JPH11329737A - Organic multilayer type electroluminescent element and synthesizing method of structure body for organic multilayer type electroluminescent element - Google Patents
Organic multilayer type electroluminescent element and synthesizing method of structure body for organic multilayer type electroluminescent elementInfo
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- JPH11329737A JPH11329737A JP10260328A JP26032898A JPH11329737A JP H11329737 A JPH11329737 A JP H11329737A JP 10260328 A JP10260328 A JP 10260328A JP 26032898 A JP26032898 A JP 26032898A JP H11329737 A JPH11329737 A JP H11329737A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電界発光素子の中
で、特に有機エレクトロルミネッセンス（ＥＬ）素子に
使用される構造体に関し、それを組み込んだ有機多層型
ＥＬ素子、及び有機多層型ＥＬ素子用構造体の合成方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure used in an organic electroluminescence (EL) device, and more particularly to an organic multilayer EL device incorporating the same, and an organic multilayer EL device incorporating the same. A method for synthesizing a structure.
【０００２】[0002]
【従来の技術】一般に有機物を用いたエレクトロルミネ
ッセンスは、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。発光
は、両電極間に電界が印加されると、陰極側から電子が
注入され、陽極から正孔が注入され、さらに、この電子
が発光層において正孔と再結合し、エネルギー準位が伝
導帯から価電子帯に戻る際にエネルギーを光として放出
する現象である。従来より有機蛍光色素を発光層とし、
有機電荷輸送化合物と積層した二層構造を有する素子
や、高分子を発光材料とした素子等各種のエレクトロル
ミネッセンスが報告されている。今日知られている有機
ＥＬ素子の一般的構造として比較的簡単なものを記載す
ると図１の様になり、陰極、発光層、有機正孔輸送層、
陽極、基板の層状構造となっており、又他の例としては
電子輸送層を加え陰極、電子輸送層、発光層、有機正孔
輸送層、陽極、基板の層状構造となっている例も見られ
る。2. Description of the Related Art In general, an electroluminescence using an organic material has a simplest structure including a light emitting layer and a pair of opposed electrodes sandwiching the layer. In light emission, when an electric field is applied between the two electrodes, electrons are injected from the cathode side, holes are injected from the anode, and the electrons recombine with holes in the light emitting layer, and the energy level is transmitted. This is a phenomenon in which energy is emitted as light when returning from the band to the valence band. Conventionally, an organic fluorescent dye is used as the light emitting layer,
Various types of electroluminescence have been reported, such as a device having a two-layer structure laminated with an organic charge transport compound and a device using a polymer as a light emitting material. FIG. 1 shows a relatively simple general structure of an organic EL device known today, as shown in FIG. 1; a cathode, a light emitting layer, an organic hole transport layer,
It has a layered structure of an anode and a substrate. As another example, there is also an example of a layered structure of a cathode, an electron transporting layer, a light emitting layer, an organic hole transporting layer, an anode, and a substrate in addition to an electron transporting layer. Can be
【０００３】一般に陰極にはアルミニウム（Ａｌ）、マ
グネシウム（Ｍｇ）、インジウム（Ｉｎ）、銀（Ａ
ｇ）、などの単体金属、あるいはＡｌ−Ｍｇ、Ａｇ−Ｍ
ｇ、Ａｌ−Ｌｉなどこれらの金属の合金で、仕事関数の
小さな材料が用いられる。In general, a cathode is made of aluminum (Al), magnesium (Mg), indium (In), silver (A
g), etc., or Al-Mg, Ag-M
g, an alloy of these metals such as Al-Li, and a material having a small work function is used.
【０００４】発光層には、蛍光を発する物質が用いら
れ、例えばアントラセン、ナフタレン、フェナントレ
ン、シクロペンタジエン、キノリン金属錯体、アミノキ
ノリン金属錯体、クマリン誘導体等各種化合物があり、
具体的に言うならば、トリス（８−キノリノール）アル
ミニウム、ビス（８−キノリノール）マグネシウム、ト
リス（５−クロロ−８−キノリノール）ガリウム等を例
示する事か出来る。For the light emitting layer, a substance emitting fluorescence is used. For example, there are various compounds such as anthracene, naphthalene, phenanthrene, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, and coumarin derivative.
Specifically, tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, tris (5-chloro-8-quinolinol) gallium and the like can be exemplified.
【０００５】有機正孔輸送層としてはＮ，Ｎ’−ジフェ
ニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１
−ビフェニル４，４’−ジアミン（ＴＤＰ）、銅フタロ
シアニン、４，４’−４‥−トリス−｛Ｎ−（３−メチ
ルフェニル）−Ｎ−フェニルアミノ｝トリフェニルアミ
ン（ＭＴＤＡＴＡ）などを例示する事が出来る。As an organic hole transport layer, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1
-Biphenyl 4,4'-diamine (TDP), copper phthalocyanine, 4,4'-4} -tris- {N- (3-methylphenyl) -N-phenylamino} triphenylamine (MTDATA) and the like. I can do things.
【０００６】電子輸送層としてはフルオレノン、アント
ラキノジメタン、ジフェノキノン、〔２−（４’−ｔ−
ブチルフェニル）−５−（ビフェニル）−１，３，４−
オキサジアゾール〕等があげられる。As the electron transporting layer, fluorenone, anthraquinodimethane, diphenoquinone, [2- (4'-t-
(Butylphenyl) -5- (biphenyl) -1,3,4-
Oxadiazole] and the like.
【０００７】陽極には、インジウム錫酸化物（ＩＴ
Ｏ）、錫酸化物など仕事関数の大きい透明導電性材料が
使用される。For the anode, indium tin oxide (IT)
A transparent conductive material having a large work function such as O) or tin oxide is used.
【０００８】基板には熱的、機械的強度を有し、透明で
あれば良く、例えばガラス基板、ポリエチレン板、ポリ
プロビレン板等の透明性の高い樹脂等が使用出来る。こ
れらの各層の形成は、真空蒸着、スパッタリング、スピ
ンコーティング等の適宜な方法を適用する事が出来る。The substrate only needs to have thermal and mechanical strength and be transparent, and for example, a highly transparent resin such as a glass substrate, a polyethylene plate or a polypropylene plate can be used. For the formation of each of these layers, an appropriate method such as vacuum evaporation, sputtering, and spin coating can be applied.
【０００９】各層の膜厚は特に限定されるものではない
が、各層は適切な膜厚に設定する必要がある。膜厚が厚
すぎると、一定の輝度を得るためには高電圧が必要とな
り、効率が低下する。さらに高電圧により劣化が進み、
寿命が短くなる不利益が生じる。一方、膜厚が薄すぎる
とピンホール等の発生により電界を加えても充分な発光
が得られない事もある。The thickness of each layer is not particularly limited, but each layer must be set to an appropriate thickness. If the film thickness is too large, a high voltage is required to obtain a certain luminance, and the efficiency is reduced. Deterioration further progresses due to high voltage,
The disadvantage is that the life is shortened. On the other hand, if the film thickness is too small, sufficient light emission may not be obtained even when an electric field is applied due to generation of pinholes or the like.
【００１０】[0010]
【発明が解決しようとする課題】これらの有機ＥＬ素子
の中で、有機正孔輸送層（以下、本発明においてホール
輸送層という）としては、前述のようにＮ，Ｎ’−ジフ
ェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，
１−ビフェニル４，４’−ジアミン（ＴＤＰ）等が使用
されており、ホール輸送層に使用される有機化合物とし
ては現在のところ最も効果的とされている。しかしなが
ら、前記化合物は、その寿命（ホール輸送層としての安
定性）に問題があり、さらには発光層に使用される物質
が本来有している発光性能をやや低下させるという問題
点をも有していた。Among these organic EL devices, the organic hole transporting layer (hereinafter referred to as the hole transporting layer in the present invention) includes N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,
1-biphenyl 4,4'-diamine (TDP) and the like are used, and are currently considered to be the most effective organic compounds used for the hole transport layer. However, the compound has a problem in its lifetime (stability as a hole transporting layer), and further has a problem in that the luminous performance inherently possessed by the substance used in the luminescent layer is slightly reduced. I was
【００１１】[0011]
【課題を解決するために手段】本発明者等は、上記課題
を解決すべく鋭意検討した結果、特定の構造を有する９
−カルバゾリルを分子内に含有する化合物（カルバゾー
ル誘導体）をホール輸送層に使用することにより、有機
多層型ＥＬ素子の寿命が飛躍的に延び、しかも発光性能
の向上も見られることを見出し、本発明に至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have a specific structure.
The present invention has been found that the use of a compound containing a carbazolyl in the molecule (carbazole derivative) for the hole transport layer dramatically increases the lifetime of the organic multilayer EL device and also improves the light emission performance. Reached.
【００１２】[0012]
【発明の実施の形態】本発明は、特定の構造を有するカ
ルバゾール誘導体を有機多層型ＥＬ素子のホール輸送層
に用いることを特徴とするものであるが、以下に本発明
に用いられるカルバゾール誘導体について説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that a carbazole derivative having a specific structure is used for a hole transport layer of an organic multilayer EL device. The carbazole derivative used in the present invention will be described below. explain.
【００１３】まず、本発明に用いられるカルバゾール誘
導体は大別して３つの系統に分類され、その第１の系統
は、First, the carbazole derivatives used in the present invention are roughly classified into three systems, the first of which is:
【化１６】 で示されるカルバゾール誘導体であり、Ｒは窒素含有ア
リル基であり、それらのうち良好なものとしてはEmbedded image Wherein R is a nitrogen-containing allyl group;
【化１７】 Embedded image
【化１８】 Embedded image
【化１９】 Embedded image
【化２０】 が挙げられる。Embedded image Is mentioned.
【００１４】これらの各種の化合物の合成工程はそれぞ
れ以下の如くなる。The steps of synthesizing these various compounds are as follows.
【化２１】 Embedded image
【化２２】 Embedded image
【化２３】 Embedded image
【化２４】 Embedded image
【００１５】次に、本発明に用いられるカルバゾール誘
導体の第２の系統は、Next, a second family of carbazole derivatives used in the present invention is:
【化２５】 で示されるジカルバゾール誘導体であり、Ｒはアリル基
であればよいのであるが、特にＲとして下記の構造式を
有するジカルバゾール誘導体がより好ましい。Embedded image Wherein R is an allyl group, and particularly preferably a dicarbazole derivative having the following structural formula as R.
【化２６】 Embedded image
【００１６】このジカルバゾール誘導体の合成の第一段
階の反応は、下式で示すようにジカルバゾールを合成す
ることであり、The first step in the synthesis of this dicarbazole derivative is to synthesize dicarbazole as shown by the following formula:
【化２７】 第二段階の反応として、得られたジカルバゾールと各種
アリル系化合物とを反応させ、ジカルバゾール誘導体を
得る。その合成方法について、Ｒ−Ｉとして４−ヨード
トルエンを使用した場合について具体例を以下に示す。
撹拌機、玉入り冷却機、温度計及び窒素ガス導入管を接
続した容量１００ｍｌの四つ口フラスコに３，３’−ジ
カルバジル０．５０ｇ（１．５０ｍｍｏｌ）、４−ヨー
ドトルエン０．９８ｇ（４．５１ｍｍｏｌ）、１８−ク
ラウン−６−エーテル０．７９ｇ（３．００ｍｍｏ
ｌ）、炭酸カリウム０．４２ｇ（３．００ｍｍｏｌ）、
ｏ−ジクロルベンゼン５０ｍｌを入れ、容器内の雰囲気
を窒素ガス置換し、銅触媒０．０９７ｇを加えて窒素雰
囲気中で加熱環流を２５時間行った。反応後、直ちに熱
時濾過し、濾液の溶媒を減圧留去し、残った残留物にエ
タノール２０ｍｌを添加して２時間かき混ぜると、沈殿
物を生じた。この沈殿物を濾取（得量０．７９ｇ）し
た。ｍｐは１６０〜１７０℃であった。この沈殿物を１
００ｍｌのベンゼンに加熱溶解し、濾過し、濾液を１０
ｍｌまで濃縮した。この濃縮液にｎ−ヘキサン５ｍｌを
添加し、析出した沈殿物（黒褐色０．１０ｇ）を濾過し
て除き、濾液にさらにヘキサンを１０ｍｌ加えて生じた
沈殿物（黄褐色０．０１ｇ）を２時間後に濾過して除去
した。さらに、同様にしてヘキサン２０ｍｌを添加して
析出して沈殿物（黄土色０．０２ｇ）を除去した濾液を
約２ｍｌまで濃縮した。この濃縮液を３日間静置し、淡
黄色の析出物０．１５ｇを得た。ｍｐは１５７〜１５９
℃であった。この合成はＲの種類により原料は異なるが
手法は同様である。Embedded image In the second step, the obtained dicarbazole is reacted with various allylic compounds to obtain a dicarbazole derivative. Specific examples of the synthesis method in the case where 4-iodotoluene is used as RI are shown below.
0.50 g (1.50 mmol) of 3,3′-dicarbazyl and 0.98 g (4 .51 mmol), 0.79 g (3.00 mmol) of 18-crown-6-ether
l), 0.42 g (3.00 mmol) of potassium carbonate,
50 ml of o-dichlorobenzene was charged, the atmosphere in the vessel was replaced with nitrogen gas, and 0.097 g of a copper catalyst was added, followed by heating and refluxing in a nitrogen atmosphere for 25 hours. Immediately after the reaction, the mixture was filtered while hot, the solvent of the filtrate was distilled off under reduced pressure, and 20 ml of ethanol was added to the remaining residue, followed by stirring for 2 hours to produce a precipitate. This precipitate was collected by filtration (yield 0.79 g). mp was 160-170 ° C. This precipitate is
The solution was dissolved by heating in 00 ml of benzene, filtered, and the filtrate was concentrated in 10 ml.
Concentrated to ml. To this concentrated solution, 5 ml of n-hexane was added, and the deposited precipitate (black-brown 0.10 g) was removed by filtration. The precipitate formed by adding 10 ml of hexane to the filtrate (0.01 g of yellow-brown) was added for 2 hours. It was later filtered off. Further, similarly, 20 ml of hexane was added and the precipitate was removed to remove the precipitate (ocher 0.02 g), and the filtrate was concentrated to about 2 ml. This concentrated liquid was allowed to stand for 3 days to obtain 0.15 g of a pale yellow precipitate. mp is 157-159
° C. In this synthesis, the raw materials differ depending on the type of R, but the method is the same.
【００１７】次に、本発明に用いられるカルバゾール誘
導体の第３の系統は、Next, a third carbazole derivative used in the present invention is:
【化２８】 で示される重合体であり、その合成方法は以下に示す
が、現在のところ、この合成工程による合成方法の他に
前記重合体は合成されないことが明らかになった。即
ち、前記カルバゾール誘導体の重合体の合成方法も新規
な合成方法といえる。Embedded image The synthesis method is shown below, but at present, it has been found that the polymer is not synthesized other than the synthesis method by this synthesis step. That is, the method of synthesizing the polymer of the carbazole derivative can be said to be a novel synthesis method.
【００１８】このカルバゾール誘導体の重合体の合成方
法は、以下に示す４つの合成工程を経て合成される。そ
れを記載すると、The method of synthesizing the polymer of the carbazole derivative is performed through the following four synthesis steps. To state it,
【化２９】 Embedded image
【００１９】この合成方法の第一の工程（）では、ジ
エチルエーテル溶媒下でＬｉＢＨ4を使用してケトンの
還元を行っているが、溶媒としてはジエチルエーテルに
限らず、又還元剤としてもＬｉＢＨ4 に限られたもので
はない。In the first step () of this synthesis method, the ketone is reduced using LiBH 4 in a diethyl ether solvent, but the solvent is not limited to diethyl ether, and LiBH is also used as a reducing agent. It is not limited to four .
【００２０】第二の工程（）では、得られた化合物
（１）とカルバゾールとを前記条件下で反応させ、化合
物（２）を合成させる。このときの溶媒としてｏ−ジク
ロルベンゼンを用いているが、ニトロベンゼンを使用し
てもよい。In the second step (), the obtained compound (1) is reacted with carbazole under the above conditions to synthesize compound (2). Although o-dichlorobenzene is used as the solvent at this time, nitrobenzene may be used.
【００２１】第三の工程（）では、得られた化合物
（２）をベンゼン溶媒下、ｐ−トルエンスルフォン酸を
触媒とし、脱水素を行い、カルバゾール化合物のビニル
誘導体（３）を合成させる。In the third step (), the obtained compound (2) is dehydrogenated in a benzene solvent using p-toluenesulfonic acid as a catalyst to synthesize a vinyl derivative (3) of a carbazole compound.
【００２２】そして第四の工程（）では、得られたカ
ルバゾールのビニル誘導体（３）を重合させ、目的の重
合体を得るのであるが、溶媒としてトルエンを使用し、
ＡＩＢＮを重合開始剤として使用しているが、溶媒とし
てはトルエンに限られるものではなく、重合開始剤もＡ
ＩＢＮに限られるものではない。In the fourth step (), the obtained vinyl derivative of carbazole (3) is polymerized to obtain the desired polymer. Toluene is used as a solvent.
AIBN is used as a polymerization initiator, but the solvent is not limited to toluene.
It is not limited to IBN.
【００２３】この化合物は重合体であり、蒸着法でな
く、スピナー法によりホール輸送層を作成できるので、
コスト的にも充分メリットが出てくる。This compound is a polymer, and a hole transport layer can be formed by a spinner method instead of a vapor deposition method.
There are enough benefits in terms of cost.
【００２４】以上のように記載した第１〜第３の系統の
カルバゾール誘導体は窒素原子を通して電子が自由に動
くことができ、電子の局在化を妨げると共に融点が高
く、化合物の安定性が高く、ホール輸送層としての寿命
が長くなる。The carbazole derivatives of the first to third systems described above can freely move electrons through a nitrogen atom, hinder the localization of electrons, have a high melting point, and have high stability of the compound. As a result, the life as a hole transport layer is prolonged.
【００２５】[0025]
【実施例】実施例１ 合成法 （１）ジフェニルアミノカルバジルビフェニル（ＤＰＣ
ＢＰ）の合成EXAMPLES Example 1 Synthesis Method (1) Diphenylaminocarbazylbiphenyl (DPC
Synthesis of BP)
【化３０】 Embedded image
【００２６】ｉ．第一段階反応；４−ヨード−４’−ニ
トロビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた３００
ｍｌの三つ口フラスコの中へビフェニル５０ｇ（３２
４．２３ｍｍｏｌ）、ヨウ素２５ｇ（９８．５０ｍｍｏ
ｌ）を入れた。撹拌しながらオイルバスを用いて７０℃
まで加熱し、ビフェニルが溶解したところでその中へ硝
酸１２０ｍｌを滴下した。１００℃以下で還流し始めて
から２時間撹拌して反応させた。反応終了後、室温に戻
し、その後氷冷した。氷水１５０ｍｌで洗浄し、デカン
テーションした後、少量の温エタノールで洗浄し、ヌッ
チェを用いて吸引濾過した。そしてデシケーター中でポ
ンプで減圧し、乾燥させた。得られた固形物を１０００
ｍｌマイヤーへ入れ、少量の熱ベンゼンで洗い、デカン
テーションした。そこへベンゼン７００ｍｌを加えて加
熱し、沸騰したら濾過し、濾液を冷室で静置して再結晶
を行った。淡黄色針状結晶の４−ヨード−４’−ニトロ
ビフェニル３０ｇを得た。合成された本化合物の収率は
６４％であり、ｍ．ｐ．は２１５〜２２０℃であった。I. First step reaction; synthesis of 4-iodo-4'-nitrobiphenyl 300 equipped with mechanical stirrer and bulb cooler
50 g of biphenyl (32 g
4.23 mmol), iodine 25 g (98.50 mmol)
l) was added. 70 ° C using an oil bath while stirring
Until biphenyl was dissolved, and 120 ml of nitric acid was added dropwise thereto. After starting to reflux at a temperature of 100 ° C. or less, the mixture was stirred and reacted for 2 hours. After the completion of the reaction, the temperature was returned to room temperature, and then ice-cooled. After washing with 150 ml of ice water and decantation, washing with a small amount of warm ethanol was performed, and suction filtration was performed using a Nutsche. Then, the pressure was reduced by a pump in a desiccator and dried. The obtained solid material is 1000
The mixture was placed in a ml Meyer, washed with a small amount of hot benzene, and decanted. Thereto, 700 ml of benzene was added and heated. After boiling, the mixture was filtered and the filtrate was allowed to stand in a cold room for recrystallization. 30 g of 4-iodo-4′-nitrobiphenyl as pale yellow needles were obtained. The yield of the synthesized compound was 64%, and m.p. p. Was 215 to 220 ° C.
【００２７】ｉｉ．第二段階反応；４−カルバゾイル−
４’−ニトロビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた２００
ｍｌの四つ口フラスコの中へ４−ヨード−４’−ニトロ
ビフェニル３２ｇ（９８．４３ｍｍｏｌ）、カルバゾー
ル１５．６７ｇ（９３．７４ｍｍｏｌ）、１８−クラウ
ン−６−エーテル８．２６ｇ（３１．２５ｍｍｏｌ）、
Ｋ2ＣＯ3１３．６０ｇ（９８．４３ｍｍｏｌ）、Ｃｕ
０．９９２８ｇ（１５．６２ｍｍｏｌ）を入れた。そし
て、溶媒としてｏ−ジクロルベンゼン１００ｍｌを加
え、Ｎ2 気流下、シリコンオイルバスで１９０℃まで加
熱し、２４時間反応させた。反応終了後、オイルの温度
を８０℃程度に保ちながら反応混合物にベンゼン３０ｍ
ｌを加えた。まだ高温の状態のままでヌッチェを用いて
吸引濾過し、濾液及び残渣を得た。残渣をメタノールで
洗浄して乾燥させた後、ＴＨＦに溶かしてヌッチェを用
いて吸引濾過した。この濾液をエバポレーターで濃縮し
て黄色結晶５．６７ｇを得た。また、濾液をエバポレー
ターで濃縮し、そして得られた固形物をジエチルエーテ
ル、メタノールで洗浄した後、乾燥させた。ベンゼンで
再結晶を行い、黄色結晶２．７３ｇを得た。合成された
本化合物の収率は２３．４％であり、ｍ．ｐ．は２７４
〜２７９℃であった。Ii. Second step reaction; 4-carbazoyl-
Synthesis of 4'-nitrobiphenyl 200 with mechanical stirrer and bulb cooler
32 g (98.43 mmol) of 4-iodo-4'-nitrobiphenyl, 15.67 g (93.74 mmol) of carbazole, 8.26 g (31.25 mmol) of 18-crown-6-ether into a ml four-necked flask. ,
13.60 g (98.43 mmol) of K 2 CO 3 , Cu
0.9928 g (15.62 mmol) were charged. Then, 100 ml of o-dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicon oil bath under a stream of N 2 and reacted for 24 hours. After the completion of the reaction, while maintaining the oil temperature at about 80 ° C., 30 m of benzene was added to the reaction mixture.
1 was added. The filtrate was suction-filtered using a nutsche while the temperature was still high to obtain a filtrate and a residue. The residue was washed with methanol and dried, then dissolved in THF, and suction-filtered using Nutsche. The filtrate was concentrated by an evaporator to obtain 5.67 g of yellow crystals. Further, the filtrate was concentrated by an evaporator, and the obtained solid was washed with diethyl ether and methanol and then dried. Recrystallization from benzene gave 2.73 g of yellow crystals. The yield of the synthesized compound was 23.4%, m.p. p. Is 274
279 ° C.
【００２８】ｉｉｉ．第三段階反応；４−カルバゾイル
ビフェニルアミンの合成 メカニカルスターラーと球管冷却機を取り付けた５００
ｍｌの四つ口フラスコの中へ４−カルバゾイル−４’−
ニトロビフェニル５．００ｇ（１３．７０ｍｍｏｌ）、
パラジウム−活性炭素（Ｐｄ１０％）２．００ｇを入れ
た。そして溶媒としてＴＨＦ２５０ｍｌ、エタノール５
０ｍｌを加え、撹拌しながらウォーターバスで５０℃ま
で加熱し、ヒドラジン１水和物３４．２ｍｌ（６８３．
２ｍｍｏｌ）を滴下した。さらに加熱し、７０〜８０℃
で２時間撹拌して反応させた。反応終了後、氷冷して０
℃でヌッチェを用いて吸引濾過した。濾液をエバポレー
ターで濃縮し、得られた固形物をメタノールで洗浄した
後、ヌッチェを用いて吸引濾過した。そしてデシケータ
ー中でポンプで減圧し乾燥させ、淡黄色の固形物４．３
０ｇを得た。合成された本化合物の収率は９３．７％で
あり、ｍ．ｐ．は２１８〜２２０℃であった。Iii. Third step reaction; synthesis of 4-carbazoylbiphenylamine 500 equipped with mechanical stirrer and bulb cooler
4-carbazoyl-4′- into a 4-neck four-neck flask.
5.00 g (13.70 mmol) of nitrobiphenyl,
2.00 g of palladium-activated carbon (Pd10%) was added. Then, THF 250 ml, ethanol 5
Then, the mixture was heated to 50 ° C. with stirring in a water bath, and 34.2 ml of hydrazine monohydrate (683.
2 mmol) was added dropwise. Further heating, 70-80 ° C
For 2 hours. After the reaction is completed, cool on ice
Suction filtration was carried out using a Nutsche at ° C. The filtrate was concentrated with an evaporator, and the obtained solid was washed with methanol and filtered with suction using a Nutsche. Then, the mixture was dried under reduced pressure by a pump in a desiccator to obtain a light yellow solid 4.3.
0 g was obtained. The yield of the synthesized compound was 93.7%, and m.p. p. Was 218 to 220 ° C.
【００２９】ｉｖ．第四段階反応；ジフェニルアミノカ
ルバジルビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた１００
ｍｌの四つ口フラスコの中へ４−カルバゾイルビフェニ
ルアミン４．２９ｇ（１２．８３ｍｍｏｌ）、ヨードベ
ンゼン６．５４ｇ（３２．０７ｍｍｏｌ）、１８−クラ
ウン−６−エーテル１．１３ｇ（４．２７６ｍｍｏ
ｌ）、Ｋ2ＣＯ3３．９０ｇ（１３．４８ｍｍｏｌ）、Ｃ
ｕ０．１３５９ｇ（２．１３８ｍｍｏｌ）を入れた。そ
して、溶媒としてｏ−ジクロルベンゼン３５ｍｌを加
え、Ｎ2 気流下、シリコンオイルバスで１９０℃まで加
熱し、２４時間反応させた。反応終了後、オイルの温度
を８０℃程度に保ちながら反応混合物にベンゼン１０ｍ
ｌを加えた。まだ高温の状態のままでヌッチェを用いて
吸引濾過した。濾液をエバポレーターで濃縮し、得られ
た固形物をメタノールで洗浄した後、乾燥させた。それ
をシリカゲルカラム（ワコーゲルＣ−２００，溶媒ベン
ゼン）にかけ、分画した。薄層クロマトグラフィーで検
索し、目的分をエバポレーターで濃縮し、さらに真空乾
燥を行い、淡緑色の固形物１．３７ｇを得た。このうち
０．３６ｇを昇華法で精製し、淡黄色の固形物０．２１
ｇを得た。 収率・・・・・・・・・・・・・・・・・１２．８％ ｍ．ｐ．・・・・・・・・・・・・・・・２０２〜２０７℃ Ｔｇ・・・・・・・・・・・・・・・・・８３℃ ＩＲ・・・・・・・・・・・・・・・・・図２参照 1Ｈ−ＮＭＲ（ＣＤＣｌ3）・・・・・・・図３参照Iv. Fourth step reaction: synthesis of diphenylaminocarbazylbiphenyl 100 equipped with mechanical stirrer and bulb cooler
4.29 g (12.83 mmol) of 4-carbazoylbiphenylamine, 6.54 g (32.07 mmol) of iodobenzene, 1.13 g of 18-crown-6-ether (4.276 mmol) were placed in a four-neck four-neck flask.
l), 3.90 g (13.48 mmol) of K 2 CO 3 , C
0.1359 g (2.138 mmol) of u. Then, 35 ml of o-dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicon oil bath under a stream of N 2 and reacted for 24 hours. After the completion of the reaction, while maintaining the oil temperature at about 80 ° C, 10 m of benzene was added to the reaction mixture.
1 was added. While still at a high temperature, suction filtration was performed using a Nutsche. The filtrate was concentrated with an evaporator, and the obtained solid was washed with methanol and dried. It was applied to a silica gel column (Wakogel C-200, solvent benzene) and fractionated. The target was concentrated by an evaporator and further dried under vacuum to obtain 1.37 g of a pale green solid. Of these, 0.36 g was purified by a sublimation method to obtain a pale yellow solid 0.21 g.
g was obtained. Yield 12.8% m.p. p.・ ・ ・ ・ ・ ・ ・ 202-207 ℃ Tg ・ ・ ・ ・ ・ ・ 83 ℃ IR ・ ・ ・ ・ ・ ・ ・ ・ ・... See FIG. 2 1 H-NMR (CDCl 3 ).
【００３０】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【化３１】 Embedded image
【００３１】（２）４−カルバゾイル−４’−ナフチル
フェニルビフェニルジアミン（ＣＮＰＢ）の合成(2) Synthesis of 4-carbazoyl-4'-naphthylphenylbiphenyldiamine (CNPB)
【化３２】 Embedded image
【００３２】ｉ．第一段階反応；４−ヨード−４’−カ
ルバゾイルビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた２００
ｍｌの四つ口フラスコの中へジヨードビフェニル２５ｇ
（６１．５８ｍｍｏｌ）、カルバゾール９．８０６ｇ
（５８．６４ｍｍｏｌ）、１８−クラウン−６−エーテ
ル５．１６７ｇ（１９．５５ｍｍｏｌ）、Ｋ2ＣＯ3８．
５１０ｇ（６１．５８ｍｍｏｌ）、Ｃｕ０．６２１ｇ
（９．７７４ｍｍｏｌ）を入れた。そして、溶媒として
ｏ−ジクロルベンゼン１２０ｍｌを加え、Ｎ2 気流下、
シリコンオイルバスで１９０℃まで加熱し、２４時間反
応させた。反応終了後、オイルの温度を８０℃程度に保
ちながら反応混合物にベンゼン３０ｍｌを加えた。まだ
高温の状態のままでヌッチェを用いて吸引濾過した。濾
液をエバポレーターで濃縮し、そして得られた固形物を
ジエチルエーテル、アセトンで洗浄した後、固形物をベ
ンゼンに完全に溶解し、自然濾過した。濾液をエバポレ
ーターで濃縮し、再び少量のベンゼンを加えて加熱した
後、室温で放置し、４０℃程度になったらヌッチェを用
いて吸引濾過し、白色の固形物７．２０ｇを得た。合成
された本化合物の収率は２６．３％であり、ｍ．ｐ．は
２６９〜２７１℃、Ｔｇは１２３℃であった。I. First step reaction; synthesis of 4-iodo-4'-carbazoylbiphenyl 200 equipped with mechanical stirrer and bulb cooler
25 g of diiodobiphenyl into a 4 ml four-necked flask
(61.58 mmol), 9.806 g of carbazole
(58.64 mmol), 5.167 g (19.55 mmol) of 18-crown-6-ether, K 2 CO 3 8.
510 g (61.58 mmol), Cu 0.621 g
(9.774 mmol). Then, 120 ml of o-dichlorobenzene was added as a solvent, and under a stream of N 2 ,
The mixture was heated to 190 ° C. in a silicone oil bath and reacted for 24 hours. After the reaction was completed, 30 ml of benzene was added to the reaction mixture while maintaining the temperature of the oil at about 80 ° C. While still at a high temperature, suction filtration was performed using a Nutsche. The filtrate was concentrated by an evaporator, and the obtained solid was washed with diethyl ether and acetone. Then, the solid was completely dissolved in benzene and subjected to gravity filtration. The filtrate was concentrated with an evaporator, added again with a small amount of benzene, heated, and allowed to stand at room temperature. When the temperature reached about 40 ° C., suction filtration was performed using a Nutsche to obtain 7.20 g of a white solid. The yield of the synthesized compound was 26.3%, m.p. p. Was 269 to 271 ° C and Tg was 123 ° C.
【００３３】ｉｉ．第二段階反応；ＣＮＰＢの合成 メカニカルスターラーと球管冷却機を取り付けた１００
ｍｌの四つ口フラスコの中へ４−ヨード−４’−カルバ
ゾイルビフェニル５．００ｇ（１１．２４ｍｍｏｌ）、
Ｎ−フェニル−１−ナフチルアミン（α−）２．９６ｇ
（１３．４８ｍｍｏｌ）、１８−クラウン−６−エーテ
ル０．４９ｇ（１．８７ｍｍｏｌ）、Ｋ 2 ＣＯ3 １．８
６ｇ（１３．４８ｍｍｏｌ）、Ｃｕ０．２３８ｇ（３．
７５ｍｍｏｌ）を入れた。そして、溶媒としてｏ−ジク
ロルベンゼン２５ｍｌを加え、Ｎ 2 気流下、シリコンオ
イルバスで１９０℃まで加熱し、２４時間反応させた。
反応終了後、オイルの温度を８０℃程度に保ちながら反
応混合物にベンゼン１０ｍｌを加えた。まだ高温の状態
のままでヌッチェを用いて吸引濾過した。濾液をエバポ
レーターで濃縮し、得られた固形物をメタノールで洗浄
した後、乾燥させた。それをシリカゲルカラム（ワコー
ゲルＣ−２００，溶媒ベンゼン：ヘキサン＝１：１）に
かけ、分画した。薄層クロマトグラフィーで検索し、目
的分をエバポレーターで濃縮し、さらに真空乾燥を行
い、黄色の固形物０．８１ｇを得た。 収率・・・・・・・・・・・・・・・・・１３．４６％ ｍ．ｐ．・・・・・・・・・・・・・・・１４０〜１４５℃ Ｔｇ・・・・・・・・・・・・・・・・・１０３℃ ＩＲ・・・・・・・・・・・・・・・・・図４参照 1Ｈ−ＮＭＲ（ＣＤＣｌ3）・・・・・・・図５参照Ii. Second step reaction; synthesis of CNPB 100 equipped with mechanical stirrer and bulb cooler
4-iodo-4'-carba into a 4 ml four-neck flask
5.00 g (11.24 mmol) of zoylbiphenyl,
2.96 g of N-phenyl-1-naphthylamine (α-)
(13.48 mmol), 18-crown-6-ate
0.49 g (1.87 mmol) of K TwoCOThree1.8
6 g (13.48 mmol), Cu 0.238 g (3.
75 mmol). And o-dic as a solvent.
Add 25 ml of rolbenzene and add N TwoUnder airflow, silicon
The mixture was heated to 190 ° C. in an ir bath and reacted for 24 hours.
After the reaction is complete, keep the oil temperature at
10 ml of benzene was added to the reaction mixture. Still hot
The mixture was subjected to suction filtration using a Nutsche as it was. Evaporate the filtrate
And the resulting solid is washed with methanol.
And then dried. Use it on a silica gel column (Wako
Gel C-200, solvent benzene: hexane = 1: 1)
And fractionated. Search by thin layer chromatography
The target is concentrated with an evaporator and dried in vacuum.
0.81 g of a yellow solid was obtained. Yield 13.46% m.p. p.・ ・ ・ ・ ・ ・ ・ 140 ～ 145 ℃ Tg ・ ・ ・ ・ ・ ・ ・ ・ ・ 103 ℃ IR ・ ・ ・ ・ ・ ・ ・ ・ ・..... see Fig. 41H-NMR (CDClThree) ······ See Fig. 5
【００３４】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【化３３】 Embedded image
【００３５】（３）ジカルバゾイルアゾベンゼン（ＤＣ
ＡＢ）の合成(3) Dicarbazoylazobenzene (DC
Synthesis of AB)
【化３４】 Embedded image
【００３６】ｉ．第一段階反応；４，４’−ジヨードア
ゾベンゼンの合成 メカニカルスターラーと塩化カルシウム管を取り付けた
３００ｍｌ三つ口フラスコの中へ氷酢酸９０ｍｌに溶解
させた過ホウ酸ナトリウム四水和物１４．２５ｇ（９
２．５９ｍｍｏｌ）を入れ、氷酢酸９０ｍｌに溶解させ
たｐ−ヨードアニリン１０ｇ（４５．６６ｍｍｏｌ）を
加えた。そしてオイルバスで４５〜５０℃まで加熱し、
３時間撹拌して反応させた。反応終了後、ヌッチェを用
いて吸引濾過し、薄茶色の４，４’−ジヨードアゾベン
ゼン６．０２ｇを得た。合成された本化合物の収率は３
２．５％であり、ｍ．ｐ．は２４５〜２４８℃であっ
た。I. First step reaction; synthesis of 4,4'-diiodoazobenzene 14.25 g of sodium perborate tetrahydrate dissolved in 90 ml of glacial acetic acid into a 300 ml three-necked flask equipped with a mechanical stirrer and a calcium chloride tube (9
2.59 mmol) was added, and 10 g (45.66 mmol) of p-iodoaniline dissolved in 90 ml of glacial acetic acid was added. And heat to 45-50 ° C in an oil bath,
The mixture was reacted by stirring for 3 hours. After completion of the reaction, suction filtration was performed using a Nutsche to obtain 6.02 g of light brown 4,4'-diiodoazobenzene. The yield of the synthesized compound is 3
2.5%, m.p. p. Was 245-248 ° C.
【００３７】ｉｉ．第二段階反応；ジカルバゾイルアゾ
ベンゼンの合成 メカニカルスターラーと球管冷却機を取り付けた１００
ｍｌの四つ口フラスコの中へ４，４’−ジヨードアゾベ
ンゼン５．３５ｇ（１２．３２ｍｍｏｌ）、カルバゾー
ル４．３３ｇ（２５．８６ｍｍｏｌ）、１８−クラウン
−６−エーテル１．０８６ｇ（４．１２ｍｍｏｌ）、Ｋ
2ＣＯ3３．５７４ｇ（２５．８６ｍｍｏｌ）、Ｃｕ０．
１３２ｇ（２．０８ｍｍｏｌ）を入れた。そして、溶媒
としてｏ−ジクロルベンゼン３０ｍｌを加え、Ｎ2 気流
下、シリコンオイルバスで１９０℃まで加熱し、２４時
間撹拌して反応させた。反応終了後、オイルの温度を８
０℃程度に保ちながら反応混合物にベンゼン１０ｍｌを
加えた。まだ高温の状態のままでヌッチェを用いて吸引
濾過した。濾液をエバポレーターで濃縮し、そして得ら
れた固形物をジエチルエーテル、アセトンで洗浄した
後、ベンゼンで再結晶した後、真空乾燥させ、橙色の固
形物４．００ｇを得た。 収率・・・・・・・・・・・・・・・・・６３．４％ ｍ．ｐ．・・・・・・・・・・・・・・・２９１〜２９３℃ ＩＲ・・・・・・・・・・・・・・・・・図６参照 1Ｈ−ＮＭＲ（ＣＤＣｌ3）・・・・・・・図７参照Ii. Second step reaction; synthesis of dicarbazoyl azobenzene 100 equipped with mechanical stirrer and bulb cooler
5.4 g (12.32 mmol) of 4,4′-diiodoazobenzene, 4.33 g (25.86 mmol) of carbazole, 1.086 g (4.12 mmol) of 18-crown-6-ether in a four-necked flask ), K
3.574 g (25.86 mmol) 2 CO 3 , Cu 0.
132 g (2.08 mmol) were charged. Then, 30 ml of o-dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicon oil bath under a stream of N 2 and reacted by stirring for 24 hours. After the reaction is completed, raise the oil temperature to 8
While maintaining the temperature at about 0 ° C., 10 ml of benzene was added to the reaction mixture. While still at a high temperature, suction filtration was performed using a Nutsche. The filtrate was concentrated by an evaporator, and the obtained solid was washed with diethyl ether and acetone, recrystallized from benzene, and dried in vacuo to obtain 4.00 g of an orange solid. Yield 63.4% m.p. p. ········· 291 to 293 ° C IR ········· Refer to FIG. 6 1 H-NMR (CDCl 3 ) ..... see Fig. 7
【００３８】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【化３５】 Embedded image
【００３９】（４）ジキシリルアミノカルバジルビフェ
ニル（ＤＸＣＢＰ）の合成(4) Synthesis of dixylylaminocarbazylbiphenyl (DXCBP)
【化３６】 Embedded image
【００４０】ｉ．第一段階反応；４−ヨード−４’−ニ
トロビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた３００
ｍｌの三つ口フラスコの中へビフェニル５０ｇ（３２
４．２３ｍｍｏｌ）、ヨウ素２５ｇ（９８．５０ｍｍｏ
ｌ）を入れた。撹拌しながらオイルバスを用いて７０℃
まで加熱し、ビフェニルが溶解したところでその中へ硝
酸１２０ｍｌを滴下した。１００℃以下で還流し始めて
から２時間撹拌して反応させた。反応終了後、室温に戻
し、その後氷冷した。氷水１５０ｍｌで洗浄し、デカン
テーションした後、少量の温エタノールで洗浄し、ヌッ
チェを用いて吸引濾過した。そしてデシケーター中でポ
ンプで減圧し、乾燥させた。得られた固形物を１０００
ｍｌマイヤーへ入れ、少量の熱ベンゼンで洗い、デカン
テーションした。そこへベンゼン７００ｍｌを加えて加
熱し、沸騰したら濾過し、濾液を冷室で静置して再結晶
を行った。淡黄色針状結晶の４−ヨード−４’−ニトロ
ビフェニル３０ｇを得た。合成された本化合物の収率は
６４％であり、ｍ．ｐ．は２１５〜２２０℃であった。I. First step reaction; synthesis of 4-iodo-4'-nitrobiphenyl 300 equipped with mechanical stirrer and bulb cooler
50 g of biphenyl (32 g
4.23 mmol), iodine 25 g (98.50 mmol)
l) was added. 70 ° C using an oil bath while stirring
Until biphenyl was dissolved, and 120 ml of nitric acid was added dropwise thereto. After starting to reflux at a temperature of 100 ° C. or less, the mixture was stirred and reacted for 2 hours. After the completion of the reaction, the temperature was returned to room temperature, and then ice-cooled. After washing with 150 ml of ice water and decantation, washing with a small amount of warm ethanol was performed, and suction filtration was performed using a Nutsche. Then, the pressure was reduced by a pump in a desiccator and dried. The obtained solid material is 1000
The mixture was placed in a ml Meyer, washed with a small amount of hot benzene, and decanted. Thereto, 700 ml of benzene was added and heated. After boiling, the mixture was filtered and the filtrate was allowed to stand in a cold room for recrystallization. 30 g of 4-iodo-4′-nitrobiphenyl as pale yellow needles were obtained. The yield of the synthesized compound was 64%, and m.p. p. Was 215 to 220 ° C.
【００４１】ｉｉ．第二段階反応；４−カルバゾイル−
４’−ニトロビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた２００
ｍｌの四つ口フラスコの中へ４−ヨード−４’−ニトロ
ビフェニル３２ｇ（９８．４３ｍｍｏｌ）、カルバゾー
ル１５．６７ｇ（９３．７４ｍｍｏｌ）、１８−クラウ
ン−６−エーテル８．２６ｇ（３１．２５ｍｍｏｌ）、
Ｋ2ＣＯ3１３．６０ｇ（９８．４３ｍｍｏｌ）、Ｃｕ
０．９９２８ｇ（１５．６２ｍｍｏｌ）を入れた。そし
て、溶媒としてｏ−ジクロルベンゼン１００ｍｌを加
え、Ｎ2 気流下、シリコンオイルバスで１９０℃まで加
熱し、２４時間反応させた。反応終了後、オイルの温度
を８０℃程度に保ちながら反応混合物にベンゼン３０ｍ
ｌを加えた。まだ高温の状態のままでヌッチェを用いて
吸引濾過し、濾液及び残渣を得た。残渣をメタノールで
洗浄して乾燥させた後、ＴＨＦに溶かしてヌッチェを用
いて吸引濾過した。この濾液をエバポレーターで濃縮し
て黄色結晶５．６７ｇを得た。また、濾液をエバポレー
ターで濃縮し、そして得られた固形物をジエチルエーテ
ル、メタノールで洗浄した後、乾燥させた。ベンゼンで
再結晶を行い、黄色結晶２．７３ｇを得た。合成された
本化合物の収率は２３．４％であり、ｍ．ｐ．は２７４
〜２７９℃であった。Ii. Second step reaction; 4-carbazoyl-
Synthesis of 4'-nitrobiphenyl 200 with mechanical stirrer and bulb cooler
32 g (98.43 mmol) of 4-iodo-4'-nitrobiphenyl, 15.67 g (93.74 mmol) of carbazole, 8.26 g (31.25 mmol) of 18-crown-6-ether into a ml four-necked flask. ,
13.60 g (98.43 mmol) of K 2 CO 3 , Cu
0.9928 g (15.62 mmol) were charged. Then, 100 ml of o-dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicon oil bath under a stream of N 2 and reacted for 24 hours. After the completion of the reaction, while maintaining the oil temperature at about 80 ° C., 30 m of benzene was added to the reaction mixture.
1 was added. The filtrate was suction-filtered using a nutsche while the temperature was still high to obtain a filtrate and a residue. The residue was washed with methanol and dried, then dissolved in THF, and suction-filtered using Nutsche. The filtrate was concentrated by an evaporator to obtain 5.67 g of yellow crystals. Further, the filtrate was concentrated by an evaporator, and the obtained solid was washed with diethyl ether and methanol and then dried. Recrystallization from benzene gave 2.73 g of yellow crystals. The yield of the synthesized compound was 23.4%, m.p. p. Is 274
279 ° C.
【００４２】ｉｉｉ．第三段階反応；４−カルバゾイル
ビフェニルアミンの合成 メカニカルスターラーと球管冷却機を取り付けた５００
ｍｌの四つ口フラスコの中へ４−カルバゾイル−４’−
ニトロビフェニル５．００ｇ（１３．７０ｍｍｏｌ）、
パラジウム−活性炭素（Ｐｄ１０％）２．００ｇを入れ
た。そして溶媒としてＴＨＦ２５０ｍｌ、エタノール５
０ｍｌを加え、撹拌しながらウォーターバスで５０℃ま
で加熱し、ヒドラジン１水和物３４．２ｍｌ（６８３．
２ｍｍｏｌ）を滴下した。さらに加熱し、７０〜８０℃
で２時間撹拌して反応させた。反応終了後、氷冷して０
℃でヌッチェを用いて吸引濾過した。濾液をエバポレー
ターで濃縮し、得られた固形物をメタノールで洗浄した
後、ヌッチェを用いて吸引濾過した。そしてデシケータ
ー中でポンプで減圧し乾燥させ、淡黄色の固形物４．３
０ｇを得た。合成された本化合物の収率は９３．７％で
あり、ｍ．ｐ．は２１８〜２２０℃であった。Iii. Third step reaction; synthesis of 4-carbazoylbiphenylamine 500 equipped with mechanical stirrer and bulb cooler
4-carbazoyl-4′- into a 4-neck four-neck flask.
5.00 g (13.70 mmol) of nitrobiphenyl,
2.00 g of palladium-activated carbon (Pd10%) was added. Then, THF 250 ml, ethanol 5
Then, the mixture was heated to 50 ° C. with stirring in a water bath, and 34.2 ml of hydrazine monohydrate (683.
2 mmol) was added dropwise. Further heating, 70-80 ° C
For 2 hours. After the reaction is completed, cool on ice
Suction filtration was carried out using a Nutsche at ° C. The filtrate was concentrated with an evaporator, and the obtained solid was washed with methanol and filtered with suction using a Nutsche. Then, the mixture was dried under reduced pressure by a pump in a desiccator to obtain a light yellow solid 4.3.
0 g was obtained. The yield of the synthesized compound was 93.7%, and m.p. p. Was 218 to 220 ° C.
【００４３】ｉｖ．第四段階反応；ジキシリルアミノカ
ルバジルビフェニルの合成 メカニカルスターラーと球管冷却機を取り付けた１００
ｍｌの四つ口フラスコの中へ４−カルバゾイルビフェニ
ルアミン４．２９ｇ（１２．８３ｍｍｏｌ）、ヨードキ
シレン７．４４ｇ（３２．０７ｍｍｏｌ）、１８−クラ
ウン−６−エーテル１．１３ｇ（４．２７６ｍｍｏ
ｌ）、Ｋ2ＣＯ3３．９０ｇ（１３．４８ｍｍｏｌ）、Ｃ
ｕ０．１３５９ｇ（２．１３８ｍｍｏｌ）を入れた。そ
して、溶媒としてｏ−ジクロルベンゼン３５ｍｌを加
え、Ｎ2 気流下、シリコンオイルバスで１９０℃まで加
熱し、２４時間反応させた。反応終了後、オイルの温度
を８０℃程度に保ちながら反応混合物にベンゼン１０ｍ
ｌを加えた。まだ高温の状態のままでヌッチェを用いて
吸引濾過した。濾液をエバポレーターで濃縮し、得られ
た固形物をメタノールで洗浄した後、乾燥させた。それ
をシリカゲルカラム（ワコーゲルＣ−２００，溶媒ベン
ゼン）にかけ、分画した。薄層クロマトグラフィーで検
索し、目的分をエバポレーターで濃縮し、さらに真空乾
燥を行い、淡黄色の固形物１．６９ｇを得た。このうち
０．３０ｇを昇華法で精製し、白色の固形物０．２４ｇ
を得た。 収率・・・・・・・・・・・・・・・・・２４．３％ ｍ．ｐ．・・・・・・・・・・・・・・・２２７℃ Ｔｇ・・・・・・・・・・・・・・・・・９９℃ ＩＲ・・・・・・・・・・・・・・・・・図８参照 1Ｈ−ＮＭＲ（ＣＤＣｌ3）・・・・・・・図９参照Iv. Fourth step reaction: Synthesis of dixylylaminocarbazylbiphenyl 100 equipped with mechanical stirrer and bulb cooler
4.29 g (12.83 mmol) of 4-carbazoylbiphenylamine, 7.44 g (32.07 mmol) of iodoxylene, 1.13 g of 18-crown-6-ether (4.276 mmol) were placed in a four-necked four-neck flask.
l), 3.90 g (13.48 mmol) of K 2 CO 3 , C
0.1359 g (2.138 mmol) of u. Then, 35 ml of o-dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicon oil bath under a stream of N 2 and reacted for 24 hours. After the completion of the reaction, while maintaining the oil temperature at about 80 ° C, 10 m of benzene was added to the reaction mixture.
1 was added. While still at a high temperature, suction filtration was performed using a Nutsche. The filtrate was concentrated with an evaporator, and the obtained solid was washed with methanol and dried. It was applied to a silica gel column (Wakogel C-200, solvent benzene) and fractionated. The target was concentrated by an evaporator and further dried under vacuum to obtain 1.69 g of a pale yellow solid. Of these, 0.30 g was purified by a sublimation method to obtain 0.24 g of a white solid.
I got Yield 24.3% m.p. p.・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 227 ℃ Tg ・ ・ ・ ・ ・ ・ ・ ・ ・ 99 ℃ IR ・ ・ ・ ・ ・ ・ ・····· See FIG. 8 1 H-NMR (CDCl 3 ) ····· See FIG.
【００４４】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【化３７】 Embedded image
【００４５】 有機ＥＬ素子の作成 （ａ）ＩＴＯ基板の洗浄 ５０ｍｍ×５０ｍｍＩＴＯ（インジウム−酸化スズ）コ
ート基板表面に付着している微粒子を完全に除去するた
めに、この基板をＴＨＦ中へ浸し、超音波を１０分間照
射した。 （ｂ）各種薄膜の作成 今回合成した化合物をホール輸送層とするため、洗浄済
みＩＴＯ基板上へ化合物をそれぞれ真空蒸着した。その
基板上へ電子輸送層としてアルミニウム錯体・Ａｌｑ３
を真空中で蒸着した。続けて陰極とするＡｌ−Ｌｉを真
空蒸着し図１０に示す有機ＥＬ素子を作成した。Preparation of Organic EL Element (a) Cleaning of ITO Substrate In order to completely remove fine particles adhering to the surface of a 50 mm × 50 mm ITO (indium-tin oxide) coated substrate, the substrate was immersed in THF, A sound wave was irradiated for 10 minutes. (B) Preparation of various thin films In order to use the compound synthesized this time as a hole transport layer, each compound was vacuum-deposited on a cleaned ITO substrate. Aluminum complex / Alq3 as electron transport layer on the substrate
Was deposited in vacuo. Subsequently, Al—Li as a cathode was vacuum-deposited to produce an organic EL device shown in FIG.
【００４６】 ＥＬ素子の輝度の測定 作成した有機ＥＬ素子のＩＴＯを陽極、Ａｌ−Ｌｉを陰
極として電圧を徐々に上昇させ輝度を測定し、それぞれ
の得られた最高輝度を求めた。尚、比較としてホール輸
送層に従来より使用されているＴＰＤ（Ｎ，Ｎ’−ジフ
ェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，
１−ビフェニル４，４’−ジアミン）を用いた。結果を
以下（表１）に示す。Measurement of Luminance of EL Element The luminance of the organic EL element thus prepared was measured by gradually increasing the voltage using ITO as an anode and Al-Li as a cathode, and the maximum luminance obtained for each was obtained. For comparison, TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1, which has been conventionally used for the hole transport layer,
1-biphenyl 4,4'-diamine) was used. The results are shown below (Table 1).
【表１】 [Table 1]
【００４７】実施例２ ジカルバゾール誘導体化合物の合成 （１）各種化合物の合成反応式Example 2 Synthesis of Dicarbazole Derivative Compound (1) Synthesis Scheme of Various Compounds
【化３８】 （２）各種化合物の融点Embedded image (2) Melting points of various compounds
【化３９】 Embedded image
【００４８】 有機ＥＬ素子の作成 前記実施例１に準じてＩＴＯ基板を洗浄し、合成した化
合物をホール輸送層とする有機ＥＬ素子を作成した。Preparation of Organic EL Device An ITO substrate was washed according to Example 1 to prepare an organic EL device using the synthesized compound as a hole transport layer.
【００４９】 ＥＬ素子の輝度の測定 作成した有機ＥＬ素子のＩＴＯを陽極、Ａｌ−Ｌｉを陰
極として電圧を徐々に上昇させ輝度を測定した。尚、比
較としてホール輸送層には従来より使用されているＴＰ
Ｄ（Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチ
ルフェニル）−１，１−ビフェニル４，４’−ジアミ
ン）を用いた。結果を図１１に示す。Measurement of Luminance of EL Element The luminance of the organic EL element thus prepared was measured by gradually increasing the voltage using ITO as an anode and Al—Li as a cathode. For comparison, TP conventionally used for the hole transport layer is used.
D (N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1-biphenyl4,4'-diamine) was used. The results are shown in FIG.
【００５０】実施例３ カルバゾール誘導体ポリマー化合物の合成 ｉ．第一段階反応；４−（１−ヒドロキシエチル）−
４’−ヨードベンゼンの合成 メカニカルスターラーと球管冷却機を取り付けた５００
ｍｌの三つ口フラスコの中へリチウムボロハイドライド
１．７７ｇ（８１．２８ｍｍｏｌ）、溶媒としてジエチ
ルエーテル２００ｍｌを入れた。氷水バス中で撹拌をし
ながらジエチルエーテル５０ｍｌに４−ヨードアセトフ
ェノン１０ｇ（４０．６４ｍｍｏｌ）を溶かした溶液を
滴下した。滴下終了後、オイルバスを用いて３５℃まで
加熱し、還流し始めてから２時間撹拌して反応させた。
反応終了後、室温に戻し、その後氷冷した。得られた溶
液を氷水２５０ｍｌ、１規定の塩酸水溶液２５０ｍｌ、
３％の炭酸水素ナトリウム水溶液２５０ｍｌ、蒸留水２
５０ｍｌの順で分液ロートを用いて洗浄した。得られた
溶液に硫酸ナトリウム２０ｇを加え一晩静置し脱水し
た。この溶液をエバポレーターで濃縮し、真空加熱乾燥
を３０℃で行い、白色結晶４−（１−ヒドロキシエチ
ル）−４’−ヨードベンゼン８．０２ｇを得た。Example 3 Synthesis of carbazole derivative polymer compound i. First step reaction; 4- (1-hydroxyethyl)-
Synthesis of 4'-iodobenzene 500 equipped with mechanical stirrer and bulb cooler
1.77 g (81.28 mmol) of lithium borohydride and 200 ml of diethyl ether as a solvent were placed in a three-necked flask having a capacity of 300 ml. While stirring in an ice water bath, a solution of 10 g (40.64 mmol) of 4-iodoacetophenone dissolved in 50 ml of diethyl ether was added dropwise. After completion of the dropwise addition, the mixture was heated to 35 ° C. using an oil bath, and stirred for 2 hours from the start of reflux to cause a reaction.
After the completion of the reaction, the temperature was returned to room temperature, and then ice-cooled. 250 ml of ice water, 250 ml of 1N hydrochloric acid aqueous solution,
250 ml of 3% aqueous sodium hydrogen carbonate solution, distilled water 2
Washing was performed using a separating funnel in the order of 50 ml. 20 g of sodium sulfate was added to the obtained solution, and the solution was left standing overnight to dehydrate. The solution was concentrated by an evaporator, and dried by heating under vacuum at 30 ° C. to obtain 8.02 g of white crystal 4- (1-hydroxyethyl) -4′-iodobenzene.
【００５１】ｉｉ．第二段階反応；９−（４−（１−ヒ
ドロキシエチル）フェニル）カルバゾールの合成 メカニカルスターラーと球管冷却管を取り付けた２００
ｍｌ三つ口フラスコの中へ４−（１−ヒドロキシエチ
ル）−４’−ヨードベンゼン１０．００ｇ（４０．３ｍ
ｍｏｌ）、カルバゾール６．１３ｇ（３６．６５ｍｍｏ
ｌ、１８−クラウン−６−エーテル３．２３ｇ（１２．
２１ｍｍｏｌ）、炭酸カリウム５．５７ｇ（４０．３１
ｍｍｏｌ）、銅０．３９ｇ（６．１１ｍｍｏｌ）を入れ
た。そして溶媒としてジクロルベンゼンを加え、Ｎ2 気
流中、シリコーンオイルバスで１９０℃まで加熱し、２
４時間撹拌して反応させた。反応終了後、高温の状態の
ままヌッチェを用いて吸引濾過し、黒色の濾液を得た。
得られた濾液を溶媒ベンゼン、ワコーゲル２００を用い
たカラムクロマトグラフィーにかけた。得られた溶液を
エバポレーターで濃縮、真空加熱乾燥を３０℃で行い、
褐色の結晶９−（４−（１−ヒドロキシエチル）フェニ
ル）カルバゾール３．１４ｇを得た。得られた上記合成
反応の化合物は、収率が８０％、ｍ．ｐ．が１３２℃で
あり、該化合物のＮＭＲチャートは図１２に示す。Ii. Second step reaction; synthesis of 9- (4- (1-hydroxyethyl) phenyl) carbazole 200 equipped with mechanical stirrer and bulb condenser
10.00 g (40.3 m) of 4- (1-hydroxyethyl) -4′-iodobenzene into a three-necked flask.
mol), 6.13 g (36.65 mmol) of carbazole
3.23 g of 1,18-crown-6-ether (12.
21 mmol), 5.57 g of potassium carbonate (40.31 g)
mmol) and 0.39 g (6.11 mmol) of copper. Then, dichlorobenzene was added as a solvent, and the mixture was heated to 190 ° C. in a silicone oil bath in an N 2 stream,
The mixture was reacted by stirring for 4 hours. After the completion of the reaction, suction filtration was carried out using a nutsche while maintaining the high temperature state, to obtain a black filtrate.
The obtained filtrate was subjected to column chromatography using the solvent benzene and Wakogel 200. The obtained solution was concentrated by an evaporator, and dried by heating under vacuum at 30 ° C.
3.14 g of brown crystalline 9- (4- (1-hydroxyethyl) phenyl) carbazole was obtained. The compound obtained in the above synthesis reaction had a yield of 80% and a m.p. p. Is 132 ° C., and the NMR chart of the compound is shown in FIG.
【００５２】ｉｉｉ．第三段階反応；４−カルバゾイル
スチレンの合成 メカニカルスターラーと球管冷却管を取り付けた５００
ｍｌ三つ口フラスコの中へｐ−トルエンスルホン酸０．
１８ｇ（１．０４ｍｍｏｌ）、溶媒としてベンゼン２５
０ｍｌを入れた。室温で撹拌しながらベンゼン５０ｍｌ
に３．００ｇ（１０．４３ｍｍｏｌ）を溶かした溶液を
滴下した。滴下終了後オイルバスを用いて８５℃まで加
熱し還流し始めてから１時間撹拌して反応させた。反応
終了後、室温に戻し、その後氷冷した。得られた溶液を
氷水２５０ｍｌ、３％の炭酸水素ナトリウム水溶液２５
０ｍｌ、蒸留水２５０ｍｌの順で分液ロートを用いて洗
浄した。得られた溶液に硫酸ナトリウム２０ｇを加え、
一晩静置し脱水した。得られた溶液に溶媒ベンゼン−ヘ
キサン（１：１）、ワコーゲル２００を用いたカラムク
ロマトグラフィーにかけた。得られた溶液をエバポレー
ターで濃縮し、真空加熱乾燥を３０℃で行い白色結晶４
−カルバゾイルスチレン０．５０ｇを得た。得られた上
記合成反応の化合物は、収率が１８％、融点が１１０℃
であり、該化合物のＮＭＲチャートは図１３に示す。Iii. Third step reaction; synthesis of 4-carbazoylstyrene 500 equipped with mechanical stirrer and bulb condenser
p-Toluenesulfonic acid into a 3-ml three-necked flask.
18 g (1.04 mmol), benzene 25 as a solvent
0 ml was charged. 50 ml of benzene with stirring at room temperature
The solution which melt | dissolved 3.00 g (10.43 mmol) in was added dropwise. After the completion of the dropwise addition, the mixture was heated to 85 ° C. using an oil bath and refluxed. After the completion of the reaction, the temperature was returned to room temperature, and then ice-cooled. The obtained solution was mixed with 250 ml of ice water and a 25% aqueous solution of 3% sodium hydrogen carbonate.
It wash | cleaned using the separating funnel in order of 0 ml and distilled water 250ml. 20 g of sodium sulfate was added to the obtained solution,
It was left overnight and dehydrated. The obtained solution was subjected to column chromatography using a solvent benzene-hexane (1: 1) and Wakogel 200. The obtained solution was concentrated by an evaporator, and dried by heating under vacuum at 30 ° C. to obtain white crystals 4.
-0.50 g of carbazoylstyrene was obtained. The obtained compound of the above synthesis reaction has a yield of 18% and a melting point of 110 ° C.
The NMR chart of the compound is shown in FIG.
【００５３】ｉｖ．第四段階反応（その１）；ポリ（４
−カルバゾイルスチレン）ラジカル重合 ４−カルバゾイルスチレン０．２ｇ（０．７ｍｍｏ
ｌ）、重合開始剤としてＡＩＢＮ２．４３ｍｇ（０．０
１ｍｍｏｌ）をガラス管に入れた。このガラス管をドラ
イアイス−メタノールバス中で冷却し、真空状態にし
た。窒素置換を３回行い、酸素を完全に除去した後、ガ
ラス管を封管し８０℃で２０時間振とうして反応させ
た。反応終了後、室温に戻し、その後氷冷した。開管し
た後、得られた溶液をメタノール中に投入し白色の沈殿
物を得た。この沈殿物をジクロロメタンに溶解させメタ
ノールで沈殿させた。この再沈殿を３回繰り返した後、
白色結晶ポリ（４−Ｎ−カルバゾイルスチレン）０．１
１ｇを得た。得られた重合体は、収率５５％、ｍ．ｐ．
２５０℃以上、Ｉｐ（イオン化ポテンシャル）６．０５
ｅＶ、軟化点２１０℃であり、該重合体のＮＭＲチャー
トは図１４に示す。Iv. Fourth step reaction (1); Poly (4)
-Carbazoyl styrene) radical polymerization 4-carbazoyl styrene 0.2 g (0.7 mmol)
l), 2.43 mg (0.00.0%) of AIBN as a polymerization initiator
1 mmol) was placed in a glass tube. The glass tube was cooled in a dry ice-methanol bath and evacuated. After purging with nitrogen three times and completely removing oxygen, the glass tube was sealed and reacted by shaking at 80 ° C. for 20 hours. After the completion of the reaction, the temperature was returned to room temperature, and then ice-cooled. After opening the tube, the obtained solution was poured into methanol to obtain a white precipitate. This precipitate was dissolved in dichloromethane and precipitated with methanol. After repeating this reprecipitation three times,
White crystalline poly (4-N-carbazoylstyrene) 0.1
1 g was obtained. The obtained polymer had a yield of 55% and a m.p. p.
250 ° C. or higher, Ip (ionization potential) 6.05
eV and softening point are 210 ° C., and the NMR chart of the polymer is shown in FIG.
【００５４】ｖ．第四段階反応（その２）；ポリ（４−
カルバゾイルスチレン）カチオン重合 １０ｍｌのなす型フラスコに４−カルバゾイルスチレン
０．２ｇ（０．７ｍｍｏｌ）、溶媒としてジクロロメタ
ン２ｍｌを入れた。このなす型フラスコにダブルゴム栓
をし、完全に密封した後、ドライアイス−メタノールバ
スを用いて−５０℃まで冷却した。その後１ｍｌの注射
針にごく少量の３フッ化ホウ素−ジメチルエーテルコン
プレックスを入れ、ダブルゴム栓に突き刺し溶液中へ注
入した。その後室温にまでゆっくりと戻した後、溶液を
メタノール中に投入し白色の沈殿物を得た。この沈殿物
をジクロロメタンに溶解させメタノールで沈殿させた。
この再沈殿を３回繰り返した後白色ポリ（４−カルバゾ
イルスチレン）０．１５ｇを得た。得られた重合体は、
収率７５％、Ｉｐ（イオン化ポテンシャル）６．０１ｅ
Ｖ、ｍ．ｐ．２５０℃以上であった。V. Fourth step reaction (No. 2); poly (4-
(Carbazoylstyrene) Cationic Polymerization 0.2 g (0.7 mmol) of 4-carbazoylstyrene and 2 ml of dichloromethane as a solvent were placed in a 10-ml eggplant type flask. The eggplant-shaped flask was covered with a double rubber stopper, completely sealed, and then cooled to -50 ° C using a dry ice-methanol bath. Thereafter, a very small amount of boron trifluoride-dimethyl ether complex was put into a 1 ml injection needle, pierced into a double rubber stopper, and injected into the solution. After slowly returning to room temperature, the solution was poured into methanol to obtain a white precipitate. This precipitate was dissolved in dichloromethane and precipitated with methanol.
After repeating this reprecipitation three times, 0.15 g of white poly (4-carbazoylstyrene) was obtained. The resulting polymer is
Yield 75%, Ip (ionization potential) 6.01e
V, m. p. It was 250 ° C or higher.
【００５５】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【化４０】 Embedded image
【００５６】 有機ＥＬ素子の作成 （ａ）ＩＴＯ基板の洗浄 ５０ｍｍ×５０ｍｍＩＴＯ（インジウム−酸化スズ）コ
ート基板表面に付着している微粒子を完全に除去するた
めに、この基板をＴＨＦ中へ浸し、超音波を１０分間照
射した。 （ｂ）薄膜の作成 合成したポリマーをホール輸送層とするため、洗浄済み
ＩＴＯ基板上へポリマースピナー法にて薄膜を作成し、
その基板上へ電子輸送層としてアルミニウム錯体・Ａｌ
ｑ３を真空中で蒸着した。続けて陰極とするＡｌ−Ｌｉ
を真空蒸着し有機ＥＬ素子を作成した。Preparation of Organic EL Element (a) Washing of ITO Substrate To completely remove fine particles adhering to the surface of a 50 mm × 50 mm ITO (indium-tin oxide) coated substrate, the substrate was immersed in THF. A sound wave was irradiated for 10 minutes. (B) Preparation of thin film In order to use the synthesized polymer as a hole transport layer, a thin film is prepared on a cleaned ITO substrate by a polymer spinner method.
Aluminum complex / Al as electron transport layer on the substrate
q3 was evaporated in vacuum. Al-Li to continue as cathode
Was vacuum deposited to produce an organic EL device.
【００５７】 ＥＬ素子の輝度の測定 作成した有機ＥＬ素子のＩＴＯを陽極、Ａｌ−Ｌｉを陰
極として電圧を徐々に上昇させ輝度を測定した。最高輝
度８１００ｃｄ／ｍ2 が得られた。尚、比較としてホー
ル輸送層に従来より使用されているＴＰＤ（Ｎ，Ｎ’−
ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−
１，１−ビフェニル４，４’−ジアミン）を用いた。結
果を図１５に示す。Measurement of Luminance of EL Device The luminance of the organic EL device thus prepared was measured by gradually increasing the voltage using ITO as an anode and Al—Li as a cathode. A maximum luminance of 8100 cd / m 2 was obtained. For comparison, the TPD (N, N'-) conventionally used for the hole transport layer was used.
Diphenyl-N, N'-bis (3-methylphenyl)-
1,1-biphenyl 4,4′-diamine) was used. FIG. 15 shows the results.
【００５８】実施例４ カルバゾール誘導体ポリマー化合物の合成 前記実施例３に準じて第一〜第三段階反応を行った。 第四段階反応；ポリ（４−カルバゾイルスチレン） ア
ニオン重合 １０ｍｌのなす型フラスコに４−カルバゾイルスチレン
０．２ｇ（０．７ｍｍｏｌ）、溶媒としてテトラヒドロ
フラン２ｍｌを入れた。このなす型フラスコにダブルゴ
ム栓をし、完全に密封した後、ドライアイス−アセトン
バスを用いて−８０℃まで冷却した。その後１００ｍｌ
の注射針にごく少量のブチルリチウムを入れ、ダブルゴ
ム栓に突き刺し溶液中へ注入した。その後室温にまでゆ
っくりと戻した後、溶液をメタノール中に投入し白色の
沈殿物を得た。この沈殿物をジクロロメタンに溶解させ
メタノールで沈殿させた。この再沈殿を３回繰り返した
後白色結晶ポリ（４−カルバゾイルスチレン）０．１２
ｇを得た。得られた重合体は、収率６０％であった。Example 4 Synthesis of Polymer Compound of Carbazole Derivative First to third step reactions were carried out according to Example 3 above. Fourth step reaction: poly (4-carbazoylstyrene) anionic polymerization 0.2 g (0.7 mmol) of 4-carbazoylstyrene and 2 ml of tetrahydrofuran as a solvent were placed in a 10-ml eggplant-shaped flask. The eggplant-shaped flask was covered with a double rubber stopper, completely sealed, and then cooled to -80 ° C using a dry ice-acetone bath. Then 100ml
A very small amount of butyllithium was put in the injection needle of No. 1 and pierced into a double rubber stopper and injected into the solution. After slowly returning to room temperature, the solution was poured into methanol to obtain a white precipitate. This precipitate was dissolved in dichloromethane and precipitated with methanol. After repeating this reprecipitation three times, white crystalline poly (4-carbazoylstyrene) 0.12
g was obtained. The obtained polymer had a yield of 60%.
【００５９】この合成方法における反応式を記すると、
以下の通りとなる。The reaction formula in this synthesis method is described as follows:
It is as follows.
【００６０】[0060]
【化４１】 Embedded image
【００６１】 有機ＥＬ素子の作成 前記実施例３に準じてＩＴＯ基板を洗浄し、合成したポ
リマーをホール輸送層とする有機ＥＬ素子を作成した。Preparation of Organic EL Device An ITO substrate was washed according to Example 3 to prepare an organic EL device using the synthesized polymer as a hole transport layer.
【００６２】 ＥＬ素子の輝度の測定 作成した有機ＥＬ素子のＩＴＯを陽極、Ａｌ−Ｌｉを陰
極として電圧を徐々に上昇させ輝度、電流密度を測定し
た。最高輝度１４０００ｃｄ／ｍ2 が得られた。結果を
図１６に示す。Measurement of Luminance of EL Element The luminance and current density of the prepared organic EL element were measured by gradually increasing the voltage using ITO as an anode and Al—Li as a cathode. A maximum luminance of 14000 cd / m 2 was obtained. FIG. 16 shows the results.
【００６３】[0063]
【発明の効果】以上説明したように本発明によれば、本
発明者らが見出した特殊な構造のカルバゾール誘導体を
ホール輸送層に用いることにより、有機多層型ＥＬ素子
の寿命が飛躍的に延び、しかも発光性能が高い有機多層
型ＥＬ素子とすることができる。As described above, according to the present invention, by using a carbazole derivative having a special structure found by the present inventors for the hole transport layer, the life of the organic multilayer EL device is greatly extended. In addition, an organic multilayer EL device having high light emission performance can be obtained.
【図１】有機多層型ＥＬ素子の一般的構造を模式的に示
す断面図である。FIG. 1 is a cross-sectional view schematically showing a general structure of an organic multilayer EL device.
【図２】実施例１にて合成されたジフェニルアミノカル
バジルビフェニル（ＤＰＣＢＰ）のＩＲチャートであ
る。FIG. 2 is an IR chart of diphenylaminocarbazylbiphenyl (DPCBP) synthesized in Example 1.
【図３】実施例１にて合成されたジフェニルアミノカル
バジルビフェニル（ＤＰＣＢＰ）の1Ｈ−ＮＭＲ（ＣＤ
Ｃｌ3）チャートである。FIG. 3 shows 1 H-NMR (CD) of diphenylaminocarbazylbiphenyl (DPCBP) synthesized in Example 1.
Cl 3 ) chart.
【図４】実施例１にて合成された４−カルバゾイル−
４’−ナフチルフェニルビフェニルジアミン（ＣＮＰ
Ｂ）のＩＲチャートである。FIG. 4 shows 4-carbazoyl- synthesized in Example 1.
4'-naphthylphenylbiphenyldiamine (CNP
It is an IR chart of B).
【図５】実施例１にて合成された４−カルバゾイル−
４’−ナフチルフェニルビフェニルジアミン（ＣＮＰ
Ｂ）の1Ｈ−ＮＭＲ（ＣＤＣｌ3）チャートである。FIG. 5: 4-carbazoyl- synthesized in Example 1
4'-naphthylphenylbiphenyldiamine (CNP
It is a 1 H-NMR (CDCl 3) chart B).
【図６】実施例１にて合成されたジカルバゾイルアゾベ
ンゼン（ＤＣＡＢ）のＩＲチャートである。FIG. 6 is an IR chart of dicarbazoylazobenzene (DCAB) synthesized in Example 1.
【図７】実施例１にて合成されたジカルバゾイルアゾベ
ンゼン（ＤＣＡＢ）の 1Ｈ−ＮＭＲ（ＣＤＣｌ3） チャ
ートである。FIG. 7 is a 1 H-NMR (CDCl 3 ) chart of dicarbazoylazobenzene (DCAB) synthesized in Example 1.
【図８】実施例１にて合成されたジキシリルアミノカル
バジルビフェニル（ＤＸＣＢＰ）のＩＲチャートであ
る。FIG. 8 is an IR chart of dixylylaminocarbazylbiphenyl (DXCBP) synthesized in Example 1.
【図９】実施例１にて合成されたジキシリルアミノカル
バジルビフェニル（ＤＸＣＢＰ）の1Ｈ−ＮＭＲ（ＣＤ
Ｃｌ3）チャートである。FIG. 9 shows 1 H-NMR (CD) of dixylylaminocarbazylbiphenyl (DXCBP) synthesized in Example 1.
Cl 3 ) chart.
【図１０】実施例１にて作成した有機ＥＬ素子の構造を
模式的に示す断面図である。FIG. 10 is a cross-sectional view schematically showing the structure of the organic EL device prepared in Example 1.
【図１１】実施例２にて作成した有機ＥＬ素子の輝度測
定の結果を示すグラフである。FIG. 11 is a graph showing a result of a luminance measurement of the organic EL element prepared in Example 2.
【図１２】実施例３にて合成された９−（４−（１−ヒ
ドロキシエチル）フェニル）カルバゾールの1Ｈ−ＮＭ
Ｒ（ＣＤＣｌ3）チャートである。FIG. 12 shows 1 H-NM of 9- (4- (1-hydroxyethyl) phenyl) carbazole synthesized in Example 3.
R (CDCl 3) is a chart.
【図１３】実施例３にて合成された４−カルバゾイルス
チレンの 1Ｈ−ＮＭＲ（ＣＤＣｌ 3） チャートである。FIG. 13 shows 4-carbazoyls synthesized in Example 3.
Chilean1H-NMR (CDCl ThreeThis is a chart.
【図１４】実施例３にて合成されたポリ（４−カルバゾ
イルスチレン）の 1Ｈ−ＮＭＲ（ＣＤＣｌ3） チャート
である。FIG. 14 is a 1 H-NMR (CDCl 3 ) chart of poly (4-carbazoylstyrene) synthesized in Example 3.
【図１５】実施例３にて作成した有機ＥＬ素子の輝度測
定の結果を示すグラフである。FIG. 15 is a graph showing the results of measuring the luminance of the organic EL device prepared in Example 3.
【図１６】実施例４にて作成した有機ＥＬ素子の輝度測
定の結果を示すグラフである。FIG. 16 is a graph showing the results of measuring the luminance of the organic EL device prepared in Example 4.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小西 孝昇 神奈川県藤沢市桐原町９番地 タイホー工 業株式会社中央研究所内 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takanobu Konishi 9th Kirihara-cho, Fujisawa-shi, Kanagawa Pref.
Claims (9)
合物をホール輸送層に用いたことを特徴とする有機多層
型エレクトロルミネッセンス素子。1. A compound of the general formula An organic multilayer electroluminescent device, characterized in that a compound containing 9-carbazolyl in its molecular structure is used for the hole transport layer.
る化合物が 【化２】 で示される一種以上のカルバゾール誘導体である事を特
徴とする請求項１に記載の有機多層型エレクトロルミネ
ッセンス素子。2. A compound containing 9-carbazolyl in a molecular structure is represented by the following formula: The organic multilayer electroluminescent device according to claim 1, wherein the organic multilayer electroluminescent device is at least one carbazole derivative represented by the following formula:
徴とする請求項２に記載の有機多層型エレクトロルミネ
ッセンス素子。3. The method according to claim 1, wherein the nitrogen-containing allyl group is Embedded image Embedded image Embedded image 3. The organic multilayer electroluminescent device according to claim 2, wherein the organic multilayer electroluminescent device is at least one carbazole derivative represented by the following formula.
る化合物が 【化７】 で示される一種以上のジカルバゾール誘導体である事を
特徴とする請求項１に記載の有機多層型エレクトロルミ
ネッセンス素子。4. A compound containing 9-carbazolyl in its molecular structure, The organic multilayer electroluminescent device according to claim 1, wherein the organic multilayer electroluminescent device is at least one dicarbazole derivative represented by the following formula:
特徴とする請求項４に記載の有機多層型エレクトロルミ
ネッセンス素子。5. An allyl group represented by the formula: 5. The organic multilayer electroluminescent device according to claim 4, wherein the organic multilayer electroluminescent device is at least one dicarbazole derivative represented by the following formula.
る化合物が 【化９】 で示される重合体である事を特徴とする請求項１に記載
の有機多層型エレクトロルミネッセンス素子。6. A compound containing 9-carbazolyl in a molecular structure is represented by the following formula: The organic multilayer electroluminescent device according to claim 1, wherein the polymer is a polymer represented by the following formula:
るカルバゾール誘導体の合成工程が 【化１０】 【化１１】 【化１２】 【化１３】 で示されることを特徴とする有機多層型エレクトロルミ
ネッセンス素子用構造体の合成方法。7. A process for synthesizing a carbazole derivative containing 9-carbazolyl in a molecular structure is represented by the following formula: Embedded image Embedded image Embedded image A method for synthesizing a structure for an organic multilayer electroluminescent element, characterized by being represented by the following formula:
るジカルバゾール誘導体の合成工程が 【化１４】 で示されることを特徴とする有機多層型エレクトロルミ
ネッセンス素子用構造体の合成方法。8. The process for synthesizing a dicarbazole derivative containing 9-carbazolyl in the molecular structure is as follows: A method for synthesizing a structure for an organic multilayer electroluminescent element, characterized by being represented by the following formula:
る重合体の合成工程が 【化１５】 で示されることを特徴とする有機多層型エレクトロルミ
ネッセンス素子用構造体の合成方法。9. The process for synthesizing a polymer containing 9-carbazolyl in the molecular structure is as follows: A method for synthesizing a structure for an organic multilayer electroluminescent element, characterized by being represented by the following formula:
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| WO2001072927A1 (en) * | 2000-03-27 | 2001-10-04 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
| WO2001096492A1 (en) * | 2000-06-13 | 2001-12-20 | Matsushita Electric Industrial Co.,Ltd. | Exciton forming substance, luminescent material using the substance, method for light emission and luminescent element, and device using the element |
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1998
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