JP3972583B2 - Triamine compound and method for producing the same - Google Patents

Description

【０００７】
［式中、Ａｒ¹およびＡｒ²は、それぞれ独立にｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基、２−メチル−１，４−フェニレン基、２，５−ジメチル−１，４−フェニレン基、１，２−ナフチレン基、１，４−ナフチレン基、１，５−ナフチレン基、９，１０−アンスリレン基、９，１０−フェナントリレン基、または、４，４ ' −ビフェニリレン基を表し、Ａｒ³、Ａｒ⁴、およびＡｒ⁵は、それぞれ独立にフェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、２，４−キシリル基、ｐ−クメニル基、メシチル基、１−ナフチル基、２−ナフチル基、１−アンスリル基、９−フェナントリル基、または、ビフェニリル基を表し、Ｒ¹〜Ｒ¹⁸は、それぞれ独立に水素原子または炭素数１〜４のアルキル基を表す。］
また、本発明は、Ａｒ¹およびＡｒ²が、それぞれ独立にフェニレン基またはビフェニレン基であることを特徴とする上記トリアミン化合物に関する。
【０００８】
また、本発明は、Ａｒ³、Ａｒ⁴、およびＡｒ⁵が、それぞれ独立にフェニル基、トリル基、ビフェニリル基、およびナフチル基からなる群より選ばれる炭素環式芳香族基であることを特徴とする上記トリアミン化合物に関する。
【０００９】
また、本発明は、Ａｒ¹およびＡｒ²がフェニレン基であり、かつ、Ａｒ³、Ａｒ⁴、およびＡｒ⁵が、フェニル基またはｐ−トリル基であることを特徴とする上記トリアミン化合物に関する。
【００１０】
また、本発明は、下記一般式［２］で表されるトリアリールアミン化合物と、下記一般式［３］および［４］で表される二級アミンとを反応させることを特徴とする上記トリアミン化合物の製造方法に関する。
一般式［２］
【００１１】
【化５】

【００１２】
［式中、Ａｒ¹およびＡｒ²は、それぞれｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基、２−メチル−１，４−フェニレン基、２，５−ジメチル−１，４−フェニレン基、１，２−ナフチレン基、１，４−ナフチレン基、１，５−ナフチレン基、９，１０−アンスリレン基、９，１０−フェナントリレン基、または、４，４ ' −ビフェニリレン基を表し、Ａｒ⁴は、フェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、２，４−キシリル基、ｐ−クメニル基、メシチル基、１−ナフチル基、２−ナフチル基、１−アンスリル基、９−フェナントリル基、または、ビフェニリル基を表し、Ｘはハロゲン原子を表す。］
【００１３】
【化６】

【００１４】
［式中、Ａｒ³およびＡｒ⁵は、それぞれフェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、２，４−キシリル基、ｐ−クメニル基、メシチル基、１−ナフチル基、２−ナフチル基、１−アンスリル基、９−フェナントリル基、または、ビフェニリル基を表し、Ｒ¹〜Ｒ¹⁸は、それぞれ水素原子または炭素数１〜４のアルキル基を表す。］
【００１５】
【発明の実施の形態】
以下、詳細にわたって本発明を説明する。
【００１６】
本発明のトリアミン化合物は、下記一般式［１］で表される化合物である。
【００１７】
一般式［１］
【化７】

【００１８】
［式中、Ａｒ¹およびＡｒ²は、それぞれ独立にｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基、２−メチル−１，４−フェニレン基、２，５−ジメチル−１，４−フェニレン基、１，２−ナフチレン基、１，４−ナフチレン基、１，５−ナフチレン基、９，１０−アンスリレン基、９，１０−フェナントリレン基、または、４，４ ' −ビフェニリレン基を表し、Ａｒ³、Ａｒ⁴、およびＡｒ⁵は、それぞれ独立にフェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、２，４−キシリル基、ｐ−クメニル基、メシチル基、１−ナフチル基、２−ナフチル基、１−アンスリル基、９−フェナントリル基、または、ビフェニリル基を表し、Ｒ¹〜Ｒ¹⁸は、それぞれ独立に水素原子または炭素数１〜４のアルキル基を表す。］
一般式［１］で表されるトリアミン化合物において、Ａｒ¹およびＡｒ²は好ましくは、ｐ−フェニレン基または４，４'−ビフェニリレン基である。さらに好ましくは、ｐ−フェニレン基である。
【００２０】
Ａｒ³、Ａｒ⁴、Ａｒ⁵は好ましくは、フェニル基、ｍ−トリル基、ｐ−トリル基、１−ナフチル基、２−ナフチル基、ビフェニリル基である。さらに好ましくは、フェニル基またはｐ−トリル基である。
【００２１】
さらに、Ｒ¹〜Ｒ¹⁸はそれぞれ水素原子または炭素数１〜４のアルキル基を表す。ここで、炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。Ｒ¹〜Ｒ¹⁸は好ましくは水素原子またはメチル基である。さらに好ましくは水素原子である。
【００２２】
本発明の一般式［１］で表される化合物の具体例としては、例えば、以下の化合物（表１〜表６）を挙げることができるが、本発明はこれらに限定されるものではない。
【００２３】
【表１】

【００２４】
【表２】

【００２５】
【表３】

【００２６】
【表４】

【００２７】
【表５】

【００２８】
【表６】

【００２９】
つぎに、本発明のトリアミン化合物の製造方法を述べる。本発明のトリアミン化合物の製造方法としては、一般式［２］で表されるトリアリールアミンと一般式［３］および［４］で表される二級アミンを窒素雰囲気下、有機溶媒中、塩基および触媒の存在下で加熱することによって反応させる方法を挙げることができる。
【００３０】
この際、用いることができる有機溶媒としては、トルエン、キシレン、ニトロベンゼン、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド等の溶媒が挙げられる。また、塩基としては、炭酸カリウム、水酸化リチウム、水酸化ナトリウムのような無機塩基、ピリジン、ピコリン、トリエチルアミン、ナトリウム−ｔ−ブトキシド、カリウム−ｔ−ブトキシド、Ｎ−メチルピロリジン、１，５−ジアザビシクロ［５．４．０］ウンデセン（ＤＢＵ）のような有機塩基が挙げられる。さらに、触媒としては、銅粉、酸化銅、ハロゲン化銅、硫酸銅等の銅系触媒、酢酸パラジウム、ビス（ジベンジリデンアセトン）パラジウム等のパラジウム源と、トリ−ｔ−ブチルホスフィン、２−（ジ−ｔ−ブチルホスフィノ）ビフェニル、２−（ジシクロヘキシルホスフィノ）ビフェニル等の配位子源より形成されるパラジウム錯体系触媒等が挙げられる。
【００３１】
【実施例】
以下、実施例にて本発明を具体的に説明するが、本発明は下記実施例に何ら限定されるものではない。
実施例１ 化合物（１）の製造方法
キシレン５００ｍｌ中に、４，４’−ジブロモトリフェニルアミン９．３ｇ、９−フェナントリルフェニルアミン１３．５ｇ、ナトリウム-t-ブトキシド４．９ｇ、酢酸パラジウム０．３８ｇおよびトリ-t-ブチルホスフィン１．１ｇを加え、窒素雰囲気下、攪拌しながら１２０℃で２時間加熱した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（１）１４．７ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。この化合物のマススペクトルを図１に、重水素化テトラヒドロフラン溶液中で測定した¹Ｈ−ＮＭＲスペクトルを図２に示した。
実施例２ 化合物（２）の製造方法
ニトロベンゼン４０ｍｌ中に、ビス−（４−ブロモフェニル）−ｐ−トリルアミン９．５ｇ、９−フェナントリルフェニルアミン１３．５ｇ、炭酸カリウム９．５ｇ、銅粉１．０ｇを加え、窒素雰囲気下、攪拌しながら２００℃で２０時間加熱した。放冷後濾過し、濾液をメタノールに投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（２）１３．１ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例３ 化合物（３）の製造方法法
キシレン５００ｍｌ中に、４，４’−ジブロモトリフェニルアミン９．３ｇ、９−フェナントリル−ｐ−トリルアミン１４．２ｇ、ナトリウム-t-ブトキシド４．９ｇ、ジベンジリデンアセトンパラジウム０．３２ｇおよびトリ-t-ブチルホスフィン０．０８９ｇを加え、窒素雰囲気下、攪拌しながら１．５時間加熱還流した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（３）１５．０ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例４ 化合物（４）の製造方法
トルエン５００ｍｌ中に、ビス−（４−ブロモフェニル）−ｐ−トリルアミン９．５ｇ、９−フェナントリル−ｐ−トリルアミン１４．２ｇ、ナトリウム-t-ブトキシド４．９ｇ、酢酸パラジウム０．３８ｇおよびトリ-t-ブチルホスフィン１．１ｇを加え、窒素雰囲気下、攪拌しながら１．５時間加熱還流した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（４）１４．９ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例５ 化合物（５）の製造方法
キシレン５００ｍｌ中に、４，４’−ジブロモトリフェニルアミン９．３ｇ、９−フェナントリル−ｍ−トリルアミン１４．２ｇ、ナトリウム-t-ブトキシド４．９ｇ、酢酸パラジウム０．１９ｇおよび２−（ジ−ｔ−ブチルホスフィノ）ビフェニル１．０ｇを加え、窒素雰囲気下、攪拌しながら１２０℃で３時間加熱した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（５）１６．１ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例６ 化合物（７）の製造方法
キシレン５００ｍｌ中に、４，４’−ジブロモトリフェニルアミン９．３ｇ、９−フェナントリル−４−ビフェニルアミン１７．３ｇ、ナトリウム-t-ブトキシド４．９ｇ、酢酸パラジウム０．１９ｇおよび２−（ジシクロヘキシルホスフィノ）ビフェニル１．２ｇを加え、窒素雰囲気下、攪拌しながら１２０℃で２時間加熱した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（７）１４．７ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例７ 化合物（１２）の製造方法
キシレン５００ｍｌ中に、４，４’−ジブロモトリフェニルアミン９．３ｇ、９−フェナントリル−２−ナフチルアミン１６．０ｇ、ナトリウム-t-ブトキシド４．９ｇ、酢酸パラジウム０．３８ｇおよびトリ-t-ブチルホスフィン１．１ｇを加え、窒素雰囲気下、攪拌しながら２時間加熱還流した。放冷後、反応液をメタノールへ投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（１２）１４．８ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
実施例８ 化合物（１４）の製造方法
ニトロベンゼン４０ｍｌ中に、ビス（４−ブロモビフェニル）フェニルアミン１２．８ｇ、９−フェナントリルフェニルアミン１３．５ｇ、水酸化ナトリウム１．５ｇ、酸化銅１．０ｇを加え、窒素雰囲気下、攪拌しながら２００℃で２０時間加熱した。放冷後濾過し、濾液をメタノールに投入し、目的物を析出させた。トルエンを用いて再結晶し、化合物（１４）１５．２ｇを得た。マススペクトル、ＮＭＲスペクトルによる分析により構造を確認した。
応用例１
洗浄したＩＴＯ電極付きガラス板上に、化合物（１）を真空蒸着して膜厚４０ｎｍの正孔注入層を得た。次いで、下記構造で示される化合物（２４）を真空蒸着して１０ｎｍの正孔輸送層を得た。さらに、トリス（８−ヒドロキシキノリン）アルミニウム錯体を真空蒸着して膜厚５０ｎｍの電子注入型発光層を作成し、その上にマグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの電極を形成して、有機ＥＬ素子を得た。正孔注入層、正孔輸送層、電子注入性発光層は１０^-6Ｔｏｒｒの真空中、蒸着速度０．５ｎｍ／ｓｅｃ、基板温度室温の条件下で蒸着した。この素子を窒素雰囲気下、１０５℃の環境で、１２．５ｍＡ／ｍ²の電流密度で１００時間連続して発光させた。その結果、初期の輝度は３５０ｃｄ／ｍ²を示し、１００時間経過後も３４０ｃｄ／ｍ²を示した。
【００３２】
【化８】

【００３３】
応用例２
正孔注入層に、化合物（２）を使用する以外は、応用例１と同様の有機ＥＬ素子を作成した。この素子を窒素雰囲気下、１０５℃の環境で、１２．５ｍＡ／ｍ²の電流密度で１００時間連続して発光させた。その結果、初期の輝度は３３０ｃｄ／ｍ²を示し、１００時間経過後も３１０ｃｄ／ｍ²を示した。
応用例３
正孔注入層に、化合物（３）を使用する以外は、応用例１と同様の有機ＥＬ素子を作成した。この素子を窒素雰囲気下、１０５℃の環境で、１２．５ｍＡ／ｍ²の電流密度で１００時間連続して発光させた。その結果、初期の輝度は３４０ｃｄ／ｍ²を示し、１００時間経過後も３２０ｃｄ／ｍ²を示した。
比較例１
正孔注入層に、下記構造で示される化合物（２５）を使用することを試みたが昇華性が低いため、正孔注入層を真空蒸着することができなかった。
【００３４】
【化９】

【００３５】
比較例２
正孔注入層に、下記構造で示される化合物（２６）を使用することを試みたが昇華性が低いため、正孔注入層を真空蒸着することができなかった。
【００３６】
【化１０】

【００３７】
比較例３
正孔注入輸送層に、下記構造で示される化合物（２７）を使用する以外は、応用例１と同様の有機ＥＬ素子を作成した。この素子を窒素雰囲気下、１０５℃の環境で、１２．５ｍＡ／ｍ²の電流密度で１００時間連続して発光させた。その結果、初期の輝度は２５０ｃｄ／ｍ²を示したが、１００時間経過後は１１０ｃｄ／ｍ²であった。
【００３８】
【化１１】

【００３９】
【発明の効果】
以上述べたように、本発明により、新規なトリアミン化合物を提供することが可能となった。特に、有機ＥＬ素子の耐熱性および昇華性に優れた正孔注入材料、正孔輸送材料として優れた特性を有するトリアミン化合物を提供することが可能になった。
【図面の簡単な説明】
【図１】化合物（１）のマススペクトル
【図２】化合物（１）の重水素化テトラヒドロフラン溶液中で測定した¹Ｈ−ＮＭＲスペクトル[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel triamine compound and a method for producing the same. More specifically, the present invention relates to a novel triamine compound suitable for a hole injection material or a hole transport material of an organic EL element and a method for producing the same.
[0002]
[Prior art]
Conventionally, aromatic amine compounds have been used as various dyes and functional materials. As a functional material, for example, it is used as a charge transport material for an electrophotographic photosensitive material. Recently, it has been used as a hole injection material and a hole transport material for organic EL devices. Examples of the hole injection material and the hole transport material of the organic EL element include amines having a triphenylamine skeleton such as 4,4′-bis [N-phenyl-N- (3-methylphenyl) amino] biphenyl. Although used, elements using these have the disadvantage of low heat resistance. In order to solve these disadvantages, compounds in which a condensed polycyclic aromatic group is introduced into a triphenylamine skeleton have been proposed (Japanese Patent Laid-Open Nos. 8-193191 and 9-222741). As a result, although the heat resistance is improved, the sublimation property is deteriorated due to an increase in the molecular weight and the like, and there is a drawback that it is difficult to produce an element by sublimation purification and vacuum deposition. Therefore, an amine compound excellent in heat resistance and sublimation property and having a high hole injection property and a high hole transport property is desired.
[0003]
[Problems to be solved by the invention]
The subject of this invention is providing the triamine compound excellent in heat resistance and sublimation property which can be used for the hole injection material, hole transport material, etc. of an organic EL element.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
[0005]
That is, the present invention relates to a triamine compound represented by the following general formula [1].
General formula [1]
[0006]
[Formula 4]

[0007]
[In the formula, Ar ¹ and Ar ² are each independently o-phenylene group, m-phenylene group, p-phenylene group, 2-methyl-1,4-phenylene group, 2,5-dimethyl-1,4- phenylene, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 9,10-anthrylene group, 9,10-phenanthrylene group or a 4,4 '- represents a biphenylene group, Ar ³ , Ar ⁴ , and Ar ⁵ are each independently a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl. Represents a group, 2-naphthyl group, 1-anthryl group, 9-phenanthryl group or biphenylyl group , and R ^{1 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The present invention also relates to the above triamine compound, wherein Ar ¹ and Ar ² are each independently a phenylene group or a biphenylene group.
[0008]
The present invention is also characterized in that Ar ³ , Ar ⁴ , and Ar ⁵ are each independently a carbocyclic aromatic group selected from the group consisting of a phenyl group, a tolyl group, a biphenylyl group, and a naphthyl group. It relates to the above triamine compound.
[0009]
The present invention also relates to the above triamine compound, wherein Ar ¹ and Ar ² are phenylene groups, and Ar ³ , Ar ⁴ , and Ar ⁵ are phenyl groups or p-tolyl groups.
[0010]
In addition, the present invention is characterized in that a triarylamine compound represented by the following general formula [2] is reacted with a secondary amine represented by the following general formulas [3] and [4]. The present invention relates to a method for producing a compound.
General formula [2]
[0011]
[Chemical formula 5]

[0012]
[In the formula, Ar ¹ and Ar ² are an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2-methyl-1,4-phenylene group, and a 2,5-dimethyl-1,4-phenylene group, respectively. , 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 9,10-anthrylene group, 9,10-phenanthrylene group or a 4,4 '- represents a biphenylene group, Ar ⁴ Are phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, It represents a 9-phenanthryl group or a biphenylyl group , and X represents a halogen atom. ]
[0013]
[Chemical 6]

[0014]
[Wherein Ar ³ and Ar ⁵ are each a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, a mesityl group, a 1-naphthyl group, A 2-naphthyl group, a 1-anthryl group, a 9-phenanthryl group, or a biphenylyl group is represented, and R ^{1 to} R ¹⁸ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0016]
The triamine compound of the present invention is a compound represented by the following general formula [1].
[0017]
General formula [1]
[Chemical 7]

[0018]
[In the formula, Ar ¹ and Ar ² are each independently o-phenylene group, m-phenylene group, p-phenylene group, 2-methyl-1,4-phenylene group, 2,5-dimethyl-1,4- phenylene, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 9,10-anthrylene group, 9,10-phenanthrylene group or a 4,4 '- represents a biphenylene group, Ar ³ , Ar ⁴ , and Ar ⁵ are each independently a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl. Represents a group, 2-naphthyl group, 1-anthryl group, 9-phenanthryl group or biphenylyl group , and R ^{1 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
In the triamine compound represented by the general formula [1] , Ar ¹ and Ar ² are preferably a p-phenylene group or a 4,4′-biphenylylene group. More preferably, it is a p-phenylene group.
[0020]
Ar ³ , Ar ⁴ and Ar ⁵ are preferably phenyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl and biphenylyl. More preferred is a phenyl group or a p-tolyl group.
[0021]
Furthermore, R < ¹ > -R < ¹⁸ > represents a hydrogen atom or a C1-C4 alkyl group, respectively. Here, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. R ^{1 to} R ¹⁸ are preferably a hydrogen atom or a methyl group. More preferred is a hydrogen atom.
[0022]
Specific examples of the compound represented by the general formula [1] of the present invention include the following compounds (Tables 1 to 6), but the present invention is not limited thereto.
[0023]
[Table 1]

[0024]
[Table 2]

[0025]
[Table 3]

[0026]
[Table 4]

[0027]
[Table 5]

[0028]
[Table 6]

[0029]
Next, a method for producing the triamine compound of the present invention will be described. As a method for producing the triamine compound of the present invention, a triarylamine represented by the general formula [2] and a secondary amine represented by the general formulas [3] and [4] are mixed with a base in an organic solvent in a nitrogen atmosphere. And a method of reacting by heating in the presence of a catalyst.
[0030]
At this time, examples of the organic solvent that can be used include solvents such as toluene, xylene, nitrobenzene, dimethyl sulfoxide, N, N-dimethylformamide and the like. Examples of the base include inorganic bases such as potassium carbonate, lithium hydroxide and sodium hydroxide, pyridine, picoline, triethylamine, sodium-t-butoxide, potassium-t-butoxide, N-methylpyrrolidine, 1,5-diazabicyclo [5.4.0] Organic bases such as undecene (DBU). Furthermore, as the catalyst, copper-based catalysts such as copper powder, copper oxide, copper halide and copper sulfate, palladium sources such as palladium acetate and bis (dibenzylideneacetone) palladium, tri-t-butylphosphine, 2- ( And palladium complex catalysts formed from a ligand source such as di-t-butylphosphino) biphenyl and 2- (dicyclohexylphosphino) biphenyl.
[0031]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example at all.
Example 1 Production Method of Compound (1) In 500 ml of xylene, 9.3 g of 4,4′-dibromotriphenylamine, 13.5 g of 9-phenanthrylphenylamine, 4.9 g of sodium-t-butoxide, palladium acetate 0.38 g and tri-t-butylphosphine 1.1 g were added, and the mixture was heated at 120 ° C. for 2 hours with stirring under a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 14.7 g of compound (1). The structure was confirmed by analysis by mass spectrum and NMR spectrum. The mass spectrum of this compound is shown in FIG. 1, and the ¹ H-NMR spectrum measured in a deuterated tetrahydrofuran solution is shown in FIG.
Example 2 Production Method of Compound (2) In 40 ml of nitrobenzene, 9.5 g of bis- (4-bromophenyl) -p-tolylamine, 13.5 g of 9-phenanthrylphenylamine, 9.5 g of potassium carbonate, copper powder 1.0g was added and it heated at 200 degreeC for 20 hours, stirring under nitrogen atmosphere. After cooling, the mixture was filtered, and the filtrate was poured into methanol to precipitate the target product. Recrystallization using toluene gave 13.1 g of Compound (2). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 3 Production Method of Compound (3) In 500 ml of xylene, 9.3 g of 4,4′-dibromotriphenylamine, 14.2 g of 9-phenanthryl-p-tolylamine, 4.9 g of sodium-t-butoxide, di 0.32 g of benzylideneacetone palladium and 0.089 g of tri-t-butylphosphine were added, and the mixture was heated to reflux for 1.5 hours with stirring in a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 15.0 g of Compound (3). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 4 Production Method of Compound (4) In 500 ml of toluene, 9.5 g of bis- (4-bromophenyl) -p-tolylamine, 14.2 g of 9-phenanthryl-p-tolylamine, 4.9 g of sodium-t-butoxide Then, 0.38 g of palladium acetate and 1.1 g of tri-t-butylphosphine were added, and the mixture was heated to reflux for 1.5 hours with stirring under a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 14.9 g of compound (4). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 5 Production Method of Compound (5) In 500 ml of xylene, 9.3 g of 4,4′-dibromotriphenylamine, 14.2 g of 9-phenanthryl-m-tolylamine, 4.9 g of sodium-t-butoxide, palladium acetate 0.19 g and 2- (di-t-butylphosphino) biphenyl 1.0 g were added, and the mixture was heated at 120 ° C. for 3 hours with stirring in a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 16.1 g of compound (5). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 6 Production Method of Compound (7) In 500 ml of xylene, 9.3 g of 4,4′-dibromotriphenylamine, 17.3 g of 9-phenanthryl-4-biphenylamine, 4.9 g of sodium-t-butoxide, acetic acid 0.19 g of palladium and 1.2 g of 2- (dicyclohexylphosphino) biphenyl were added, and the mixture was heated at 120 ° C. for 2 hours with stirring under a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 14.7 g of compound (7). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 7 Production Method of Compound (12) In 500 ml of xylene, 9.3 g of 4,4′-dibromotriphenylamine, 16.0 g of 9-phenanthryl-2-naphthylamine, 4.9 g of sodium t-butoxide, palladium acetate 0.38 g and tri-t-butylphosphine 1.1 g were added, and the mixture was refluxed for 2 hours with stirring under a nitrogen atmosphere. The reaction liquid was thrown into methanol after standing_to_cool, and the target object was deposited. Recrystallization using toluene gave 14.8 g of Compound (12). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Example 8 Production Method of Compound (14) In 40 ml of nitrobenzene, 12.8 g of bis (4-bromobiphenyl) phenylamine, 13.5 g of 9-phenanthrylphenylamine, 1.5 g of sodium hydroxide, 1. 0g was added and it heated at 200 degreeC for 20 hours, stirring under nitrogen atmosphere. After cooling, the mixture was filtered, and the filtrate was poured into methanol to precipitate the target product. Recrystallization using toluene gave 15.2 g of Compound (14). The structure was confirmed by analysis by mass spectrum and NMR spectrum.
Application example 1
On the washed glass plate with an ITO electrode, the compound (1) was vacuum-deposited to obtain a hole injection layer having a thickness of 40 nm. Subsequently, the compound (24) shown by the following structure was vacuum-deposited, and the 10-nm hole transport layer was obtained. Further, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injection type light-emitting layer having a thickness of 50 nm, and an electrode having a thickness of 150 nm is formed of an alloy in which magnesium and silver are mixed at a ratio of 10: 1. Thus, an organic EL device was obtained. The hole injection layer, the hole transport layer, and the electron injecting light emitting layer were deposited in a vacuum of 10 ⁻⁶ Torr at a deposition rate of 0.5 nm / sec and a substrate temperature of room temperature. This device was allowed to emit light continuously in a nitrogen atmosphere at 105 ° C. at a current density of 12.5 mA / m ² for 100 hours. As a result, the initial luminance indicates 350 cd / m ^2, after 100 hours showed 340 cd / m ^2.
[0032]
[Chemical 8]

[0033]
Application example 2
The organic EL element similar to the application example 1 was produced except using a compound (2) for a positive hole injection layer. This device was allowed to emit light continuously in a nitrogen atmosphere at 105 ° C. at a current density of 12.5 mA / m ² for 100 hours. As a result, the initial luminance indicates 330cd / m ^2, after 100 hours showed 310 cd / m ^2.
Application example 3
An organic EL device similar to Application Example 1 was prepared except that the compound (3) was used for the hole injection layer. This device was allowed to emit light continuously in a nitrogen atmosphere at 105 ° C. at a current density of 12.5 mA / m ² for 100 hours. As a result, the initial luminance indicates 340 cd / m ^2, after 100 hours showed 320 cd / m ^2.
Comparative Example 1
Although an attempt was made to use the compound (25) represented by the following structure for the hole injection layer, the hole injection layer could not be vacuum deposited because of its low sublimation property.
[0034]
[Chemical 9]

[0035]
Comparative Example 2
Although an attempt was made to use the compound (26) represented by the following structure for the hole injection layer, the hole injection layer could not be vacuum-deposited due to low sublimation properties.
[0036]
[Chemical Formula 10]

[0037]
Comparative Example 3
An organic EL device similar to Application Example 1 was prepared, except that the compound (27) represented by the following structure was used for the hole injecting and transporting layer. This device was allowed to emit light continuously in a nitrogen atmosphere at 105 ° C. at a current density of 12.5 mA / m ² for 100 hours. As a result, the initial luminance showed 250 cd / m ^2, after 100 hours was 110 cd / m ^2.
[0038]
Embedded image

[0039]
【The invention's effect】
As described above, according to the present invention, a novel triamine compound can be provided. In particular, it is possible to provide a triamine compound having excellent characteristics as a hole injection material and a hole transport material excellent in heat resistance and sublimation property of an organic EL element.
[Brief description of the drawings]
FIG. 1 Mass spectrum of compound (1) FIG. 2 ¹ H-NMR spectrum measured in deuterated tetrahydrofuran solution of compound (1)

Claims (5)

A triamine compound represented by the following general formula [1]. General formula [1]

[In the formula, Ar ¹ and Ar ² are each independently o-phenylene group, m-phenylene group, p-phenylene group, 2-methyl-1,4-phenylene group, 2,5-dimethyl-1,4- phenylene, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 9,10-anthrylene group, 9,10-phenanthrylene group or a 4,4 '- represents a biphenylene group, Ar ³ , Ar ⁴ , and Ar ⁵ are each independently a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl. Represents a group, 2-naphthyl group, 1-anthryl group, 9-phenanthryl group or biphenylyl group , and R ^{1 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The triamine compound according to claim 1, wherein Ar ¹ and Ar ² are each independently a phenylene group or a biphenylene group. ^3. Ar ³ , Ar ⁴ , and Ar ⁵ are each independently a carbocyclic aromatic group selected from the group consisting of a phenyl group, a tolyl group, a biphenylyl group, and a naphthyl group. The triamine compound described. The triamine compound according to any one of claims 1 to 3, wherein Ar ¹ and Ar ² are phenylene groups, and Ar ³ , Ar ⁴ , and Ar ⁵ are phenyl groups or p-tolyl groups. 5. The triamine according to claim 1, wherein the triarylamine compound represented by the following general formula [2] is reacted with a secondary amine represented by the following general formulas [3] and [4]. Compound production method.
General formula [2]

[In the formula, Ar ¹ and Ar ² are an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2-methyl-1,4-phenylene group, and a 2,5-dimethyl-1,4-phenylene group, respectively. , 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 9,10-anthrylene group, 9,10-phenanthrylene group or a 4,4 '- represents a biphenylene group, Ar ⁴ Are phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, It represents a 9-phenanthryl group or a biphenylyl group , and X represents a halogen atom. ]

[Wherein Ar ³ and Ar ⁵ are each a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, a mesityl group, a 1-naphthyl group, A 2-naphthyl group, a 1-anthryl group, a 9-phenanthryl group, or a biphenylyl group is represented, and R ^{1 to} R ¹⁸ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

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