JP5012185B2 - 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, a hole injection layer, or a light emitting host for 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 that is soluble in an organic solvent and excellent in film formability and excellent in carrier transportability as 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は下記一般式（２）〜（４）

{In the formula, Ar ¹ represents the following general formulas (2) to (4)

（式中、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。ｍは１〜４の整数、ａは０≦ａ≦２ｍ＋４の範囲となる整数である。）
のいずれかから選択される縮合環基である。Ａｒ^２は下記一般式（５）または（６）

(In the formula, R ¹ 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. M is an integer of 1 to 4, and a is 0 ≦ a ≦ 2m + 4. An integer that is a range.)
A fused ring group selected from any of the above. Ar ² represents the following general formula (5) or (6)

［式中、Ｒ^２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（７）〜（１０）

[Wherein R ² 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 (7) to (10)

（式中、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８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。ｃ、ｄ、ｅ及びｆは０〜５の整数である。ｑは１または２の整数である。）
で表される基である。ｐは１または２の整数、ｂは０≦ｂ≦４ｐ＋１の範囲となる整数である。Ｒ^３及びＲ^４は各々独立して炭素数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。］
のいずれかから選択される基である。Ａ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。ｎは１以上の整数である。｝
で表される有機ＥＬのキャリア輸送材料としての使用が期待されるトリアリールアミンポリマーとその簡便な製造方法に関する。

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ 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, c, d, e and f are integers of 0 to 5. q is an integer of 1 or 2.)
It is group represented by these. p is an integer of 1 or 2, and b is an integer in the range of 0 ≦ b ≦ 4p + 1. R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms. ]
A group selected from any one of A is a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. n is an integer of 1 or more. }
And a simple production method thereof.

  The polyarylamine in the present invention includes a monomer having n = 1, a dimer having n = 2 and a trimer having n = 3, and is preferably a polyarylamine having n = 5 or more.

  In the general formula (1), A is not particularly limited as long as it falls within the above definition. For example, phenylene group, biphenylene group, terphenylene group, fluorene group, naphthalene group, anthracene group, phenanthrene group, etc. Can be mentioned. A structure represented by the following general formula (11) or (12) is more preferable.

（式中、Ｒ^９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。ｒは１または２の整数、ｇは０≦ｇ≦４ｒの範囲となる整数である。）
前記一般式（２）、（５）、（６）、（７）、（８）、（９）、（１０）及び（１１）において、Ｒ^１〜Ｒ^９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、また、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 ⁹ 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. (An integer of 1 or 2 and g is an integer in the range of 0 ≦ g ≦ 4r.)
In the general formulas (2), (5), (6), (7), (8), (9), (10), and (11), R ^{1 to} R ⁹ particularly satisfy the above definition. Specific examples include, but are not limited to, hydrogen atom, methyl group, 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-methylcyclohexyl group, Alkyl such as cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, trifluoromethyl group, adamantyl group, etc. Group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyl Oxy group, 2-ethylbutoxy group, 3,3-dimethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n -Alkoxy group such as 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-hydroxy Phenyl group, 4-hydroxyphenyl group, 2-trifluoromethylphenyl 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, Examples include aryl groups such as 4-methylnaphthyl group, 9-anthracenyl group, and 9,9-disubstituted-2-fluorenyl group. .

Ar ¹ of the triarylamine polymer represented by the general formula (1) of the present invention is a condensed ring group selected from any one of the general formulas (2) to (4). Triarylamine polymers having the structures of 13) to (17) are preferred.

（式中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５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、または炭素数６〜１８のアリール基である。ｎは１以上の整数である。）
前記一般式（１３）〜（１７）において、Ｒ^１０〜Ｒ^１５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、具体的には前記明細書中で例示したＲ^１〜Ｒ^９と同じ置換基を挙げることができる。

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. A linear, branched or cyclic alkoxy group, or an aryl group having 6 to 18 carbon atoms, n is an integer of 1 or more.)
In the general formulas (13) to (17), R ^{10 to} R ¹⁵ are not particularly limited as long as they fall under the above definitions, but specifically, R ^{1 to} R ⁹ exemplified in the specification. And the same substituents.

  The triarylamine polymer represented by the general formula (1) of the present invention has a condensed ring group at the main chain site and has high carrier transportability. The reason why the amine compound containing the condensed ring group exhibits good carrier transportability is not clear, but the coexistence of the pi-electron responsible for carrier movement by coexisting the condensed ring group and the amine structure site spreads within the molecule. It is considered that one of the factors is that the carrier movement of the molecule is likely to occur, and that the expanded pi electron cloud is likely to be overlapped between the molecules, thereby facilitating the carrier movement between the molecules.

  Moreover, the triarylamine polymer represented by the general formula (1) of the present invention is not particularly limited as long as it falls within the above definition, but the polymer terminal is a substituted or unsubstituted aryl group. Is particularly preferable from the viewpoint of heat resistance.

  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 from 2,000 to 100, with n = 4 or more from the viewpoint of solubility and film formability. 000 range.

  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 (18):

（式中、Ａｒ^１は上記一般式（２）〜（４）のいずれかから選択される縮合環基であり、Ａ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はハロゲン原子である。）
で表される芳香族ジハライドと下記一般式（１９）

(In the formula, Ar ¹ is a condensed ring group selected from any ^one of the above general formulas (2) to (4), and A is a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. X ¹ and X ² are halogen atoms.)
And the following general formula (19)

（式中、Ａｒ^２は上記一般式（５）または（６）のいずれかから選択される基である。）
で表される芳香族一級アミンを、パラジウム化合物とホスフィンからなる触媒並びに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, Ar ² is a group selected from the general formulas (5) and (6)).
Is polymerized in the presence of a catalyst comprising a palladium compound and a phosphine and a base, and can be easily and efficiently produced.

  The aromatic dihalide represented by the general formula (18) is not particularly limited, but specific examples thereof include the following general formulas (22) to (29).

（式中、Ｘ^１及びＸ^２はハロゲンである。）
前記一般式（１９）で表される芳香族一級アミン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（３０）〜（３７）を例示することができる。好ましくは４位に炭素数１〜８の直鎖、分岐若しくは環状のアルキル基を有するアニリン誘導体である。

(Wherein X ¹ and X ² are halogens.)
The aromatic primary amine represented by the general formula (19) is not particularly limited, and specific examples thereof include the following general formulas (30) to (37). Preferred is an aniline derivative having a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms at the 4-position.

（式中、Ｒ’はそれぞれ独立して水素原子、または炭素数１〜１８のアルキル基若しくはアルコキシ基である。）
また、本発明の前記一般式（１）で表されるトリアリールアミンポリマーは、その他の合成法として、下記反応式（３８）で示されるボロン酸またはボロン酸エステル類と芳香族ハライドまたは芳香族トリフラート化合物との反応により合成することもできる。

(In the formula, each R ′ is independently a hydrogen atom, or an alkyl or alkoxy group having 1 to 18 carbon atoms.)
In addition, the triarylamine polymer represented by the general formula (1) of the present invention is prepared by other boronic acid or boronic acid esters represented by the following reaction formula (38) and an aromatic halide or aromatic. It can also be synthesized by reaction with a triflate compound.

（式中、Ｙ及びＺはそれぞれハロゲン原子とボロン酸若しくはボロン酸エステル、またはトリフルオロメタンスルホニルオキシ基とボロン酸若しくはボロン酸エステルの組み合せとなる基である。また、Ａｒ^１及びＡｒ^２は前記と同じである。ｎは１以上の整数である。）
触媒成分として使用するパラジウム化合物は特に限定されるものではないが、例えば、ヘキサクロロパラジウム（ＩＶ）酸ナトリウム四水和物、ヘキサクロロパラジウム（ＩＶ）酸カリウム等の４価のパラジウム化合物類、塩化パラジウム（ＩＩ）、臭化パラジウム（ＩＩ）、酢酸パラジウム（ＩＩ）、パラジウム（ＩＩ）アセチルアセトナート、ジクロロビス（ベンゾニトリル）パラジウム（ＩＩ）、ジクロロビス（アセトニトリル）パラジウム（ＩＩ）、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）、ジクロロテトラアンミンパラジウム（ＩＩ）、ジクロロ（シクロオクタ−１，５−ジエン）パラジウム（ＩＩ）、パラジウム（ＩＩ）トリフルオロアセテート等の２価のパラジウム化合物類、及びトリス（ジベンジリデンアセトン）二パラジウム（０）、トリス（ジベンジリデンアセトン）二パラジウム（０）クロロホルム錯体、テトラキス（トリフェニルホスフィン）パラジウム（０）等の０価のパラジウム化合物類を挙げることができる。

(Wherein Y and Z are a halogen atom and a boronic acid or boronic acid ester, or a group that is a combination of a trifluoromethanesulfonyloxy group and a boronic acid or boronic acid ester. Ar ¹ and Ar ² are as defined above. (N is an integer of 1 or more.)
The palladium compound used as the catalyst component is not particularly limited. For example, tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate, potassium hexachloropalladium (IV), palladium chloride ( II), palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), divalent palladium compounds such as dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroacetate, and tris (dibenzylide) Acetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, can be mentioned tetrakis (triphenylphosphine) palladium (0) 0-valent palladium compounds such as.

  The amount of the palladium compound used is not particularly limited. For example, it is usually in the range of 0.00001 to 20 mol% in terms of palladium with respect to 1 mol of the halogen atom of the aromatic dihalide as a raw material, and expensive palladium. Since the compound is used, it is preferably in the range of 0.001 to 5 mol% in terms of palladium with respect to 1 mol of the halogen atom of the aromatic dihalide as a raw material.

  In the method of the present invention, phosphines used as a catalyst component are not particularly limited, and examples thereof include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-sec. -Trialkylphosphine such as butylphosphine and tri-tert-butylphosphine, and triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, 2,2'- And triarylphosphine such as bis (diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, and diphenylphosphinoferrocene. . Of these, tri-tert-butylphosphine is preferably used because it has a particularly high reaction activity as a catalyst.

  The amount of phosphine to be used is not particularly limited, but it may be used in a range of usually 0.01 to 10000 times mol with respect to the palladium compound, preferably considering expensive trialkylphosphine and triarylphosphine. Is in the range of 0.1 to 10 moles relative to the palladium compound.

  The method for adding the catalyst is not particularly limited, and the catalyst may be added to the reaction system alone as a catalyst component, or may be added after preparing in the form of a complex comprising these catalyst components in advance.

  The base is not particularly limited, and examples thereof include inorganic bases such as sodium and potassium carbonates and alkali metal alkoxides, and organic bases such as tertiary amines. 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 may be added to the system as it is, or may be prepared in situ from an alkali metal, alkali metal hydride or alkali metal hydroxide and an alcohol and used in the reaction system. More preferably, a 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 is not particularly limited, but is preferably 0.5 times mol or more of the aromatic dihalide or the halogen atom of the aromatic halide added to the reaction system, and a post-treatment operation after completion of the reaction. Is more preferably in the range of 1 to 5 moles relative to the halogen atom.

  Although the polymer obtained in this manner varies depending on the conditions such as the raw material and its charging ratio, the terminal of the terminal is capped from the viewpoint of heat resistance and color resistance because there are halogens derived from the raw material and secondary amine terminal sites. It is preferable to do. Therefore, the general formula (20) corresponding to each of halogen and secondary amine terminals.

（式中、Ａｒ^３及びＡｒ^４は各々独立して置換若しくは無置換の炭素数６〜６０のアリール基である。）
で表される芳香族二級アミン及び／または一般式（２１）

(In the formula, Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.)
An aromatic secondary amine represented by the general formula (21)

（式中、Ｘ^３はハロゲン原子であり、Ａｒ^５は置換若しくは無置換の炭素数６〜６０のアリール基である。）
で表される芳香族ハライドをさらに反応させることにより、ポリマーの安定性を向上させることができる。

(Wherein X ³ is a halogen atom, and Ar ⁵ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.)
The stability of the polymer can be improved by further reacting with an aromatic halide represented by the formula:

  The aromatic secondary amine represented by the general formula (20) is not particularly limited, but specifically, diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, N-phenyl-2. -A naphthylamine etc. can be illustrated. Diphenylamine is preferred.

  The aromatic halide represented by the general formula (21) is not particularly limited, but specifically, substituted or unsubstituted bromobenzenes (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-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-di-n-octyl Luolene, etc.), substituted or unsubstituted chlorobenzenes (chlorobenzene, 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-propyl Benzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-tert-butylbenzene, 1-chloro-5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloro Anisole, 1-chloronaphthalene, 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-chloro Carbazole, 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-hexylluolene 2-chloro-9,9-di-n-octyl-fluorene, etc.) and substituted or unsubstituted iodobenzenes (iodobens) 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, 1-iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenane Lene, 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 Etc.). Preferred are halobenzenes such as bromobenzene, chlorobenzene and iodobenzene.

  In the treatment method of the present invention, the aromatic secondary amine represented by the general formula (20) and / or the aromatic halide represented by the general formula (21) is a fragrance represented by the general formula (18). The triarylamine polymer obtained by the reaction of the aromatic dihalide with the aromatic primary amine represented by the general formula (19) may be produced and then added, or in the process of producing the triarylamine polymer The reaction may be carried out by adding directly into the reactor. 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.

  In the treatment method of the present invention, the addition amount of the aromatic secondary amine represented by the general formula (20) and / or the aromatic halide represented by the general formula (21) is the same as that of the triarylamine polymer used in the reaction. Although it is not particularly limited because it is not constant depending on the molecular weight and polymerization reaction conditions, it is 0.01% with respect to the aromatic dihalide represented by the general formula (18) as a raw material when added directly during the polymerization reaction. It is preferable to add in the ratio of -0.8 times mole, More preferably, it is the ratio of 0.1-0.5 times mole.

  In the treatment method of the present invention, the amount of palladium compound, phosphine and base used as the catalyst is not particularly limited because it is not constant depending on the molecular weight of the triarylamine polymer used in the reaction. In the case of directly adding the group secondary amine and / or aromatic halide, it is not necessary to add a palladium compound, and simplification is possible.

  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. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The production of the triarylamine polymer of the present invention is preferably carried out under an atmospheric pressure and an inert gas atmosphere such as nitrogen and argon, but it can be carried out even under pressurized conditions.

  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 is usually 20 to 300 ° C, preferably 50 to 200 ° C, more preferably. It is the range of 100-160 degreeC.

  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 triarylamine polymer of the present invention has very high carrier mobility, and is extremely useful as a hole transport material, a buffer material, a light emitting material and a light emitting host material of an organic electroluminescence device.

  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 2,6-di (4-chlorophenyl) naphthalene (1-B))

滴下漏斗を装着した２００ｍｌ丸底フラスコに、室温、窒素雰囲気下、２，６−ジヒドロキシナフタレン ４．８ｇ（３０ｍｍｏｌ）、トルエン６０ｍｌ及びピリジン１８ｍｌを仕込んだ。氷浴中にて冷却した後、トリフルオロメタンスルホン酸無水物２２．０ｇ（７８ｍｍｏｌ）をゆっくり滴下し、その状態でゆっくり昇温させながら終夜攪拌した。純水を加えて反応を終了させた後、この反応混合物にトルエンを加えて抽出した。さらに１０％塩酸、純水、飽和食塩水の順に有機層を洗浄後、硫酸マグネシウムで乾燥、溶媒を減圧留去した。この時析出した固体に対し、ヘキサンを用いて洗浄することで淡褐色粉体を１０．７ｇ得た（８４％）。ＮＭＲ測定から目的物１−Ａであることを確認した。

A 200 ml round bottom flask equipped with a dropping funnel was charged with 4.8 g (30 mmol) of 2,6-dihydroxynaphthalene, 60 ml of toluene and 18 ml of pyridine under a nitrogen atmosphere at room temperature. After cooling in an ice bath, 22.0 g (78 mmol) of trifluoromethanesulfonic anhydride 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. The solid precipitated at this time was washed with hexane to obtain 10.7 g of a light brown powder (84%). From NMR measurement, it was confirmed to be the target product 1-A.

¹ H-NMR (CDCl ₃ ): 7.9 (2H, d, 9.2 Hz), 7.83 (2H, d, 2.6 Hz), 7.50 (2H, dd, 8.8, 2.2 Hz) )
¹³ C-NMR (CDCl ₃ ): 147.78, 132.30, 130.75, 121.46, 119.41, 115.51
A 200 ml four-necked round bottom flask equipped with a condenser and a thermometer was charged with 4.3 g (10 mmol) of 1-A, 3.5 g (21 mmol) of 4-chlorophenylboronic acid (CPBA), 80 ml of THF and 20% carbonic acid at room temperature. A sodium aqueous solution (43 g, 80 mmol) was charged. To this mixed solution, 462 mg (0.4 mmol) of tetrakistriphenylphosphine palladium was added, and then the temperature was raised to 65 ° C. under a nitrogen atmosphere, followed by aging for 8 hours while stirring with heating. After completion of the reaction, the reaction mixture was cooled to room temperature, and toluene was added to extract the organic layer. After washing with saturated brine and evaporating the solvent under reduced pressure, the precipitated solid was washed with dichloromethane to obtain 2.1 g as a pale yellow powder (yield 60%). From FD-MS and NMR, it was confirmed to be the target product 1-B.

FD-MS = 348
¹ H-NMR (CDCl ₃ ): 8.15 (2H, s), 8.01 (2H, d, 8.4 Hz), 7.82 (2H, d, 8.0 Hz), 7.79 (4H, d, 8.0 Hz), 7.49 (4H, d, 8.4 Hz)
Example 1 (Synthesis of Compound 39)
To a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, 1-B 698 mg (2 mmol), 4-octylaniline 452 mg (2.2 mmol), sodium-tert-butoxide 576 mg (6 mmol) and o were added at room temperature. -10 ml of xylene was charged. To this mixed solution was added a solution of 18.3 mg (0.02 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and 0.18 ml of o-xylene (3 ml) of tri-tert-butylphosphine. . Thereafter, the temperature was raised to 150 ° C. in a nitrogen atmosphere, and the mixture was aged for 16 hours with heating and stirring at 150 ° C. Thereafter, bromobenzene was added, and the mixture was further heated and stirred in this state for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, toluene (5 ml) and pure water (10 ml) were added, and then slowly added to a stirred solution of 90% aqueous acetone (250 ml). The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure. Furthermore, column chromatography using toluene was performed, and a pale yellow powder was obtained by performing reprecipitation treatment using acetone again (88%). 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 (39). The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 1 and FIG. 2, respectively.

また、得られたポリマーをＴＨＦ系ＧＰＣにて分析した結果、ポリスチレン換算で重量平均分子量２０，９００及び数平均分子量１３，５００（分散度１．５５）であった。ガラス転移温度は１１９℃を示した。紫外可視分光光度計及び光電子分光法を用い測定した結果、バンドギャップ２．８ｅＶ、ＨＯＭＯ準位５．４ｅＶ、ＬＵＭＯ準位２．６ｅＶであった。

Moreover, as a result of analyzing the obtained polymer by THF type | system | group GPC, it was the weight average molecular weight 20,900 and the number average molecular weight 13,500 (dispersion degree 1.55) in polystyrene conversion. The glass transition temperature was 119 ° C. As a result of measurement using an ultraviolet-visible spectrophotometer and photoelectron spectroscopy, the band gap was 2.8 eV, the HOMO level was 5.4 eV, and the LUMO level was 2.6 eV.

Example 2 (Synthesis of Compound 39 with varying charge ratio)
In Example 1, a pale yellow powder was obtained (99%) according to Example 1 except that the amount of 4-octylaniline used was changed from 452 mg (2.2 mmol) to 411 mg (2 mmol). The obtained polymer had a weight average molecular weight of 52,600 and a number average molecular weight of 27,500 (dispersity 1.91) in terms of polystyrene.

Example 3 (Synthesis of Compound 41)
In Example 1, Compound (40) instead of 698 mg (2 mmol) of 1-B

を７９９ｍｇ（２ｍｍｏｌ）用いた以外は実施例１に従い、淡黄色粉体を得た（９１％）。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（４１）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。元素分析及び赤外分光分析の測定結果をそれぞれ表２及び図３に示す。

A pale yellow powder was obtained (91%) according to Example 1 except that 799 mg (2 mmol) was used. 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 (41). The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 2 and FIG. 3, respectively.

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１９，２００及び数平均分子量１２，３００（分散度１．５７）であった。ガラス転移温度は１７７℃を示した。紫外可視分光光度計及び光電子分光法を用い測定した結果、バンドギャップ２．７ｅＶ、ＨＯＭＯ準位５．５ｅＶ、ＬＵＭＯ準位２．８ｅＶであった。

Moreover, the obtained polymer was the weight average molecular weight 19,200 and the number average molecular weight 12,300 (dispersion degree 1.57) in polystyrene conversion. The glass transition temperature was 177 ° C. As a result of measurement using an ultraviolet-visible spectrophotometer and photoelectron spectroscopy, the band gap was 2.7 eV, the HOMO level was 5.5 eV, and the LUMO level was 2.8 eV.

Example 4 (Synthesis of Compound 43)
In Example 1, Compound (42) instead of 698 mg (2 mmol) of 1-B

を７９９ｍｇ（２ｍｍｏｌ）用いた以外は実施例１に従い、淡黄色粉体を得た（８５％）。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（４３）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１６，０００及び数平均分子量１０，０００（分散度１．６０）であった。

A pale yellow powder was obtained (85%) according to Example 1 except that 799 mg (2 mmol) was used. 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 (43). The obtained polymer had a weight average molecular weight of 16,000 and a number average molecular weight of 10,000 (dispersion degree 1.60) in terms of polystyrene.

実施例５（化合物４５の合成）
実施例１において、１−Ｂ ６９８ｍｇ（２ｍｍｏｌ）の代わりに化合物（４４）

Example 5 (Synthesis of Compound 45)
In Example 1, Compound (44) instead of 698 mg (2 mmol) of 1-B

を８９９ｍｇ（２ｍｍｏｌ）用いた以外は実施例１に従い、淡黄色粉体を得た（８３％）。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（４５）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１８，５００及び数平均分子量１２，０００（分散度１．５４）であった。

Was obtained according to Example 1 except that 899 mg (2 mmol) was used (83%). 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 (45). Moreover, the obtained polymer was the weight average molecular weight 18,500 and the number average molecular weight 12,000 (dispersion degree 1.54) in polystyrene conversion.

実施例６（化合物（３９）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 (39))
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 the compound (39) synthesized in Example 1 was formed to a thickness of 1 to 5 μm. The film thickness after film formation as measured with a stylus type film thickness meter (DEKTAK) was 1.4 μm. The 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.). 1.7 × 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 (39) was measured, the mobility at an electric field strength of about 600 (V / cm) ^1/2 was 1.5 × 10 ⁻³ cm ² / V · sec.

Example 7 (Measurement of charge mobility of compound (41))
A device was produced in the same manner as in Example 6 except that compound (41) was used instead of compound (39). When the charge mobility of the compound (41) was measured, the mobility at an electric field strength of about 600 (V / cm) ^1/2 was 1.8 × 10 ⁻³ cm ² / V · sec.

The main element structural example of an organic EL element is shown. The measurement result of the infrared spectroscopy analysis of the compound (39) obtained in Example 1 is shown. The measurement result of the infrared spectroscopy analysis of the compound (41) obtained in Example 3 is shown.

Claims (11)

A triarylamine polymer represented by the following general formula (1).

{In the formula, Ar ¹ represents the following general formulas (2) to (4)

(In the formula, R ¹ 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. M is an integer of 1 to 4, and a is 0 ≦ a ≦ 2m + 4. An integer that is a range.)
A fused ring group selected from any of the above. Ar ² represents the following general formula (5)

[Wherein, R ² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms . b is an integer ranging from 0 to 5 . ]
It is group represented by these . A is a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. n is an integer of 1 or more. } 2. The triarylamine polymer according to claim 1, wherein in the general formula (1), A is an arylene group selected from any one of the following general formulas (11) and (12).

(Wherein R ⁹ 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. (An integer of 1 or 2 and g is an integer in the range of 0 ≦ g ≦ 4r.) The triarylamine polymer according to claim 1, wherein the general formula (1) is a structure selected from any of the following general formulas (13) to (17).

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. linear, branched or cyclic alkoxy group .n is an integer of 1 or more.) The triarylamine polymer according to any one of claims 1 to 3, wherein the weight average molecular weight in terms of polystyrene is 500 to 500,000. The triarylamine polymer according to claim 4, 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 5, wherein the terminal of the triarylamine polymer is a substituted or unsubstituted aryl group. General formula (18)

(In the formula, Ar ¹ is a condensed ring group selected from any ^one of the above general formulas (2) to (4), and A is a substituted or unsubstituted arylene group or heteroarylene group having 6 to 36 carbon atoms. X ¹ and X ² are halogen atoms.)
Aromatic dihalides represented by general formula (19)

(In the formula, Ar ² is a group represented by the general formula (5)).
The method for producing a triarylamine polymer according to any one of claims 1 to 5, wherein the aromatic primary amine represented by the formula (1) is polymerized in the presence of a catalyst comprising a palladium compound and a phosphine and a base. The triarylamine polymer obtained in claim 7 has the general formula (20)

(In the formula, Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.)
An aromatic secondary amine represented by the general formula (21)

(Wherein X ³ is a halogen atom, and Ar ⁵ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.)
The method for producing a triarylamine polymer according to claim 6, wherein the aromatic halide represented by the formula (1) is reacted in the presence of a catalyst comprising a palladium compound and a phosphine and a base. The method for producing a triarylamine polymer according to any one of claims 7 to 8 , wherein the phosphine is tri-tert-butylphosphine. The method for producing a triarylamine polymer according to claim 8, wherein the aromatic halide is halobenzene and the aromatic secondary amine is diphenylamine. An organic electroluminescence device, wherein the triarylamine polymer according to any one of claims 1 to 6 is used as a hole transport layer, a hole injection layer, and / or a light emitting host.

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