JP5125213B2 - Novel triarylamine polymer, its production method and use - Google Patents

Description

  The present invention relates to a novel triarylamine polymer soluble in an organic solvent suitable as a hole transport layer or a hole injection layer of organic electroluminescence (EL) and a method for producing the same.

  FIG. 1 shows a main schematic configuration example of an organic EL element, which is composed of a light emitting layer, a layer for transporting holes or electrons, a cathode, and an anode on a transparent substrate.

  As a material used for the organic EL element, various low molecular weight materials and high molecular weight materials are used for the light emitting layer and the layer for transporting holes or electrons. An EL element is manufactured. However, the vacuum vapor deposition method requires a vacuum vapor deposition device that connects a plurality of vapor deposition kettles, and has a problem that the productivity is low and the manufacturing cost is very high when looking at future large screens. .

  On the other hand, a wet coating method in which a polymer material is dissolved in a solvent and formed by a method such as spin coating can form a layer by coating or printing under atmospheric pressure, so that the equipment cost is low and the productivity is low. There is an advantage that it is excellent.

  By the way, as a polymer organic EL material, for example, a conductive π-conjugated polymer such as poly (p-phenylene vinylene) or polyalkylthiophene is known (for example, see Patent Document 1), and a hole transport material. In addition to the polythiophene series, recently, polymers containing triarylamines have been reported (for example, see Patent Documents 2 to 6). Currently, polythiophene-based compounds are widely used, and a hole transport layer is formed by applying an acid group-containing polymer blended with polythiophene to form an aqueous dispersion on the anode. 7).

  However, the water dispersion of the polythiophene has disadvantages such as a drying process of water, corrosion due to acid groups, and remaining impurities, and a satisfactory material has not been obtained.

JP-A-3-230787 JP-A-8-054833 JP-A-8-259935 Japanese Patent Laid-Open No. 11-035687 JP-A-11-292828 Japanese Patent Laid-Open No. 13-098023 Special Table 2000-514590

  Therefore, an object of the present invention is to obtain a novel polymer which is soluble in an organic solvent and excellent in film formability and excellent in carrier transportability as a hole transport layer of an organic EL device.

  The above-mentioned subject is achieved by the following present invention.

  That is, the present invention provides the following general formula (1)

（式中、Ａｒ^１は置換若しくは無置換の炭素数６〜６０のアリール基若しくはヘテロアリール基であり、Ａは単結合か置換若しくは無置換の炭素数６〜３６のアリーレン基若しくはヘテロアリーレン基であり、Ｂは置換若しくは無置換の炭素数６〜３６のアリーレン基若しくはヘテロアリーレン基である。Ｒ^１は水素原子、炭素数１〜１８のアルキル基若しくはアルコキシ基、または炭素数６〜１８のアリール基である。Ｒ^１は隣り合う炭素原子と縮合環を形成してもよい。ａは０〜２の整数、ｍは１〜４の整数であり、ｎは１以上の整数である。）
で表されるトリアリールアミンポリマー及びその製造方法に関する。

(In the formula, Ar ¹ is a substituted or unsubstituted aryl group or heteroaryl group having 6 to 60 carbon atoms, and A is a single bond or a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. And B is a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms, R ¹ is a hydrogen atom, an alkyl or alkoxy group having 1 to 18 carbon atoms, or an aryl having 6 to 18 carbon atoms R ¹ may form a condensed ring with an adjacent carbon atom, a is an integer of 0 to 2, m is an integer of 1 to 4, and n is an integer of 1 or more.)
The triarylamine polymer represented by these, and its manufacturing method.

  The arylamine polymer in the present invention also includes an n = 1 monomer, an n = 2 dimer, and an n = 3 trimer, but is preferably an arylamine polymer having n = 4 or more.

  The triarylamine polymer of the present invention has a structural unit represented by the general formula (1) in the structural unit.

  In the general formula (1), A and B are not particularly limited as long as they fall under the above definition, but are particularly preferably arylene groups represented by the following general formulas (2) to (4). preferable.

（式中、Ｒ^２は水素原子、炭素数１〜１８のアルキル基若しくはアルコキシ基、または炭素数６〜１８のアリール基であり、隣り合う炭素原子と縮合環を形成してもよい。ｏ及びｑは１または２の整数、ｐは１〜４の整数、ｂは０〜４の整数である。）
前記一般式（１）及び（２）において、Ｒ^１及びＲ^２は前記の定義に該当すれば特に限定されるものではないが、具体的には水素原子の他、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、２−エチルブチル基、３，３−ジメチルブチル基、シクロヘキシル基、ｎ−ヘプチル基、４−メチル−シクロヘキシル基、シクロヘキシルメチル基、ｎ−オクチル基、ｔｅｒｔ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、トリフルオロメチル基、アダマンチル基等のアルキル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、シクロペンチルオキシ基、ｎ−ヘキシルオキシ基、２−エチルブトキシ基、３，３−ジメチルブトキシ基、シクロヘキシルオキシ基、ｎ−ヘプチルオキシ基、シクロヘキシルメチルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基、トリフルオロメトキシ基等のアルコキシ基、フェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−ヒドロキシフェニル基、３−ヒドロキシフェニル基、４−ヒドロキシフェニル基、２−トリフルオロメチルフェニル基、３−トリフルオロメチルフェニル基、４−トリフルオロメチルフェニル基、２，６−ジメチルフェニル基、３，６−ジメチルフェニル基、２，３−ジメチルフェニル基、３，４−ジメチルフェニル基、２，４−ジメチルフェニル基、３，５−ジメチルフェニル基、３−（トリフルオロメトキシ）フェニル基、４−（トリフルオロメトキシ）フェニル基、３，４−（メチレンジオキシ）フェニル基、２−ビフェニル基、３−ビフェニル基、４−ビフェニル基、４−ターフェニル基、１−ナフチル基、２−ナフチル基、２−メチルナフチル基、４−メチルナフチル基、９−アントラセニル基、９，９−二置換−２−フルオレニル基等のアリール基を挙げることができる。

(Wherein R ² is a hydrogen atom, an alkyl or alkoxy group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and may form a condensed ring with an adjacent carbon atom, o and q is an integer of 1 or 2, p is an integer of 1 to 4, and b is an integer of 0 to 4.)
In the general formulas (1) and (2), R ¹ and R ² are not particularly limited as long as they fall under the above definition. Specifically, in addition to a hydrogen atom, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2 -Ethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, 4-methyl-cyclohexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group , N-decyl group, trifluoromethyl group, alkyl group such as adamantyl group, methoxy group, ethoxy group, n-propoxy group, Sopropoxy group, n-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, 2-ethylbutoxy group, 3,3-dimethyl Alkoxy groups such as butoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, trifluoromethoxy group, phenyl Group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-trifluoromethyl Tylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,6-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3- (trifluoromethoxy) phenyl group, 4- (trifluoromethoxy) phenyl group, 3,4- (methylenedioxy) phenyl group, 2 -Biphenyl group, 3-biphenyl group, 4-biphenyl group, 4-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthyl group, 4-methylnaphthyl group, 9-anthracenyl group, 9,9 -An aryl group such as a disubstituted-2-fluorenyl group may be mentioned.

Further, in the general formula (1), but Ar ¹ is not particularly limited if applicable to the above definition, is particularly preferably a structure represented by the following general formula (5).

［式中、Ｒ^３は水素原子、炭素数１〜１８の直鎖、分岐若しくは環状のアルキル基、炭素数１〜１８の直鎖、分岐若しくは環状のアルコキシ基、または下記一般式（６）〜（９）

[Wherein R ³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or the following general formula (6) to (9)

（式中、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は各々独立して水素原子、炭素数１〜１８の直鎖、分岐若しくは環状のアルキル基、炭素数１〜１８の直鎖、分岐若しくは環状のアルコキシ基である。ｄ、ｅ、ｆ及びｇは０〜５の整数である。ｓは１または２の整数である。）
で表される基である。ｃは０〜５の整数、ｒは１または２の整数である。］
また、前記一般式（１）のＡｒ^１は、下記一般式（１０）で表されるアリール基であることも好ましい。

(Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a straight chain having 1 to 18 carbon atoms, branched or A cyclic alkoxy group, d, e, f and g are integers of 0 to 5. s is an integer of 1 or 2.)
It is group represented by these. c is an integer of 0 to 5, and r is an integer of 1 or 2. ]
In addition, Ar ^{1 in the} general formula (1) is preferably an aryl group represented by the following general formula (10).

（式中、Ｒ^８及びＲ^９は各々独立して水素原子、炭素数１〜８のアルキル基、または炭素数６〜１８のアリール基である。）
前記一般式（５）〜（１０）において、置換基Ｒ^３〜Ｒ^９は上記の定義に該当すれば特に限定されるものではないが、具体的には前記明細書中で例示したＲ^１及びＲ^２の一部の置換基を挙げることができる。

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 18 carbon atoms.)
In the general formulas (5) to (10), the substituents R ^{3 to} R ⁹ are not particularly limited as long as they fall within the above definition, but specifically, R ¹ and Mention may be made of some substituents of R ² .

  Among the triarylamine polymers of the present invention, the triarylamine polymers represented by the following general formulas (11) to (13) have a long main chain conjugate length and are excellent in solubility and film formability. Particularly preferred.

（式中、Ｒ^１０、Ｒ^１１及びＲ^１２は各々独立して炭素数８〜１８の直鎖、分岐若しくは環状のアルキル基、または炭素数８〜１８の直鎖、分岐若しくは環状のアルコキシ基である。ｔ、ｕ及びｖは１または２の整数であり、ｎは１以上の整数である。）
本発明において、トリアリールアミンポリマーのポリスチレン換算の重量平均分子量は、５００〜５００，０００の範囲が好ましく、溶解性及び成膜性の点からさらに好ましくは２，０００〜１００，０００の範囲である。

Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently a linear, branched or cyclic alkyl group having 8 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 8 to 18 carbon atoms. T, u and v are integers of 1 or 2, and n is an integer of 1 or more.)
In the present invention, the polystyrene-equivalent weight average molecular weight of the triarylamine polymer is preferably in the range of 500 to 500,000, more preferably in the range of 2,000 to 100,000 from the viewpoint of solubility and film formability. .

  Next, the manufacturing method of the triarylamine polymer of this invention is demonstrated.

  The triarylamine polymer represented by the general formula (1) of the present invention has the following general formula (14).

（式中、Ａｒ^１は置換若しくは無置換の炭素数６〜６０のアリール基若しくはヘテロアリール基であり、Ｂは置換若しくは無置換の炭素数６〜３６のアリーレン基若しくはヘテロアリーレン基である。Ｘ^１及びＸ^２はハロゲン原子、炭素数１〜６のアルキルスルホニルオキシ基、または炭素数６〜１２のアリールスルホニルオキシ基である。）
で表されるトリアリールアミン化合物と下記一般式（１５）

(In the formula, Ar ¹ represents a substituted or unsubstituted aryl group or heteroaryl group having 6 to 60 carbon atoms, and B represents a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. X ¹ and X ² are a halogen atom, an alkylsulfonyloxy group having 1 to 6 carbon atoms, or an arylsulfonyloxy group having 6 to 12 carbon atoms.
And a triarylamine compound represented by the following general formula (15)

（式中、Ａは単結合か置換若しくは無置換の炭素数６〜３６のアリーレン基若しくはヘテロアリーレン基であり、Ｒ^１は水素原子、炭素数１〜１８のアルキル基若しくはアルコキシ基、または炭素数６〜１８のアリール基である。Ｒ^１は隣り合う炭素原子と縮合環を形成してもよい。Ｙ^１及びＹ^２はボロン酸またはボロン酸エステルである。ａは０〜２の整数、ｍは１〜４の整数である。）
で表されるビスボロン酸またはビスボロン酸エステルを、触媒及び塩基の存在下で重合させることにより、簡便かつ効率的に製造することができる。

(In the formula, A is a single bond or a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms, R ¹ is a hydrogen atom, an alkyl group or alkoxy group having 1 to 18 carbon atoms, or a carbon number. An aryl group of 6 to 18. R ¹ may form a condensed ring with an adjacent carbon atom, Y ¹ and Y ² are boronic acids or boronic esters, a is an integer of 0 to 2, m Is an integer from 1 to 4.)
Can be easily and efficiently produced by polymerizing the bisboronic acid or bisboronic acid ester represented by the above in the presence of a catalyst and a base.

In X ¹ and X ² of the general formula (14), examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, a chlorine atom and a bromine atom are preferable, and a bromine atom is particularly preferable. The alkylsulfonyloxy group may be substituted with a fluorine atom, and examples thereof include a trifluoromethanesulfonyl group. The arylsulfonyloxy group may be substituted with an alkyl group, and examples thereof include a phenylsulfonyloxy group and a tolylsulfonyloxy group.

  The triarylamine compound represented by the general formula (14) is not particularly limited, but specific examples thereof include the following general formulas (16) to (22).

また前記一般式（１５）で表されるビスボロン酸またはビスボロン酸エステルは特に限定されるものではないが、具体的には下記一般式（２３）〜（２７）等を例示することができる。

The bisboronic acid or bisboronic acid ester represented by the general formula (15) is not particularly limited, but specific examples thereof include the following general formulas (23) to (27).

上記の化合物（１６）〜（２７）において、Ｒ’は各々独立して水素原子、または炭素数１〜１８のアルキル基若しくはアルコキシ基を表す。

In the above compounds (16) to (27), R ′ each independently represents a hydrogen atom, or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

  The palladium compound used as the catalyst component is not particularly limited. For example, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, 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) Divalent palladium compounds such as trifluoroacetate, and bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) Fin) palladium (0) 0-valent palladium compounds such like.

Although not particularly limited The amount of the palladium compound, for example, the general formula is a raw material to leaving groups X ¹ and X ^{2 1} mole of (14), normally 0.001 to 20 mol palladium terms %, And since an expensive palladium compound is used, it is preferably in the range of 0.1 to 5 mol% in terms of palladium with respect to 1 mol of the leaving group.

  The base is not particularly limited, and examples thereof include sodium and potassium carbonates, inorganic bases such as barium hydroxide and cesium fluoride, and organic bases such as triethylamine.

  Although the usage-amount of a base is not specifically limited, It is made to react by adding more than equivalent, preferably 1-20 equivalent with respect to a triarylamine compound and bisboronic acid or bisboronic acid ester.

  In the method of the present invention, the reaction temperature is not particularly limited as long as it is a reaction temperature capable of producing a triarylamine polymer, but it is usually in the range of 20 to 200 ° C, preferably 50 to 150 ° C. .

  In the method of the present invention, the reaction time is not particularly limited because it is not constant depending on the triarylamine polymer to be produced, but in many cases, it may be selected from the range of several minutes to 72 hours. Preferably it is less than 24 hours.

  The production of the triarylamine polymer of the present invention is usually preferably carried out in the presence of an inert solvent. The solvent to be used is not particularly limited as long as it does not significantly inhibit this reaction, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene, diethyl ether, tetrahydrofuran, dioxane and the like. Examples thereof include ether solvents, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide and the like. These solvents can be used alone or in combination. A solvent such as water can also be used as a co-solvent.

  The polymer thus obtained varies depending on conditions such as the raw material and its charging ratio, but terminal elimination of halogen, boronic acid and the like derived from the raw material as shown in the following general formulas (28) to (30) A group is present.

これら末端が残存した場合、耐熱性、耐色性等の材料特性に悪影響が出る傾向にある。すなわち、末端には単量体の脱離基が実質的に残っていないことが好ましい。そこで、原料に由来して残存する末端に対し、芳香族ボロン酸及び／または芳香族ハロゲン化物を加え、末端の処理を行う。

If these ends remain, the material properties such as heat resistance and color resistance tend to be adversely affected. That is, it is preferable that substantially no monomer leaving group remains at the terminal. Therefore, an aromatic boronic acid and / or aromatic halide is added to the terminal remaining from the raw material, and the terminal treatment is performed.

  The aromatic boronic acid used for the terminal treatment is not particularly limited. Specifically, phenylboronic acid, o-tolylboronic acid, m-tolylboronic acid, p-tolylboronic acid, 2,6-dimethylphenylboron Acid, 3,5-dimethylphenylboronic acid, 2,3-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,4,6-trimethylphenylboronic acid, 2,4,5-trimethylphenylboronic acid 2,3,5,6-tetramethylphenylboronic acid, 4-ethylphenylboronic acid, 2-ethylphenylboronic acid, 4-propylphenylboronic acid, 4-n-butylphenylboronic acid, 4-tert-butyl Phenylboronic acid, 4-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, 2-methoxyphenylboronic acid, , 6-dimethoxyphenylboronic acid, 3,4-dimethoxyphenylboronic acid, 2,4-dimethoxyphenylboronic acid, 2,5-dimethoxyphenylboronic acid, 2,3-dimethoxyphenylboronic acid, 2,3,4- Trimethoxyphenylboronic acid, 4-fluorophenylboronic acid, 3-fluorophenylboronic acid, 2-fluorophenylboronic acid, 2,4-difluorophenylboronic acid, 3,4-difluorophenylboronic acid, 2,6-difluoro Phenylboronic acid, 3,5-difluorophenylboronic acid, 2,5-difluorophenylboronic acid, 2,3-difluorophenylboronic acid, 4-trifluoromethylphenylboronic acid, 3,5-bis (trifluoromethyl) Phenylboronic acid, 3-fluoro-4-methoxyphenylboronic acid, 3 4- (methylenedioxy) phenylboronic acid, 1-naphthaleneboronic acid, 2-naphthaleneboronic acid, 6-methoxy-2-naphthaleneboronic acid, 6-ethoxy-2-naphthaleneboronic acid, 4-methyl-1-naphthalene Examples thereof include boronic acid, pyrene-1-boronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, and 4-biphenylboronic acid. Preferred is phenylboronic acid.

  Although it does not specifically limit as an aromatic halide, 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-bromonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromine Biphenyl, 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- Substituted or unsubstituted bromobenzenes such as hexylfluorene and 2-bromo-9,9-di-n-octylfluorene; Lobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 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, 1-chloronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chloroph Enanthrene, 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-butylfluorene, 2-chloro-9,9-di-n-hexylfluorene, 2-chloro-9,9-di-n-octylfluorene Substituted or unsubstituted chlorobenzenes, and the like, and iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotol 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, 1-iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl-3- Carbazole, 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- Examples thereof include substituted or unsubstituted iodobenzenes such as butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9,9-di-n-octylfluorene. Preferred is halobenzene, and more preferred is bromobenzene.

  The aromatic boronic acid and / or aromatic halide used in the terminal treatment of the present invention includes a triarylamine compound represented by the general formula (14) and a bisboronic acid or bisboron represented by the general formula (15). A triarylamine polymer obtained by a polymerization reaction with an acid ester may be produced and then added, and the reaction may be carried out, or may be directly added to the reactor in the course of producing the triarylamine polymer. Preferably, it is a method of reacting by sequentially adding into the reactor after the polymerization reaction for a certain time at the time of polymer production.

  The amount of aromatic boronic acid and / or aromatic halide used in the terminal treatment of the present invention is not particularly limited because it is not constant depending on the molecular weight of the polymer produced by the polymerization reaction and the polymerization reaction conditions, When adding directly at the time of superposition | polymerization, it is preferable to add in the ratio of 0.01-0.8 times mole with respect to the triarylamine compound represented by the said General formula (14) which is a raw material, More preferably, it is 0. .1 to 0.5 mole ratio.

  In the treatment method of the present invention, the amount of palladium catalyst and base used as a catalyst is not particularly limited because it is not constant depending on the molecular weight of the triarylamine polymer produced by the polymerization reaction. When the aromatic boronic acid and / or aromatic halide is directly added after a certain time, it is not necessary to add a palladium compound, and simplification is possible.

  The triarylamine polymer of the present invention has very high carrier mobility, and is extremely useful as a hole transport material and buffer material for organic electroluminescence devices.

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

  The analytical instruments and measurement methods used in this example are listed below.

[Elemental analysis]
Element analyzer: Perkin Elmer fully automatic element analyzer 2400II
Oxygen flask combustion-IC measurement method: Tosoh ion chromatography IC-2001
[Mass spectrometry]
Mass spectrometer: M-80B manufactured by Hitachi, Ltd.
Measuring method: FD-MS analysis [NMR measurement]
NMR measuring apparatus: VARIAN Gemini-200
[Infrared spectroscopy]
Infrared Spectrometer: Perkin Elmer Infrared Spectrometer System 2000
Measurement method: Nujol method [GPC measurement]
Measuring method: Tosoh HLC-8220; Column: Tosoh G5000H _XL- G3000H _XL
Solvent: THF, concentration: 0.5% by weight, flow rate: 1.0 ml / min [glass transition temperature measurement]
Measuring device: Mac Science DSC-3100
Measuring method: standard sample = Al ₂ O ₃ 5.0 mg, temperature rising rate = 10 ° C./min (nitrogen atmosphere)
[UV-visible spectroscopy]
UV-Vis spectrophotometer: Hitachi, Ltd. UV-Vis spectrophotometer [Photoelectron Spectroscopy]
Photoelectron spectrometer: Photoelectron spectroscopy AC-2, manufactured by Riken Keiki
Experimental Example 1 (Synthesis of N, N-bis (2-naphthalene-6-trifluoromethanesulfonyloxy) -4-n-dodecylaniline (1-C))

冷却管、温度計を装着した３００ｍｌ四つ口丸底フラスコに、室温下、２−ブロモ−６−メトキシナフタレン １３．０ｇ（５５ｍｍｏｌ）、４−ｎ−ドデシルアニリン ７．３ｇ（２５ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ５．８ｇ（６０．５ｍｍｏｌ）及びｏ−キシレン １１０ｍｌを仕込んだ。この混合液に、予め窒素雰囲気下で調製したトリス（ジベンジリデンアセトン）二パラジウムクロロホルム錯体１２６ｍｇ（０．１４ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン １．２ｍｌのｏ−キシレン溶液（１０ｍｌ，０．２ｍｇ／ｍｌ）を添加した。その後窒素雰囲気下、温度を１２０℃まで昇温し、１２０℃で加熱攪拌しながら終夜熟成した。反応終了後、この反応混合物を室温まで冷却して、トルエンを用いて有機層を抽出した。硫酸マグネシウムで乾燥、溶媒を減圧留去後、ヘキサン溶媒を用いたカラムクロマトグラフィーを実施した。さらにヘキサンとエタノールを用いて再結晶を実施し、白色固体として１１．７ｇ得た（収率８１％）。ＮＭＲ測定により目的物１−Ａであることを確認した。

To a 300 ml four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 13.0 g (55 mmol) of 2-bromo-6-methoxynaphthalene, 7.3 g (25 mmol) of 4-n-dodecylaniline, sodium- 5.8 g (60.5 mmol) of tert-butoxide and 110 ml of o-xylene were charged. To this mixed solution, 126 mg (0.14 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and an o-xylene solution (10 ml, 0.2 mg / 0.2 mg) of tri-tert-butylphosphine 1.2 ml were prepared. ml) was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged overnight with heating and stirring at 120 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with toluene. After drying over magnesium sulfate and distilling off the solvent under reduced pressure, column chromatography using a hexane solvent was performed. Furthermore, recrystallization was performed using hexane and ethanol to obtain 11.7 g as a white solid (yield 81%). It was confirmed by NMR measurement that it was the desired product 1-A.

¹ H-NMR (CDCl ₃ ): 7.62 (2H, d, 8.8 Hz), 7.49 (2H, d, 8.8 Hz), 7.39 (2H, s), 7.29 (2H, d, 8.8 Hz), 7.28 (2H, d, 8.8 Hz), 7.0-7.15 (6H, m), 3.90 (6H, s), 2.57 (2H, t, 8.2 Hz), 1.5-1.75 (2 H, m), 1.15-1.45 (18 H, m), 0.88 (3 H, t, 6.6 Hz)
¹³ C-NMR (CDCl ₃ ): 156.71, 145.54, 143.91, 137.74, 130.86, 129.76, 129.06, 128.36, 127.56, 125.12, 123 .90, 120.44, 118.79, 105.90, 55.37, 35.45, 31.99, 31.59, 29.74, 29.61, 29.50, 29.43, 22.76 , 14.19
A 100 ml round bottom flask equipped with a dropping funnel was charged with 5.74 g (10 mmol) of 1-A and 50 ml of dichloromethane under a nitrogen atmosphere at room temperature. After cooling in an ice bath, 20 ml (20 mmol) of a boron tribromide 1M dichloromethane solution was slowly added dropwise. The mixture was stirred overnight under a nitrogen atmosphere while slowly raising the temperature. After adding pure water to terminate the reaction, toluene was added to the reaction mixture to extract an organic layer. Column chromatography using a solvent of toluene: ethyl acetate = 4: 1 was performed to obtain 3.91 g (yield 72%) as a yellowish green oily substance. It was confirmed by NMR measurement that it was the desired product 1-B.

¹ H-NMR (CDCl ₃ ): 6.9-7.7 (16H, m), 5.01 (2H, br-s), 2.4-2.7 (2H, m), 1.5- 1.75 (2H, m), 1.1-1.5 (18H, m), 0.87 (3H, t, 6.6 Hz)
A 100 ml eggplant flask equipped with a dropping funnel was charged with 3.22 g (5.9 mmol) of 1-B, 50 ml of toluene, and 15 ml of pyridine under a nitrogen atmosphere at room temperature. After cooling in an ice bath, 4.66 g (16.5 mmol) of trifluoromethanesulfonic anhydride (Tf ₂ O) was slowly added dropwise, and the mixture was stirred overnight while slowly raising the temperature. After adding pure water to terminate the reaction, toluene was added to the reaction mixture for extraction. Further, the organic layer was washed in order of 10% hydrochloric acid, pure water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. This was subjected to column chromatography using a toluene solvent to obtain 4.83 g (quant.) As a yellow oily substance. It was confirmed by NMR measurement that it was the target product 1-C.

¹ H-NMR (CDCl ₃ ): 7.75 (2H, d, 8.8 Hz), 7.67 (2H, s), 7.64 (2H, d, 8.8 Hz), 7.0-7. 5 (10H, m), 2.57 (2H, t, 7.8 Hz), 1.5-1.75 (2H, m), 1.15-1.45 (18H, m), 0.88 ( 3H, t, 6.6Hz)
Example 1 (Synthesis of Compound 31)
In a 50 ml four-necked round bottom flask equipped with a condenser and a thermometer, 564 mg (1.1 mmol) of 2,2′-bithiophene-5,5′-diboronic acid bispinacol ester, 810 mg of 1-C (1 mmol) at room temperature. ), Aliquat 336 0.6 g, sodium carbonate 640 mg (32 mmol), pure water 6 g and toluene 10 ml. To this mixed solution, 5.8 mg (0.005 mmol) of tetrakistriphenylphosphine palladium was added, the temperature was raised to 95 ° C., and the mixture was aged for about 16 hours while stirring with heating. Thereafter, bromobenzene was added, and the mixture was further heated and stirred for 1 day. After completion of the reaction, the reaction mixture was cooled to room temperature and then slowly added to a stirred solution of 90% aqueous acetone (300 ml). The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure. Further, column chromatography using a toluene solvent was carried out, and the concentrated solution was slowly added again into acetone to precipitate it, followed by drying to obtain an ocher powder (yield 40%). When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (31). The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 1 and FIG. 2, respectively. Further, the obtained polymer had a weight average molecular weight of 12,000 and a number average molecular weight of 7,500 (dispersion degree of 1.58) in terms of polystyrene. As a result of measurement by photoelectron spectroscopy, the HOMO level was 5.4 eV. The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 1 and FIG. 2, respectively.

実施例２（仕込比を変更した化合物３１の合成）
実施例１において、１−Ｂ ４２０ｍｇ（１ｍｍｏｌ）の代わりに２−Ｃ ８１０ｍｇ（１ｍｍｏｌ）及び炭酸ナトリウム６４０ｍｇ（３２ｍｍｏｌ）の代わりに炭酸カリウム５５３ｍｇ（４ｍｍｏｌ）を用いた以外は実施例１と同様の方法で実施し、黄土色粉末を得た（収率７０％）。また、得られたポリマーは、ポリスチレン換算で重量平均分子量２２，０００及び数平均分子量１２，３００（分散度１．９５）であった。

Example 2 (Synthesis of Compound 31 with varying charge ratio)
In Example 1, 810 mg (1 mmol) of 2-C instead of 420 mg (1 mmol) of 1-B and 553 mg (4 mmol) of potassium carbonate instead of 640 mg (32 mmol) of sodium carbonate were used. To obtain an ocherous powder (yield 70%). The obtained polymer had a weight average molecular weight of 22,000 and a number average molecular weight of 12,300 (dispersity 1.95) in terms of polystyrene.

  Experimental Example 2 (Synthesis of N, N-bis (4'-bromophenyl) -4-n-octylaniline (2-B))

冷却管、温度計を装着した３００ｍｌ四つ口丸底フラスコに、室温下、ブロモベンゼン１７．３ｇ（１１０ｍｍｏｌ）、４−ｎ−オクチルアニリン １０．３ｇ（５０ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド １２．７ｇ（１３２ｍｍｏｌ）及びｏ−キシレン １７０ｍｌを仕込んだ。この混合液に、予め窒素雰囲気下で調製したトリス（ジベンジリデンアセトン）二パラジウムクロロホルム錯体２２９ｍｇ（０．２５ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン ２．２ｍｌのｏ−キシレン溶液（５ｍｌ，０．２ｍｇ／ｍｌ）を添加した。その後窒素雰囲気下、温度を１２０℃まで昇温し、１２０℃で加熱攪拌しながら４時間熟成した。反応終了後、この反応混合物を室温まで冷却し、トルエンを用いて有機層を抽出した。硫酸マグネシウムで乾燥、溶媒を減圧留去後、ヘキサン溶媒を用いたカラムクロマトグラフィーを実施し、淡黄色油状物として１４．１ｇ得た（収率７８％）。

In a 300 ml four-necked round bottom flask equipped with a condenser and a thermometer, 17.3 g (110 mmol) of bromobenzene, 10.3 g (50 mmol) of 4-n-octylaniline, 12.7 g of sodium tert-butoxide at room temperature. (132 mmol) and 170 ml of o-xylene were charged. To this mixed solution, 229 mg (0.25 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and an o-xylene solution (5 ml, 0.2 mg / 0.2 mg) of tri-tert-butylphosphine 2.2 ml were prepared. ml) was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 4 hours while heating and stirring at 120 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with toluene. After drying over magnesium sulfate and distilling off the solvent under reduced pressure, column chromatography using a hexane solvent was performed to obtain 14.1 g as a pale yellow oil (yield 78%).

  A 300 ml four-necked round bottom flask was charged with 14.1 g (39 mmol) of 2-A and 150 ml of N, N-dimethylformamide at room temperature. A solution prepared by dissolving 9.8 g (55 mmol) of N-bromosuccinimide in 50 ml of N, N-dimethylformamide was slowly added dropwise to this mixed solution, and after completion of the addition, the mixture was reacted at room temperature for 3 hours. After completion of the reaction, toluene was added to the reaction mixture to extract the organic layer, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and column chromatography was performed using a hexane solvent to obtain 17.8 g as a pale yellow oil. Obtained (yield 87%). It was confirmed to be the desired product 2-B by NMR measurement.

¹ H-NMR (CDCl ₃ ): 6.8-7.7 (12H, m), 2.57 (2H, t, 7.6 Hz), 1.45-1.70 (2H, m), 1. 15-1.45 (10H, m), 0.90 (3H, t, 6.6Hz)
¹³ C-NMR (CDCl ₃ ): 143.63, 144.28, 138.86, 132.14, 129.43, 124.93, 114.91, 35.46, 31.96, 31.52, 29 .54, 29.45, 29.32, 22.75, 14.20
Example 3 (Synthesis of Compound 32)
In Example 1, it implemented by the method similar to Example 1 except having used 2-B420 mg (1 mmol) instead of 1-C 810 mg (1 mmol), and the ocher-colored powder was obtained. When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (32). Moreover, the obtained polymer was the weight average molecular weight 5,000 and the number average molecular weight 3,000 (dispersion degree 1.7) in polystyrene conversion. As a result of measurement by photoelectron spectroscopy, the HOMO level was 5.3 eV.

実験例３（化合物３−Ｄの合成）

Experimental Example 3 (Synthesis of Compound 3-D)

冷却管、温度計を装着した２００ｍｌ四つ口丸底フラスコに、室温下、２−ブロモ−６−メトキシナフタレン ４．７ｇ（２０ｍｍｏｌ）、４−クロロフェニルボロン酸 ３．３ｇ（２１ｍｍｏｌ）、ＴＨＦ７５ｍｌ及び２０％炭酸ナトリウム水溶液 ４５ｇを仕込んだ。この混合液に、テトラキストリフェニルホスフィンパラジウム１１．６ｍｇ（０．０１ｍｍｏｌ）を添加し、その後窒素雰囲気下、温度を６０℃まで昇温し、加熱攪拌しながら６時間熟成した。反応終了後、この反応混合物を室温まで冷却し、トルエンを用いて有機層を抽出した。硫酸マグネシウムで乾燥、溶媒を減圧留去後、エタノールを用いて再結晶を実施し、淡褐色結晶として４．２ｇ得た（収率７８％）。ＮＭＲ測定により目的物３−Ａであることを確認した。

In a 200 ml four-necked round bottom flask equipped with a condenser and a thermometer, 4.7 g (20 mmol) of 2-bromo-6-methoxynaphthalene, 3.3 g (21 mmol) of 4-chlorophenylboronic acid, 75 ml of THF and 20 at room temperature. A 45% aqueous sodium carbonate solution was charged. Tetrakistriphenylphosphinepalladium (11.6 mg, 0.01 mmol) was added to the mixed solution, and then the temperature was raised to 60 ° C. in a nitrogen atmosphere, followed by aging for 6 hours with heating and stirring. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with toluene. After drying over magnesium sulfate and distilling off the solvent under reduced pressure, recrystallization was carried out using ethanol to obtain 4.2 g of light brown crystals (yield 78%). It was confirmed by NMR measurement that it was the desired product 3-A.

¹ H-NMR (CDCl ₃ ): 7.93 (1H, s), 7.80 (1H, d, 8.4 Hz), 7.78 (1H, d, 8.8 Hz), 7.61-7. 69 (2H, m), 7.60 (1H, s), 7.43 (2H, d, 8.4 Hz), 7.13-7.22 (2H, m), 3.94 (3H, s)
¹³ C-NMR (CDCl ₃ ): 157.81, 139.57, 135.03, 133.82, 133.05, 129.63, 129.04, 128.88, 128.35, 127.34, 125 .60, 125.47, 119.28, 105.55, 55.37
In a 200 ml four-necked round bottom flask equipped with a condenser and a thermometer, 4.2 g (15.6 mmol) of 3-A, 2.0 g (7 mmol) of 4-n-dodecylaniline, sodium-tert-butoxide at room temperature. 1.6 g (17.2 mmol) and 55 ml of o-xylene were charged. To this mixed solution, 35.7 mg (0.04 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and 0.2 mg / ml toluene solution of tri-tert-butylphosphine 0.34 ml of o- Xylene (5 ml) solution was added. Thereafter, the temperature was raised to 140 ° C. in a nitrogen atmosphere, and the mixture was aged overnight with heating and stirring at 140 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with toluene. After drying over magnesium sulfate and distilling off the solvent under reduced pressure, column chromatography was performed with a toluene solvent. Furthermore, recrystallization was performed using hexane and ethanol to obtain 5.0 g as a white solid (yield 99%). It was confirmed by NMR measurement that the product was the desired product 3-B.

¹ H-NMR (CDCl ₃ ): 7.95 (2H, s), 7.66-7.83 (8H, m), 7.60 (2H, d, 8.4 Hz), 7.1-7. 3 (12H, m), 3.94 (6H, s), 2.60 (2H, t, 8.0 Hz), 1.5-1.75 (2H, m), 1.15-1.45 ( 18H, m), 0.88 (3H, t, 7.0 Hz)
¹³ C-NMR (CDCl ₃ ): 157.50, 146.95, 138.20, 135.82, 134.88, 133.44, 129.54, 129.25, 129.19, 127.72, 127 13, 125.69, 124.90, 124.81, 123.81, 119.01, 105.59, 97.27, 55.36, 48.53, 29.76, 29.72, 29.61. , 29.43, 22.76, 14.19.
A 50 ml eggplant-shaped flask equipped with a dropping funnel was charged with 5.0 g (6.9 mmol) of 3-B and 50 ml of dichloromethane under a nitrogen atmosphere at room temperature. After cooling in an ice bath, 14 ml (14 mmol) of boron tribromide 1M dichloromethane solution was slowly added dropwise. The mixture was stirred overnight under a nitrogen atmosphere while slowly raising the temperature. After adding pure water to terminate the reaction, the organic layer was extracted from this reaction mixture using toluene. This was subjected to column chromatography with toluene: ethyl acetate = 4: 1 solvent to obtain 4.7 g of 3-C as a yellowish green oil.

A 100 ml eggplant-shaped flask equipped with a dropping funnel was charged with 4.7 g of 3-C, 60 ml of toluene and 18 ml of pyridine under a nitrogen atmosphere at room temperature. After cooling in an ice bath, 5.14 g (18.2 mmol) of trifluoromethanesulfonic anhydride (Tf ₂ O) was slowly added dropwise, and the mixture was stirred overnight while slowly raising the temperature. After adding pure water to terminate the reaction, toluene was added to the reaction mixture for extraction. Further, the organic layer was washed in order of 10% hydrochloric acid, pure water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. This was subjected to column chromatography with toluene: hexane = 1: 1 solvent, and then washed with hexane to obtain 3.74 g as a pale yellow powder (yield was 56 in two steps from 3-B). %). It was confirmed to be the desired product 3-D by NMR measurement.

¹ H-NMR (CDCl ₃ ): 8.06 (2H, s), 7.72-8.02 (8H, m), 7.62 (4H, d, 8.8 Hz), 7.39 (2H, d, 9.2 Hz), 7.24 (4H, d, 7.6 Hz), 7.15 (4H, s), 2.61 (2H, t, 8.4), 1.55-1.75 ( 2H, m), 1.15-1.45 (18H, m), 0.88 (3H, t, 6.6Hz)
Example 4 (Synthesis of Compound 33)
In Example 1, it implemented by the method similar to Example 1 except having used 3-D 810 mg (1 mmol) instead of 1-B 420 mg (1 mmol), and obtained ocherous powder (yield 40%) ). When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (33). Moreover, the obtained polymer was the weight average molecular weight 5,500 and the number average molecular weight 4,200 (dispersion degree 1.31) in polystyrene conversion.

実施例５（化合物３５の合成）
実施例１において、１−Ｂ ４２０ｍｇ（１ｍｍｏｌ）の代わりに下記一般式（３４）で表される化合物

Example 5 (Synthesis of Compound 35)
In Example 1, the compound represented by the following general formula (34) instead of 1-B 420 mg (1 mmol)

を用いた以外は実施例１と同様の方法で実施し、黄土色粉体を得た（収率５６％）。得られた粉体を元素分析及び赤外分光分析により測定したところ、下記一般式（３５）で表されるトリアリールアミンポリマーであることが確認された。また、得られたポリマーは、ポリスチレン換算で重量平均分子量１３，０００及び数平均分子量８，０００（分散度１．６）であった。

Except that was used, it was carried out in the same manner as in Example 1 to obtain an ocher powder (yield 56%). When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (35). Moreover, the obtained polymer was the weight average molecular weight 13,000 and the number average molecular weight 8,000 (dispersion degree 1.6) in polystyrene conversion.

実施例６（化合物（３１）の電荷移動度の測定）
基板には２ｍｍ幅のＩＴＯ（酸化インジウム錫）膜がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用いた（シート抵抗：２０Ω／Ｓｑ）。この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。洗浄後の基板に、スピンコート法による有機材料の成膜及び真空蒸着法による陰極の蒸着を行い、移動度測定素子を作製した。

Example 6 (Measurement of charge mobility of compound (31))
As the substrate, a glass substrate with an ITO transparent electrode in which an ITO (indium tin oxide) film having a width of 2 mm was patterned in a stripe shape was used (sheet resistance: 20Ω / Sq). The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. An organic material film was formed by spin coating on the cleaned substrate, and a cathode was deposited by vacuum vapor deposition to produce a mobility measuring element.

As the spin coater, 1H-D2 (manufactured by Mikasa) was used. The organic material to be spin-coated was a solution previously dissolved in toluene and passed through a 0.45 μm filter. After the ITO substrate was set in a spin coater, a toluene solution of compound (31) was formed to a thickness of 1 to 5 μm. The film thickness after film formation measured by a stylus type film thickness meter (DEKTAK) was 1.6 μm. This substrate was vacuum-dried at 60 ° C. for 1 hour in a Pelger type vacuum oven (BV-001, manufactured by Shibata Kagaku Co., Ltd.), and then set in a vacuum deposition apparatus (EG-240, manufactured by Tokyo Vacuum Co., Ltd.). After reducing the pressure to 10 ⁻⁶ Torr, an Al film having a width of 2 mm was vacuum-deposited with a thickness of 10 nm so as to be orthogonal to the ITO stripe. As a result, an operation area of 2 mm square for mobility measurement was obtained. This substrate was sealed in a nitrogen atmosphere glove box having an oxygen / water concentration of 1 ppm or less. For the sealing, an ultraviolet curable epoxy resin XNR5516 (manufactured by Nagase ChemteX Corporation) was used.

The mobility of the charge transport material can be measured by any method, but this time, a time-of-flight mobility measurement method, which is a general measurement method, was used. The mobility measuring apparatus manufactured by Optel Co., Ltd. was used. The measurement was performed at an arbitrary temperature, and the mobility was determined from the moving speed of the charge generated when the nitrogen laser of 337 nm was irradiated from the Al electrode side to the ITO electrode. When the charge mobility of the compound (31) was measured, the mobility at an electric field strength of about 600 (V / cm) ^1/2 was 1.0 to 2.0 × 10 ⁻⁴ cm ² / V · sec. It was.

Example 7 (Measurement of charge mobility of compound (32))
In Example 6, a device was produced in the same manner as in Example 6 except that compound (32) was used instead of compound (31). When the charge mobility of the compound (32) was measured, the mobility at an electric field strength of about 600 (V / cm) ^1/2 was 1.0 to 2.0 × 10 ⁻⁴ cm ² / V · sec. It was.

The main element structural example of an organic EL element is shown. The measurement result of the infrared spectroscopy analysis of the compound (31) obtained in Example 1 is shown.

Claims (5)

A triarylamine polymer having a structure selected from any of the following general formulas (11) to (13):

(Wherein R ¹⁰ , R ¹¹ And R ¹² Are each independently a linear, branched or cyclic alkyl group having 8 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 8 to 18 carbon atoms. t, u, and v are integers of 1 or 2, and n is an integer of 1 or more. ) The triarylamine polymer according to claim 1, which has a polystyrene-reduced weight average molecular weight of 500 to 500,000. The triarylamine polymer according to claim 2 , wherein the polystyrene-equivalent weight average molecular weight is 2,000 to 100,000. The triarylamine polymer according to any one of claims 1 to 3 , wherein the terminal of the triarylamine polymer is a substituted or unsubstituted phenyl group. An organic electroluminescence device comprising the triarylamine polymer according to any one of claims 1 to 4 as a hole transport layer and / or a hole injection layer.

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