JP6379712B2 - Arylamine polymer, production method thereof and use thereof - Google Patents

Description

  The present invention relates to an arylamine polymer, a method for producing the same, and an application thereof.

  An organic EL (electroluminescence) element usually has a structure in which a plurality of organic thin films are sandwiched between a pair of electrodes, and has recently been used in various applications such as portable displays and lighting fixtures. Low molecular weight compounds are the current mainstream materials used for the organic thin film layer, but the production cost is high because vacuum deposition is generally used to form the organic thin film layer of the low molecular weight compound. There was a problem. For this reason, there is a demand for the development of high-molecular materials that can be applied and formed at low manufacturing costs.

Moreover, in an organic EL element, it is industrially strongly desired to use a phosphorescent material having excellent luminous efficiency. In such phosphorescent organic EL devices, it is generally known that it is necessary to use peripheral materials (a hole transport material and an electron transport material) having a high excited triplet level (T ₁ ).

Examples of the polymer hole injection material, hole transport material, and light-emitting host material include PEDOT-PSS, poly- (N, N′-bis (4-butylphenyl) -N, N′-bis ( Arylamine polymers represented by (phenyl) benzidine) and the like have been proposed (for example, see Patent Documents 1 to 6). However, these conventionally known materials are sufficient in phosphorescent organic EL devices because T ₁ is not high. Performance was not obtained.

  In addition, the arylamine polymer disclosed in Patent Document 7 cannot be said to have sufficient performance in terms of crystallinity, heat resistance, and solubility suitable for the coating process, and further improvements are possible. It was sought after.

JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A JP-T-2001-527102 JP-A-56-135448 JP 59-046249 A JP 2007-65164 A

  The present invention has been made in view of the above-described background art, and an object thereof is an arylamine polymer having a higher excited triplet level than conventionally known ones and excellent in driving voltage and luminous efficiency of an organic EL device, and a method for producing the same And an organic EL device containing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found an arylamine polymer in which at least two or more structures represented by the following general formula (1) are linked repeatedly, and complete the present invention. It came to.

  That is, the present invention relates to an arylamine polymer in which at least two or more structures represented by the following general formula (1) are linked repeatedly (hereinafter referred to as “arylamine polymer (1)” as appropriate), a production method and use thereof, The present invention also relates to an organic EL device using the arylamine polymer (1).

（式中、
Ａｒ^１及びＡｒ^２は、各々独立して、連結若しくは縮環していてもよい炭素数６〜２０の芳香族炭化水素基又は連結若しくは縮環していてもよい炭素数４〜２４のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、及び異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す。
Ｒ^１及びＲ^２は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、又は炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基を表す。
ａは１又は２を表す。）

(Where
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms that may be linked or condensed or a heteroaromatic group having 4 to 24 carbon atoms that may be linked or condensed. Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
a represents 1 or 2; )

  The arylamine polymer (1) of the present invention was found to have a higher excited triplet level based on its structural characteristics as compared with conventionally known polymer compounds. Since the excited triplet level is high, the organic EL device using the arylamine polymer (1) of the present invention is expected to be excellent in luminous efficiency and current efficiency. Therefore, the arylamine polymer (1) of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

  The arylamine polymer of the present invention has a high molecular weight and high durability. Therefore, a long-life organic EL element can be provided.

  Further, since the arylamine polymer of the present invention is excellent in selective solubility in a specific solvent, it is suitable for a coating process using a good solvent. Further, even if the light emitting layer is overcoated by a coating process using a poor solvent, the arylamine polymer layer is not eroded. Therefore, the arylamine polymer of the present invention can provide a material necessary for a continuous coating film forming process of an organic EL element.

  The present invention is described in detail below.

  The arylamine polymer (1) of the present invention is one in which at least two structures represented by the above general formula (1) are repeatedly connected.

In the arylamine polymer (1) of the present invention, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or linked or condensed. An optionally substituted heteroaromatic group having 4 to 24 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and two aryl groups which may be different) And may have one or more substituents selected from the group consisting of diarylamino groups having 6 to 24 carbon atoms in total.

  The aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a naphthalenyl group, a phenylnaphthyl group, a naphthylphenyl group, Anthracenyl group, pyrenyl group, terphenylenyl group, phenanthracenyl group, perylenyl group, triphenylenyl group and the like can be mentioned.

  The heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed includes at least one heteroaromatic ring, and is not particularly limited, but examples thereof include a furanyl group and a benzofuranyl group. , Dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl group, quinolinyl group, isoquinolinyl group, acridinyl group, benzothiazolyl group, quinazolyl group, quinoxalyl group, 1,6-naphthyridinyl group 1,8-naphthyridinyl group, carbazolyl group, pyridyl-phenyl group, phenyl-pyridyl group, pyridylbi-phenylyl group, pyrimidyl-phenyl group, phenyl-pyrimidyl group, phenyl-carbazolyl group, carbazolyl-phenyl group, or phenyl-carbazolyl -Fe Le, and the like.

  The alkyl group having 1 to 18 carbon atoms can be rewritten as a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, and is not particularly limited, for example, methyl group, ethyl Group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, i-butyl group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group, adamantyl group , A trifluoromethyl group, a benzyl group, a phenethyl group, and the like. Of these, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or an adamantyl group is preferable.

  The alkoxy group having 1 to 18 carbon atoms can be rewritten as a linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms, and is not particularly limited, for example, methoxy group, ethoxy Group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, i-butoxy group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group, octyloxy Group, tetrahydrofuranyloxy group, trifluoromethoxy group, benzyloxy group, phenethyloxy group and the like. Of these, a methoxy group, an ethoxy group, or an n-butoxy group is preferable.

  Although it does not specifically limit as a C6-C24 diarylamino group which has two aryl groups which may differ, For example, N, N- diphenylamino group, N, N-ditolylamino group, N, N-dibiphenylylamino group, N, N-dinaphthylamino group, N-phenyl-N-tolylamino group, N-phenyl-N-biphenylylamino group, N-tolyl-N-biphenylylamino group, N- Examples include a phenyl-N-naphthylamino group, an N-biphenylyl-N-naphthylamino group, and an N-terphenylnaphth-N-naphthylamino group. Among these, N, N-diphenylamino group, N, N-ditolylamino group, N, N-dibiphenylylamino group, N-phenyl-N-tolylamino group, or N-phenyl-N-biphenylylamino group preferable. Of these, an N, N-diphenylamino group is more preferred.

  In addition, about "the C1-C18 alkyl group, the C1-C18 alkoxy group, and the C6-C24 diarylamino group which has two different aryl groups", the effect of this invention In the range which does not impair the above, it is bonded to a C6-C20 aromatic hydrocarbon group which may be linked or condensed or a C4-C24 heteroaromatic group which may be linked or condensed. It may be. Among these, as the number of “a C1-C18 alkyl group, a C1-C18 alkoxy group, and a diarylamino group having a total of 6 to 24 carbon atoms having two different aryl groups”, 0 may be used. The range of ˜3 is preferable, and the types of substituents may be the same or different.

Ar ¹ and Ar ² are each independently a phenyl group, a biphenylyl group, a fluorenyl group, a benzofluorenyl group, a carbazolyl group, a phenylcarbazolyl group, in that the hole transport property of the arylamine polymer is excellent. Carbazolylphenyl group, phenylcarbazolylphenyl group, dibenzothienyl group, dibenzothienylphenyl group, phenyldibenzothienyl group, dibenzothienylcarbazolyl group, dibenzofuryl group, dibenzofurylphenyl group, phenyldibenzofuryl group, or dibenzo A thienylcarbazolyl group, which may each independently have an alkyl group having 1 to 18 carbon atoms or a diarylamino group having 6 to 24 carbon atoms having two aryl groups which may be different from each other. ) Is preferable.

  Of these, each independently a phenyl group, biphenylyl group, fluorenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, phenylcarbazolylphenyl group, dibenzothienyl group, dibenzothienylcarbazolyl group A dibenzofuryl group (which may each independently have an alkyl group having 1 to 18 carbon atoms or a diarylamino group having 6 to 24 carbon atoms and two aryl groups which may be different). More preferably.

  Of these, each independently a phenyl group, 4-methylphenyl group, 4-n-butylphenyl group, 4-tert-butylphenyl group, 4- (1-adamantyl) phenyl group, 4- (2 -Adamantyl) phenyl group, dibenzothienyl group, dibenzothienylphenyl group, N-phenylcarbazolyl group, or N-dibenzothienylcarbazolyl group is more preferable.

In the arylamine polymer (1) of the present invention, Ar ¹ and Ar ² may be the same or different from each other. However, considering the ease of synthesis, Ar ¹ and Ar ² are preferably the same.

When a is 2, the two “divalent phenylene groups substituted by R ¹ and R ² ” may be the same or different.

  That is, the arylamine polymer (1) can also be represented as an arylamine polymer represented by the following general formula (1 ′).

（式中、Ａｒ^１、Ａｒ^２、Ｒ^１、及びＲ^２は、各々独立して、一般式（１）と同じ定義を表わす。ｂ、ｃ、ｄ、e、ｆ及びｇは、各々独立して、０、又は１を表し、ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１又は２である。）
アリールアミンポリマー（１）において、Ｒ^１及びＲ^２の置換した二価のフェニレン基は、ｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基のいずれでもよいが、合成の容易性、生成したアリールアミンポリマーの成膜性の点からｍ−フェニレン基、ｐ−フェニレン基であることがより好ましい。すなわち、アリールアミンポリマー（１）は、下記式で表される構造（１ａ）〜（１ｃ）で表されるアリールアミンポリマーであることが好ましい。

(In the formula, Ar ¹ , Ar ² , R ¹ , and R ² each independently represent the same definition as in general formula (1). B, c, d, e, f, and g are each independently Represents 0 or 1, and b + c + d + e + f + g = 1 or 2.)
In the arylamine polymer (1), the divalent phenylene group substituted by R ¹ and R ² may be any of an o-phenylene group, an m-phenylene group, and a p-phenylene group. From the viewpoint of the film formability of the arylamine polymer, m-phenylene group and p-phenylene group are more preferable. That is, the arylamine polymer (1) is preferably an arylamine polymer represented by structures (1a) to (1c) represented by the following formula.

（式中、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、及びａは、一般式（１）と同じ定義を表わす。）
さらに、アリールアミンポリマー（１）において、Ｒ^１及びＲ^２の置換した二価のフェニレン基は、４−Ｒ^１−５−Ｒ^２−ベンゼン−１，２−ジイル基、２−Ｒ^１−５−Ｒ^２−ベンゼン−１，３−ジイル基、２−Ｒ^１−５−Ｒ^２−ベンゼン−１，４−ジイル基のいずれかであることがより好ましい。すなわち、アリールアミンポリマー（１）は、下記式で表される構造（１ａ’）〜（１ｃ’）で表されるアリールアミンポリマーであることが好ましい。

(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , and a represent the same definition as in the general formula (1).)
Furthermore, in the arylamine polymer (1), the divalent phenylene group substituted by R ¹ and R ² is 4-R ¹ -5-R ² -benzene-1,2-diyl group, 2-R ¹ -5. -R ² - 1,3-diyl ^{group, 2-R 1 -5-R} 2 - and more preferably is either benzene-1,4-diyl group. That is, the arylamine polymer (1) is preferably an arylamine polymer represented by structures (1a ′) to (1c ′) represented by the following formula.

（式中、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、及びａは、一般式（１）と同じ定義を表わす。）
アリールアミンポリマー（１）において、Ｒ^１及びＲ^２は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、又は炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基を表す。

(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , and a represent the same definition as in the general formula (1).)
In the arylamine polymer (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or a carbon group having 1 to 18 carbon atoms. A phenyl group having an alkyl group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a phenyl group having a dialkylamino group composed of an alkyl group which may have 1 to 6 carbon atoms may be represented.

With respect to the following substituents represented by R ¹ and R ² , the same substituents as those represented by Ar ¹ and Ar ² can be exemplified.
-C1-C18 alkyl group-C1-C18 alkoxy group Although it does not specifically limit as a phenyl group which has a C1-C18 alkyl group, o-tolyl group, m-tolyl group P-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, o- n-butylphenyl group, mn-butylphenyl group, pn-butylphenyl group, o-sec-butylphenyl group, m-sec-butylphenyl group, p-sec-butylphenyl group, oi- Examples thereof include a butylphenyl group, a mi-butylphenyl group, and a pi-butylphenyl group. Among these, o-tolyl group, m-tolyl group, p-tolyl group, m-ethylphenyl group, p-ethylphenyl group, pn-butylphenyl group, mn-butylphenyl group, or p A -tert-butylphenyl group is preferred.

  Although it does not specifically limit as a phenyl group which has a C1-C18 alkoxy group, For example, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m -Ethoxyphenyl group, p-ethoxyphenyl group, o-tert-butoxyphenyl group, m-tert-butoxyphenyl group, p-tert-butoxyphenyl group, pn-butoxyphenyl group, o-n-butoxyphenyl group M-n-butoxyphenyl group, pn-butoxyphenyl group, o-sec-butoxyphenyl group, m-sec-butoxyphenyl group, p-sec-butoxyphenyl group, oi-butoxyphenyl group, Examples include mi-butoxyphenyl group, pi-butoxyphenyl group, and the like. Among these, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, pn-butoxyphenyl group, mn-butoxyphenyl group, Or a p-tert-butoxyphenyl group is preferred.

  Although it does not specifically limit as a phenyl group which has a dialkylamino group which consists of a C1-C6 alkyl group which may differ, For example, a dimethylaminophenyl group, a diethylaminophenyl group, a dibutylaminophenyl group, a dihexyl Aminophenyl group, methylethylaminophenyl group, methylbutylaminophenyl group, methylhexylaminophenyl group and the like can be mentioned.

In addition, R ¹ and R ² are each independently a hydrogen atom, a methyl group, a tert-butyl group, a phenyl group, a tolyl group, or a methoxyphenyl group in that the production efficiency of the arylamine polymer is excellent. preferable.

Regarding R ¹ and R ² , among these substituents, each independently is a hydrogen atom, a methyl group, a tert-butyl group, or a phenyl group in that the hole transport property of the arylamine polymer is excellent. More preferred.

R ¹ and R ² are preferably the same substituent from the viewpoint of ease of synthesis.

  About a, it is preferable that it is 1 or 2 at the point of the ease of the synthesis | combination of an arylamine polymer, and it is more preferable that it is 1 at the point of a raw material acquisition.

  Moreover, about the arylamine polymer (1), it is preferable that the terminal is a substituent represented by following General formula (2) from the point of the light emission characteristic as an organic EL element, and durability.

（式中、Ａｒ^３は各々独立して、連結若しくは縮環していてもよい炭素数６〜２０の芳香族炭化水素基又は連結若しくは縮環していてもよい炭素数４〜２４のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、及び異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す。）
Ａｒ^３で示される下記置換基については、Ａｒ^１及びＡｒ^２で示した置換基と同じ置換基を例示することができる。
・連結又は縮環していてもよい炭素数６〜２０の芳香族炭化水素基
・連結又は縮環していてもよい炭素数４〜２４のヘテロ芳香族基
・炭素数１〜１８のアルキル基
・炭素数１〜１８のアルコキシ基
・異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基
Ａｒ^３については、アリールアミンポリマーの製造効率に優れる点で、各々独立して、フェニル基、又はビフェニリル基（これらの基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基を有していてもよい）であることが好ましく、各々独立して、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、フェニル基、又はビフェニリル基であることがより好ましい。

(In the formula, each Ar ³ is independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed) Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups).
The following substituent represented by Ar ^3, can be exemplified the same substituents as the substituents shown by Ar ¹ and Ar ^2.
A C6-C20 aromatic hydrocarbon group which may be linked or condensed ring A C4-C24 heteroaromatic group which may be linked or condensed ring C1-C18 alkyl group -Alkoxy group having 1 to 18 carbon atoms-Diarylamino group Ar ³ having a total of 6 to 24 carbon atoms having two aryl groups which may be different from each other independently in terms of excellent production efficiency of arylamine polymer , Phenyl group, or biphenylyl group (these groups are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a total of 6 carbon atoms having two aryl groups which may be different). May have a diarylamino group of ˜24) and each independently represents an o-tolyl group, an m-tolyl group, a p-tolyl group, a phenyl group, or a biphenylyl group. More preferable.

  That is, the arylamine polymer (1) is preferably an arylamine polymer represented by the following general formula (3).

（式中、
Ａｒ^１及びＡｒ^２は、各々独立して、連結若しくは縮環していてもよい炭素数６〜２０の芳香族炭化水素基又は連結若しくは縮環していてもよい炭素数４〜２４のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、及び異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す。
Ｒ^１及びＲ^２は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、又は炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基を表す。
ａは１又は２を表す。
Ａｒ^３は各々独立して、連結若しくは縮環していてもよい炭素数６〜２０の芳香族炭化水素基又は連結若しくは縮環していてもよい炭素数４〜２４のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、及び異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基からなる群より選ばれる１種以上の置換基を有していてもよい）
を表す。）
なお、一般式（３）中、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２及びａは、各々独立して、前記一般式（１）と同じ定義を示し、Ａｒ^３は、各々独立して、前記一般式（２）と同じ定義を表す。）また、一般式（３）におけるＡｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２及びａの好ましい範囲については、前述と同じである。

(Where
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms that may be linked or condensed or a heteroaromatic group having 4 to 24 carbon atoms that may be linked or condensed. Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
a represents 1 or 2;
Ar ³ is each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed or a heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed (these Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a diarylamino group having 6 to 24 carbon atoms having two aryl groups which may be different from each other. One or more substituents selected from the group consisting of:
Represents. )
In general formula (3), Ar ¹ , Ar ² , R ¹ , R ² and a each independently represent the same definition as in general formula (1), and Ar ³ is each independently The same definition as the general formula (2) is represented. In addition, the preferred ranges of Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² and a in the general formula (3) are the same as described above.

As in the case of the arylamine polymer (1), in the arylamine polymer (3) represented by the general formula (3), when “a” is 2, two “substitutions of R ¹ and R ² ” The “divalent phenylene group” may be the same or different.

  That is, the arylamine polymer (3) can also be represented as an arylamine polymer represented by the following general formula (3 ′).

（式中、Ａｒ^１、Ａｒ^２、Ｒ^１、及びＲ^２は、各々独立して、一般式（１）と同じ定義を表わす。Ａｒ^３は一般式（２）と同じ定義を表す。ｂ、ｃ、ｄ、e、ｆ及びｇは、各々独立して、０、又は１を表し、ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ＝１又は２である。）
本発明のアリールアミンポリマー（１）としては、前述の定義に該当すれば特に限定するものではないが、有機ＥＬ素子の発光効率及び寿命等の物性の点で、下記一般式（６）〜（１１）のいずれかに表されるものであることが好ましい。

(In the formula, Ar ¹ , Ar ² , R ¹ and R ² each independently represent the same definition as in the general formula (1). Ar ³ represents the same definition as in the general formula (2) b, c, d, e, f and g each independently represent 0 or 1, and b + c + d + e + f + g = 1 or 2.)
The arylamine polymer (1) of the present invention is not particularly limited as long as it falls within the above definition, but the following general formulas (6) to (6) are used in terms of physical properties such as the luminous efficiency and lifetime of the organic EL device. 11) is preferable.

（上記一般式（６）〜（１１）中、Ｒ^１及びＲ^２は、前記一般式（１）と同じ定義である。
Ｒ^３、Ｒ^４及びＲ^５は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、又は異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基を表す。
Ｒ^６、及びＲ^７は、前記一般式（１）におけるＲ^１及びＲ^２と同じ定義である。
Ｒ^８、Ｒ^９及びＲ^１０は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、又は異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基を表す。
ｎは２以上の整数を表す。）
Ｒ^３、Ｒ^４及びＲ^５で示される下記置換基については、Ａｒ^１、Ａｒ^２、Ｒ^１、及びＲ^２で示した置換基と同じ置換基を例示することができる。
・炭素数１〜１８のアルキル基
・炭素数１〜１８のアルコキシ基
・炭素数１〜１８のアルキル基を有するフェニル基
・炭素数１〜１８のアルコキシ基を有するフェニル基
・異なっていてよい２つのアリール基を有する総炭素数６〜２４のジアリールアミノ基
なお、Ｒ^３、Ｒ^４及びＲ^５は、ポリマーの製造効率に優れ、耐熱性も高い点で、各々独立して、水素原子又は炭素数１〜８のアルキル基であることが好ましく、各々独立して、水素原子、メチル基、ブチル基であることがより好ましい。

(In the general formulas (6) to (11), R ¹ and R ² have the same definition as in the general formula (1).
R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. Group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a diarylamino group having 6 to 24 carbon atoms having two aryl groups which may be different.
R ⁶ and R ⁷ have the same definition as R ¹ and R ² in the general formula (1).
R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. Group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a diarylamino group having 6 to 24 carbon atoms having two aryl groups which may be different.
n represents an integer of 2 or more. )
With respect to the following substituents represented by R ³ , R ⁴ and R ⁵ , the same substituents as those represented by Ar ¹ , Ar ² , R ¹ and R ² can be exemplified.
-C1-C18 alkyl group-C1-C18 alkoxy group-Phenyl group having a C1-C18 alkyl group-Phenyl group having a C1-C18 alkoxy group-2 different A diarylamino group having 6 to 24 carbon atoms having one aryl group. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or carbon in terms of excellent polymer production efficiency and high heat resistance. It is preferably a C 1-8 alkyl group, more preferably each independently a hydrogen atom, a methyl group, or a butyl group.

With respect to the following substituents represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , the same substituents as those represented by Ar ¹ , Ar ² , R ¹ and R ² can be exemplified. .
-C1-C18 alkyl group-C1-C18 alkoxy group-Phenyl group having a C1-C18 alkyl group-Phenyl group having a C1-C18 alkoxy group-2 different A diarylamino group having 6 to 24 carbon atoms having one aryl group, wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen in terms of excellent production efficiency of the arylamine polymer. An atom or a methyl group is preferred.

  Next, the manufacturing method of the arylamine polymer (1) of this invention is demonstrated.

  The arylamine polymer (1) of the present invention is not particularly limited, but various dibenzofuran halide compounds and arylene diamine compounds or arylene halide compounds and dibenzofuran amine compounds can be converted into trialkyl as shown in the following reaction formula. It can be synthesized by polymerization in the presence of a catalyst comprising a phosphine and / or palladium compound and a base.

（反応式１および反応式２において、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２及びａは上記一般式（１）と同じ定義を表す。Ｘ^２及びＸ^３は各々独立して、塩素原子、臭素原子、又はヨウ素原子を表す。ｎは２以上の整数を表す。）
反応式１又は反応式２の反応（以下、「重合工程」という）により得られる一般式（１）で表される構造を有する化合物は、通常、末端が二級アミノ基又はハロゲン基、又は二級アミノ基とハロゲン基の両方である。

(In Reaction Formula 1 and Reaction Formula 2, Ar ¹ , Ar ² , R ¹ , R ² and a represent the same definition as in the general formula (1). X ² and X ³ are each independently a chlorine atom, Represents a bromine atom or an iodine atom, and n represents an integer of 2 or more.)
The compound having the structure represented by the general formula (1) obtained by the reaction of the reaction formula 1 or the reaction formula 2 (hereinafter referred to as “polymerization step”) usually has a secondary amino group or a halogen group, or Both a primary amino group and a halogen group.

  Further, in the presence of a palladium catalyst and a base, a compound having a structure represented by the general formula (1) obtained in the polymerization step and an aromatic halogen compound represented by the following general formula (4) or the following general formula (5) ) Is reacted with an aromatic amine compound represented by formula (1), or both, and the terminal secondary amino group and / or halogen group of the compound represented by formula (1a) is protected (hereinafter referred to as “protection”). The process is referred to as a “forming step”.

（式中、Ａｒ^３は、上記一般式（２）におけるＡｒ^３と同じ定義である。Ｘ^１は、塩素原子、臭素原子、又はヨウ素原子を表す。）

(In the formula, Ar ³ has the same definition as Ar ³ in the general formula (2). X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.)

（式中、Ａｒ^３は、各々独立して、上記一般式（２）におけるＡｒ^３と同じ定義である。）
保護化工程の生成物として反応末端を保護したアリールアミンポリマー（１）、すなわち下記一般式（３）で表されるアリールアミンポリマーを得ることが出来る。

(In the formula, Ar ³ each independently has the same definition as Ar ³ in the general formula (2).)
As a product of the protection step, an arylamine polymer (1) whose reaction ends are protected, that is, an arylamine polymer represented by the following general formula (3) can be obtained.

（式中、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２及びａは、各々独立して、前述の一般式（１）と同じ定義を示す。Ａｒ^３は、各々独立して、前記一般式（２）と同じ定義を表す。ｎは２以上の整数を表す。）
なお、保護化工程は、重合工程に引き続きワンポットで行なってもよいし、一旦、重合工程の生成物である一般式（１）のアリールアミンポリマーを単離した後、別途、パラジウム触媒及び塩基の存在下行なってもよい。

(In the formula, Ar ¹ , Ar ² , R ¹ , R ² and a each independently represent the same definition as in the general formula (1) described above. Ar ³ each independently represents the above general formula ( 2) represents the same definition, n represents an integer of 2 or more.)
The protection step may be carried out in one pot following the polymerization step, or once the arylamine polymer of the general formula (1), which is a product of the polymerization step, is isolated, separately, a palladium catalyst and a base It may be performed in the presence.

  In the protection step, it is possible to carry out the reaction using the aromatic halogen compound represented by the general formula (4) and the aromatic amine compound represented by the general formula (5) at the same time. In terms of reaction efficiency, the reaction with the aromatic halogen compound and the reaction with the aromatic amine compound are preferably performed separately. In the case of performing the reaction separately, either the reaction using an aromatic halogen compound or the reaction using an aromatic amine compound may be performed first.

  In the protection step, the reaction using the aromatic halogen compound and the reaction using the aromatic amine compound can be carried out continuously in one pot. After one reaction, the reaction product is isolated and separated in a separate batch. The other reaction can also be performed.

  The aromatic halogen compound represented by the general formula (4) is not particularly limited. For example, bromobenzenes which may have a substituent [specifically, bromobenzene, 2-bromotoluene] 3-bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene , 5-bromo-m-xylene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-bromo-4-propylbenzene, 1-bromo-4-n-butylbenzene, 1-bromo-4 -Tert-butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1- Lomonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3- Bromocarbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethylfluorene, 2-bromo-9,9-diethylfluorene, 2- Bromo-9,9-diisopropylfluorene, 2-bromo-9,9-di-n-butylfluorene, 2-bromo-9,9-di-tert-butylfluorene, 2-bromo-9,9-di-sec -Butylfluorene, 2-bromo-9,9-di-n-hexylfluorene, 2-bromo-9,9- -N-octylfluorene, 2-bromodibenzothiophene, 2-bromodibenzofuran, etc.], chlorobenzenes optionally having a substituent [specifically, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chloro Toluene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-2-ethylbenzene, 1-chloro-4-ethylbenzene, 1-chloro-4-propylbenzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-tert-butylbenzene, 1-chloro -5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, Loronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3- Chlorocarbazole, N-propyl-3-chlorocarbazole, N-butyl-3-chlorocarbazole, 2-chlorofluorene, 2-chloro-9,9-dimethylfluorene, 2-chloro-9,9-diethylfluorene, 2- Chloro-9,9-diisopropylfluorene, 2-chloro-9,9-di-n-butylfluorene, 2-chloro-9,9-di-tert-butylfluorene, 2-chloro-9,9-di-sec -Butyl fluorene, 2-chloro-9,9-di-n-hexyl fluorene, 2-chloro-9,9-di n-octylfluorene, 2-chlorodibenzothiophene, 2-chlorodibenzofuran, etc.] and iodobenzenes which may have a substituent [specifically, iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m -Xylene, 1-iodo-2-ethylbenzene, 1-iodo-4-ethylbenzene, 1-iodo-4-propylbenzene, 1-iodo-4-n-butylbenzene, 1-iodo-4-tert-butylbenzene, 1-iodo-5- (trifluoromethoxy) benzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole, -Iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl-3 -Iodocarbazole, N-propyl-3-iodocarbazole, N-butyl-3-iodocarbazole, 2-iodofluorene, 2-iodo-9,9-dimethylfluorene, 2-iodo-9,9-diethylfluorene, 2 -Iodo-9,9-diisopropylfluorene, 2-iodo-9,9-di-n-butylfluorene, 2-iodo-9,9-di-tert-butylfluorene, 2-iodo-9,9-di- sec-Butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9,9 -Di-n-octylfluorene, 2-iododibenzothiophene, 2-iododibenzofuran, etc.].

  The aromatic amine compound represented by the general formula (5) is not particularly limited, and examples thereof include diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine. , Di (biphenyl-4-yl) amine and the like.

  The polymerization step and the protection step are both carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but the following may be used. it can. The palladium catalyst usually comprises a palladium compound and a ligand.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds [Specifically, sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV Potassium diacid), divalent palladium compounds (for example, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II ), Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroa Tate etc.], and zero-valent palladium compounds [specifically, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) etc.].

  The ligand that is a constituent component of the palladium catalyst is not particularly limited, but may be any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene-based ligands, and the like. Is mentioned.

  Although it does not specifically limit as trialkyl phosphine, For example, a triethyl phosphine, a tricyclohexyl phosphine, a triisopropyl phosphine, a tri-n-butyl phosphine, a triisobutyl phosphine, a tri-sec-butyl phosphine, a tri-tert- And butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  The aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand used in the palladium catalyst is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of 1 mol of palladium atom in the palladium compound, and expensive trialkyl. Since phosphines, arylphosphines, and carbene-based ligands are used, the range of 0.1 to 10 moles per mole of palladium atom in the palladium compound is preferable.

  The amount of the palladium catalyst used in the polymerization step is not particularly limited. For example, in the polymerization step of Reaction Formula 1 or Reaction Formula 2, it is usually 0.0000001 in terms of palladium atom with respect to 1 mol of the halogen atom of the raw material. It is preferably in the range of ˜0.20 times mole. Of these, from the viewpoint of catalytic activity and the use of an expensive palladium compound, it is usually more preferably in the range of 0.00001 to 0.05 times mole.

  Although the usage-amount of the palladium catalyst in a protection process is not specifically limited, The halogen atom 1 of the aromatic halogen compound represented by General formula (10), or the polymer represented by General formula (11) It is preferably within a range of usually 0.0000001 to 0.20 times moles in terms of palladium atoms with respect to moles. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.00001 to 0.10 times mole.

  The method for adding the palladium catalyst in the polymerization step and the protection step is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system in the polymerization step or the protection step. The catalyst components may be added in advance and mixed in the form of a palladium complex.

  Although it does not specifically limit as a base used for a superposition | polymerization process and a protection process, For example, inorganic bases, such as a hydroxide of alkali metals (specifically sodium, potassium, etc.), carbonate, an alkoxide, or Organic bases such as tertiary amines can be mentioned. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It can be added as it is to the system, or it can be prepared in situ by subjecting an alkali metal, alkali metal hydride or alkali metal hydroxide and alcohol to the reaction system. More preferred is a method in which an alkali metal tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of the base used in the polymerization step is not particularly limited, but is not particularly limited. For example, in the reaction of arylene halide represented by Reaction Formula 1 with arylamine, the arylene raw material It is selected from the range of 1 to 1000 times moles per mole of halide halogen atoms. Among these, the range of 1 to 20 times mol is more preferable in consideration of the post-treatment operation after completion of the reaction.

  The amount of the base used in the protection step is not particularly limited, but is usually in the range of 1 to 1000 times mol, preferably 1 mol per mol of the halogen atom of the aromatic halogen compound represented by the general formula (10). The range is 1 to 20 times mol, or 1 to 100000 times mol, preferably 1 to 1000 times mol per mol of the halogen atom of the polymer having the structure represented by the general formula (1). It is.

  Both the polymerization step and the protection step are usually preferably carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The polymerization step and the protection step are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization step and the protection step is not particularly limited as long as the reaction proceeds at an economically acceptable rate, but is usually 20 to 300 ° C., preferably 50 to 200 ° C. Preferably it is the range of 100-150 degreeC.

  The reaction time in the polymerization step and the protection step is not particularly limited because it is not constant depending on the arylamine polymer to be produced, the palladium catalyst, the reaction temperature, etc. In many cases, the reaction time is from a range of several minutes to 72 hours. Just choose. Preferably it is less than 24 hours.

  The arylamine polymer (1a) or (1b) produced by the polymerization step and the protection step is preferably separated and purified from unreacted low molecular weight compounds by reprecipitation or the like. Moreover, it is preferable to perform adsorption treatment with silica gel, activated alumina or the like in order to remove impurities such as a palladium catalyst.

  The arylamine polymer (1) of the present invention is used as a conductive polymer material in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic EL devices. In particular, it is extremely useful as a hole transport material, a light emitting material and a buffer material of an organic EL device.

  If the organic EL element of this invention is equipped with the organic layer containing the arylamine polymer (1) of this invention, element structure will not be specifically limited.

  Since the arylamine polymer (1) of the present invention is excellent in solubility, for example, using a solution, a mixed solution, or a melt of these materials, a spin coating method, a casting method, a dipping method, a bar coating method, The element can be easily produced by a conventionally known coating method such as a roll coating method. It can also be easily produced by an inkjet method, a Langmuir Blodget method, or the like.

  The basic structure of the organic EL device that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

  The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. The organic EL element operates by applying a potential between the anode and the cathode.

  Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the cathode.

  The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element of the present invention is not limited to such a form.

  The substrate may be light transmissive or opaque depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.

  When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.

  The general transparent anode (anode) material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. . Other metal oxides such as aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

  The anode can be modified with plasma deposited fluorocarbon. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

  A hole injection layer can be provided between the anode and the hole transport layer. The hole injection material serves to improve the subsequent film-forming properties of the organic layer and to facilitate injection of holes into the hole transport layer.

  Examples of materials suitable for use in the hole injection layer include polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, preferably examples of materials suitable for use in the hole injection layer, preferably Examples include polythiophene derivatives.

  For the hole transport layer of the organic EL device, the arylamine polymer of the present application is preferably used. In addition to the arylamine polymer of the present application, the hole transport layer may contain one or more hole transport compounds such as aromatic tertiary amines. An aromatic tertiary amine means a compound containing one or more trivalent nitrogen atoms, and these trivalent nitrogen atoms are bonded only to carbon atoms, and one of these carbon atoms One or more form an aromatic ring. Specifically, aromatic tertiary amines include arylamines, monoarylamines, diarylamines, triarylamines, or polymeric arylamines. More specifically, for example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, NPD (N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), α- NPD (N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), TPBi (1,3,5-tris (1-phenyl-) 1H-benzimidazol-2-yl) benzene), or TPD (N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4 - diamine), and the like.

  Dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer A layer containing (HAT-CN) may be provided.

  The light emitting layer of the organic EL element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.

  The emissive layer may consist of a single material that includes both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, where the emission occurs primarily from the dopant, Can have a color.

  Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole / electron recombination (support), or a combination of these materials. Good.

  Examples of fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

  As an example of the phosphorescent dopant, an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples include tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)), and the like.

  Examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolinate) 1-naphthyl Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

  In the organic EL device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, low voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitride and oxynitride can also be used.

If light emission is confirmed only through the anode, the cathode used in the present invention can be formed from any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to these Examples.

  Polymer molecular weight: THF-based GPC (HLC-8220 (manufactured by Tosoh Corporation), column connected with TSKgel-SuperH3000, TSKgel-SuperH2000, TSKgel-SuperH1000 (both manufactured by Tosoh Corporation)), and molecular weight measurement of the synthesized polymer. Went. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using DSC200F3 (manufactured by Netch).

  HOMO level: Measured using an atmospheric photoelectron spectrometer apparatus AC-3 (manufactured by Riken Keiki Co., Ltd.).

  LUMO level: The energy gap (Eg) was calculated from the absorption edge of the UV-vis absorption spectrum and subtracted from HOMO.

  Elemental analysis: Analysis was performed using a fully automatic elemental analyzer 2400II (Perkin Elmer).

  Phosphorescence spectrum measurement: Measured using a fluorimeter F-2500 (manufactured by Hitachi).

Example 1 Synthesis of Arylamine Polymer (1) In a 50 mL three-neck round bottom flask equipped with a condenser and a thermometer, N, N′-bis (4-methylphenyl) -m- 0.71 g (2.45 mmol) of phenylenediamine, 0.80 g (2.45 mmol) of 2,8-dibromodibenzofuran, 0.94 g (9.80 mmol) of sodium tert-butoxide and 14.8 g of o-xylene were charged. To this mixture, 22.4 mg (0.0245 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 0.0397 g (0.196 mmol) of tri-tert-butylphosphine o-xylene (0.16 g) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 16 hours with heating and stirring at 120 ° C.

  Subsequently, 0.19 g (1.23 mmol) of bromobenzene was added, and the reaction was further performed at 120 ° C. for 3 hours. Next, 0.42 g (2.46 mmol) of diphenylamine was added, and the reaction was further performed at 120 ° C. for 3 hours.

  After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirring solution of 90% aqueous acetone (300 mL) to precipitate a solid. The solid was collected by filtration and washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.45 g (yield 41%) of a white solid of the arylamine polymer (1).

得られたアリールアミンポリマー（１）は、ポリスチレン換算で重量平均分子量７，０００及び数平均分子量４，２００（分散度１．７）であった。

The obtained arylamine polymer (1) had a weight average molecular weight of 7,000 and a number average molecular weight of 4,200 (dispersion degree 1.7) in terms of polystyrene.

  The glass transition temperature was 199 ° C.

  The HOMO level was 5.55 eV, and the LUMO level was 2.46 eV.

  Table 1 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例２ アリールアミンポリマー（２）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−メチルフェニル）−ｐ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（２）の淡黄色固体を０．７６ｇ（収率６８％）得た。

Example 2 Synthesis of arylamine polymer (2) In Example 1, N, N'-bis instead of 0.71 g (2.45 mmol) of N, N'-bis (4-methylphenyl) -m-phenylenediamine Except that 0.74 g (2.45 mmol) of (4-methylphenyl) -p-phenylenediamine was used, the same procedure as in Example 1 was carried out, and 0.76 g (yield) of the pale yellow solid of the arylamine polymer (2) was obtained. 68%).

得られたアリールアミンポリマー（２）は、ポリスチレン換算で重量平均分子量２９，０００及び数平均分子量８，１００（分散度３．６）であった。

The obtained arylamine polymer (2) had a weight average molecular weight of 29,000 and a number average molecular weight of 8,100 (dispersion degree 3.6) in terms of polystyrene.

  The glass transition temperature was 261 ° C.

  The HOMO level was 5.30 eV, and the LUMO level was 2.37 eV.

  The measurement results of elemental analysis are shown in Table 2.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例３ アリールアミンポリマー（３）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−ｎ−ブチルフェニル）−ｐ−フェニレンジアミン ０．９２ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（３）の淡黄色固体を０．８９ｇ（収率６７％）得た。

Example 3 Synthesis of Arylamine Polymer (3) In Example 1, N, N′-bis instead of 0.71 g (2.45 mmol) of N, N′-bis (4-methylphenyl) -m-phenylenediamine Except that 0.92 g (2.45 mmol) of (4-n-butylphenyl) -p-phenylenediamine was used, the same procedure as in Example 1 was carried out, and 0.89 g of a pale yellow solid of the arylamine polymer (3) was obtained. Yield 67%).

得られたアリールアミンポリマー（３）は、ポリスチレン換算で重量平均分子量８，９００及び数平均分子量４，６００（分散度１．９）であった。

The obtained arylamine polymer (3) had a weight average molecular weight of 8,900 and a number average molecular weight of 4,600 (dispersity 1.9) in terms of polystyrene.

  The glass transition temperature was 163 ° C.

  The HOMO level was 5.31 eV, and the LUMO level was 2.35 eV.

  Table 3 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例４ アリールアミンポリマー（４）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−メチルフェニル）−２，５−ジメチル−ｐ−フェニレンジアミン ０．７８ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（４）の淡黄色固体を０．５５ｇ（収率４７％）得た。

Example 4 Synthesis of Arylamine Polymer (4) In Example 1, N, N′-bis instead of 0.71 g (2.45 mmol) of N, N′-bis (4-methylphenyl) -m-phenylenediamine Except that 0.78 g (2.45 mmol) of (4-methylphenyl) -2,5-dimethyl-p-phenylenediamine was used, the light yellow solid of the arylamine polymer (4) was obtained in the same manner as in Example 1. 0.55 g (yield 47%) was obtained.

得られたアリールアミンポリマー（２）は、ポリスチレン換算で重量平均分子量２４，５００及び数平均分子量６，８００（分散度３．６）であった。

The obtained arylamine polymer (2) had a weight average molecular weight of 24,500 and a number average molecular weight of 6,800 (dispersion degree 3.6) in terms of polystyrene.

  The glass transition temperature was 268 ° C.

  The HOMO level was 5.51 eV, and the LUMO level was 2.41 eV.

  Table 4 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例１３ アリールアミンポリマー（５）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−ｔｅｒｔ−ブチルフェニル）−ｍ−フェニレンジアミン ０．９１ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（５）の白色固体を１．０３ｇ（収率７８％）得た。

Example 13 Synthesis of Arylamine Polymer (5) In Example 1, N, N′-bis instead of 0.71 g (2.45 mmol) of N, N′-bis (4-methylphenyl) -m-phenylenediamine The same procedure as in Example 1 was carried out except that 0.91 g (2.45 mmol) of (4-tert-butylphenyl) -m-phenylenediamine was used, and 1.03 g (yield of white solid) of the arylamine polymer (5) was obtained. 78%).

得られたアリールアミンポリマー（５）は、ポリスチレン換算で重量平均分子量２９，０００及び数平均分子量２４，０００（分散度１．２）であった。

The obtained arylamine polymer (5) had a weight average molecular weight of 29,000 and a number average molecular weight of 24,000 (dispersity of 1.2) in terms of polystyrene.

  The glass transition temperature was 242 ° C.

  The HOMO level was 5.61 eV, and the LUMO level was 2.53 eV.

  Table 5 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例１４ アリールアミンポリマー（６）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−ｔｅｒｔ−ブチルフェニル）−ｐ−フェニレンジアミン ０．９１ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（６）の淡黄色固体を１．０３ｇ（収率７８％）得た。

Example 14 Synthesis of Arylamine Polymer (6) In Example 1, N, N′-bis instead of 0.71 g (2.45 mmol) of N, N′-bis (4-methylphenyl) -m-phenylenediamine The same procedure as in Example 1 was conducted except that 0.91-g (2.45 mmol) of (4-tert-butylphenyl) -p-phenylenediamine was used, and 1.03 g of a pale yellow solid of the arylamine polymer (6) ( Yield 78%).

得られたアリールアミンポリマー（６）は、ポリスチレン換算で重量平均分子量２０，０００及び数平均分子量１２，０００（分散度１．７）であった。

The obtained arylamine polymer (6) had a weight average molecular weight of 20,000 and a number average molecular weight of 12,000 (dispersity of 1.7) in terms of polystyrene.

  The glass transition temperature was 284 ° C.

  The HOMO level was 5.38 eV and the LUMO level was 2.43 eV.

  Table 6 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例１５ アリールアミンポリマー（７）の合成
実施例１において、Ｎ，Ｎ’−ビス（４−メチルフェニル）−ｍ−フェニレンジアミン ０．７１ｇ（２．４５ｍｍｏｌ）の代わりにＮ，Ｎ’−ビス（４−ｔｅｒｔ−ブチルフェニル）−２，５−ジメチル−ｐ−フェニレンジアミン ０．９８ｇ（２．４５ｍｍｏｌ）を使用した以外は、実施例１と同様に行い、アリールアミンポリマー（７）白色固体を０．８７ｇ（収率６３％）得た。

Example 15 Synthesis of Arylamine Polymer (7) In Example 1, N, N′-bis instead of 0.71 g (2.45 mmol) of N, N′-bis (4-methylphenyl) -m-phenylenediamine Except that 0.98 g (2.45 mmol) of (4-tert-butylphenyl) -2,5-dimethyl-p-phenylenediamine was used, the same procedure as in Example 1 was carried out to prepare an arylamine polymer (7) white solid. 0.87 g (yield 63%) was obtained.

得られたアリールアミンポリマー（７）は、ポリスチレン換算で重量平均分子量３３，３００及び数平均分子量１０，５００（分散度３．２）であった。

The obtained arylamine polymer (7) had a weight average molecular weight of 33,300 and a number average molecular weight of 10,500 (dispersion degree 3.2) in terms of polystyrene.

  The glass transition temperature was 275 ° C.

  The HOMO level was 5.55 eV, and the LUMO level was 2.43 eV.

  Table 7 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例５ アリールアミンポリマー（１）の励起三重項準位の測定
ＵＶ−Ｖｉｓスペクトル測定用サンプルチューブ内でアリールアミンポリマー（１） １ｍｇと２−メチルテトラヒドロフラン １ｍＬとをよく混合し、均一な溶液を調製した。この溶液を窒素ガスで１０分間バブリングすることによって脱気した後、このサンプルチューブを密栓し、燐光スペクトルを測定した。燐光スペクトルから算出されたアリールアミンポリマー（１）の励起三重項準位は、２．７２ｅＶであった。

Example 5 Measurement of excited triplet level of arylamine polymer (1) In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (1) and 1 mL of 2-methyltetrahydrofuran were mixed well to obtain a homogeneous solution. Prepared. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The excited triplet level of the arylamine polymer (1) calculated from the phosphorescence spectrum was 2.72 eV.

Example 6 Measurement of excited triplet level of arylamine polymer (2) The same operation as in Example 5 was carried out except that, in Example 5, arylamine polymer (2) was used instead of arylamine polymer (1). As a result of measuring the phosphorescence spectrum, the excited triplet level of the arylamine polymer (2) was 2.56 eV.

Example 7 Measurement of excited triplet level of arylamine polymer (3) The same operation as in Example 5 was carried out except that the arylamine polymer (3) was used instead of the arylamine polymer (1) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (3) was 2.58 eV.

Example 8 Measurement of excited triplet level of arylamine polymer (4) The same operation as in Example 5 was carried out except that the arylamine polymer (4) was used instead of the arylamine polymer (1) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (4) was 2.68 eV.

Example 16 Measurement of excited triplet level of arylamine polymer (5) The same operation as in Example 5 was carried out except that the arylamine polymer (5) was used instead of the arylamine polymer (1) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (5) was 2.72 eV.

Example 17 Measurement of excited triplet level of arylamine polymer (6) The same operation as in Example 5 was carried out except that the arylamine polymer (6) was used instead of the arylamine polymer (1) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (6) was 2.55 eV.

Example 18 Measurement of Excited Triplet Level of Arylamine Polymer (7) The same operation as in Example 5 was performed except that the arylamine polymer (7) was used instead of the arylamine polymer (1) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (7) was 2.68 eV.

Comparative Example 1 Measurement of Triplet Level of Arylamine Polymer (100) In Example 1, instead of arylamine polymer (1), poly- (N, N′-bis (4-butylphenyl) -N, N′— The phosphorescence spectrum was measured by performing the same operation as in Example 1 except that bis (phenyl) benzidine) (ADS254BE: manufactured by American Dye Source) (100) was used. The phosphorescence spectrum was calculated from the obtained phosphorescence spectrum. The triplet level of the arylamine polymer (100) was 2.35 eV.

  The measurement results of the above triplet levels are summarized in Table 8.

実施例９（素子の作製と評価）
厚さ２００ｎｍのＩＴＯ透明電極（陽極）を積層したガラス基板をアセトンおよび純水による超音波洗浄、イソプロピルアルコールによる沸騰洗浄を行った。さらに紫外線オゾン洗浄を行った。

Example 9 (Production and Evaluation of Device)
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed.

  On this substrate, a suspension of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (manufactured by Bayer, Baytron P CH8000) was applied by spin coating, and dried at 200 ° C. for 1 hour. As a result, a hole injection layer having a thickness of 80 nm was formed.

  Next, a 0.5 wt% chlorobenzene solution of the arylamine polymer (1) obtained in Example 1 was applied by spin coating, and dried at 160 ° C. for 3 hours. As a result, a 20 nm hole transport layer of the arylamine polymer (1) was formed.

Next, after installing in a vacuum evaporation apparatus, it exhausted with the vacuum pump until it became 5x10 <^-4> Pa or less. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer.

Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris). (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation.

A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and current efficiency were measured. Further, the luminance half life when the initial luminance was 2000 cd / m ² was examined. The evaluation results are shown in Table 9.

Example 10 (Production and Evaluation of Device)
In Example 9, except that the arylamine polymer (2) synthesized in Example 2 was used instead of the arylamine polymer (1), a device was prepared in the same manner as in Example 9 to obtain the emission characteristics and luminance half-life. It was measured. The evaluation results are shown in Table 9.

Example 11 (Production and Evaluation of Device)
In Example 9, a device was prepared in the same manner as in Example 9 except that the arylamine polymer (3) synthesized in Example 3 was used instead of the arylamine polymer (1), and the light emission characteristics and luminance half-life were improved. It was measured. The evaluation results are shown in Table 9.

Example 12 (Production and Evaluation of Device)
In Example 9, except that the arylamine polymer (4) synthesized in Example 4 was used instead of the arylamine polymer (1), a device was prepared in the same manner as in Example 9 to obtain the emission characteristics and luminance half-life. It was measured. The evaluation results are shown in Table 9.
Example 19 (Production and Evaluation of Device)
In Example 9, a device was prepared in the same manner as in Example 9 except that the arylamine polymer (5) synthesized in Example 13 was used instead of the arylamine polymer (1), and the light emission characteristics and luminance half-life were improved. It was measured. The evaluation results are shown in Table 9.

Example 20 (Production and Evaluation of Device)
In Example 9, except that the arylamine polymer (6) synthesized in Example 14 was used instead of the arylamine polymer (1), a device was prepared in the same manner as in Example 9 to obtain the emission characteristics and luminance half-life. It was measured. The evaluation results are shown in Table 9.

Example 21 (Production and Evaluation of Device)
In Example 9, except that the arylamine polymer (7) synthesized in Example 15 was used instead of the arylamine polymer (1), a device was prepared in the same manner as in Example 9 to obtain the light emission characteristics and luminance half-life. It was measured. The evaluation results are shown in Table 9.

Comparative Example 2 (device fabrication and evaluation)
In Example 9, instead of the arylamine polymer (1), poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) (ADS254BE: American Die Source) Except for using (manufactured) (100), an element was produced in the same manner as in Example 9, and the emission characteristics were measured. The results are shown in the table below.

  In Table 6, the measurement results of Examples 9 to 12 are shown as relative values obtained by standardizing measured values of driving voltage, luminous efficiency, and luminance half-life of 100 in Comparative Example 2.

このように、本発明のアリールアミンポリマーは、従来公知のアリールアミンポリマーに比べて化合物の三重項準位が高いという有機ＥＬ素子用電荷輸送材料として優れた特長を有する。また、本発明のアリールアミンポリマーは、従来公知のアリールアミンポリマーに比べて、輝度が高く、消費電力の少なく、耐久性の高い燐光発光性又は蛍光発光性の有機ＥＬ素子を提供できる。

As described above, the arylamine polymer of the present invention has an excellent feature as a charge transport material for an organic EL device in which the triplet level of the compound is higher than that of a conventionally known arylamine polymer. In addition, the arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having higher luminance, less power consumption, and higher durability than conventionally known arylamine polymers.

  The arylamine polymer (1) of the present invention has a high excited triplet level as compared with conventionally known polymer compounds. Therefore, if the arylamine polymer (1) of the present invention is used, it is possible to provide an organic EL device having excellent luminous efficiency and current efficiency. Therefore, the arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

Claims (7)

A triarylamine polymer represented by the following general formula (3):

(Where
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms that may be linked or condensed or a heteroaromatic group having 4 to 24 carbon atoms that may be linked or condensed. Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
a represents 1, 2 or 3.
Ar ³ is each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed or a heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed (these Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a diarylamino group having 6 to 24 carbon atoms having two aryl groups which may be different from each other. Which may have one or more substituents selected from the group consisting of:
n represents an integer of 2 or more. ) Ar ¹ and Ar ² are each independently a phenyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, phenylcarbazolylphenyl group, dibenzo Thienyl group, dibenzothienylphenyl group, phenyldibenzothienyl group, dibenzothienylcarbazolyl group, dibenzofuryl group, dibenzofurylphenyl group, phenyldibenzofuryl group, or dibenzothienylcarbazolyl group, which are each independently , according to claim 1, characterized in that it has a total diarylamino group having 6 to 24 carbon atoms having an alkyl group or different and may have two aryl groups having from 1 to 18 carbon atoms is also be) Arylamine polymer. The arylamine polymer according to claim 1, wherein R ¹ and R ² are each independently a hydrogen atom, a methyl group, a tert-butyl group, a phenyl group, a tolyl group, or a methoxyphenyl group. The arylamine polymer according to claim 1, wherein a is 1 or 2. An arylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are linked, and a terminal is a secondary amino group, a halogen atom, or both a secondary amino group and a halogen atom On the other hand, in the presence of a palladium catalyst and a base, an aryl halide represented by the following general formula (4), a diarylamine represented by the following general formula (5), or an aryl halide represented by the general formula (4) And the diarylamine represented by the general formula (5) are reacted. The method for producing an arylamine polymer according to claim 1 .

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms that may be linked or condensed or 4 to 4 carbon atoms that may be linked or condensed) 24 heteroaromatic groups (each of these substituents is independently a total number of carbon atoms having an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and two aryl groups which may be different) And may have one or more substituents selected from the group consisting of 6 to 24 diarylamino groups).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
a represents 1, 2 or 3. )

(In the formula, each Ar ³ is independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed) Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups).
X ¹ represents a chlorine atom, a bromine atom, or an iodine atom. )

(In the formula, each Ar ³ is independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a heteroaromatic group having 4 to 24 carbon atoms which may be linked or condensed) Group groups (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a total of 6 to 24 carbon atoms having two aryl groups which may be different). It may have one or more substituents selected from the group consisting of diarylamino groups). A charge transport material comprising the arylamine polymer according to claim 1 . A hole transport material, a hole injection material, or a light emitting host material comprising the arylamine polymer according to claim 1 .