JPH07126615A - Electroluminescence device - Google Patents
Electroluminescence deviceInfo
- Publication number
- JPH07126615A JPH07126615A JP5273883A JP27388393A JPH07126615A JP H07126615 A JPH07126615 A JP H07126615A JP 5273883 A JP5273883 A JP 5273883A JP 27388393 A JP27388393 A JP 27388393A JP H07126615 A JPH07126615 A JP H07126615A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hole transport
- hydrogen atom
- transport layer
- electroluminescent device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、少なくとも正孔輸送
層、発光層および電子輸送層を有し、各種の表示装置と
して広範囲に利用される発光素子であって、低い印加電
圧、高輝度、かつ安定性にも優れた有機電界発光素子
(EL素子)に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a light emitting device having at least a hole transporting layer, a light emitting layer and an electron transporting layer, which is widely used as various display devices, and has a low applied voltage, high brightness, The present invention also relates to an organic electroluminescence device (EL device) which is excellent in stability.
【0002】[0002]
【従来の技術】EL素子は自己発光のために液晶素子に
くらべて明るく、鮮明な表示が可能であるため、古くか
ら多くの研究者によって研究されてきた。現在実用レベ
ルに達した発光素子としては、無機蛍光体であるZnS
を用いた素子がある。しかし、このような無機のEL素
子は、発光のための印加電圧として200V以上が必要
であるため、広く使用されるには至ってない。2. Description of the Related Art EL devices have been researched by many researchers for a long time because they are self-luminous and thus are brighter and more vivid than liquid crystal devices. ZnS, which is an inorganic phosphor, is currently used as a light-emitting element that has reached a practical level.
There is an element using. However, since such an inorganic EL element requires an applied voltage of 200 V or more for light emission, it has not been widely used.
【0003】これに対して有機材料を用いた発光素子
は、従来実用的なレベルからは遠いものであったが、1
987年にコダック社のC.W.Tangらによって開
発された積層構造素子によりその特性が飛躍的に進歩し
た。彼らは蒸着膜の構造が安定で電子を輸送することの
できる蛍光体と、正孔を輸送することのできる有機物と
を積層し、両方のキャリヤーを蛍光体中に注入して発光
させることに成功した。これによって有機電界発光素子
の発光効率が向上し、10V以下の電圧で1000cd
/m2 以上の発光が得られるようになった。その後多く
の研究者によってその特性向上のための研究が行なわ
れ、現在では短時間の発光では10000cd/m2 以
上の発光特性が得られている。On the other hand, a light emitting element using an organic material is far from a practical level, but
In 987, the C.I. W. The laminated structure element developed by Tang et al. Has dramatically improved its characteristics. They succeeded in stacking a phosphor with a stable structure of vapor-deposited film that can transport electrons and an organic substance that can transport holes, and injecting both carriers into the phosphor to emit light. did. As a result, the luminous efficiency of the organic electroluminescent device is improved, and 1000 cd at a voltage of 10 V or less.
A light emission of / m 2 or more can be obtained. Since then, many researchers have conducted researches to improve the characteristics, and at present, light emission characteristics of 10,000 cd / m 2 or more are obtained in short-time light emission.
【0004】このような有機発光素子の基本的な発光特
性はすでに十分実用範囲にあり、現在その実用化を妨げ
ている最も大きな原因は、第1にその駆動時の発光安定
性の不足であり、第2に保存安定性の不足である。ここ
で言う駆動時の発光安定性の不足とは、素子電流を印加
して駆動した時に発光輝度が低下し、ダークスポットと
呼ばれる発光しない領域が発生したり、素子の短絡によ
り破壊が起こる現象を言い、保存安定性の不足とは、製
作した素子を保存しているだけでも発光特性が低下する
現象を言う。The basic light-emitting characteristics of such an organic light-emitting device are already in a practical range, and the most important factor that hinders its practical use is the lack of light-emission stability during driving. Second, there is a lack of storage stability. Insufficient light emission stability at the time of driving here means that the light emission luminance is lowered when an element current is applied to drive, and a region called a dark spot which does not emit light is generated, or destruction occurs due to a short circuit of the element. That is, the lack of storage stability refers to a phenomenon in which the light emitting characteristics deteriorate even when the manufactured device is stored.
【0005】本発明者らはこのようなEL素子の発光の
安定性、保存安定性に関する問題点を解決するためその
劣化の機構を検討した。その結果、特性劣化の大きな原
因の一つがその正孔輸送層にあることが分かった。即
ち、正孔輸送層として一般に利用される(化5:略称T
PD)、(化6:略称TPAC)のような正孔輸送材料
は、(1)湿度、温度、電流により結晶化して薄膜形状
が一様でなくなる。(2)正孔輸送層が通電により分解
する、などの変化を起こし、それによって発光性が著し
く劣化することが分かった。The present inventors have examined the mechanism of deterioration in order to solve the problems concerning the emission stability and storage stability of such EL devices. As a result, it was found that one of the major causes of the characteristic deterioration was the hole transport layer. That is, it is generally used as a hole transport layer (Chemical formula 5: abbreviated to T
A hole transport material such as PD) or (Chemical Formula 6: Abbreviation TPAC) is crystallized by (1) humidity, temperature, and current, and the shape of the thin film becomes uneven. (2) It has been found that the hole transport layer undergoes changes such as decomposition due to energization, which causes the light emitting property to remarkably deteriorate.
【化5】 [Chemical 5]
【化6】 [Chemical 6]
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、この
ような知見に基づき、発光安定性、保存安定性に優れた
正孔輸送層を有する有機EL素子を提供することにあ
る。このような正孔輸送材料の具備しなければならない
条件としては、(1)優れた正孔輸送能力を持つこと、
(2)熱的に安定で、ガラス状態が安定であること、
(3)薄膜を形成できること、(4)電気的、化学的に
安定であること、等を挙げることができる。An object of the present invention is to provide an organic EL device having a hole transport layer which is excellent in light emission stability and storage stability based on such findings. The conditions that such a hole transport material must have are (1) having an excellent hole transport ability,
(2) It is thermally stable and the glass state is stable,
(3) A thin film can be formed, (4) Electrical and chemical stability, etc. can be mentioned.
【0007】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明者らは、ITO電極、正孔輸送層、発光層、
電子輸送層およびマグネシュウム/銀電極からなるEL
素子を試作し、新たに合成した数多くの正孔輸送材料の
評価を行なった。発光層としては主に電子輸送層を兼ね
るアルミキノリン3量体を用いた。上記正孔輸送層の材
料として、少なくとも(化7)で記述されるテトラフェ
ニルベンジジン化合物、(化8)で記述されるトリフェ
ニルアミン3量体、(化9)で記述されるベンジジン2
量体を使用した。In order to achieve the above object, the present inventors have made an ITO electrode, a hole transport layer, a light emitting layer,
EL consisting of electron transport layer and magnesium / silver electrode
A device was made as a prototype, and a number of newly synthesized hole transport materials were evaluated. As the light emitting layer, an aluminum quinoline trimer mainly serving also as an electron transport layer was used. As the material of the hole transport layer, at least a tetraphenylbenzidine compound described in (Chemical formula 7), a triphenylamine trimer described in (Chemical formula 8), and a benzidine 2 described in (Chemical formula 9)
A quantity was used.
【0008】[0008]
【化7】 [Chemical 7]
【0009】ただし、R1 、R2 は水素原子、低級アル
キル基、低級アルコキシ基、フェニル基、低級アルキル
基または低級アルコキシ基を置換基として有するフェニ
ル基、R3 は水素原子、メチル基、メトキシ基、または
クロル原子を表す。また、R 1 、R2 の少なくとも一方
は、ノルマルブチル基、イソブチル基、セカンダリブチ
ル基、ターシャルブチル基、フェニル基、低級アルキル
基または低級アルコキシ基を有するフェニル基を表す。However, R1, R2Is a hydrogen atom,
Kill group, lower alkoxy group, phenyl group, lower alkyl
Or phenyl having a lower alkoxy group as a substituent
Lu group, R3Is a hydrogen atom, a methyl group, a methoxy group, or
Represents a chlorine atom. Also, R 1, R2At least one of
Is a normal butyl group, an isobutyl group, a secondary butyl group.
Group, tertiary butyl group, phenyl group, lower alkyl
Represents a phenyl group having a group or a lower alkoxy group.
【0010】[0010]
【化8】 [Chemical 8]
【0011】ただし、R1 、R2 、R3 は水素原子、低
級アルキル基、または低級アルコキシ基、R4 は水素原
子、メチル基、メトキシ基、またはクロル原子を表す。However, R 1 , R 2 and R 3 represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R 4 represents a hydrogen atom, a methyl group, a methoxy group or a chloro atom.
【0012】[0012]
【化9】 [Chemical 9]
【0013】ただし、R1 、R2 、R3 は水素原子、低
級アルキル基、または低級アルコキシ基、R4 は水素原
子、メチル基、メトキシ基、またはクロル原子を表す。
またXは以下の構造を有する置換基を表し、R5 は水素
原子、メチル基、メトキシ基、またはクロル原子を表
す。However, R 1 , R 2 and R 3 represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R 4 represents a hydrogen atom, a methyl group, a methoxy group or a chloro atom.
X represents a substituent having the following structure, and R 5 represents a hydrogen atom, a methyl group, a methoxy group, or a chloro atom.
【0014】[0014]
【化10】 [Chemical 10]
【0015】[0015]
【作用】本発明は、上記のような正孔輸送材料を使用し
た結果、それらが優れた正孔輸送能力を有しているばか
りでなく、良好な薄膜を形成し、さらに熱的にも安定で
あることが分かった。この結果、優れた発光安定性、保
存安定性を有するEL素子が実現できることが明らかに
なり、表示素子として広範囲に利用することができた。As a result of using the above hole transporting material, the present invention not only has excellent hole transporting ability but also forms a good thin film and is thermally stable. It turned out that As a result, it became clear that an EL device having excellent light emission stability and storage stability could be realized, and it could be widely used as a display device.
【0016】[0016]
【実施例1】本発明の正孔輸送材料の一つであるテトラ
フェニルベンジジン化合物は、相当する4,4’−ジハ
ロゲン化ビフェニルと相当するジフェニルアミン化合物
との縮合反応、または相当するベンジジン化合物と相当
するハロゲン化アリールとの縮合反応により合成するこ
とができる。これら縮合反応はウルマン反応として知ら
れる方法である。Example 1 A tetraphenylbenzidine compound, which is one of the hole transporting materials of the present invention, corresponds to a condensation reaction between a corresponding 4,4′-dihalogenated biphenyl and a corresponding diphenylamine compound, or a corresponding benzidine compound. It can be synthesized by a condensation reaction with an aryl halide. These condensation reactions are methods known as the Ullmann reaction.
【0017】また、本発明の別の正孔輸送材料であるト
リフェニルアミン3量体は、相当するアニリン化合物と
相当する4’−ハロゲン化ビフェニルアセトアニリド化
合物との縮合反応、そしてその加水分解により得られる
トリアミン化合物とハロゲン化アリールとの縮合反応に
より得られる。これら縮合反応はウルマン反応として知
られる方法である。The triphenylamine trimer which is another hole transporting material of the present invention is obtained by a condensation reaction between a corresponding aniline compound and a corresponding 4'-halogenated biphenylacetanilide compound, and hydrolysis thereof. It is obtained by a condensation reaction of the obtained triamine compound and an aryl halide. These condensation reactions are methods known as the Ullmann reaction.
【0018】さらに、本発明の別の正孔輸送材料である
ベンジジン2量体は、新規な化合物であり、これは、相
当するトリフェニルベンジジン化合物とジハロゲン化物
との縮合反応、または相当するジアミン化合物のN,
N’−ジアセチル体と相当する4’−ハロゲン化ビフェ
ニルアセトアニリド化合物との縮合反応による生成物を
加水分解した後、相当するハロゲン化アリールと縮合反
応することにより合成することができる。これら縮合反
応はウルマン反応として知られる方法である。Furthermore, another hole transporting material of the present invention, benzidine dimer, is a novel compound, which is a condensation reaction of a corresponding triphenylbenzidine compound and a dihalide, or a corresponding diamine compound. N of
It can be synthesized by hydrolyzing the product obtained by the condensation reaction of the N′-diacetyl derivative and the corresponding 4′-halogenated biphenylacetanilide compound, and then subjecting the product to the condensation reaction with the corresponding aryl halide. These condensation reactions are methods known as the Ullmann reaction.
【0019】これらの化合物の同定は、元素分析、IR
測定により行ない、さらに溶媒による再結晶法、真空昇
華法により精製し、純度を99.8%以上とした。純度
の確認はTLCスキャナー、TG−DTA、融点測定に
より行なった。融点、分解点は正孔輸送層の熱安定性の
目安となり、ガラス転移点はガラス状態の安定性の目安
となる。発明者らは上記3種類の化合物の置換基を種々
に変えて材料を合成した。その結果、融点、分解点の大
きさが置換基により変化し、いくつかの置換基の場合に
は、融点、分解点が高い材料を得ることができた。以下
にいくつかの代表的な合成実施例を示す。Identification of these compounds was carried out by elemental analysis, IR
The purity was set to 99.8% or more by performing the measurement and further refining by the solvent recrystallization method and the vacuum sublimation method. The purity was confirmed by TLC scanner, TG-DTA and melting point measurement. The melting point and the decomposition point serve as a measure of the thermal stability of the hole transport layer, and the glass transition point serves as a measure of the stability of the glass state. The inventors synthesized materials by changing the substituents of the above three kinds of compounds in various ways. As a result, the sizes of the melting point and the decomposition point changed depending on the substituents, and in the case of some substituents, a material having a high melting point and a high decomposition point could be obtained. Below are some representative synthetic examples.
【0020】(合成実施例1)p−イソブチルアニリ
ン、70.0g(0.47モル)を氷酢酸126mlに
溶解して、30°Cで無水酢酸59.9g(0.58モ
ル)を滴下し、滴下終了後40°Cで1時間反応させ
た。反応液を水300ml中へ注加し、析出した結晶を
ろ過、水洗、乾燥した。この結晶をトルエン140ml
とn−ヘキサン、700mlの混合溶液で再結晶し、p
−イソブチルアセトアニリド、60.4g(収率67.
3%)を得た。融点は124.5〜125.0°Cであ
った。(Synthesis Example 1) 70.0 g (0.47 mol) of p-isobutylaniline was dissolved in 126 ml of glacial acetic acid, and 59.9 g (0.58 mol) of acetic anhydride was added dropwise at 30 ° C. After completion of the dropwise addition, the mixture was reacted at 40 ° C for 1 hour. The reaction solution was poured into 300 ml of water, and the precipitated crystals were filtered, washed with water and dried. 140 ml of this crystal
Recrystallized with a mixed solution of 700 ml of n-hexane and
-Isobutylacetanilide, 60.4 g (yield 67.
3%) was obtained. The melting point was 124.5-125.0 ° C.
【0021】上記得られた、p−イソブチルアセトアニ
リド、17.9g(0.094モル)とブロムベンゼン
22.1g(0.14モル)、無水炭酸カリウム、1
6.9g(0.12モル)、銅粉、0.89g(0.0
14モル)を混合し、168〜217°Cで14時間反
応させた。反応生成物をトルエン100mlで抽出し、
不溶分を濾別、除去後、濃縮乾固した。これをイソアミ
ルアルコール、30mlで溶解し、水、3.4g、85
%水酸化カリウム、11.8g(0.18モル)を加
え、131°Cで加水分解した。水蒸気蒸留でイソアミ
ルアルコール、過剰のブロムベンゼンを留去後、トルエ
ン、120mlで抽出し、水洗、乾燥して濃縮した。濃
縮物は乾燥し、N−4−イソブチルフェニルアニリン、
17.6g(収率86.8%)を得た。The above-obtained p-isobutylacetanilide, 17.9 g (0.094 mol), brombenzene 22.1 g (0.14 mol), anhydrous potassium carbonate, 1
6.9 g (0.12 mol), copper powder, 0.89 g (0.0
14 mol) were mixed and reacted at 168 to 217 ° C for 14 hours. The reaction product is extracted with 100 ml of toluene,
The insoluble matter was filtered off, removed, and concentrated to dryness. This was dissolved in 30 ml of isoamyl alcohol, and water, 3.4 g, 85
% Potassium hydroxide (11.8 g, 0.18 mol) was added, and the mixture was hydrolyzed at 131 ° C. After distilling off isoamyl alcohol and excess bromine by steam distillation, the mixture was extracted with 120 ml of toluene, washed with water, dried and concentrated. The concentrate is dried, N-4-isobutylphenylaniline,
17.6 g (yield 86.8%) was obtained.
【0022】さらに、N−4−イソブチルフェニルアニ
リン、17.6g(0.078モル)、4,4’−ジョ
ードビフェニル、12.6g(0.031モル)、無水
炭酸カリウム、12.9g(0.093モル)および銅
粉、0.89g(0.014モル)を混合し、190〜
220°Cで12時間反応させた。反応生成物をトルエ
ン、70mlで抽出し、不溶分を濾別、除去後、濃縮し
てオイル状物とした。得られた粗製物は、カラムクロマ
トにより精製して(担体:シリカゲル、溶離液:トルエ
ン/n−ヘキサン=1/6)、N,N’−ビス(p−イ
ソブチルフェニル)−N,N’−ジフェニルベンジジ
ン、8.5g(収率45.7%)を得た。融点は13
3.8〜135.3°Cであった。元素分析、IR測定
により生成物の同定を行なった。元素分析値は次の通り
である。炭素:測定値87.77%、理論値:87.9
6%、水素:測定値7.43%、理論値7.38%、窒
素:測定値4.51%、理論値4,66%。Further, N-4-isobutylphenylaniline, 17.6 g (0.078 mol), 4,4'-jodobiphenyl, 12.6 g (0.031 mol), anhydrous potassium carbonate, 12.9 g (0 0.093 mol) and copper powder, 0.89 g (0.014 mol) are mixed,
The reaction was carried out at 220 ° C for 12 hours. The reaction product was extracted with 70 ml of toluene, the insoluble matter was filtered off, removed, and concentrated to give an oily substance. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/6) and N, N′-bis (p-isobutylphenyl) -N, N′- 8.5 g (yield 45.7%) of diphenylbenzidine was obtained. Melting point is 13
The temperature was 3.8 to 135.3 ° C. The product was identified by elemental analysis and IR measurement. The elemental analysis values are as follows. Carbon: measured value 87.77%, theoretical value: 87.9
6%, hydrogen: measured value 7.43%, theoretical value 7.38%, nitrogen: measured value 4.51%, theoretical value 4,66%.
【0023】(合成実施例2)アセトアニリド、23.
0g(0.17モル)と4,4’−ジョードビフェニ
ル、85.3g(0.21モル)、無水炭酸カリウム、
24.9g(0.18モル)、銅粉、2.48g(0.
039モル)、ニトロベンゼン、40mlを混合し、1
90〜205°Cで10時間反応させた。反応生成物を
トルエン200mlで抽出し、不溶分を濾別、除去後、
濃縮乾固した。これをカラムクロマトにより精製して
(担体:シリカゲル、溶離液:トルエン/n−ヘキサン
=1/6)、N−(4’−ヨード−4−ビフェニリル)
アセトアニリド、45.5g(収率64.8%)を得
た。融点は135.0〜136.0°Cであった。(Synthesis Example 2) Acetanilide, 23.
0 g (0.17 mol) and 4,4'-jodobiphenyl, 85.3 g (0.21 mol), anhydrous potassium carbonate,
24.9 g (0.18 mol), copper powder, 2.48 g (0.
039 mol), nitrobenzene and 40 ml are mixed, and 1
The reaction was carried out at 90 to 205 ° C for 10 hours. The reaction product was extracted with 200 ml of toluene, and the insoluble matter was filtered off and removed.
It was concentrated to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/6), N- (4′-iodo-4-biphenylyl).
Acetanilide (45.5 g, yield 64.8%) was obtained. The melting point was 135.0 to 136.0 ° C.
【0024】続いてN−(4’−ヨード−4−ビフェニ
リル)アセトアニリド、18.2g(0.044モ
ル)、アニリン、1.84g(0.020モル)、無水
炭酸カリウム、6.91g(0.050モル)および銅
粉、0.64g(0.010モル)、ニトロベンゼン、
10mlを混合し、190〜215°Cで15時間反応
させた。反応生成物をトルエン100mlで抽出し、不
溶分を濾別、除去後、濃縮してオイル状物とした。オイ
ル状物はイソアミルアルコール、50mlに溶解し、水
1ml、85%水酸化カリウム、2.64g(0.04
0モル)を加え、130°Cで加水分解した。水蒸気蒸
留でイソアミルアルコールを留去後、トルエン250m
lで抽出し、水洗、乾燥して濃縮した。濃縮物はカラム
クロマトにより精製して(担体:シリカゲル、溶離液:
トルエン/n−ヘキサン=3/1)、N,N’−ビス
(4’−フェニルアミノ−4−ビフェニリル)アニリ
ン、8.85g(収率76.3%)を得た。Subsequently, N- (4'-iodo-4-biphenylyl) acetanilide, 18.2 g (0.044 mol), aniline, 1.84 g (0.020 mol), anhydrous potassium carbonate, 6.91 g (0 0.050 mol) and copper powder, 0.64 g (0.010 mol), nitrobenzene,
10 ml was mixed and reacted at 190 to 215 ° C for 15 hours. The reaction product was extracted with 100 ml of toluene, the insoluble matter was filtered off, removed, and concentrated to give an oily substance. The oily substance was dissolved in 50 ml of isoamyl alcohol, and 1 ml of water, 85% potassium hydroxide, 2.64 g (0.04
0 mol) was added, and the mixture was hydrolyzed at 130 ° C. After distilling off isoamyl alcohol by steam distillation, toluene 250m
It was extracted with 1, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier: silica gel, eluent:
Toluene / n-hexane = 3/1) and N, N′-bis (4′-phenylamino-4-biphenylyl) aniline (8.85 g, yield 76.3%) were obtained.
【0025】さらにN,N’−ビス(4’−フェニルア
ミノ−4−ビフェニリル)アニリン、8.70g(0.
015モル)、ヨードベンゼン、6.74g(0.03
3モル)、無水炭酸カリウム、4.56g(0.33モ
ル)、銅粉、0.48g(0.0075モル)、ニトロ
ベンゼン、10mlを混合し、195〜205°Cで1
6時間反応させた。反応生成物をトルエン100mlで
抽出し、不溶分を濾別、濃縮後、n−ヘキサンを加えて
粗結晶を取り出した。粗結晶はカラムクロマトにより精
製し、N,N’−ビス(4’−ジフェニルアミノ−4−
ビフェニリル)アニリン、5.50g(収率:50.1
%)を得た。明瞭な融点は見られなかった。元素分析、
IR測定により生成物の同定を行なった。元素分析値は
以下の通りである。炭素:測定値88.80%、理論
値:88.61%、水素:測定値5.77%、理論値
5.65%、窒素:測定値5.62%、理論値5.74
%。Further, N, N'-bis (4'-phenylamino-4-biphenylyl) aniline, 8.70 g (0.
015 mol), iodobenzene, 6.74 g (0.03
3 mol), anhydrous potassium carbonate, 4.56 g (0.33 mol), copper powder, 0.48 g (0.0075 mol), nitrobenzene, and 10 ml are mixed, and 1 at 195 to 205 ° C
The reaction was carried out for 6 hours. The reaction product was extracted with 100 ml of toluene, the insoluble matter was filtered off, and after concentration, n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography, and N, N'-bis (4'-diphenylamino-4-
Biphenylyl) aniline, 5.50 g (yield: 50.1
%) Was obtained. No clear melting point was seen. Elemental analysis,
The product was identified by IR measurement. The elemental analysis values are as follows. Carbon: measured value 88.80%, theoretical value: 88.61%, hydrogen: measured value 5.77%, theoretical value 5.65%, nitrogen: measured value 5.62%, theoretical value 5.74
%.
【0026】(合成実施例3)アセトアニリド、20.
3g(0.15モル)と4,4’−ジョードビフェニ
ル、73.1g(0.18モル)、無水炭酸カリウム、
22.1g(0.16モル)、銅粉、2.16g(0.
034モル)、ニロトベンゼン、35mlを混合し、1
90〜205°Cで10時間反応させた。反応生成物を
トルエン200mlで抽出し、不溶分を濾別、除去後、
濃縮乾固した。これをカラムクロマトにより精製して
(担体:シリカゲル、溶離液:トルエン/酢酸エチル=
6/1)、N−(4’−ヨード−4−ビフェニリル)ア
セトアニリド、40.2g(収率64.8%)を得た。
融点は135.0〜136.0°Cであった。(Synthesis Example 3) Acetanilide, 20.
3 g (0.15 mol) and 4,4'-jodobiphenyl, 73.1 g (0.18 mol), anhydrous potassium carbonate,
22.1 g (0.16 mol), copper powder, 2.16 g (0.
(034 mol), nitobenzene, and 35 ml are mixed, and 1
The reaction was carried out at 90 to 205 ° C for 10 hours. The reaction product was extracted with 200 ml of toluene, and the insoluble matter was filtered off and removed.
It was concentrated to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate =
6/1), N- (4'-iodo-4-biphenylyl) acetanilide, 40.2 g (yield 64.8%) were obtained.
The melting point was 135.0 to 136.0 ° C.
【0027】続いてN−(4’−ヨード−4−ビフェニ
リル)アセトアニリド、13.2g(0.032モ
ル)、ジフェニルアミン、6.60g(0.039モ
ル)、無水炭酸カリウム、5.53g(0.040モ
ル)および銅粉、0.45g(0.007モル)、ニト
ロベンゼン、10mlを混合し、200〜212°Cで
15時間反応させた。反応生成物をトルエン100ml
で抽出し、不溶分を濾別、除去後、濃縮してオイル状物
とした。オイル状物はイソアミルアルコール、60ml
に溶解し、水1ml、85%水酸化カリウム、2.64
g(0.040モル)を加え、130°Cで加水分解し
た。水蒸気蒸留でイソアミルアルコールを留去後、トル
エン250mlで抽出し、水洗、乾燥して濃縮した。濃
縮物はカラムクロマトにより精製して(担体:シリカゲ
ル、溶離液:トルエン/n−ヘキサン=1/2)、N,
N,N’−トリフェニルベンジジン、10.5g(収率
72.2%)を得た。融点は167.5〜168.5°
Cであった。Subsequently, N- (4'-iodo-4-biphenylyl) acetanilide, 13.2 g (0.032 mol), diphenylamine, 6.60 g (0.039 mol), anhydrous potassium carbonate, 5.53 g (0 0.040 mol) and copper powder, 0.45 g (0.007 mol), nitrobenzene, and 10 ml were mixed and reacted at 200 to 212 ° C for 15 hours. 100 ml of toluene as the reaction product
After extraction, the insoluble matter was filtered off, removed, and concentrated to give an oily substance. Oily substance is isoamyl alcohol, 60 ml
Dissolved in water, 1 ml of water, 85% potassium hydroxide, 2.64
g (0.040 mol) was added and the mixture was hydrolyzed at 130 ° C. After distilling off isoamyl alcohol by steam distillation, it was extracted with 250 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), N,
10.5 g (yield 72.2%) of N, N'-triphenylbenzidine was obtained. Melting point is 167.5-168.5 °
It was C.
【0028】さらにN,N,N’−トリフェニルベンジ
ジン8.66g(0.021モル)、4,4’−ジョー
ドビフェニル、4.06g(0.01モル)、無水炭酸
カリウム、2.90g(0.021モル)、銅粉、0.
32g(0.005モル)、ニトロベンゼン、10ml
を混合し、195〜210°Cで20時間反応させた。
反応生成物をトルエン140mlで抽出し、不溶分を濾
別、濃縮後、n−ヘキサン120mlを加えて粗結晶を
取り出した。粗結晶はカラムクロマトにより精製し(担
体:シリカゲル、溶離液:トルエン/n−ヘキサン=1
/2)、N,N’−ビス(4’−ジフェニルアミノ−4
−ビフェニリル)−N,N’−ジフェニルベンジジン、
4.73g(収率:48.5%)を得た。融点は24
2.5〜243.5°Cであった。元素分析、IR測定
により生成物の同定を行なった。元素分析値は以下の通
りである。炭素:測定値88.75%、理論値:88.
67%、水素:測定値5.70%、理論値5.58%、
窒素:測定値5.68%、理論値5.75%。Further, N, N, N'-triphenylbenzidine 8.66 g (0.021 mol), 4,4'-jodobiphenyl, 4.06 g (0.01 mol), anhydrous potassium carbonate, 2.90 g ( 0.021 mol), copper powder, 0.
32 g (0.005 mol), nitrobenzene, 10 ml
Were mixed and reacted at 195 to 210 ° C for 20 hours.
The reaction product was extracted with 140 ml of toluene, the insoluble matter was filtered off, and after concentration, 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1).
/ 2), N, N'-bis (4'-diphenylamino-4)
-Biphenylyl) -N, N'-diphenylbenzidine,
4.73 g (yield: 48.5%) was obtained. Melting point is 24
It was 2.5 to 243.5 ° C. The product was identified by elemental analysis and IR measurement. The elemental analysis values are as follows. Carbon: measured value 88.75%, theoretical value: 88.
67%, hydrogen: measured value 5.70%, theoretical value 5.58%,
Nitrogen: measured value 5.68%, theoretical value 5.75%.
【0029】[0029]
【実施例2】次に、これらを実際にEL素子として評価
し、その素子の発光特性、発光特性の安定性、保存安定
性を検討した。EL素子は、図1に示すように、ガラス
基板1上に透明電極2としてITO電極をあらかじめ形
成したものの上に、正孔輸送層3、電子輸送層兼発光層
4、Mg/Ag電極5の順に蒸着して作成した。まず、
十分に洗浄したガラス基板(ITO電極は生膜済み)、
正孔輸送材、電子輸送性発光材として精製したアルミキ
ノリン3量体を蒸着装置にセットした。0.1nm/秒
の速度で正孔輸送層を蒸着し、膜厚を変えた試料を作成
して最適の発光が得られる厚さを決定した。膜厚は材料
によって異なるが、最適膜厚は40〜60nmの間の厚
さであった。なお膜厚は水晶振動子によってモニターし
た。アルミキノリン3量体の蒸着は同じく0.1nm/
秒の速度で行ない、その膜厚は50nmとした。Mg/
Ag電極は0.4nm/秒の速度で行ない、その厚さを
100nmとした。これらの蒸着はいずれも真空を破ら
ずに連続して行なった。素子作製後、直ちに乾燥窒素中
で電極の取り出しを行ない、引続き特性測定を行なっ
た。[Embodiment 2] Next, these were actually evaluated as EL devices, and the emission characteristics of the devices, the stability of the emission characteristics, and the storage stability were examined. As shown in FIG. 1, the EL element comprises a hole transport layer 3, an electron transport layer / light emitting layer 4, and a Mg / Ag electrode 5 on which an ITO electrode is preliminarily formed as a transparent electrode 2 on a glass substrate 1. It vapor-deposited in order and created. First,
A glass substrate that has been thoroughly washed (ITO electrode is a biofilm),
The purified aluminum quinoline trimer as a hole transport material and an electron transport light emitting material was set in a vapor deposition apparatus. A hole transport layer was vapor-deposited at a rate of 0.1 nm / sec, samples having different film thicknesses were prepared, and the thickness at which optimum light emission was obtained was determined. Although the film thickness depends on the material, the optimum film thickness was between 40 and 60 nm. The film thickness was monitored by a crystal oscillator. The vapor deposition of aluminum quinoline trimer is also 0.1 nm /
The film thickness was set to 50 nm at a speed of 2 seconds. Mg /
The Ag electrode was formed at a speed of 0.4 nm / sec and its thickness was 100 nm. All of these vapor depositions were continuously performed without breaking the vacuum. Immediately after the device was manufactured, the electrode was taken out in dry nitrogen and the characteristics were continuously measured.
【0030】得られた素子の発光特性は100mA/c
m2 の電流を印加した場合の発光輝度で定義した。ま
た、発光の安定性は200cd/m2 の発光が得られる
電流を連続で印加し、その時の発光輝度の変化を測定し
た。発光の寿命は輝度が半分の100cd/m2 になる
までの時間と定義した。保存安定性は室温、乾燥空気中
に一定時間素子を放置後、20mA/cm2 の電流を印
加し、輝度が初期発光特性の半分になるまでの時間で定
義した。The emission characteristics of the obtained device are 100 mA / c
It was defined by the emission brightness when a current of m 2 was applied. The stability of light emission was measured by continuously applying a current capable of obtaining a light emission of 200 cd / m 2 and measuring the change in the light emission luminance at that time. The lifetime of light emission was defined as the time until the luminance reached to half, 100 cd / m 2 . The storage stability was defined as the time until the luminance became half of the initial emission characteristics after applying a current of 20 mA / cm 2 after leaving the device in room temperature and dry air for a certain period of time.
【0031】本発明の正孔輸送材料の評価のために、電
子輸送層兼発光層4としてアルミキノリン3量体を用い
たが、もちろん本発明では発光層の材料として各種の希
土類錯体、オキサゾール誘導体、ポリパラフェニレンビ
ニレンなどの各種の材料を用いることができる。また、
発光層にキナクリドンやクマリンなどのドーパントを添
加することにより、さらに高性能のELを作製すること
ができる。さらにまた、電子輸送層、発光層、正孔輸送
層の3層からなる電界発光素子とすることもできる。ま
た、本発明の正孔輸送材料と適性な電子輸送材料とを組
み合わせることにより、正孔輸送層を発光層として用い
ることもできる。In order to evaluate the hole transport material of the present invention, an aluminum quinoline trimer was used as the electron transport layer / light emitting layer 4. Of course, in the present invention, various rare earth complexes and oxazole derivatives are used as the material of the light emitting layer. Various materials such as polyparaphenylene vinylene can be used. Also,
By adding a dopant such as quinacridone or coumarin to the light emitting layer, a higher performance EL can be manufactured. Furthermore, an electroluminescent device having three layers of an electron transport layer, a light emitting layer, and a hole transport layer can be used. Further, by combining the hole transport material of the present invention with a suitable electron transport material, the hole transport layer can be used as a light emitting layer.
【0032】このような検討の結果、正孔輸送材料が1
30°C以上の融点、300°C以上の分解点を有する
場合には優れた発光の安定性、保存安定性が得られるこ
とが分かった。したがって、上記化合物の置換基は、本
発明の置換基に限らず、上記以上の融点、分解点を持つ
ものであれば使用できる。As a result of such a study, the hole transport material is 1
It was found that excellent emission stability and storage stability can be obtained when the melting point is 30 ° C. or higher and the decomposition point is 300 ° C. or higher. Therefore, the substituent of the above compound is not limited to the substituent of the present invention, and any compound having a melting point and a decomposition point above the above can be used.
【0033】また、本発明による正孔輸送材料は、単独
で用いることもできるが、2種類以上を共蒸着などで生
膜して混合状態で用いることができる。さらに、本発明
の正孔輸送材料を従来の正孔輸送材料であるTPACや
TPDとの共蒸着によって使用することができる。2種
類以上を同時蒸着して用いることにより、その結晶化を
起こし難くする効果をしばしば呈する。The hole-transporting material according to the present invention can be used alone, but can be used in a mixed state by forming a film of two or more kinds by co-evaporation or the like. Furthermore, the hole transport material of the present invention can be used by co-evaporation with conventional hole transport materials TPAC and TPD. When two or more kinds are simultaneously vapor-deposited and used, the effect of making it difficult to cause crystallization is often exhibited.
【0034】(素子実施例1)十分に洗浄したITO電
極、正孔輸送材としてテトラフェニルベンジジン化合物
(1)(R1 =p−n−Bu、R2 =H、R3 =H、m
p=132.9°C)、電子輸送性発光材として精製し
たアルミキノリン3量体を蒸着装置にセットした。0.
1nm/秒の速度で化合物(1)を50nmの厚さで蒸
着した。なお膜厚は水晶振動子によってモニターした。
アルキミノリンの蒸着は同じく0.1nm/秒の速度で
行ない、その膜厚は50nmとした。Mg/Ag電極は
0.4nm/秒の速度で行ない、その厚さを100nm
とした。これらの蒸着はいずれも真空を破らずに連続し
て行なった。素子作製後、直ちに乾燥窒素中で電極の取
り出しを行ない、引続き特性測定を行なった。発光特性
は2500cd/m2 、発光の寿命は620Hr、保存
安定性は2200Hrであった。(Element Example 1) A thoroughly washed ITO electrode, a tetraphenylbenzidine compound (1) as a hole transport material (R 1 = p-n-Bu, R 2 = H, R 3 = H, m
p = 132.9 ° C.), and the purified aluminum quinoline trimer as an electron-transporting luminescent material was set in the vapor deposition apparatus. 0.
Compound (1) was vapor-deposited in a thickness of 50 nm at a rate of 1 nm / sec. The film thickness was monitored by a crystal oscillator.
Alkyminoline was also vapor-deposited at a rate of 0.1 nm / sec, and its film thickness was 50 nm. The Mg / Ag electrode is performed at a speed of 0.4 nm / sec, and its thickness is 100 nm.
And All of these vapor depositions were continuously performed without breaking the vacuum. Immediately after the device was manufactured, the electrode was taken out in dry nitrogen and the characteristics were continuously measured. The light emission property was 2500 cd / m 2 , the light emission life was 620 hr, and the storage stability was 2200 hr.
【0035】比較のために正孔輸送材として(化5:略
称TPD)、(化6:略称TPAC)を用いて同じ条件
でEL素子を作製し、その特性を調べた。TPDでの発
光特性、発光の寿命性、保存安定性はそれぞれ、220
0cd/m2 、220Hr、460Hrであった。一
方、TPACでの発光性、発光の寿命性、保存安定性は
それぞれ、2500cd/m2 、280Hr、560H
rであった。このことから本実施例におけるテトラフェ
ニルベンジジン化合物(1)は、発光寿命、保存安定性
に優れていることが分かった。For comparison, EL devices were manufactured under the same conditions using (Chemical formula 5: abbreviated TPD) and (Chemical 6: abbreviated TPAC) as hole transport materials, and their characteristics were examined. The light emission characteristics of TPD, the longevity of light emission, and the storage stability are respectively 220
It was 0 cd / m 2 , 220 Hr, and 460 Hr. On the other hand, the light emission property of TPAC, the life property of light emission, and the storage stability are 2500 cd / m 2 , 280 Hr, and 560 H, respectively.
It was r. From this, it was found that the tetraphenylbenzidine compound (1) in this example was excellent in luminescence life and storage stability.
【0036】(素子実施例2)素子実施例1と同様の方
法でそれぞれ、テトラフェニルベンジジン化合物(2)
(R1 =iBu、R2 =H、R3 =H)、(3)(R1
=iBu、R2 =H、R3 =CH3 )、(4)(R1 =
tBu、R2 =H、R3 =H)、(5)(R1=tB
u、R2 =tBu、R3 =H)、(6)(R1=C6 H
5 、R2 =H、R 3 =H)、(7)(R1 =C6 H5 、
R2 =C6 H5 、R3 =H)、(8)(R 1 =C
6 H5 、R2 =C6 H5 、R3 =CH3 )、(9)(R
1 =p−CH3 −C6 H4 、R2 =H、R3 =OC
H3 )、(10)(R1 =p−CH3 −C6 H 6 、R2
=p−CH3 −C6 H4 、R3 =H)を正孔輸送材とし
て使用したEL素子を作製し、その特性を評価した。そ
の結果を図2に示す。なお、上記テトラフェニルベンジ
ジン化合物(2)〜(10)のR1 およびR2 の置換位
置はすべてp−位を示す。このことから本発明によるテ
トラフェニルベンジジン化合物(2)〜(10)は、発
光寿命、保存安定性に優れていることが分かった。(Element Example 2) One similar to Element Example 1
Tetraphenylbenzidine compound (2)
(R1= IBu, R2= H, R3= H), (3) (R1
= IBu, R2= H, R3= CH3), (4) (R1=
tBu, R2= H, R3= H), (5) (R1= TB
u, R2= TBu, R3= H), (6) (R1 = C6H
Five, R2= H, R 3= H), (7) (R1= C6HFive,
R2= C6HFive, R3= H), (8) (R 1= C
6HFive, R2= C6HFive, R3= CH3), (9) (R
1= P-CH3-C6HFour, R2= H, R3= OC
H3), (10) (R1= P-CH3-C6H 6, R2
= P-CH3-C6HFour, R3= H) as a hole transport material
The EL element used as above was manufactured and its characteristics were evaluated. So
The results are shown in FIG. In addition, the above tetraphenyl benz
R of gin compounds (2) to (10)1And R2Substitution position of
All the positions indicate the p-position. Therefore, according to the present invention,
The traphenylbenzidine compounds (2) to (10) are
It was found that it has excellent light life and storage stability.
【0037】(素子実施例3)素子実施例1と同様の方
法でそれぞれ、トリフェニルアミン3量体化合物(1
1)(R1 =H、R2 =H、R3 =H、R4 =H)、
(12)(R1 =H、R2=H、R3 =H、R4 =CH
3 )、(13)(R1 =tBu、R2 =p−CH3、R
3 =p−CH3 、R4 =H)、(14)(R1 =H、R
2 =H、R3 =H、R4 =OCH3 )、(15)(R1
=H、R2 =m−CH3 、R3 =m−CH3、R4 =
H)、(16)(R1 =H、R2 =p−OCH3 、R3
=p−OCH3、R4 =H)、(17)(R1 =p−C
H3 、R2 =H、R3 =H、R4 =CH 3 )、(18)
(R1 =p−CH3 、R2 =p−iBu、R3 =p−i
Bu、R 4 =H)、(19)(R1 =p−nBu、R2
=m−CH3 、R3 =H、R4 =Cl)(20)(R1
=p−OC2 H5 、R2 =p−CH3 、R3 =p−CH
3、R4 =H)を正孔輸送材として使用したEL素子を
作製し、その特性を評価した。その結果を図3に示す。
このことから本発明によるトリフェニルアミン3量体化
合物(11)〜(20)は、発光寿命、保存安定性に優
れていることが分かった。(Element Example 3) One similar to Element Example 1
Method by triphenylamine trimer compound (1
1) (R1= H, R2= H, R3= H, RFour= H),
(12) (R1= H, R2= H, R3= H, RFour= CH
3), (13) (R1= TBu, R2= P-CH3, R
3= P-CH3, RFour= H), (14) (R1= H, R
2= H, R3= H, RFour= OCH3), (15) (R1
= H, R2= M-CH3, R3= M-CH3, RFour=
H), (16) (R1= H, R2= P-OCH3, R3
= P-OCH3, RFour= H), (17) (R1= P-C
H3, R2= H, R3= H, RFour= CH 3), (18)
(R1= P-CH3, R2= P-iBu, R3= P-i
Bu, R Four= H), (19) (R1= P-nBu, R2
= M-CH3, R3= H, RFour= Cl) (20) (R1
= P-OC2HFive, R2= P-CH3, R3= P-CH
3, RFour= H) as a hole transport material
It was produced and its characteristics were evaluated. The result is shown in FIG.
From this, the triphenylamine trimerization according to the present invention
Compounds (11) to (20) have excellent emission life and storage stability.
I found out that
【0038】(素子実施例4)素子実施例1と同様の方
法でそれぞれ、ベンジジン2量体化合物(21)(R 1
=H、R2 =H、R3 =H、R4 =H、X=(A))、
(22)(R1 =H、R2 =H、R3 =H、R4 =H、
X=(B))、(23)(R1 =H、R2 =H、R3 =
H、R4 =H、R5 =H、X=(C))、(24)(R
1 =H、R2 =H、R3 =H、R4 =CH3 、R5 =C
H3 、X=(C))、(25)(R1 =H、R2 =H、
R3 =H、R4 =H、X=(D))、(26)(R1 =
H、R2=H、R3 =H、R4 =CH3 、X=
(D))、(27)(R1 =H、R2 =m−OCH3 、
R3 =m−OCH3 、R4 =OCH3 、X=(E:結合
位置は1,4−である))、(28)(R1 =H、R2
=p−tBu、R3 =H、R4 =Cl、X=(F))、
(29)(R1 =p−OC2 H5 、R2 =H、R3 =
H、R 4 =H、X=(G))(30)(R1 =H、R2
=p−nPr、R3 =p−nPr、R4 =H、X=
(H))を正孔輸送材として使用したEL素子を作製
し、その特性を評価した。その結果を図4に示す。この
ことから本発明によるベンジジン2量体化合物(21)
〜(30)は、発光寿命、保存安定性に優れていること
が分かった。(Element Example 4) One similar to Element Example 1
Benzidine dimer compound (21) (R 1
= H, R2= H, R3= H, RFour= H, X = (A)),
(22) (R1= H, R2= H, R3= H, RFour= H,
X = (B)), (23) (R1= H, R2= H, R3=
H, RFour= H, RFive= H, X = (C)), (24) (R
1= H, R2= H, R3= H, RFour= CH3, RFive= C
H3, X = (C)), (25) (R1= H, R2= H,
R3= H, RFour= H, X = (D)), (26) (R1=
H, R2= H, R3= H, RFour= CH3, X =
(D)), (27) (R1= H, R2= M-OCH3,
R3= M-OCH3, RFour= OCH3, X = (E: bond
Position is 1,4-)), (28) (R1= H, R2
= P-tBu, R3= H, RFour= Cl, X = (F)),
(29) (R1= P-OC2HFive, R2= H, R3=
H, R Four= H, X = (G)) (30) (R1= H, R2
= P-nPr, R3= P-nPr, RFour= H, X =
Fabrication of EL device using (H)) as hole transport material
Then, the characteristics were evaluated. The result is shown in FIG. this
Therefore, the benzidine dimer compound (21) according to the present invention
~ (30) has excellent luminescence life and storage stability
I understood.
【0039】(素子実施例5)素子実施例1と同様の方
法でそれぞれ、トリフェニルアミン3量体化合物(1
1)(R1 =H、R2 =H、R3 =H、R4 =H)とテ
トラフェニルベンジジン化合物(4)(R1 =p−tB
u、R2 =H、R3 =H)を共蒸着し、正孔輸送材とし
て使用したEL素子を作製し、その特性を評価した。発
光特性は3300cd/m2 、発光の寿命は720H
r、保存安定性は2900Hrであった。その結果から
本発明によるトリフェニルアミン3量体化合物(11)
とテトラフェニルベンジジン化合物(4)の共蒸着によ
って形成された正孔輸送層は、発光寿命、保存安定性に
優れていることが分かった。(Device Example 5) In the same manner as in Device Example 1, the triphenylamine trimer compound (1
1) (R 1 = H, R 2 = H, R 3 = H, R 4 = H) and tetraphenylbenzidine compound (4) (R 1 = p-tB
u, R 2 = H, R 3 = H) was co-evaporated to prepare an EL device used as a hole transport material, and its characteristics were evaluated. Luminescent property is 3300 cd / m 2 , luminescence life is 720H
r, the storage stability was 2900 Hr. From the results, the triphenylamine trimer compound (11) according to the present invention
It was found that the hole transport layer formed by the co-evaporation of and the tetraphenylbenzidine compound (4) was excellent in light emission life and storage stability.
【0040】(素子実施例6)素子実施例1と同様の方
法で正孔輸送材としてベンジジン2量体化合物(23)
(R1 =H、R2 =H、R3 =H、R4 =H、R5 =
H、X=(C))、電子輸送材として精製したトリアゾ
ールを使用したEL素子を作製し、その特性を評価し
た。なお、この場合はトリアゾールの正孔ブロッキング
性が高いために正孔輸送材からの青色発光が確認され
た。発光特性は200cd/m2 、発光の寿命は300
Hr、保存安定性は2700Hrであった。比較のため
に正孔輸送材として(化5:略称TPD)を用いて同じ
条件でEL素子を作製しその特性を調べた。TPDでの
発光特性、発光の寿命特性、保存安定性は、それぞれ1
00cd/m2 、110Hr、410Hrであった。こ
のことから本発明によるベンジジン2量体化合物(2
3)は発光寿命、保存安定性に優れていることが分かっ
た。(Device Example 6) A benzidine dimer compound (23) was used as a hole transport material in the same manner as in Device Example 1.
(R 1 = H, R 2 = H, R 3 = H, R 4 = H, R 5 =
H, X = (C)), an EL device using purified triazole as an electron transport material was prepared, and its characteristics were evaluated. In this case, blue emission from the hole transport material was confirmed because the hole blocking property of triazole was high. Luminescent property is 200 cd / m 2 , luminescence life is 300
Hr, storage stability was 2700 hr. For comparison, an EL device was manufactured under the same conditions using (Chemical Formula 5: Abbreviation TPD) as a hole transport material, and its characteristics were examined. The emission characteristics, emission lifetime characteristics, and storage stability of TPD are each 1
It was 00 cd / m 2 , 110 Hr, and 410 Hr. From this fact, the benzidine dimer compound (2
It was found that 3) had excellent emission life and storage stability.
【0041】[0041]
【発明の効果】以上のように、本発明は、正孔輸送層の
材料として、テトラフェニルベンジジン化合物、トリフ
ェニルアミン3量体、ベンジジン2量体を用いたことを
特徴とする電界発光素子であり、本発明の材料を用いる
ことにより、従来の有機電界発光素子の最も大きな問題
点であった発光安定性および保存安定性を格段に改良し
た電界発光素子を実現することができる。As described above, the present invention provides an electroluminescent device characterized by using a tetraphenylbenzidine compound, a triphenylamine trimer and a benzidine dimer as materials for the hole transport layer. Therefore, by using the material of the present invention, it is possible to realize an electroluminescent device having significantly improved luminescence stability and storage stability, which are the biggest problems of the conventional organic electroluminescent device.
【図1】本発明の一実施例における電界発光素子の構成
を示す部分断面拡大斜視図FIG. 1 is a partially enlarged cross-sectional perspective view showing a configuration of an electroluminescent device according to an embodiment of the present invention.
【図2】本発明の一実施例における正孔輸送層としてテ
トラフェニルベンジジン化合物を用いた電界発光素子の
特性を示す一覧図FIG. 2 is a list view showing characteristics of an electroluminescence device using a tetraphenylbenzidine compound as a hole transport layer in one example of the present invention.
【図3】本発明の一実施例における正孔輸送層としてト
リフェニルアミン3量体化合物を用いた電界発光素子の
特性を示す一覧図FIG. 3 is a list chart showing characteristics of an electroluminescent device using a triphenylamine trimer compound as a hole transport layer in one example of the present invention.
【図4】本発明の一実施例における正孔輸送層としてベ
ンジジン2量体量体化合物を用いた電界発光素子の特性
を示す一覧図FIG. 4 is a list showing characteristics of an electroluminescent device using a benzidine dimer compound as a hole transport layer in an example of the present invention.
1 ガラス基板 2 透明電極 3 正孔輸送層 4 電子輸送層兼発光層 5 Mg/Ag電極 1 Glass Substrate 2 Transparent Electrode 3 Hole Transport Layer 4 Electron Transport Layer and Light Emitting Layer 5 Mg / Ag Electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村 上 睦 明 神奈川県川崎市多摩区東三田3丁目10番1 号 松下技研株式会社内 (72)発明者 南 部 太 郎 神奈川県川崎市多摩区東三田3丁目10番1 号 松下技研株式会社内 (72)発明者 富 山 裕 光 茨城県つくば市御幸ケ丘45番地 保土谷化 学工業株式会社筑波研究所内 (72)発明者 押 野 雅 彦 茨城県つくば市御幸ケ丘45番地 保土谷化 学工業株式会社筑波研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mutsumi Murakami 3-10-1 Higashisanda, Tama-ku, Kawasaki-shi, Kanagawa Matsushita Giken Co., Ltd. (72) Taro Minabe Tama-ku, Kawasaki-shi, Kanagawa 3-10-10 Higashisanda Matsushita Giken Co., Ltd. (72) Inventor Hiromitsu Toyama 45 Miyukigaoka, Tsukuba City, Ibaraki Prefecture Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Institute (72) Inventor Masahiko Oshino 45, Miyukigaoka, Tsukuba City, Ibaraki Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Center
Claims (7)
ベンジジン化合物を用いたことを特徴とする電界発光素
子。 【化1】 ただし、R1 、R2 は水素原子、低級アルキル基、低級
アルコキシ基、フェニル基、低級アルキル基または低級
アルコキシ基を置換基として有するフェニル基、R3 は
水素原子、メチル基、メトキシ基、またはクロル原子を
表す。また、R1、R2 の少なくとも一方は、ノルマル
ブチル基、イソブチル基、セカンダリブチル基、ターシ
ャルブチル基、フェニル基、低級アルキル基または低級
アルコキシ基を有するフェニル基を表す。1. An electroluminescent device comprising a tetraphenylbenzidine compound represented by the following general formula. [Chemical 1] However, R 1 and R 2 are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a phenyl group having a lower alkyl group or a lower alkoxy group as a substituent, and R 3 is a hydrogen atom, a methyl group, a methoxy group, or Represents a chlorine atom. At least one of R 1 and R 2 represents a phenyl group having a normal butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a phenyl group, a lower alkyl group or a lower alkoxy group.
ミン3量体を用いたことを特徴とする電界発光素子。 【化2】 ただし、R1 、R2 、R3 は水素原子、低級アルキル
基、または低級アルコキシ基、R4 は水素原子、メチル
基、メトキシ基、またはクロル原子を表す。2. An electroluminescent device comprising a triphenylamine trimer represented by the following general formula. [Chemical 2] However, R 1 , R 2 , and R 3 represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R 4 represents a hydrogen atom, a methyl group, a methoxy group, or a chloro atom.
体を用いたことを特徴とする電界発光素子。 【化3】 ただし、R1 、R2 、R3 は水素原子、低級アルキル
基、または低級アルコキシ基、R4 は水素原子、メチル
基、メトキシ基、またはクロル原子を表す。またXは以
下の構造を有する置換基を表す。 【化4】 このうちR5 は水素原子、メチル基、メトキシ基、また
はクロル原子を表す。3. An electroluminescent device comprising a benzidine dimer represented by the following general formula. [Chemical 3] However, R 1 , R 2 , and R 3 represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R 4 represents a hydrogen atom, a methyl group, a methoxy group, or a chloro atom. X represents a substituent having the following structure. [Chemical 4] Of these, R 5 represents a hydrogen atom, a methyl group, a methoxy group, or a chloro atom.
および電極を有することを特徴とする請求項1または2
または3記載の電界発光素子。4. An electrode, a hole transporting layer, a light emitting layer, an electron transporting layer and an electrode.
Alternatively, the electroluminescent element according to the item 3.
および電極を有し、上記正孔輸送層として、請求項1記
載のテトラフェニルベンジジン化合物、請求項2記載の
トリフェニルアミン3量体、請求項3記載のベンジジン
2量体の内から選定された少なくとも2種類を含む材料
を用いたことを特徴とする電界発光素子。5. A tetraphenylbenzidine compound according to claim 1, and a triphenylamine 3 according to claim 2, which have an electrode, a hole transport layer, a light emitting layer, an electron transport layer and an electrode, and which serve as the hole transport layer. An electroluminescent device, characterized in that a material containing at least two kinds selected from a mer and a benzidine dimer according to claim 3 is used.
特徴とする請求項4または5記載の電界発光素子。6. The electroluminescent device according to claim 4, wherein the electron transport layer also serves as a light emitting layer.
特徴とする請求項4または5記載の電界発光素子。7. The electroluminescent device according to claim 4, wherein the hole transport layer also serves as a light emitting layer.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27388393A JP3194657B2 (en) | 1993-11-01 | 1993-11-01 | EL device |
EP19940117206 EP0650955B1 (en) | 1993-11-01 | 1994-10-31 | Amine compound and electro-luminescence device comprising same |
DE1994612567 DE69412567T2 (en) | 1993-11-01 | 1994-10-31 | Amine compound and electroluminescent device containing it |
US08/332,726 US5639914A (en) | 1993-11-01 | 1994-11-01 | Tetraaryl benzidines |
US08/738,326 US5707747A (en) | 1993-11-01 | 1996-10-25 | Amine compound and electro-luminescence device comprising same |
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---|---|---|---|
JP27388393A JP3194657B2 (en) | 1993-11-01 | 1993-11-01 | EL device |
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JP2001049489A Division JP3529735B2 (en) | 2001-02-23 | 2001-02-23 | Electroluminescent device |
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JPH07126615A true JPH07126615A (en) | 1995-05-16 |
JP3194657B2 JP3194657B2 (en) | 2001-07-30 |
Family
ID=17533907
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JP27388393A Expired - Lifetime JP3194657B2 (en) | 1993-11-01 | 1993-11-01 | EL device |
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