLDOC01-appb-I000077
Figure JPOXMLDOC01-appb-I000078
Figure JPOXMLDOC01-appb-I000079
Figure JPOXMLDOC01-appb-I000080
Figure JPOXMLDOC01-appb-I000081
Figure JPOXMLDOC01-appb-I000082
Figure JPOXMLDOC01-appb-I000083
Figure JPOXMLDOC01-appb-I000084
Figure JPOXMLDOC01-appb-I000085
Figure JPOXMLDOC01-appb-I000086
Figure JPOXMLDOC01-appb-I000081
Figure JPOXMLDOC01-appb-I000082
Figure JPOXMLDOC01-appb-I000083
Figure JPOXMLDOC01-appb-I000084
Figure JPOXMLDOC01-appb-I000085
Figure JPOXMLDOC01-appb-I000086
  上記一般式（１）で表されるインドロカルバゾール化合物は、基板上に、陽極、複数の有機層及び陰極が積層されてなる有機ＥＬ素子の少なくとも１つの有機層に含有させることにより、優れた有機電界発光素子を与える。含有させる有機層としては、発光層、正孔輸送層、電子輸送層、正孔阻止層又は電子阻止層が適する。より好ましくは、燐光発光ドーパントを含有する発光層のホスト材料として含有させることがよい。 The indolocarbazole compound represented by the general formula (1) is excellent by being contained in at least one organic layer of an organic EL device in which an anode, a plurality of organic layers and a cathode are laminated on a substrate. An organic electroluminescent device is provided. As the organic layer to be contained, a light emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer or an electron blocking layer is suitable. More preferably, it may be contained as a host material of a light emitting layer containing a phosphorescent dopant.
  次に、本発明の有機ＥＬ素子について説明する。 Next, the organic EL element of the present invention will be described.
  本発明の有機ＥＬ素子は、基板上に積層された陽極と陰極の間に、少なくとも一つの発光層を有する有機層を有し、且つ少なくとも一つの有機層は、上記インドロカルバゾール化合物を含む。有利には、燐光発光ドーパントと共に本発明の有機電界発光素子用材料を発光層中に含む。 The organic EL device of the present invention has an organic layer having at least one light emitting layer between an anode and a cathode laminated on a substrate, and at least one organic layer contains the indolocarbazole compound. Advantageously, the organic electroluminescent device material of the present invention is included in the light emitting layer together with a phosphorescent dopant.
  次に、本発明の有機ＥＬ素子の構造について、図面を参照しながら説明するが、本発明の有機ＥＬ素子の構造は何ら図示のものに限定されるものではない。 Next, the structure of the organic EL element of the present invention will be described with reference to the drawings. However, the structure of the organic EL element of the present invention is not limited to the illustrated one.
  図１は本発明に用いられる一般的な有機ＥＬ素子の構造例を示す断面図であり、１は基板、２は陽極、３は正孔注入層、４は正孔輸送層、５は発光層、６は電子輸送層、７は陰極を各々表わす。本発明の有機ＥＬ素子では発光層と隣接して励起子阻止層を有してもよく、また、発光層と正孔注入層との間に電子阻止層を有しても良い。励起子阻止層は発光層の陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。本発明の有機ＥＬ素子では、基板、陽極、発光層及び陰極を必須の層として有するが、必須の層以外の層に、正孔注入輸送層、電子注入輸送層を有することがよく、更に発光層と電子注入輸送層の間に正孔阻止層を有することがよい。なお、正孔注入輸送層は、正孔注入層と正孔輸送層のいずれか又は両者を意味し、電子注入輸送層は、電子注入層と電子輸送層のいずれか又は両者を意味する。 FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represents an electron transport layer, and 7 represents a cathode. The organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, and may have an electron blocking layer between the light emitting layer and the hole injection layer. The exciton blocking layer can be inserted on either the anode side or the cathode side of the light emitting layer, or both can be inserted simultaneously. The organic EL device of the present invention has a substrate, an anode, a light emitting layer and a cathode as essential layers, but it is preferable to have a hole injecting and transporting layer and an electron injecting and transporting layer in layers other than the essential layers, and further emit light. It is preferable to have a hole blocking layer between the layer and the electron injecting and transporting layer. The hole injection / transport layer means either or both of a hole injection layer and a hole transport layer, and the electron injection / transport layer means either or both of an electron injection layer and an electron transport layer.
  なお、図１とは逆の構造、すなわち、基板１上に陰極７、電子輸送層６、発光層５、正孔輸送層４、陽極２の順に積層することも可能であり、この場合も、必要により層を追加したり、省略したりすることが可能である。 In addition, it is also possible to laminate | stack the cathode 7, the electron carrying layer 6, the light emitting layer 5, the positive hole transport layer 4, and the anode 2 in order on the board | substrate 1 in the reverse structure, FIG. Layers can be added or omitted as necessary.
－基板－
  本発明の有機ＥＬ素子は、基板に支持されていることが好ましい。この基板については、特に制限はなく、従来から有機ＥＬ素子に慣用されているものであればよく、例えば、ガラス、透明プラスチック、石英などからなるものを用いることができる。 -substrate-
The organic EL element of the present invention is preferably supported on a substrate. The substrate is not particularly limited as long as it is conventionally used for an organic EL element. For example, a substrate made of glass, transparent plastic, quartz, or the like can be used.
－陽極－
  有機ＥＬ素子における陽極としては、仕事関数の大きい（４ｅＶ以上）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としてはＡｕ等の金属、ＣｕＩ、インジウムチンオキシド（ＩＴＯ）、ＳｎＯ2、ＺｎＯ等の導電性透明材料が挙げられる。また、ＩＤＩＸＯ（Ｉｎ2Ｏ3－ＺｎＯ）等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極物質を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は（１００μｍ以上程度）、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。あるいは、有機導電性化合物のように塗布可能な物質を用いる場合には、印刷方式、コーティング方式等湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を１０％より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω／□以下が好ましい。更に膜厚は材料にもよるが、通常１０～１０００ｎｍ、好ましくは１０～２００ｎｍの範囲で選ばれる。 -anode-
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO. Alternatively, an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
－陰極－
  一方、陰極としては、仕事関数の小さい（４ｅＶ以下）金属（電子注入性金属と称する）、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム－カリウム合金、マグネシウム、リチウム、マグネシウム／銅混合物、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ2Ｏ3）混合物、インジウム、リチウム／アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ2Ｏ3）混合物、リチウム／アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω／□以下が好ましく、膜厚は通常１０ｎｍ～５μｍ、好ましくは５０～２００ｎｍの範囲で選ばれる。なお、発光した光を透過させるため、有機ＥＬ素子の陽極又は陰極のいずれか一方が、透明又は半透明であれば発光輝度が向上し好都合である。 -cathode-
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode 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 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
  また、陰極に上記金属を１～２０ｎｍの膜厚で作製した後に、陽極の説明で挙げた導電性透明材料をその上に作製することで、透明又は半透明の陰極を作製することができ、これを応用することで陽極と陰極の両方が透過性を有する素子を作製することができる。 In addition, a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
－発光層－
  発光層は燐光発光層であり、燐光発光ドーパントとホスト材料を含む。燐光発光ドーパント材料としては、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金及び金から選ばれる少なくとも一つの金属を含む有機金属錯体を含有するものがよい。具体的には以下の特許公報に記載されている化合物が挙げられるが、これらの化合物に限定されない。 -Light emitting layer-
The light emitting layer is a phosphorescent light emitting layer and includes a phosphorescent dopant and a host material. The phosphorescent dopant material preferably contains an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold. Specific examples include compounds described in the following patent publications, but are not limited to these compounds.
  WO2009-073245号公報、WO2009-046266号公報、WO2007-095118号公報、WO2008-156879号公報、WO2008-140657号公報、US2008-261076号公報、特表2008-542203号公報、WO2008-054584号公報、特表2008-505925号公報、特表2007-522126号公報、特表2004-506305号公報、特表2006-513278号公報、特表2006-50596号公報、WO2006-046980号公報、WO2005113704号公報、US2005-260449号公報、US2005-2260448号公報、US2005-214576号公報、WO2005-076380号公報、US2005-119485号公報、WO2004-045001号公報、WO2004-045000号公報、WO2006-100888号公報、WO2007-004380号公報、WO2007-023659号公報、WO2008-035664号公報、特開2003-272861号公報、特開2004-111193号公報、特開2004-319438号公報、特開2007-2080号公報、特開2007-9009号公報、特開2007-227948号公報、特開2008-91906号公報、特開2008-311607号公報、特開2009-19121号公報、特開2009-46601号公報、特開2009-114369号公報、特開2003-253128号公報、特開2003-253129号公報、特開2003-253145号公報、特開2005-38847号公報、特開2005-82598号公報、特開2005-139185号公報、特開2005-187473号公報、特開2005-220136号公報、特開2006-63080号公報、特開2006-104201号公報、特開2006-111623号公報、特開2006-213720号公報、特開2006-290891号公報、特開2006-298899号公報、特開2006-298900号公報、WO2007-018067号公報、WO2007/058080号公報、WO2007-058104号公報、特開2006-131561号公報、特開2008-239565号公報、特開2008-266163号公報、特開2009-57367号公報、特開2002-117978号公報、特開2003-123982号公報、特開2003-133074号公報、特開2006-93542号公報、特開2006-131524号公報、特開2006-261623号公報、特開2006-303383号公報、特開2006-303394号公報、特開2006-310479号公報、特開2007-88105号公報、特開2007-258550号公報、特開2007-324309号公報、特開2008-270737号公報、特開2009-96800号公報、特開2009-161524号公報、WO2008-050733号公報、特開2003-73387号公報、特開2004-59433号公報、特開2004-155709号公報、特開2006-104132号公報、特開2008-37848号公報、特開2008-133212号公報、特開2009-57304号公報、特開2009-286716号公報、特開2010-83852号公報、特表2009-532546号公報、特表2009-536681号公報、特表2009-542026号公報等。 WO2009-073245 Publication, WO2009-046266 Publication, WO2007-095118 Publication, WO2008-156879 Publication, WO2008-140657 Publication, US2008-261076 Publication, Special Table 2008-542203 Publication, WO2008-054584 Publication, Special Table 2008-505925, Special Table 2007-522126, Special Table 2004-506305, Special Table 2006-513278, Special 2006-50596, WO2006-046980, WO2005113704, US2005-260449, US2005-2260448, US2005-214576, WO2005-076380, US2005-119485, WO2004-045001, WO2004-045000, WO2006-100888, WO2007- 004380, WO2007-023659, WO2008-035664, JP2003-272861, JP2004-111193, JP2004-319438, JP2007-2080, JP JP 2007-9009, JP 2007-227948, JP 2008-91906, JP 2008-311607, JP 2009-19121, JP 2009-46601, JP 2009- No. 114369, JP 2003- JP 253128, JP 2003-253129, JP 2003-253145, JP 2005-38847, JP 2005-82598, JP 2005-139185, JP 2005-187473 JP, JP 2005-220136, JP 2006-63080, JP 2006-104201, JP 2006-111623, JP 2006-213720, JP 2006-290891, JP 2006-298899, JP 2006-298900, WO 2007-018067, WO 2007/058080, WO 2007-058104, JP 2006-131561, JP 2008-239565, JP 2008-266163, JP 2009-57367, JP 2002-117978, JP 2003-123982, JP 2003-133074, JP 2006-93542, JP JP 2006-131524, JP 2006-261623, JP 2006-303383, JP 2006-303394, JP 2006-310479, JP 2007-88105, JP 2007- JP 258550, JP 2007-324309, JP 2008-270737, JP 2009-968 00, JP 2009-161524, WO 2008-050733, JP 2003-73387, JP 2004-59433, JP 2004-155709, JP 2006-104132, JP 2008-37848, JP 2008-133212, JP 2009-57304, JP 2009-286716, JP 2010-83852, Special 2009-532546, Special No. 2009-536681, No. 2009-542026, etc.
  好ましい燐光発光ドーパントとしては、Ir等の貴金属元素を中心金属として有するIr(ppy)3等の錯体類、Ir(bt)2・acac3等の錯体類、PtOEt3等の錯体類が挙げられる。これらの錯体類の具体例を以下に示すが、下記の化合物に限定されない。 Preferable phosphorescent dopants include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as Ir (bt) 2 · acac3, and complexes such as PtOEt3. Specific examples of these complexes are shown below, but are not limited to the following compounds.
Figure JPOXMLDOC01-appb-I000087
Figure JPOXMLDOC01-appb-I000088
Figure JPOXMLDOC01-appb-I000087
Figure JPOXMLDOC01-appb-I000088
  前記燐光発光ドーパントが発光層中に含有される量は、２～４０重量％、好ましくは５～３０重量％の範囲にあることがよい。 The amount of the phosphorescent dopant contained in the light emitting layer is 2 to 40% by weight, preferably 5 to 30% by weight.
  発光層におけるホスト材料としては、前記一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましい。しかし、該インドロカルバゾール化合物を発光層以外の他の何れかの有機層に使用する場合は、発光層に使用する材料はインドロカルバゾール化合物以外の他のホスト材料であってもよい。また、インドロカルバゾール化合物と他のホスト材料を併用してもよい。更に、公知のホスト材料を複数種類併用して用いてもよい。 As the host material in the light emitting layer, it is preferable to use an indolocarbazole compound represented by the general formula (1). However, when the indolocarbazole compound is used in any organic layer other than the light emitting layer, the material used for the light emitting layer may be a host material other than the indolocarbazole compound. An indolocarbazole compound and another host material may be used in combination. Furthermore, a plurality of known host materials may be used in combination.
  使用できる公知のホスト化合物としては、正孔輸送能、電子輸送能を有し、かつ発光の長波長化を防ぎ、なおかつ高いガラス転移温度を有する化合物であることが好ましい。 A known host compound that can be used is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents a long wavelength of light emission, and has a high glass transition temperature.
  このような他のホスト材料は、多数の特許文献等により知られているので、それらから選択することができる。ホスト材料の具体例としては、特に限定されるものではないが、インドール誘導体、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三アミン化合物、スチリルアミン化合物、芳香族ジメチリデン系化合物、ポルフィリン系化合物、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン誘導体、８―キノリノール誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾール誘導体の金属錯体に代表される各種金属錯体、ポリシラン系化合物、ポリ（N-ビニルカルバゾール）誘導体、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン誘導体、ポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリフルオレン誘導体等の高分子化合物等が挙げられる。 Such other host materials are known from a large number of patent documents and can be selected from them. Specific examples of host materials are not particularly limited, but include indole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine. Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquino Heterocyclic tetracarboxylic acid anhydrides such as dimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, Various metal complexes typified by metal complexes of Russianine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes of benzoxazole and benzothiazole derivatives, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Examples thereof include polymer compounds such as thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like.
－注入層－
  注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、正孔注入層と電子注入層があり、陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。注入層は必要に応じて設けることができる。 -Injection layer-
The injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission. There are a hole injection layer and an electron injection layer, and between the anode and the light emitting layer or the hole transport layer. And between the cathode and the light emitting layer or the electron transport layer. The injection layer can be provided as necessary.
－正孔阻止層－
  正孔阻止層とは広い意味では電子輸送層の機能を有し、電子を輸送する機能を有しつつ正孔を輸送する能力が著しく小さい正孔阻止材料からなり、電子を輸送しつつ正孔を阻止することで電子と正孔の再結合確率を向上させることができる。 -Hole blocking layer-
The hole blocking layer has a function of an electron transport layer in a broad sense, and is composed of a hole blocking material that has a function of transporting electrons and has a very small ability to transport holes, and transports holes while transporting electrons. The probability of recombination of electrons and holes can be improved by blocking.
  正孔阻止層には一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましいが、インドロカルバゾール化合物を他の何れかの有機層に使用する場合は、公知の正孔阻止層材料を用いてもよい。また、正孔阻止層材料としては、後述する電子輸送層の材料を必要に応じて用いることができる。 It is preferable to use the indolocarbazole compound represented by the general formula (1) for the hole blocking layer. However, when the indolocarbazole compound is used for any other organic layer, a known hole blocking layer is used. Materials may be used. Moreover, as a hole-blocking layer material, the material of the electron carrying layer mentioned later can be used as needed.
－電子阻止層－
　電子阻止層とは、正孔を輸送する機能を有しつつ電子を輸送する能力が著しく小さい材料から成り、正孔を輸送しつつ電子を阻止することで電子と正孔が再結合する確率を向上させることができる。 -Electron blocking layer-
The electron blocking layer is made of a material that has a function of transporting holes and has a very small ability to transport electrons. The electron blocking layer blocks the electrons while transporting holes, and the probability of recombination of electrons and holes. Can be improved.
  電子阻止層の材料としては、本発明に係る一般式（１）で表されるインドロカルバゾール化合物を用いることができるが、他の材料として、後述する正孔輸送層の材料を必要に応じて用いることもできる。電子阻止層の膜厚は好ましくは３～１００ｎｍであり、より好ましくは５～３０ｎｍである。 As the material for the electron blocking layer, the indolocarbazole compound represented by the general formula (1) according to the present invention can be used. As other materials, the material for the hole transport layer described later is used as necessary. It can also be used. The thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
－励起子阻止層－
  励起子阻止層とは、発光層内で正孔と電子が再結合することにより生じた励起子が電荷輸送層に拡散することを阻止するための層であり、本層の挿入により励起子を効率的に発光層内に閉じ込めることが可能となり、素子の発光効率を向上させることができる。励起子阻止層は発光層に隣接して陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。 -Exciton blocking layer-
The exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved. The exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  励起子阻止層の材料としては、一般式（１）で表されるインドロカルバゾール化合物を用いることができるが、他の材料として、例えば、１，３－ジカルバゾリルベンゼン（ｍＣＰ）や、ビス（２－メチル－８－キノリノラト）－４－フェニルフェノラトアルミニウム（III）（ＢＡｌｑ）が挙げられる。 As the material for the exciton blocking layer, an indolocarbazole compound represented by the general formula (1) can be used. As other materials, for example, 1,3-dicarbazolylbenzene (mCP), Bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III) (BAlq).
－正孔輸送層－
  正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層又は複数層設けることができる。 -Hole transport layer-
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  正孔輸送材料としては、正孔の注入又は輸送、電子の障壁性のいずれかを有するものであり、有機物、無機物のいずれであってもよい。正孔輸送層には一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましいが、従来公知の化合物の中から任意のものを選択して用いることができる。使用できる公知の正孔輸送材料としては例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、また導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられるが、ポルフィリン化合物、芳香族第３級アミン化合物及びスチリルアミン化合物を用いることが好ましく、芳香族第３級アミン化合物を用いることがより好ましい。 The hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. Although it is preferable to use the indolocarbazole compound represented by General formula (1) for a positive hole transport layer, arbitrary things can be selected and used from a conventionally well-known compound. Examples of known hole transport materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, Examples include styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. Porphyrin compounds, aromatic tertiary amine compounds, and styryl. It is preferable to use an amine compound, and it is more preferable to use an aromatic tertiary amine compound.
－電子輸送層－
  電子輸送層とは電子を輸送する機能を有する材料からなり、電子輸送層は単層又は複数層設けることができる。 -Electron transport layer-
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  電子輸送材料（正孔阻止材料を兼ねる場合もある）としては、陰極より注入された電子を発光層に伝達する機能を有していればよい。電子輸送層には本発明に係る一般式（１）で表される材料を用いることが好ましいが、従来公知の化合物の中から任意のものを選択して用いることができ、例えば、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタン及びアントロン誘導体、オキサジアゾール誘導体等が挙げられる。更に、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子輸送材料として用いることができる。更にこれらの材料を高分子鎖に導入した、又はこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。 As an electron transport material (which may also serve as a hole blocking material), it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. Although it is preferable to use the material represented by the general formula (1) according to the present invention for the electron transport layer, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  以下、本発明を実施例によって更に詳しく説明するが、本発明は勿論、これらの実施例に限定されるものではなく、その要旨を越えない限りにおいて、種々の形態で実施することが可能である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is of course not limited to these examples, and can be implemented in various forms as long as the gist thereof is not exceeded. .
  以下に示すルートにより燐光発光素子用材料となるインドロカルバゾール化合物を合成した。尚、化合物番号は、上記例示化合物に付した番号に対応する。 (1) An indolocarbazole compound to be a phosphorescent light emitting device material was synthesized by the following route. In addition, a compound number respond | corresponds to the number attached | subjected to the said exemplary compound.
合成例１
化合物（B-27）の合成 Synthesis example 1
Synthesis of compound (B-27)
Figure JPOXMLDOC01-appb-I000089
Figure JPOXMLDOC01-appb-I000090
Figure JPOXMLDOC01-appb-I000091
Figure JPOXMLDOC01-appb-I000089
Figure JPOXMLDOC01-appb-I000090
Figure JPOXMLDOC01-appb-I000091
  窒素雰囲気下、1,2-シクロヘキサンジオン33.3 g (0.30 mol)、フェニルヒドラジン塩酸塩86.0 g (0.60 mol)とエタノール1000 mlを室温で撹拌しながら、濃硫酸3.0 g (0.031 mol)を5分かけて滴下した後に、65℃で加熱しながら4時間撹拌した。反応溶液を室温まで冷却した後に、析出した結晶をろ取し、エタノール(2 × 500 ml)を用いて洗浄を行い、紫茶色結晶80.0 gを得た。この結晶72.0 g (0.26 mol)、トリフルオロ酢酸72.0 gと酢酸720.0 gを100℃で加熱しながら15時間撹拌した。反応溶液を室温まで冷却した後に、析出した結晶をろ取し、酢酸(200 ml)で洗浄した。リスラリー精製を行い、白色結晶として１１，１２‐ジヒドロインドロ［２，３‐ａ］カルバゾール（ＩＣ－１） 30.0 g (収率45%)を得た。 Concentrated sulfuric acid 3.0 g (0.031 mol) over 5 minutes while stirring 33.3 シ ク ロ ヘ キ サ ン g (0.30 mol) of 1,2-cyclohexanedione, 86.0 g (0.60 mol) of phenylhydrazine hydrochloride and 1000 ml of ethanol at room temperature under nitrogen atmosphere Then, the mixture was stirred for 4 hours while being heated at 65 ° C. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration and washed with ethanol (2 × 500 ml) to obtain 80.0 g of purple brown crystals. 72.0 g of the crystals (0.26 mol), 72.0 g of trifluoroacetic acid and 720.0 g of acetic acid were stirred for 15 hours while heating at 100 ° C. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration and washed with acetic acid (200 ml). Re-slurry purification was performed to obtain 11,12-dihydroindolo [2,3-a] carbazole (IC-1) 30.0 g (yield 45%) as white crystals.
  窒素雰囲気下、11,12-ジヒドロインドロ[2,3-a]カルバゾール（ＩＣ－１） 3.51 g（13.69 mmol）、3-ヨード-9-フェニルカルバゾール5.01 g（13.57 mmol）、銅5.00 g（78.68 mmol）、炭酸カリウム3.59 g（25.97 mmol）、テトラグライム100 mlを加えて撹拌した。その後、190 ℃まで加熱し、24時間撹拌した。反応溶液を室温まで冷却した後に、銅、無機物をろ別した。ろ液に水200 mlを加えて撹拌し、析出した結晶をろ別した。これを減圧乾燥した後、カラムクロマトグラフィーで精製して白色粉末の中間体Ａ 5.99g（12.0 mmol、収率88 ％）を得た。 Under a nitrogen atmosphere, 11,12-dihydroindolo [2,3-a] carbazole (IC-1) 3.51 g (13.69 mmol), 3-iodo-9-phenylcarbazole 5.01 g (13.57 mmol), copper 5.00 g ( 78.68 mmol), 3.59 g (25.97 カ リ ウ ム mmol) of potassium carbonate and 100 ml of tetraglyme were added and stirred. Thereafter, the mixture was heated to 190 ° C. and stirred for 24 hours. After cooling the reaction solution to room temperature, copper and inorganic substances were separated by filtration. The filtrate was added with 200 ml of water and stirred, and the precipitated crystals were filtered off. This was dried under reduced pressure and then purified by column chromatography to obtain 5.99 g (12.0 mmol, yield 88%) of Intermediate A as a white powder.
  窒素雰囲気下、60%水素化ナトリウム0.34 g、脱水N,N-ジメチルホルムアミド15 mlを加え、撹拌を行った。次に中間体Ａ 4.0 g（8.04 mmol）を脱水N,N-ジメチルホルムアミド20 mlに溶解させた溶液を10分かけて滴下した。その後、45分間撹拌を続けた。次に2,4-ジクロロ-6-フェニル-1,3,5-トリアジン2.01 g（8.84 mmol）を脱水N,N-ジメチルホルムアミド30 mlに溶解させた溶液を5分かけて滴下した。その後、7時間半撹拌を続けた。次に同フラスコ内に蒸留水50 mlを加え、析出した黄色固体をろ取した。ろ取した黄色固体をリスラリー精製し、乾燥させ中間体Ｂ 4.18 g（6.08 mmol、収率76 %）を得た。 Under a nitrogen atmosphere, 0.34 g of 60% sodium hydride and 15 ml of dehydrated N, N-dimethylformamide were added and stirred. Next, a solution of 4.0 g (8.04 mmol) of Intermediate A dissolved in 20 ml of dehydrated N, N-dimethylformamide was added dropwise over 10 minutes. Thereafter, stirring was continued for 45 minutes. Next, a solution prepared by dissolving 2.01 g (8.84 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine in 30 ml of dehydrated N, N-dimethylformamide was added dropwise over 5 minutes. Thereafter, stirring was continued for 7 and a half hours. Next, 50 ml of distilled water was added to the flask, and the precipitated yellow solid was collected by filtration. The yellow solid collected by filtration was subjected to reslurry purification and dried to obtain 4.18 g (6.08 mmol, 76% yield) of Intermediate B.
  窒素雰囲気下、中間体Ｂ 4.00 g（5.82 mmol）、フェニルボロン酸0.99 g（8.12 mmol）、テトラキス（トリフェニルホスフィン）パラジウム（0）0.20 g（0.17 mmol）、炭酸ナトリウム4.93 g（46.5 mmol）、トルエン50 ml、エタノール25 mlを加えて撹拌した。その後、蒸留水33 mlを加えて１時間半還流した。反応溶液を室温まで冷却した後に、有機層を蒸留水20 mlとブライン（3×20 ml）で洗浄し、有機層を活性炭およびフラー土で処理後、有機層を無水硫酸マグネシウムで乾燥した。次に硫酸マグネシウムをろ別し、溶媒を減圧留去し、得られた残渣をシリカゲルカラムクロマトグラフィー精製およびリスラリー精製することで、化合物Ｂ－２７を1.54 g（2.11 mmol、収率36 ％）白色個体として得た。
APCI-TOFMS, m/z 729 [M+H]+、1Ｈ－ＮＭＲ測定結果（測定溶媒：ＴＨＦ－ｄ8）を図２に示す。 Under nitrogen atmosphere, Intermediate B 4.00 g (5.82 mmol), phenylboronic acid 0.99 g (8.12 mmol), tetrakis (triphenylphosphine) palladium (0) 0.20 g (0.17 mmol), sodium carbonate 4.93 g (46.5 mmol), Toluene 50 ml and ethanol 25 ml were added and stirred. Thereafter, 33 ml of distilled water was added and refluxed for 1.5 hours. After cooling the reaction solution to room temperature, the organic layer was washed with 20 ml of distilled water and brine (3 × 20 ml), the organic layer was treated with activated carbon and fuller's earth, and the organic layer was dried over anhydrous magnesium sulfate. Next, the magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography and reslurry purification to obtain 1.54 g (2.11 mmol, 36% yield) of Compound B-27 in white. Obtained as an individual.
APCI-TOFMS, m / z 729 [M + H] + , 1 H-NMR measurement results (measuring solvent: THF-d 8 ) are shown in FIG.
実施例１
  膜厚110 nmのITOからなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度4.0×10-5 Paで積層させた。まず、ITO上に銅フタロシアニン(CuPC)を25 nmの厚さに形成した。次に、正孔輸送層として4,4'-ビス[N-(1-ナフチル)-N-フェニルアミノ]ビフェニル（NPB）を40 nmの厚さに形成した。次に、正孔輸送層上に、ホスト材料としての化合物（Ｂ－２７）と、燐光発光ドーパントとしてのトリス（2‐フェニルピリジン）イリジウム（III）（Ir(ppy)3）とを異なる蒸着源から、共蒸着し、40 nmの厚さに発光層を形成した。発光層中のIr(ppy)3の濃度は10.0 wt％であった。次に、電子輸送層としてトリス（８－ヒドロキシキノリナト）アルミニウム（III）（Alq3）を20 nmの厚さに形成した。更に、電子輸送層上に、電子注入層としてフッ化リチウム（LiF）を1.0 nmの厚さに形成した。最後に、電子注入層上に、電極としてアルミニウム（Al）を70 nmの厚さに形成し、有機ＥＬ素子を作製した。 Example 1
Each thin film was laminated at a vacuum degree of 4.0 × 10 −5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 110 nm was formed. First, copper phthalocyanine (CuPC) was formed to a thickness of 25 nm on ITO. Next, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) was formed to a thickness of 40 nm as a hole transport layer. Next, a compound (B-27) as a host material and tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) as a phosphorescent dopant are differently deposited on the hole transport layer. Then, the light emitting layer was formed by co-evaporation to a thickness of 40 nm. The concentration of Ir (ppy) 3 in the light emitting layer was 10.0 wt%. Next, tris (8-hydroxyquinolinato) aluminum (III) (Alq3) was formed to a thickness of 20 nm as an electron transport layer. Further, on the electron transport layer, lithium fluoride (LiF) was formed to a thickness of 1.0 nm as an electron injection layer. Finally, on the electron injection layer, aluminum (Al) was formed as an electrode to a thickness of 70 nm to produce an organic EL element.
  得られた有機ＥＬ素子に外部電源を接続し直流電圧を印加したところ、表１のような発光特性を有することが確認された。表１において、輝度、電圧及び発光効率は、20mA/cm2での値を示す。素子発光スペクトルの極大波長は520 nmであり、Ir(ppy)3からの発光が得られていることがわかった。 When an external power source was connected to the obtained organic EL element and a DC voltage was applied, it was confirmed that the organic EL element had the light emission characteristics as shown in Table 1. In Table 1, the luminance, voltage, and luminous efficiency show values at 20 mA / cm 2 . The maximum wavelength of the device emission spectrum was 520 nm, indicating that light emission from Ir (ppy) 3 was obtained.
実施例２～１６
  合成例１と同様にして、化合物Ａ－２７、Ａ－３８、Ａ－７４、Ｂ－５６、Ｃ－２３、Ｄ－２１、Ｄ－４３、Ｅ－１０、Ｅ－２１、Ｇ－１９、Ｇ－２９、Ｈ－１６、Ｈ－２５、Ｊ－２４及びＫ－１５を合成した。実施例１の発光層のホスト材料として、化合物Ｂ－２７に代えて化合物Ａ－２７、Ａ－３８、Ａ－７４、Ｂ－５６、Ｃ－２３、Ｄ－２１、Ｄ－４３、Ｅ－１０、Ｅ－２１、Ｇ－１９、Ｇ－２９、Ｈ－１６、Ｈ－２５、Ｊ－２４及びＫ－１５を用いた以外は実施例１と同様にして有機ＥＬ素子を作成した。各々の素子発光スペクトルの極大波長は520 nmであり、Ir(ppy)3からの発光が得られていることがわかった。各々の発光特性を表１に示す。 Examples 2 to 16
In the same manner as in Synthesis Example 1, compounds A-27, A-38, A-74, B-56, C-23, D-21, D-43, E-10, E-21, G-19, G -29, H-16, H-25, J-24 and K-15 were synthesized. As a host material of the light emitting layer of Example 1, instead of Compound B-27, Compound A-27, A-38, A-74, B-56, C-23, D-21, D-43, E-10 , E-21, G-19, G-29, H-16, H-25, J-24 and K-15 were used to produce an organic EL device in the same manner as in Example 1. The maximum wavelength of the emission spectrum of each device was 520 nm, and it was found that light emission from Ir (ppy) 3 was obtained. The respective emission characteristics are shown in Table 1.
例１７（比較１）
  発光層のホスト材料として、CBPを用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 17 (Comparison 1)
An organic EL device was produced in the same manner as in Example 1 except that CBP was used as the host material of the light emitting layer.
例１８（比較２）
  発光層のホスト材料として、下記化合物（Ho-1）を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 18 (Comparison 2)
An organic EL device was produced in the same manner as in Example 1 except that the following compound (Ho-1) was used as the host material for the light emitting layer.
Figure JPOXMLDOC01-appb-I000092
Figure JPOXMLDOC01-appb-I000092
例１９（比較３）
  発光層のホスト材料として、下記化合物（Ho-2）を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。
Figure JPOXMLDOC01-appb-I000093
Example 19 (Comparison 3)
An organic EL device was produced in the same manner as in Example 1 except that the following compound (Ho-2) was used as the host material for the light emitting layer.
Figure JPOXMLDOC01-appb-I000093
  例１７～１９で作成した有機ＥＬ素子の素子発光スペクトルの極大波長はいずれも520 nmであり、Ir(ppy)3からの発光が得られていることがわかった。ホスト材料として使用した化合物及び各々の20mA/cm2での発光特性を表１に示す。X数はＸ1～Ｘ4の総数である。 The maximum wavelengths of the device emission spectra of the organic EL devices prepared in Examples 17 to 19 were all 520 nm, indicating that light emission from Ir (ppy) 3 was obtained. Table 1 shows the compounds used as host materials and the emission characteristics at 20 mA / cm 2 for each. The X number is the total number of X 1 to X 4 .
Figure JPOXMLDOC01-appb-T000094
Figure JPOXMLDOC01-appb-T000094
  表１より、一般式（１）で表されるインドロカルバゾール化合物を用いた有機ＥＬ素子は、燐光ホストとして一般的に知られているCBPを用いた場合に対して良好な発光特性を示すことが判る。また、インドロカルバゾールの２つの何れの窒素上にもカルバゾリル基を持たない化合物であるＨｏ－１およびＨｏ－２を用いた場合と比較して、良好な発光特性を示すことが判る。以上より、上記インドロカルバゾール化合物を用いた有機ＥＬ素子の優位性は明らかである。 From Table 1, the organic EL device using the indolocarbazole compound represented by the general formula (1) exhibits good emission characteristics compared with the case where CBP generally known as a phosphorescent host is used. I understand. In addition, it can be seen that better light emission characteristics are exhibited as compared with the case where Ho-1 and Ho-2, which are compounds having no carbazolyl group on any two nitrogens of indolocarbazole, are used. From the above, the superiority of the organic EL device using the indolocarbazole compound is clear.
産業上の利用の可能性Industrial applicability
  本発明の有機電界発光素子において使用されるインドロカルバゾール化合物は、インドロカルバゾール骨格の窒素上に少なくとも１つのＮ置換カルバゾリル基を有することを特徴としている。上記インドロカルバゾール化合物はインドロカルバゾール骨格の２つのＮ上の一方にＮ置換カルバゾリル基を有することにより良好な正孔と電子の注入輸送特性を示し、かつ高い耐久性を有すると考えられる。さらに、もう１つのＮ上の置換基である芳香環の種類または数を変えることにより、正孔、電子移動速度の微調整、並びにＩＰ、ＥＡ、Ｔ１の各種エネルギー値の制御が可能となる。特に芳香環を４つ以上、好ましくは５つ以上連結する場合には、共役系が広がることで分子間の重なりが良くなり、分子の電子的安定性の向上が期待できるだけでなく、移動度の高い材料を提供することが可能となる。以上のことから、該インドロカルバゾール化合物を用いた有機ＥＬ素子は、発光層中の多様なドーパントに対し最適なキャリアバランスを実現することができ、その結果、発効特性を大幅に改善した有機ＥＬ素子を提供することが可能となる。さらに、該インドロカルバゾール化合物は酸化、還元、励起の各活性状態で安定性を向上させることが可能であり、同時に良好なアモルファス特性を有することから、駆動寿命が長く、耐久性の高い有機ＥＬ素子を実現できる。 The indolocarbazole compound used in the organic electroluminescent device of the present invention is characterized by having at least one N-substituted carbazolyl group on the nitrogen of the indolocarbazole skeleton. The indolocarbazole compound is considered to have excellent hole and electron injecting and transporting properties and having high durability by having an N-substituted carbazolyl group on one of two Ns of the indolocarbazole skeleton. Furthermore, by changing the type or number of the aromatic ring that is another substituent on N, fine adjustment of the hole and electron transfer speed and control of various energy values of IP, EA, and T1 are possible. In particular, when four or more aromatic rings are connected, preferably five or more aromatic rings, the conjugated system spreads to improve the overlap between molecules, and not only can improve the electronic stability of the molecules, but also the mobility. It is possible to provide a high material. From the above, the organic EL device using the indolocarbazole compound can realize an optimum carrier balance for various dopants in the light emitting layer, and as a result, the organic EL device with greatly improved efficacy characteristics. An element can be provided. Furthermore, the indolocarbazole compound can improve stability in each active state of oxidation, reduction, and excitation, and at the same time has good amorphous characteristics, so that it has a long driving life and high durability. An element can be realized.
  本発明による有機ＥＬ素子は、発光特性、駆動寿命ならびに耐久性において、実用上満足できるレベルにあり、フラットパネルディスプレイ（携帯電話表示素子、車載表示素子、ＯＡコンピュータ表示素子やテレビ等）、面発光体としての特徴を生かした光源（照明、複写機の光源、液晶ディスプレイや計器類のバックライト光源）、表示板や標識灯等への応用において、その技術的価値は大きいものである。 The organic EL device according to the present invention has practically satisfactory levels in terms of light emission characteristics, driving life and durability, flat panel display (mobile phone display device, in-vehicle display device, OA computer display device, television, etc.), surface light emission, etc. Its technical value is great in applications to light sources (lighting, light sources for copying machines, backlight light sources for liquid crystal displays and instruments), display boards, and sign lamps that make use of the characteristics of the body.

Claims (6)

  1.   基板上に、陽極、燐光発光層を含む複数の有機層及び陰極が積層されてなる有機電界発光素子において、燐光発光層、正孔輸送層、電子輸送層正孔阻止層及び電子阻止層からなる群れから選ばれる少なくとも一つの有機層中に、一般式（１）で表されるインドロカルバゾール化合物を含有することを特徴とする有機電界発光素子。
    Figure JPOXMLDOC01-appb-I000001
    　一般式（１）中、環Ｉは隣接環と任意の位置で縮合する式（１ａ）で表される芳香族炭化水素環を示し、環IIは隣接環と任意の位置で縮合する式（１ｂ）で表される複素環を表し、Ａは炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を表し、一般式(１)及び式(１ａ)中、Ｒはそれぞれ独立に、炭素数１～１０の脂肪族炭化水素基、炭素数６～１８の芳香族炭化水素基又は炭素数３～１７の芳香族複素環基を示し、ｐはそれぞれ独立に０～４の整数、ｑは０～２の整数を表す。式(１ｂ)中、Ｘ1～Ｘ4はそれぞれ独立に炭素数６～１８の芳香族炭化水素基または炭素数３～１７の芳香族複素環基を示し、ｌ、ｍおよびｎは各々独立に０～５の整数を表す。ここで、ｌ、ｍまたはｎが２以上の場合、Ｘ2、Ｘ3およびＸ4はそれぞれ同一でも異なってもよい。     In an organic electroluminescent device in which a plurality of organic layers including an anode, a phosphorescent light emitting layer, and a cathode are laminated on a substrate, the phosphorescent light emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, and an electron blocking layer are included. An organic electroluminescent device comprising an indolocarbazole compound represented by the general formula (1) in at least one organic layer selected from a group.
    Figure JPOXMLDOC01-appb-I000001
    In general formula (1), ring I represents an aromatic hydrocarbon ring represented by formula (1a) that is condensed with an adjacent ring at an arbitrary position, and ring II is a formula (1b) that is condensed with an adjacent ring at an arbitrary position. And A represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms, and in general formulas (1) and (1a), R independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 3 to 17 carbon atoms, and p represents each independently 0 An integer of -4, q represents an integer of 0-2. In the formula (1b), X 1 to X 4 each independently represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 17 carbon atoms, and each of l, m and n is independently An integer of 0 to 5 is represented. Here, when l, m or n is 2 or more, X 2 , X 3 and X 4 may be the same or different.
  2.   一般式(１)で表されるインドロカルバゾール化合物が、一般式(２)～(５)のいずれかで表されるインドロカルバゾール化合物である請求項１に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-I000002
    　一般式(２)～(５)中、Ａ、Ｒ、Ｘ1～Ｘ4、p及びｑは一般式(１)と同意であり、ｌ、ｍ及びｎは０～３の整数を表す。ここで、ｌ、ｍまたはｎが２以上の場合、Ｘ2、Ｘ3およびＸ4は同一でも異なってもよい。     The organic electroluminescent device according to claim 1, wherein the indolocarbazole compound represented by the general formula (1) is an indolocarbazole compound represented by any one of the general formulas (2) to (5).
    Figure JPOXMLDOC01-appb-I000002
    In the general formulas (2) to (5), A, R, X 1 to X 4 , p and q are the same as those in the general formula (1), and l, m and n each represents an integer of 0 to 3. Here, when l, m or n is 2 or more, X 2 , X 3 and X 4 may be the same or different.
  3.   式(１ｂ)において、Ｘ1～Ｘ4の総数が４～７であることを特徴とする請求項１に記載の有機電界発光素子。 2. The organic electroluminescent element according to claim 1, wherein the total number of X 1 to X 4 in the formula (1b) is 4 to 7.
  4.   式(１ｂ)におけるＸ1～Ｘ4が、下記式（６）～(８)のいずれかで表される化合物から生じる芳香族炭化水素基または芳香族複素環基であることを特徴とする請求項１に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-I000003
    Figure JPOXMLDOC01-appb-I000004
    　式(６)～(８)中、Ｙはそれぞれ独立してメチンまたは窒素を表し、Ｚは単結合、－Ｓ－、－Ｏ－または－ＮＡｒ－のいずれかを表す。ここで、Ａｒは、炭素数６～１８の芳香族炭化水素基または炭素数６～１７の芳香族複素環基を表す。     X 1 to X 4 in the formula (1b) are aromatic hydrocarbon groups or aromatic heterocyclic groups generated from a compound represented by any one of the following formulas (6) to (8) Item 2. The organic electroluminescent device according to Item 1.
    Figure JPOXMLDOC01-appb-I000003
    Figure JPOXMLDOC01-appb-I000004
    In formulas (6) to (8), Y independently represents methine or nitrogen, and Z represents a single bond, —S—, —O— or —NAr—. Here, Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 6 to 17 carbon atoms.
  5.   式(６)～(８)のいずれかで表される化合物が、ベンゼン、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、ナフタリン、キノリン、イソキノリン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、カルバゾール、ジベンゾチオフェン、及びジベンゾフランからなる群れから選ばれるいずれかであることを特徴とする請求項４に記載の有機電界発光素子。 The compound represented by any one of formulas (6) to (8) is benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, naphthalene, quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline, carbazole, dibenzothiophene, and The organic electroluminescent element according to claim 4, which is any one selected from the group consisting of dibenzofuran.
  6.   インドロカルバゾール化合物を含む有機層が、燐光発光ドーパントを含有する発光層であることを特徴とする請求項１～５のいずれかに記載の有機電界発光素子。 6. The organic electroluminescent device according to claim 1, wherein the organic layer containing an indolocarbazole compound is a light emitting layer containing a phosphorescent dopant.
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TWI509050B (en) 2015-11-21
CN104011893B (en) 2016-06-22
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JPWO2013088973A1 (en) 2015-04-27
TW201329204A (en) 2013-07-16

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