JPWO2014203818A1 - Thiophene derivative and use thereof and method for producing thiophene derivative - Google Patents

Abstract

A thiophene derivative represented by the following formula (1) is provided. (R1 to R4 are alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkynylthio, aryloxy, heteroaryloxy, arylthio or heteroarylthio, R5 to R8 are hydrogen, alkyl, alkenyl, Alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkynylthio, aryloxy, heteroaryloxy, arylthio or heteroarylthio, R9 to R12 are hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, Represents alkylthio, alkynylthio or aryl.)

Description

  The present invention relates to a thiophene derivative and use thereof, and a method for producing a thiophene derivative. More specifically, the thiophene derivative is substituted at the 2, 3, 4 and 5 positions with a 2-thienyl group having a substituent at least at the 3 position. And its use as a charge transporting substance, and a method for producing a thiophene derivative.

  In an organic electroluminescence (hereinafter referred to as organic EL) element, a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer. In particular, the hole injection layer is responsible for charge transfer between the anode and the hole transport layer or the light emitting layer, and plays an important function to achieve low voltage driving and high luminance of the organic EL element.

  The method of forming the hole injection layer is roughly divided into a dry process typified by vapor deposition and a wet process typified by spin coating. Compared with these processes, the wet process is flatter in a larger area. A highly efficient thin film can be produced efficiently. Therefore, at the present time when the area of the organic EL display is being increased, a hole injection layer that can be formed by a wet process is desired.

  In view of such circumstances, the present inventors are applicable to various wet processes and have a charge transport property that provides a thin film that can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element. Compounds having good solubility in materials and organic solvents used therefor have been developed (see, for example, Patent Documents 1 to 4).

International Publication No. 2008/032616 International Publication No. 2008/129947 International Publication No. 2006/025342 International Publication No. 2010/058777

  The present invention, like the technology of the above-mentioned patent document that has been developed so far, exhibits good solubility in an organic solvent, and has excellent lifetime characteristics when applied to a hole injection layer after being thinned. It is an object to provide a novel thiophene derivative that can realize an EL element.

  As a result of intensive studies to achieve the above object, the present inventors have shown that a specific thiophene derivative exhibits high solubility in an organic solvent, and from a varnish prepared by dissolving it in an organic solvent together with a dopant. The present invention has been completed by finding that the obtained thin film has high charge transporting properties, and that when the thin film is applied to a hole injection layer of an organic EL device, excellent life characteristics can be realized.

（式中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルコキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルオキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルオキシ基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルチオ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールオキシ基、Ｚ²で置換されていてもよい炭素数２〜２０のヘテロアリールオキシ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールチオ基又はＺ²で置換されていてもよい炭素数２〜２０のヘテロアリールチオ基を表し、
Ｒ⁵〜Ｒ⁸は、それぞれ独立に、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルコキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルオキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルオキシ基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルチオ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールオキシ基、Ｚ²で置換されていてもよい炭素数２〜２０のヘテロアリールオキシ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールチオ基又はＺ²で置換されていてもよい炭素数２〜２０のヘテロアリールチオ基を表し、
また、Ｒ⁵〜Ｒ⁸が水素原子でない場合、Ｒ¹とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁷及び／又はＲ⁴とＲ⁸は、それぞれ互いに結合して２価の基を形成していてもよく、
Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルコキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルオキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルオキシ基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルチオ基又はＺ²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹は、ハロゲン原子、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数２〜２０のアルキニルオキシ基、炭素数１〜２０のアルキルチオ基、炭素数２〜２０のアルケニルチオ基、炭素数２〜２０のアルキニルチオ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のヘテロアリールオキシ基、炭素数６〜２０のアリールチオ基又は炭素数２〜２０のヘテロアリールチオ基を表し、
Ｚ²は、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数２〜２０のアルキニルオキシ基、炭素数１〜２０のアルキルチオ基、炭素数２〜２０のアルケニルチオ基、炭素数２〜２０のアルキニルチオ基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のヘテロアリールオキシ基、炭素数６〜２０のアリールチオ基又は炭素数２〜２０のヘテロアリールチオ基を表す。）
２．Ｒ¹〜Ｒ⁴が、それぞれ独立に、Ｚ¹で置換されていてもよい炭素数１〜２０のアルコキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルオキシ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルオキシ基、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニルチオ基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニルチオ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールオキシ基、Ｚ²で置換されていてもよい炭素数２〜２０のヘテロアリールオキシ基、Ｚ²で置換されていてもよい炭素数６〜２０のアリールチオ基又はＺ²で置換されていてもよい炭素数２〜２０のヘテロアリールチオ基である１のチオフェン誘導体。
３．Ｒ⁵〜Ｒ⁸が、それぞれ独立に、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基又はＺ¹で置換されていてもよい炭素数１〜２０のアルコキシ基である１又は２のチオフェン誘導体。
４．Ｒ⁹〜Ｒ¹²が、それぞれ独立に、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基又はＺ¹で置換されていてもよい炭素数２〜２０のアルキニル基である１〜３のいずれかのチオフェン誘導体。
５．下記式（２）で表されるチオフェン化合物と式（３）〜（６）で表されるトリアルキルスタニルチオフェン化合物とを、触媒存在下で反応させることを特徴とする１のチオフェン誘導体の製造方法。

（式中、Ｈａｌはそれぞれ独立にハロゲン原子又は擬ハロゲン基を表し、Ｒ^aはそれぞれ独立に炭素数１〜２０のアルキル基を表す。Ｒ¹〜Ｒ¹²は上記と同じ。）
６．１〜４のいずれかのチオフェン誘導体からなる電荷輸送性物質。
７．１〜４のいずれかのチオフェン誘導体、ドーパント及び有機溶媒を含む電荷輸送性ワニス。
８．７の電荷輸送性ワニスを用いて作製される電荷輸送性薄膜。
９．１〜４のいずれかのチオフェン誘導体を含む電荷輸送性薄膜。
１０．８又は９の電荷輸送性薄膜を少なくとも１層備える電子デバイス。
１１．８又は９の電荷輸送性薄膜を少なくとも１層備える有機エレクトロルミネッセンス素子。
１２．前記電荷輸送性薄膜が、正孔注入層又は正孔輸送層である１１の有機エレクトロルミネッセンス素子。That is, the present invention provides the following thiophene derivatives and uses thereof, and methods for producing thiophene derivatives.
1. A thiophene derivative represented by the following formula (1):

(Wherein, R ¹ to R ⁴ are each independently, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹ , Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms in Z ^1, Z ¹ is optionally carbon atoms, which may 2 substituted with 20 alkenyloxy group, alkynyloxy group which may C2-20 optionally substituted by Z ^1, alkylthio group with carbon atoms which may have from 1 to 20 substituted by Z ^1, be substituted with Z ¹ An alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms that may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms that may be substituted with Z ² , Z ² carbon atoms which may be substituted with 2-20 heteroaryl of Aryloxy group, a heteroarylthio group arylthio group or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2,
R ⁵ to R ⁸ are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms which may be substituted with Z ² , Z carbon atoms which may be substituted with ² to 20 heteroar- of Aryloxy group, a heteroarylthio group arylthio group or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2,
When R ^{5 to} R ⁸ are not hydrogen atoms, R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ and / or R ⁴ and R ⁸ are bonded to each other to form a divalent group. May be formed,
R ⁹ to R ¹² are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² ;
Z ¹ is a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkenylthio group, C2-C20 alkynylthio group, C6-C20 aryl group, C6-C20 aryloxy group, C2-C20 heteroaryloxy group, C6-C20 An arylthio group or a C2-C20 heteroarylthio group,
Z ² is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. Oxy group, alkynyloxy group having 2-20 carbon atoms, alkylthio group having 1-20 carbon atoms, alkenylthio group having 2-20 carbon atoms, alkynylthio group having 2-20 carbon atoms, aryloxy having 6-20 carbon atoms Group, a C2-C20 heteroaryloxy group, a C6-C20 arylthio group, or a C2-C20 heteroarylthio group is represented. )
2. R ¹ to R ⁴ are each independently, Z ¹ in the optionally substituted alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group optionally 2 to 20 carbon atoms optionally substituted by Z ^1, Z ¹ in good C2-20 substituted alkynyloxy group, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, Z ¹ which may be 2-20 carbons substituted with alkenylthio group, alkynylthio group Z ¹ may C2-20 optionally substituted with, aryloxy group carbon atoms which may be have 6-20 substituted with Z ^2, optionally substituted by Z ² heteroaryl group having 2 to 20 carbon atoms, in heteroarylthio groups arylthio groups or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ² One thiophene derivative.
3. R ⁵ to R ⁸ are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, 1 or 2 of the thiophene derivatives are alkoxy groups of alkynyl or Z ¹ carbon atoms which may be substituted by 1 to 20 of good 2 to 20 carbon atoms optionally substituted by Z ^1.
4). R ⁹ to R ¹² are each independently a hydrogen atom, an alkyl group of Z ¹ is carbon atoms and optionally 1 to 20 substituted by an alkenyl group which may C2-20 optionally substituted by Z ¹ or one of thiophene derivatives of 1-3 alkynyl group which may C2-20 optionally substituted by Z ^1.
5). 1. Production of thiophene derivative according to 1, wherein a thiophene compound represented by the following formula (2) and a trialkylstannylthiophene compound represented by formulas (3) to (6) are reacted in the presence of a catalyst: Method.

(In the formula, each Hal independently represents a halogen atom or a pseudohalogen group, and each R ^a independently represents an alkyl group having 1 to 20 carbon atoms. R ^{1 to} R ¹² are the same as above.)
6. A charge transporting substance comprising the thiophene derivative according to any one of 1 to 4.
7. A charge transporting varnish containing the thiophene derivative according to any one of 1 to 4, a dopant and an organic solvent.
A charge transporting thin film produced using the charge transporting varnish of 8.7.
9. A charge transporting thin film comprising the thiophene derivative according to any one of 9.1 to 4.
An electronic device comprising at least one charge transporting thin film of 10.8 or 9.
An organic electroluminescent device comprising at least one charge-transporting thin film of 11.8 or 9.
12 11. The organic electroluminescence device according to 11, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.

The thiophene derivative of the present invention is easily soluble in an organic solvent, and it can be easily dissolved in an organic solvent together with a dopant to easily prepare a charge transporting varnish.
Since the thin film produced from the charge transport varnish of the present invention exhibits high charge transport properties, it can be suitably used as a thin film for electronic devices including organic EL elements. In particular, by applying this thin film to a hole injection layer of an organic EL element, an organic EL element having excellent lifetime characteristics can be obtained.
In addition, since the charge transporting varnish of the present invention can produce a thin film excellent in charge transporting properties with good reproducibility even when using various wet processes capable of forming a large area such as a spin coating method and a slit coating method, It can sufficiently cope with recent progress in the field of organic EL elements.

[Thiophene derivatives]
The thiophene derivative according to the present invention is represented by the following formula (1).

Wherein, R ¹ to R ⁴ are each independently, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms which may be substituted with Z ² , Z carbon atoms which may be substituted with ² to 20 heteroarylene of Oxy group, a heteroarylthio group Z ² good 2 to 20 carbon atoms optionally substituted by arylthio group or Z ² having 6 to 20 carbon atoms which may be substituted with.

R ⁵ to R ⁸ are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms which may be substituted with Z ² , Z carbon atoms which may be substituted with ² to 20 heteroar- of Aryloxy group, a heteroarylthio group arylthio group or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2.

When R ^{5 to} R ⁸ are not hydrogen atoms, R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ and / or R ⁴ and R ⁸ are bonded to each other to form a divalent group. You may do it.

R ⁹ to R ¹² are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ good alkenylthio group having 2 to 20 carbon atoms, represents an unsubstituted or good C20 have alkynylthio or Z ² optionally substituted by aryl group having 6 to 20 carbon atoms in Z ^1.

Z ¹ is a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkenylthio group, C2-C20 alkynylthio group, C6-C20 aryl group, C6-C20 aryloxy group, C2-C20 heteroaryloxy group, C6-C20 An arylthio group or a heteroarylthio group having 2 to 20 carbon atoms.

Z ² is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. Oxy group, alkynyloxy group having 2-20 carbon atoms, alkylthio group having 1-20 carbon atoms, alkenylthio group having 2-20 carbon atoms, alkynylthio group having 2-20 carbon atoms, aryloxy having 6-20 carbon atoms Group, a C2-C20 heteroaryloxy group, a C6-C20 arylthio group, or a C2-C20 heteroarylthio group is represented.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

  The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, a linear or branched alkyl group having 1 to 20 carbon atoms such as an n-heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, C3-C20 cyclic such as cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclodecyl group An alkyl group etc. are mentioned.

  The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkenyl group include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, and n-3-butenyl group. 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n Examples include a -1-decenyl group and an n-1-eicosenyl group.

  The alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkynyl group include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl- 2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n-butynyl group 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecynyl group, n-1-eicosinyl group, etc. Can be mentioned.

  The alkoxy group having 1 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyl. C1-C20 linear or branched alkoxy groups such as oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group; cyclopropyloxy group, cyclobutyloxy Group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group, bicyclobutyloxy group, bicyclopentyloxy group, bicyclohexyloxy group, bicycloheptyloxy group, Bicyclooctyloxy group, bicyclononyloxy , Cyclic alkoxy group having 3 to 20 carbon atoms such as bicyclo-decyl group and the like.

  The alkenyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkenyloxy group include ethenyloxy group, n-1-propenyloxy group, n-2-propenyloxy group, 1-methylethenyloxy group, n-1-butenyloxy group, n-2-butenyloxy group, n-3-butenyloxy group, 2-methyl-1-propenyloxy group, 2-methyl-2-propenyloxy group, 1-ethylethenyloxy group, 1-methyl-1-propenyloxy group, 1-methyl-2 -Propenyloxy group, n-1-pentenyloxy group, n-1-decenyloxy group, n-1-eicocenyloxy group, etc. are mentioned.

  The alkynyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkynyloxy group include ethynyloxy group, n-1-propynyloxy group, n-2-propynyloxy group, n-1-butynyloxy group, n-2-butynyloxy group, n-3-butynyloxy group, 1-methyl-2-propynyloxy group, n-1-pentynyloxy group, n-2-pentynyloxy group, n-3-pentynyloxy group, n-4-pentynyloxy group, 1-methyl- n-butynyloxy group, 2-methyl-n-butynyloxy group, 3-methyl-n-butynyloxy group, 1,1-dimethyl-n-propynyloxy group, n-1-hexynyloxy group, n-1-decynyloxy group, n Examples include a -1-pentadecynyloxy group and an n-1-eicosinyloxy group.

  The alkylthio group having 1 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group. A linear or branched alkylthio group having 1 to 20 carbon atoms such as a group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group; cyclopropylthio group, cyclobutylthio group, cyclopentyl Thio group, cyclohexylthio group, cycloheptylthio group, cyclooctylthio group, cyclononylthio group, cyclodecylthio group, bicyclobutylthio group, bicyclopentylthio group, bicyclohexylthio group, bicycloheptylthio group, bicyclooctylthio group Group, bicyclononylthio group, bicyclodecylthio group Cyclic alkylthio group having 3 to 20 carbon atoms group and the like.

  The alkenylthio group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkenylthio group include ethenylthio group, n-1-propenylthio group, n-2-propenylthio group, 1-methylethenylthio group, n-1-butenylthio group, n-2-butenylthio group, n -3-butenylthio group, 2-methyl-1-propenylthio group, 2-methyl-2-propenylthio group, 1-ethylethenylthio group, 1-methyl-1-propenylthio group, 1-methyl-2-propenyl A thio group, an n-1-pentenylthio group, an n-1-decenylthio group, an n-1-eicosenylthio group, and the like can be given.

  The alkynylthio group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples of the alkynylthio group include ethynylthio group, n-1-propynylthio group, n-2-propynylthio group, n-1-butynylthio group, n-2-butynylthio group, n-3-butynylthio group, 1 -Methyl-2-propynylthio group, n-1-pentynylthio group, n-2-pentynylthio group, n-3-pentynylthio group, n-4-pentynylthio group, 1-methyl-n-butynylthio group, 2-methyl- n-butynylthio group, 3-methyl-n-butynylthio group, 1,1-dimethyl-n-propynylthio group, n-1-hexynylthio group, n-1-decynylthio group, n-1-pentadecynylthio group, and n-1-eicosinylthio group.

  The number of carbon atoms of the alkyl group, alkenyl group, alkynyl group, alkoxy group, alkenyloxy group, alkynyloxy group, alkylthio group, alkenylthio group and alkynylthio group is preferably 12 or less, more preferably 6 or less, and more preferably 4 or less. Even more preferred.

  Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

  Specific examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, and 9-anthryloxy. Group, 1-phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 4-phenanthryloxy group, 9-phenanthryloxy group and the like.

  Specific examples of the heteroaryloxy group having 2 to 20 carbon atoms include 2-thienyloxy group, 3-thienyloxy group, 2-furanyloxy group, 3-furanyloxy group, 2-oxazolyloxy group, and 4-oxazolyl. Ruoxy group, 5-oxazolyloxy group, 3-isoxazolyloxy group, 4-isoxazolyloxy group, 5-isoxazolyloxy group, 2-thiazolyloxy group, 4-thiazolyloxy group, 5 -Thiazolyloxy group, 3-isothiazolyloxy group, 4-isothiazolyloxy group, 5-isothiazolyloxy group, 2-imidazolyloxy group, 4-imidazolyloxy group, 2-pyridyloxy group, 3-pyridyloxy Group, 4-pyridyloxy group and the like.

  Specific examples of the arylthio group having 6 to 20 carbon atoms include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 1-anthrylthio group, 2-anthrylthio group, 9-anthrylthio group, 1-phenanthrylthio group, 2 -Phenanthrylthio group, 3-phenanthrylthio group, 4-phenanthrylthio group, 9-phenanthrylthio group and the like can be mentioned.

  Specific examples of the heteroarylthio group having 2 to 20 carbon atoms include 2-thienylthio group, 3-thienylthio group, 2-furanylthio group, 3-furanylthio group, 2-oxazolylthio group, 4-oxazolylthio group, and 5-oxazolylthio group. 3-isoxazolylthio group, 4-isoxazolylthio group, 5-isoxazolylthio group, 2-thiazolylthio group, 4-thiazolylthio group, 5-thiazolylthio group, 3-isothiazolylthio group, 4- Examples include isothiazolylthio group, 5-isothiazolylthio group, 2-imidazolylthio group, 4-imidazolylthio group, 2-pyridylthio group, 3-pyridylthio group, 4-pyridylthio group and the like.

  The number of carbon atoms in the aryl group, aryloxy group, heteroaryloxy group, arylthio group and heteroarylthio group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

The R ¹ to R ^4, alkoxy group with carbon atoms which may have from 1 to 20 substituted by Z ^1, alkenyloxy group optionally having 2 to 20 carbon atoms optionally substituted by Z ^1, is substituted by Z ¹ An optionally substituted alkynyloxy group having 2 to 20 carbon atoms, ¹ to 20 carbon atoms that may be substituted with Z ¹ , an alkylthio group having 2 to 20 carbon atoms, and a carbon number that may be optionally substituted with Z ¹ 2-20 alkenylthio groups, Z ^{1-substituted} good 2-20 carbon atoms which may have alkynylthio group, an aryloxy group of carbon atoms which may be have 6-20 substituted with Z ^2, substituted with Z ² has been also heteroaryl group having 2 to 20 carbon atoms, heteroaryl of Z ² may C2-20 optionally substituted by arylthio group or Z ² having 6 to 20 carbon atoms which may be substituted with arylthio group are preferred, it is substituted with Z ¹ Alkoxy group having 1 to 20 carbon atoms also, Z ¹ optionally substituted by a good C2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, more preferably heteroaryloxy group which may C20 substituted in the aryl group, or Z ² good C6-20 be substituted with Z ^2, optionally substituted by Z ¹ A good alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms which may be substituted with Z ² is more preferable.

As the R ⁵ to R ^8, a hydrogen atom, Z ¹ with an alkyl group of carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ^1, Z alkoxy group having 1 to 20 carbon atoms is preferably substituted with an alkynyl group, or Z ¹ good 2 to 20 carbon atoms optionally substituted with ^1, hydrogen atom, optionally substituted by Z ¹ carbon more preferably an alkoxy group having 1 to 20 carbon atoms which may be substituted with an alkyl group or Z ¹ number 1 to 20, an alkoxy group having a hydrogen atom or Z ¹ carbon atoms which may be substituted with from 1 to 20 Even more preferred is a hydrogen atom.

The R ⁹ to R ^12, a hydrogen atom, an alkyl group of Z ¹ is carbon atoms and optionally 1 to 20 substituted with an alkenyl group, or Z ¹ good 2 to 20 carbon atoms optionally substituted by Z ¹ An optionally substituted alkynyl group having 2 to 20 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms optionally substituted with Z ¹ is more preferred, and a hydrogen atom is most suitable.

In R ^{1 to} R ¹² , the substituent Z ¹ is preferably a halogen atom or an aryl group having 6 to 14 carbon atoms, more preferably a halogen atom or a phenyl group, and absence (that is, unsubstituted). ) Is optimal.
In addition, as the substituent Z ² , a halogen atom or an alkyl group having 1 to 20 carbon atoms is preferable, a halogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, and it is not present (that is, unsubstituted). Is the best.

In the thiophene derivative represented by the formula (1), it is preferable that all 2-thienyl groups having a substituent at the 3-position have the same structure from the viewpoint of ease of synthesis. That is, in formula (1), it is preferred that R ^{1 to} R ⁴ are all the same group, R ^{5 to} R ⁸ are all the same group, and R ^{9 to} R ¹² are all the same group. It is.

  Hereinafter, although the specific example of the thiophene derivative represented by Formula (1) is given, it is not limited to these. In the formula, Me, Et, Pr, Bu, Pen, and Hex represent a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, respectively.

（式中、Ｈａｌはそれぞれ独立にハロゲン原子又は擬ハロゲン基を表し、Ｒ^aはそれぞれ独立に炭素数１〜２０のアルキル基を表す。Ｒ¹〜Ｒ¹²は上記と同じ。）[Method for producing thiophene derivative]
The thiophene derivative of the present invention can be produced, for example, by reacting the thiophene compound represented by the formula (2) with the trialkylstannylthiophene compound represented by the formulas (3) to (6) in the presence of a catalyst. .

(In the formula, each Hal independently represents a halogen atom or a pseudohalogen group, and each R ^a independently represents an alkyl group having 1 to 20 carbon atoms. R ^{1 to} R ¹² are the same as above.)

Examples of the halogen atom are the same as described above.
Pseudohalogen groups include (fluoro) alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and nonafluorobutanesulfonyloxy group; aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group Is mentioned.
Examples of the trialkylstannyl group include trimethylstannyl group, triethylstannyl group, tri-n-propylstannyl group, triisopropylstannyl group, tri-n-butylstannyl group, tri-n-pentylstannyl group, Examples thereof include a cyclohexylstannyl group, a trioctylstannyl group, and an n-butyldimethylstannyl group.

  Specific examples of the thiophene compound represented by the formula (2) include, but are not limited to, tetrachlorothiophene, tetrabromothiophene, tetraiodothiophene, and the like.

  Examples of trialkylstannylthiophene compounds represented by formulas (3) to (6) include 3-methoxy-2- (tri-n-butylstannyl) thiophene and 3-methylthio-2- (tri-n-butylstannyl) thiophene. , 3-hexyl- (tri-n-butylstannyl) thiophene, 3,4-ethylenedioxy-2- (tri-n-butylstannyl) thiophene, and the like, but are not limited thereto.

  The charging ratio between the thiophene compound represented by the formula (2) and the trialkylstannyl thiophene compound represented by the formulas (3) to (5) is different from that for the thiophene compound represented by the formula (2). Each of the thiophene compounds represented by (3) to (5) can be 1 equivalent or more, and preferably about 1 to 1.2 equivalents.

Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, copper iodide; tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), bis (triphenylphosphine) dichloropalladium. (Pd (PPh ₃ ) ₂ Cl ₂ ), bis (benzylideneacetone) palladium (Pd (dba) ₂ ), tris (benzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ), bis (tri-t-butylphosphine) Examples thereof include palladium catalysts such as palladium (Pd (Pt-Bu ₃ ) ₂ ). These catalysts may be used alone or in combination of two or more. These catalysts may be used together with a known appropriate ligand.

The amount of the catalyst used can be about 0.01 to 0.2 mol with respect to 1 mol of the thiophene compound represented by the formula (2), but about 0.05 mol is preferable.
Moreover, when using a ligand, although the usage-amount can be made into 0.1-5 equivalent with respect to the metal complex to be used, 1-2 equivalent is suitable.

  The above reaction may be performed in a solvent. When a solvent is used, the type is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic Group hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, Methyl isobutyl ketone, di-n Butyl ketone, cyclohexanone, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), ureas (N, N-dimethylimidazo) Lizinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) and the like. These solvents may be used alone or in combination of two or more.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, but is preferably about 0 to 200 ° C and more preferably 20 to 150 ° C.
After completion of the reaction, the desired thiophene derivative can be obtained by post-treatment according to a conventional method.

  Although the manufacturing method of the trialkylstannyl thiophene compound represented by Formula (3)-(6) used for the synthesis | combination of the thiophene derivative of this invention is not specifically limited, For example, it can synthesize | combine according to the following Reaction Formula (Scheme). 1). In addition, in the following reaction formula, although the synthesis | combining method of the trialkylstannyl thiophene compound represented by Formula (3) is shown, the trialkylstannyl thiophene compound represented by Formula (4)-(6) is also the following reaction. Following the formula, the corresponding thiophene compound can be lithiated and then synthesized in the same manner by reacting it with a trialkyltin halide.

（式中、Ｒ¹、Ｒ⁵、Ｒ⁹及びＲ^aは、上記と同じ。Ｘはハロゲン原子を表す）

(Wherein R ¹ , R ⁵ , R ⁹ and R ^a are the same as above, X represents a halogen atom)

（式中、Ｒ^a、Ｒ及びＸは上記と同じ。Ｒ¹³は配位性置換基を表し、Ｒ¹⁴は水素原子又は非配位性置換基を表す。）In particular, this synthesis method is a thiophene compound in which the 2- and 5-positions are unsubstituted, the 3-position has a coordinating substituent, and the 4-position is substituted with an unsubstituted or non-coordinating substituent ( Since the 2-position of the formula (7 ″)) can be highly selectively lithiated, it is particularly suitable for the synthesis of the thiophene compound represented by the formula (7) (Scheme 2).

(Wherein R ^a , R and X are the same as above, R ¹³ represents a coordinating substituent, and R ¹⁴ represents a hydrogen atom or a non-coordinating substituent.)

  A coordinating substituent refers to a substituent having an atom capable of coordinating to a lithium atom, such as an oxygen, nitrogen, or sulfur atom, and a non-coordinating substituent refers to a substituent that does not contain such an atom. Refers to the group.

The coordinating substituent, alkoxy group with carbon atoms which may have 1 to 20 substituted by Z ^1, alkenyloxy group optionally having 2 to 20 carbon atoms optionally substituted by Z ^1, is substituted by Z ¹ have also good alkynyloxy group having a carbon number of 2 to 20, Z ² an aryloxy group having 6 to 20 carbon atoms which may be substituted, heteroaryl Z ² good 2 to 20 carbon atoms optionally substituted by oxy group, Z ¹ in the optionally substituted alkylthio group having 1 to 20 carbon atoms, alkenylthio group optionally 2 to 20 carbon atoms optionally substituted by Z ^1, the carbon may be substituted with Z ¹ 2-20 alkynylthio group include heteroarylthio groups arylthio groups or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2.

The non-coordinating substituent is substituted with an alkenyl group, or Z ¹ alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹ of carbon atoms which may be have 1-20 substituted with Z ¹ Examples thereof include an alkynyl group having 2 to 20 carbon atoms.

These alkoxy groups, alkenyloxy groups, alkynyloxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, alkenylthio groups, alkynylthio groups, arylthio groups, heteroarylthio groups, alkyl groups, alkenyl groups, alkynyl groups, and these As the substituents Z ¹ and Z ² , those similar to the above can be mentioned.

  Examples of the thiophene compound represented by the formula (3 ″) include 3-methylthiophene, 3-ethylthiophene, 3-n-propylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n- Hexylthiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-n-propoxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-ethylenedioxythiophene, 3-methylthiothiophene, etc. For example, but not limited to.

  Examples of the thiophene compound represented by the formula (7 ″) include, but are not limited to, 3-methoxythiophene, 3-ethoxythiophene, 3-n-propoxythiophene, and 3-methylthiothiophene.

  Examples of the lithiating agent include organic lithium compounds such as n-butyllithium, s-butyllithium, t-butyllithium, isobutyllithium, methyllithium, n-propyllithium, isopropyllithium, ethyllithium, and n-hexyl. Lithium, trimethylsilylmethyl lithium, propynyl lithium, 2-ethylhexyl lithium, 2,4-pentadienyl lithium, allyl lithium, 1,3-butadienyl-2-lithium, t-butoxymethyl lithium, 1-methoxyallyl lithium, trichloromethyl Alkyl lithium or aryl lithium compounds such as lithium, pentyl lithium, phenyl lithium, 2,6-dimethoxyphenyl lithium, lithium hexamethyldisilazide, lithium diisopropylamide, lithium Examples of the lithium amide compound include, but are not limited to, perizide, lithium diethylamide, lithium tetramethylpiperidide, lithium bis (dimethylethylsilyl) amide, lithium dimethylamide, and lithium dicyclohexylamide.

  The trialkyltin halide is not particularly limited as long as it can introduce a trialkylstannyl group. However, considering the balance of availability, handleability and reactivity, tri (n-butyl) tin chloride is Is preferred. The trialkyltin halide can be synthesized by a known method (for example, the method described in Chem. Commun., 2001, 1840-1841), but is also commercially available.

  The charging ratio of the thiophene compound represented by the formula (3 ″) or the thiophene compound represented by the formula (7 ″) and the lithiating agent is the thiophene compound represented by the formula (3 ″) or the formula ( Although the lithiating agent can be about 1 to 1.5 equivalents relative to the thiophene compound represented by 7 ″), about 1.1 equivalents are preferred.

  The charging ratio of the thiophene compound represented by the formula (3 ′) or the thiophene compound represented by the formula (7 ′) and the trialkyltin halide is the thiophene compound or formula represented by the formula (3 ′). The trialkyltin halide can be about 1 to 5 equivalents relative to the thiophene compound represented by (7 ′), but about 1.2 equivalents are preferred.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is preferably about -78 to 20 ° C, more preferably -20 to 0 ° C.
After completion of the reaction, the target thiophene derivative can be obtained by post-treatment according to a conventional method.

  The reaction solvent is not particularly limited as long as it does not inhibit the reaction, but a chain or cyclic ether is preferable. In particular, in Scheme 2, from the viewpoint of improving the yield of the thiophene compound represented by the formula (7) by improving the lithiation selectivity at the 2-position, a chain ether is more preferable and has at least one branched chain. A chain ether is even more preferred.

As the chain ether, a symmetric or asymmetric chain having a linear or branched chain alkyl group or a cyclic alkyl group such as diethyl ether, diisopropyl ether, di-n-butyl ether, t-butyl methyl ether, cyclopentyl methyl ether, etc. Examples include, but are not limited to, dialkyl ethers. Cyclic ethers include, but are not limited to, tetrahydrofuran, tetrahydropyran, hexamethylene oxide, heptamethylene oxide, and the like.
Among these, diisopropyl ether, t-butyl methyl ether, and cyclopentyl methyl ether are particularly preferable from the viewpoint of lithiation selectivity at the 2-position.

[Charge transport varnish]
The charge transporting varnish of the present invention includes a charge transporting substance composed of a thiophene derivative represented by the formula (1) and an organic solvent. In order to improve the charge transporting ability, a dopant is added as necessary. May be included.

  As a dopant, if it melt | dissolves in the at least 1 sort (s) of solvent used for a varnish, it will not specifically limit, Both an inorganic type dopant and an organic type dopant can be used.

Inorganic dopants include inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum chloride (III) (AlCl ₃ ), titanium tetrachloride (IV) (TiCl ₄ ), boron tribromide (BBr ₃ ), Boron trifluoride ether complex (BF ₃ · OEt ₂ ), iron chloride (III) (FeCl ₃ ), copper chloride (II) (CuCl ₂ ), antimony pentachloride (V) (SbCl ₅ ), antimony pentafluoride ( Metal halides such as V) (SbF ₅ ), arsenic pentafluoride (V) (AsF ₅ ), phosphorus pentafluoride (PF ₅ ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF _{4 and} other halogens; heteropolyacids such as phosphomolybdic acid and phosphotungstic acid.

  Examples of the organic dopant include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2 , 5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1 -Naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphtho Lensulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, 1,4-benzo described in WO2005 / 000832 Dioxane disulfonic acid compounds, aryl sulfonic acid compounds described in WO 2006/025342, aryl sulfonic acid compounds described in WO 2009/096352, aryl sulfonic acid compounds such as polystyrene sulfonic acid; 10-camphor sulfonic acid, etc. Non-aryl sulfonic acid compounds; organic oxidants such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) Can be mentioned.

  These inorganic and organic dopants may be used singly or in combination of two or more.

  Of these dopants, heteropolyacids are preferred. By using heteropolyacid as a dopant, not only high hole acceptability from a transparent electrode typified by indium tin oxide (ITO) and indium zinc oxide (IZO) but also from a metal anode typified by aluminum A thin film having a high hole acceptability and excellent charge transportability can be obtained.

  The heteropolyacid is typically a Keggin type represented by the formula (A1) or a Dawson type chemical structure represented by the formula (A2), and has a structure in which a hetero atom is located at the center of the molecule. V), molybdenum (Mo), tungsten (W) and other oxoacids such as isopolyacids, and polyacids formed by condensation of oxoacids of different elements. Examples of such oxo acids of different elements mainly include silicon (Si), phosphorus (P), and arsenic (As) oxo acids.

  Specific examples of the heteropolyacid include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid. You may use these individually by 1 type or in combination of 2 or more types. In addition, the heteropolyacid used by this invention is available as a commercial item, and can also be synthesize | combined by a well-known method.

  In particular, when the dopant is composed of one type of heteropolyacid, the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid. Moreover, when a dopant consists of 2 or more types of heteropolyacids, it is preferable that at least 1 sort (s) of the 2 or more types of heteropolyacids is phosphotungstic acid or phosphomolybdic acid, and it is more preferable that it is phosphotungstic acid.

  In addition, in the quantitative analysis such as elemental analysis, the heteropolyacid may be a commercially available product obtained from a structure represented by the general formula or a small number of elements, or a known synthesis method. As long as it is appropriately synthesized according to the above, it can be used in the present invention.

That is, for example, phosphotungstic acid is generally represented by the chemical formula H ₃ (PW ₁₂ O ₄₀ ) · nH ₂ O, and phosphomolybdic acid is represented by the chemical formula H ₃ (PMo ₁₂ O ₄₀ ) · nH ₂ O. In quantitative analysis, even if the number of P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product, or As long as it is appropriately synthesized according to a known synthesis method, it can be used in the present invention. In this case, the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthesized product or commercially available product, but a commercially available form and a known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydration water and other impurities.

  Moreover, an aryl sulfonic acid compound can also be used suitably as a dopant. In particular, an aryl sulfonic acid compound represented by the formula (B1) or (B2) is preferable.

In formula (B1), A ¹ represents —O— or —S—, preferably —O—. A ² represents a naphthalene ring or an anthracene ring, and a naphthalene ring is preferable. A ³ represents a divalent to tetravalent perfluorobiphenyl group, p represents the number of bonds between A ¹ and A ^3, and is an integer satisfying 2 ≦ p ≦ 4, but A ³ is a divalent perfluorobiphenyl group. It is preferable that p is 2. q represents the number of sulfonic acid groups bonded to A ² and is an integer satisfying 1 ≦ q ≦ 4, but 2 is preferable.

In formula (B2), A ^{4 to} A ⁸ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Wherein at least three of A ^{4 to} A ⁸ are halogen atoms. r represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1 ≦ r ≦ 4, preferably 2 to 4, and more preferably 2.

  Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3- Trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4, 4-nonafluorobutyl group etc. are mentioned. Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include a perfluorovinyl group, a 1-perfluoropropenyl group, a perfluoroallyl group, and a perfluorobutenyl group.

  Examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms are the same as those described above.

Among these, A ⁴ to A ⁸ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or a halogenated alkenyl group having 2 to 10 carbon atoms having 1 to 10 carbon atoms And at least three of A ^{4 to} A ⁸ are preferably fluorine atoms. And a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkenyl group having 2 to 5 carbon atoms, and A ^{4 to} A ^8. More preferably, at least three of them are fluorine atoms. Furthermore, it is a hydrogen atom, a fluorine atom, a cyano group, a C 1-5 perfluoroalkyl group or a C 1-5 perfluoroalkenyl group, and A ⁴ , A ⁵ and A ⁸ are fluorine atoms. Even more preferred.

  The perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group are substituted with fluorine atoms.

  Although the specific example of an arylsulfonic acid compound suitable as another dopant in this invention is given, it is not limited to these.

  When a dopant is included in the charge transporting varnish of the present invention, the amount of dopant used is appropriately determined in consideration of the type of dopant, the desired degree of charge transportability, etc. The charge transporting material (hereinafter simply referred to as charge transporting material) 1 comprising the thiophene derivative of the invention is generally in the range of about 0.01 to 50.

  In particular, when a heteropolyacid is used as a dopant, the heteropolyacid is about 0.5 to 30.0, preferably about 1.0 to 20.0, more preferably 2. Charge transport that provides high luminance when used in an organic EL device, by setting it to about 0 to 15.0, more preferably about 3.0 to 12.0, and still more preferably about 4.0 to 11.0. Can be obtained with good reproducibility.

  On the other hand, when an aryl sulfonic acid compound is used as a dopant, the aryl sulfonic acid compound is 0.05 to 15.0, preferably 0.10 to 10.0, more preferably, with respect to the charge transporting material 1 in molar ratio. Is from 0.25 to 7.0, more preferably from 0.50 to 5.0, and even more preferably from 0.75 to 3.0, so that charge transport that gives high luminance when used in an organic EL device. Can be obtained with good reproducibility.

  Furthermore, the charge transporting varnish of the present invention may contain an organosilane compound. By including the organic silane, the hole injection ability to the layer laminated so as to be in contact with the hole injection layer on the side opposite to the anode, such as the hole transport layer and the light emitting layer, can be increased, and as a result, higher Brightness characteristics can be realized.

  Examples of the organosilane compound include dialkoxysilane compounds, trialkoxysilane compounds, and tetraalkoxysilane compounds. You may use these individually by 1 type or in combination of 2 or more types.

  In particular, as the organosilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.

Examples of the dialkoxysilane compound, trialkoxysilane compound, and tetraalkoxysilane compound include those represented by the formulas (C1) to (C3).
SiR ' ₂ (OR) ₂ (C1)
SiR '(OR) ₃ (C2)
Si (OR) ₄ (C3)

In the formula, R is a substituted each independently, Z ³ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^3, with Z ³ is an alkynyl group having a carbon number of 2 to 20 even if, heteroaryl group Z ⁴ aryl group or Z ⁴ may C2-20 optionally substituted with from 6 to 20 carbon atoms which may be substituted with Represents. R 'is independently, Z ⁵ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^5, substituted by Z ⁵ an alkynyl group having 2 to 20 carbon atoms also represents a heteroaryl group the aryl group or Z ⁶ may C2-20 optionally substituted with from 6 to 20 carbon atoms which may be substituted with Z ⁶ .

Z ³ represents a halogen atom, the heteroaryl group of the aryl group or Z ⁷ may C2-20 optionally substituted with from 6 to 20 carbon atoms which may be substituted with Z ^7.
Z ⁴ represents a halogen atom, optionally substituted alkenyl group, or Z ⁷ alkyl group, carbon atoms and optionally substituted by Z ⁷ 2 to 20 of carbon atoms which may be have 1-20 substituted by Z ⁷ Or an alkynyl group having 2 to 20 carbon atoms.
Z ⁵ represents a halogen atom, Z ^{7-substituted} having 6 to 20 carbon atoms which may have an aryl group, a heteroaryl group which may C2-20 optionally substituted by Z ^7, epoxycyclohexyl group, a glycidoxy group , Methacryloxy group, acryloxy group, ureido group (—NHCONH ₂ ), thiol group, isocyanate group (—NCO), amino group, —NHY ¹ group or —NY ² Y ³ group.

Z ⁶ represents a halogen atom, Z ⁷ alkyl group carbon atoms which may be have 1 to 20 substituted by an alkenyl group which may C2-20 optionally substituted by Z ^7, optionally substituted by Z ⁷ alkynyl group which may having 2 to 20 carbon atoms, an epoxycyclohexyl group, a glycidoxy group, a methacryloxy group, an acryloxy group, a ureido group (-NHCONH _2), thiol group, isocyanate group (-NCO), amino group, -NHY ¹ group or -NY represents a ² Y ³ group.

Y ¹ to Y ³ each independently represent an alkyl group having carbon atoms which may be have 1-20 substituted by Z ^7, an alkenyl group which may C2-20 optionally substituted by Z ^7, with Z ⁷ an optionally substituted alkynyl group having 2 to 20 carbon atoms, heteroaryl is a 6-20 carbon atoms which may have an aryl group or Z ⁷ may 2-20 carbon atoms optionally substituted by at Z ⁷ Represents a group.
Z ⁷ represents a halogen atom, an amino group, a nitro group, a cyano group or a thiol group.

  As the halogen atom, the C1-C20 alkyl group, the C2-C20 alkenyl group, the C2-C20 alkynyl group and the C6-C20 aryl group in the formulas (C1) to (C3), The thing similar to the above is mentioned. Examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, and 3-isoxazolyl group. Group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl Group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like.

  In R and R ′, the carbon number of the alkyl group, alkenyl group, and alkynyl group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The carbon number of the aryl group and heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

The R, optionally substituted alkenyl group, or Z ⁴ alkyl group, Z ³ may C2-20 optionally substituted by a Z ³ are carbon atoms and optionally 1 to 20 replaced by carbon An aryl group having 6 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms which may be substituted with Z ³ , an alkenyl group having 2 to 6 carbon atoms or a phenyl group which may be substituted with Z ⁴ is more preferable. Preferably, an alkyl group having 1 to 4 carbon atoms which may be substituted with Z ³ or a phenyl group which may be substituted with Z ⁴ is more preferable, and a methyl group or an ethyl group which may be substituted with Z ³ Is more preferable.

R ′ is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ⁵ or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ⁶ , and is substituted with Z ^5. more preferably an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group or Z ⁶ 1-10 carbon atoms which may have alkyl having 1 to 6 carbon atoms which may be substituted with Z ⁵ more preferably more aryl group which may having 6 to 10 carbon atoms optionally substituted by a group or Z ^6, which may be substituted with an alkyl group or Z ⁶ of 1 to 4 carbon atoms which may be substituted with Z ⁵ A good phenyl group is more preferred.

  A plurality of R may be the same or different, and a plurality of R ′ may all be the same or different.

Z ³ is preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ⁷ , more preferably a fluorine atom or a phenyl group which may be substituted with Z ⁷ , and not present ( That is, it is optimal to be unsubstituted.

As the Z ^4, a halogen atom or Z ⁷ preferably an alkyl group which may having 6 to 20 carbon atoms which may be substituted with a fluorine atom or Z ⁷ is an optionally substituted alkyl group having 1 to 10 carbon atoms substituted with Is more preferred and not present (ie, unsubstituted).

On the other hand, the Z ^5, a halogen atom, Z a phenyl group optionally substituted by ^7, optionally substituted furanyl group Z ^7, epoxycyclohexyl group, a glycidoxy group, a methacryloxy group, an acryloxy group, a ureido group, thiol group, isocyanate group, amino group, good diphenylamino group optionally substituted by a phenyl amino group or Z ⁷ optionally substituted by Z ⁷ preferably, the more preferred is a halogen atom, no fluorine atom or presence ( That is, it is even more preferable that it is unsubstituted.

As the Z ^6, halogen atom, Z alkyl group carbon atoms which may be have 1-20 replaced by ^7, Z ⁷ with an optionally substituted furanyl group, an epoxycyclohexyl group, a glycidoxy group, a methacryloxy group, acryloxy group, ureido group, a thiol group, isocyanate group, amino group, good diphenylamino group optionally substituted by a phenyl amino group or Z ⁷ optionally substituted by Z ⁷ preferably, more preferably a halogen atom, fluorine Even more preferred is an atom or absence (ie, unsubstituted).

Z ⁷ is preferably a halogen atom, more preferably a fluorine atom or not (ie, unsubstituted).

Specific examples of the organosilane compound that can be used in the present invention will be given below, but the present invention is not limited thereto.
Specific examples of dialkoxysilane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, and phenylmethyl. Dimethoxysilane, vinylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3-methacryloxy Propylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyl Diethoxy silane, N- (2- aminoethyl) aminopropyl methyl dimethoxy silane, 3,3,3-trifluoropropyl methyl dimethoxy silane, and the like.

  Specific examples of trialkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy Silane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyl Rutrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropyltriethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, dodecyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, (triethoxysilyl) cyclohexane , Perfluorooctylethyltriethoxysilane, triethoxyfluorosilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluoro Phenyltriethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane, triethoxy-2-thienylsilane, 3- (triethoxysilyl) Examples include francs.

  Specific examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

  Among these, 3,3,3-trifluoropropylmethyldimethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, 3,3,3-trifluoropropyltrimethoxysilane, perfluorooctylethyltriethoxysilane , Pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, and the like are preferable.

  When the organosilane compound is included in the charge transporting varnish of the present invention, the content thereof is usually based on the total mass of the charge transporting material and the dopant in consideration of maintaining the high charge transporting property of the obtained thin film. Although it is about 0.1 to 50% by mass, it is laminated so as to suppress a decrease in charge transportability of the obtained thin film and to be in contact with the hole injection layer on the side opposite to the anode such as a hole transport layer and a light emitting layer. In consideration of increasing the hole injection ability into the layer, the amount is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and still more preferably 1 to 20% by mass.

  The charge transporting varnish of the present invention may use other known charge transporting materials in addition to the above-described charge transporting materials composed of thiophene derivatives.

  As the organic solvent used when preparing the charge transporting varnish, a highly soluble solvent that can dissolve the charge transporting substance and the dopant well can be used.

  Examples of such highly soluble solvents include organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and diethylene glycol monomethyl ether. Can be used. These solvents can be used singly or in combination of two or more, and the amount used can be 5 to 100% by mass with respect to the total solvent used in the varnish.

  The charge transporting substance and the dopant are preferably either completely dissolved or uniformly dispersed in the solvent, and more preferably completely dissolved.

  In the present invention, the varnish has a viscosity of 10 to 200 mPa · s, particularly 35 to 150 mPa · s at 25 ° C., and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure). By containing at least one high-viscosity organic solvent, it becomes easy to adjust the viscosity of the varnish. As a result, it is possible to adjust the varnish according to the coating method to be used, which gives a highly flat thin film with good reproducibility.

  The high-viscosity organic solvent is not particularly limited. For example, cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol and the like. These solvents may be used alone or in combination of two or more.

  The addition ratio of the high-viscosity organic solvent to the entire solvent used in the varnish of the present invention is preferably within a range where no solid precipitates, and the addition ratio is preferably 5 to 80% by mass as long as no solid precipitates.

  Furthermore, for the purpose of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., the other solvent is preferably 1 to 90% by mass with respect to the total solvent used in the varnish, More preferably, it can also mix in the ratio of 1-50 mass%.

  Examples of such solvents include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol. Examples include, but are not limited to, monoethyl ether, diacetone alcohol, γ-butyrolactone, ethyl lactate, and n-hexyl acetate. These solvents can be used alone or in combination of two or more.

  The viscosity of the varnish of the present invention is appropriately set according to the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa · s at 25 ° C.

  The solid content concentration of the charge transporting varnish in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc. In consideration of improving the coatability of the varnish, it is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass.

  A charge transporting thin film can be formed on the substrate by applying the charge transporting varnish onto the substrate and baking it.

  The coating method of the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an ink jet method, a spray method, and a slit coating method. Accordingly, it is preferable to adjust the viscosity and surface tension of the varnish.

  Further, when the varnish of the present invention is used, the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and a high charge transport property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum. Can be obtained.

  The firing temperature is appropriately set within a range of about 100 to 260 ° C. in consideration of the use of the obtained thin film, the degree of charge transportability imparted to the obtained thin film, and the like. When used as a hole injection layer of an EL element, about 140 to 250 ° C is preferable, and about 145 to 240 ° C is more preferable.

  In firing, two or more steps of temperature change may be applied for the purpose of expressing higher uniform film forming property or allowing the reaction to proceed on the substrate. The heating may be performed using an appropriate device such as a hot plate or an oven.

  The thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 200 nm when used as a hole injection layer in an organic EL device. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate during coating.

[Organic EL device]
Examples of materials used and methods for producing an OLED element using the charge transporting varnish of the present invention include, but are not limited to, the following.

  The electrode substrate to be used is preferably cleaned in advance by cleaning with a liquid such as a detergent, alcohol, or pure water. For example, the anode substrate is subjected to surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use. It is preferable. However, when the anode material is mainly composed of an organic material, the surface treatment may not be performed.

  The example of the manufacturing method of the OLED element which has a positive hole injection layer which consists of a thin film obtained from the charge transportable varnish of this invention is as follows.

  By the above method, the charge transporting varnish of the present invention is applied onto the anode substrate and baked to produce a hole injection layer on the electrode. This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron transport layer / hole block layer, and a cathode metal are sequentially deposited to form an OLED element. If necessary, an electron blocking layer may be provided between the light emitting layer and the hole transport layer.

  Examples of the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metal anodes typified by aluminum, alloys thereof, and the like. What performed the chemical conversion process is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.

  Other metals constituting the metal anode include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, and cadmium. , Indium, scandium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, platinum, gold, titanium Lead, bismuth, and alloys thereof, but are not limited thereto.

As a material for forming the hole transport layer, (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, N, N′-bis (naphthalen-1-yl) -N, N′-bis (Phenyl) -benzidine (α-NPD), N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl)- N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis ( Naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9, 9-Dimethyl-fluorene, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-dimethyl-fluorene N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-diphenyl-fluorene, N, N′-bis (naphthalen-1-yl) -N, N ′ -Bis (phenyl) -9,9-diphenyl-fluorene, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -2,2'-dimethylbenzidine, 2,2 ' , 7,7'-Tetrakis (N, N-diphenylamino) -9,9-spirobifluorene, 9,9-bis [4- (N, N-bis-biphenyl-4-yl-amino) phenyl]- 9H-fluorene, 9,9-bis [4- (N, N-bis-naphthalen-2-yl-amino) phenyl] -9H-fluorene, 9,9-bis [4- (N-naphthalen-1-yl) -N-phenylamino) -phenyl] -9H-fluorene, 2,2 ', 7,7'-tetrakis [N-naphthalenyl (phenyl) -amino] -9,9 Spirobifluorene, N, N′-bis (phenanthren-9-yl) -N, N′-bis (phenyl) -benzidine, 2,2′-bis [N, N-bis (biphenyl-4-yl) amino ] -9,9-spirobifluorene, 2,2′-bis (N, N-diphenylamino) -9,9-spirobifluorene, di- [4- (N, N-di (p-tolyl) amino] ) -Phenyl] cyclohexane, 2,2 ′, 7,7′-tetra (N, N-di (p-tolyl)) amino-9,9-spirobifluorene, N, N, N ′, N′-tetra -Naphthalen-2-yl-benzidine, N, N, N ', N'-tetra- (3-methylphenyl) -3,3'-dimethylbenzidine, N, N'-di (naphthalenyl) -N, N' -Di (naphthalen-2-yl) -benzidine, N, N, N ', N'-tetra (naphthalenyl) -benzidine, N, N'-di (naphthalen-2-yl) -N, N'-diphenyl Benzidine-1,4-diamine, N ^1, N ⁴ - diphenyl -N ^1, N ⁴ - di (m-tolyl) ^{benzene-1,4-diamine, N 2, N 2, N} 6, N 6 - tetraphenyl Naphthalene-2,6-diamine, tris (4- (quinolin-8-yl) phenyl) amine, 2,2′-bis (3- (N, N-di (p-tolyl) amino) phenyl) biphenyl, 4 , 4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ″ -tris [1-naphthyl (phenyl) amino] triphenylamine Triarylamines such as (1-TNATA), 5,5 ″ -bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2 ′: 5 ′, 2 ″ -terthiophene And oligothiophenes such as (BMA-3T).

As a material for forming the light emitting layer, tris (8-quinolinolato) aluminum (III) (Alq ₃ ), bis (8-quinolinolato) zinc (II) (Znq ₂ ), bis (2-methyl-8-quinolinolato) ( p-phenylphenolate) aluminum (III) (BAlq), 4,4′-bis (2,2-diphenylvinyl) biphenyl, 9,10-di (naphthalen-2-yl) anthracene, 2-t-butyl- 9,10-di (naphthalen-2-yl) anthracene, 2,7-bis [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4-methylphenyl) Fluorene, 2-methyl-9,10-bis (naphthalen-2-yl) anthracene, 2- (9,9-spirobifluoren-2-yl) -9,9-spirobifluorene, 2,7-bis ( 9,9-spirobifluoren-2-yl) -9,9-spi Bifluorene, 2- [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4-methylphenyl) fluorene, 2,2'-dipyrenyl-9,9-spirobi Fluorene, 1,3,5-tris (pyren-1-yl) benzene, 9,9-bis [4- (pyrenyl) phenyl] -9H-fluorene, 2,2'-bi (9,10-diphenylanthracene) 2,7-dipyrenyl-9,9-spirobifluorene, 1,4-di (pyren-1-yl) benzene, 1,3-di (pyren-1-yl) benzene, 6,13-di (biphenyl) -4-yl) pentacene, 3,9-di (naphthalen-2-yl) perylene, 3,10-di (naphthalen-2-yl) perylene, tris [4- (pyrenyl) -phenyl] amine, 10,10 '-Di (biphenyl-4-yl) -9,9'-bianthracene, N, N'-di (naphthalene-1- ) -N, N′-diphenyl- [1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl] -4,4 ′ ″-diamine, 4,4′- Di [10- (naphthalen-1-yl) anthracen-9-yl] biphenyl, dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd : 1 ', 2', 3'-lm] perylene, 1- (7- (9,9'-bianthracen-10-yl) -9,9-dimethyl-9H-fluoren-2-yl) pyrene, -(7- (9,9'-bianthracen-10-yl) -9,9-dihexyl-9H-fluoren-2-yl) pyrene, 1,3-bis (carbazol-9-yl) benzene, 3,5-tris (carbazol-9-yl) benzene, 4,4 ′, 4 ″ -tris (carbazol-9-yl) triphenylamine, 4,4′-bis (carbazol-9-yl) biphenyl ( CBP) 4,4 '-Bis (carbazol-9-yl) -2,2'-dimethylbiphenyl, 2,7-bis (carbazol-9-yl) -9,9-dimethylfluorene, 2,2', 7,7'-tetrakis (Carbazol-9-yl) -9,9-spirobifluorene, 2,7-bis (carbazol-9-yl) -9,9-di (p-tolyl) fluorene, 9,9-bis [4- ( Carbazol-9-yl) -phenyl] fluorene, 2,7-bis (carbazol-9-yl) -9,9-spirobifluorene, 1,4-bis (triphenylsilyl) benzene, 1,3-bis ( Triphenylsilyl) benzene, bis (4-N, N-diethylamino-2-methylphenyl) -4-methylphenylmethane, 2,7-bis (carbazol-9-yl) -9,9-dioctylfluorene, 4, 4 ″ -di (triphenylsilyl) -p-terphenyl, 4,4 ′ -Di (triphenylsilyl) biphenyl, 9- (4-t-butylphenyl) -3,6-bis (triphenylsilyl) -9H-carbazole, 9- (4-t-butylphenyl) -3,6- Ditrityl-9H-carbazole, 9- (4-t-butylphenyl) -3,6-bis (9- (4-methoxyphenyl) -9H-fluoren-9-yl) -9H-carbazole, 2,6-bis (3- (9H-carbazol-9-yl) phenyl) pyridine, triphenyl (4- (9-phenyl-9H-fluoren-9-yl) phenyl) silane, 9,9-dimethyl-N, N-diphenyl- 7- (4- (1-Phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -9H-fluoren-2-amine, 3,5-bis (3- (9H-carbazol-9-yl) Phenyl) pyridine, 9,9-spirobifluorene- 2-yl-diphenyl-phosphine oxide, 9,9 ′-(5- (triphenylsilyl) -1,3-phenylene) bis (9H-carbazole), 3- (2,7-bis (diphenylphosphoryl) -9 -Phenyl-9H-fluoren-9-yl) -9-phenyl-9H-carbazole, 4,4,8,8,12,12-hexa (p-tolyl) -4H-8H-12H-12C-azadibenzo [cd , mn] pyrene, 4,7-di (9H-carbazol-9-yl) -1,10-phenanthroline, 2,2′-bis (4- (carbazol-9-yl) phenyl) biphenyl, 2,8- Bis (diphenylphosphoryl) dibenzo [b, d] thiophene, bis (2-methylphenyl) diphenylsilane, bis [3,5-di (9H-carbazol-9-yl) phenyl] diphenylsilane, 3,6-bis ( Carbazol-9-yl)- -(2-Ethyl-hexyl) -9H-carbazole, 3- (diphenylphosphoryl) -9- (4- (diphenylphosphoryl) phenyl) -9H-carbazole, 3,6-bis [(3,5-diphenyl) phenyl ] -9-phenylcarbazole and the like, and the light emitting layer may be formed by co-evaporation with a light emitting dopant.

As the luminescent dopant, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-10- (2-Benzothiazolyl) quinolidino [9,9a, 1gh] coumarin, quinacridone, N, N′-dimethyl-quinacridone, tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ), bis (2-phenyl) Pyridine) (acetylacetonate) iridium (III) (Ir (ppy) ₂ (acac)), tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) ₃ ), 9,10-bis [N, N-di (p-tolyl) amino] anthracene, 9,10-bis [phenyl (m-tolyl) amino] anthracene, bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (II), N ¹⁰ , N ¹⁰ , N ¹⁰ , N ¹⁰ -tetra (p-tolyl) -9,9′-bian Tracene-10,10′-diamine, N ¹⁰ , N ¹⁰ , N ¹⁰ , N ¹⁰ -tetraphenyl-9,9′-bianthracene-10,10′-diamine, N ¹⁰ , N ¹⁰ -diphenyl-N ¹⁰ , N ¹⁰ -Dinaphthalenyl-9,9′-bianthracene-10,10′-diamine, 4,4′-bis (9-ethyl-3-carbazovinylene) -1,1′-biphenyl, perylene, 2,5,8 , 11-Tetra-t-butylperylene, 1,4-bis [2- (3-N-ethylcarbazolyl) vinyl] benzene, 4,4′-bis [4- (di-p-tolylamino) styryl] Biphenyl, 4- (di-p-tolylamino) -4 '-[(di-p-tolylamino) styryl] stilbene, bis [3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) Iridium (III), 4,4′-bis [4- (diphenylamino) styryl] biphenyl, (2,4-difluorophenylpyridinato) tetrakis (1-pyrazolyl) borateiridium (III), N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -tris ( 9,9-dimethylfluorenylene), 2,7-bis {2- [phenyl (m-tolyl) amino] -9,9-dimethyl-fluoren-7-yl} -9,9-dimethyl-fluorene, N -(4-((E) -2- (6 ((E) -4- (diphenylamino) styryl) naphthalen-2-yl) vinyl) phenyl) -N-phenylbenzenamine, fac-iridium (III) tris (1-phenyl-3-methylbenzamide 2-ylidene -C, C ^2), mer- iridium (III) tris (1-phenyl-3-methylbenzamide 2-ylidene -C, C ^{2), 2} , 7-bis [4- (diphenylamino) styryl] -9,9-spirobi Fluorene, 6-methyl-2- (4- (9- (4- (6-methylbenzo [d] thiazol-2-yl) phenyl) anthracen-10-yl) phenyl) benzo [d] thiazole, 1,4- Di [4- (N, N-diphenyl) amino] styrylbenzene, 1,4-bis (4- (9H-carbazol-9-yl) styryl) benzene, (E) -6- (4- (diphenylamino) Styryl) -N, N-diphenylnaphthalen-2-amine, bis (2,4-difluorophenylpyridinato) (5- (pyridin-2-yl) -1H-tetrazolate) iridium (III), bis (3- Trifluoromethyl-5- (2-pyridyl) pyrazole) ((2,4-difluorobenzyl) diphenylphosphinate) iridium (III), bis (3-trifluoromethyl-5- (2-pyridyl) pyrazolate) (benzyl Diphenylphosphinate) Lidium (III), bis (1- (2,4-difluorobenzyl) -3-methylbenzimidazolium) (3- (trifluoromethyl) -5- (2-pyridyl) -1,2,4-triazolate) Iridium (III), bis (3-trifluoromethyl-5- (2-pyridyl) pyrazolate) (4 ′, 6′-difluorophenylpyridinate) iridium (III), bis (4 ′, 6′-difluorophenyl) Pyridinato) (3,5-bis (trifluoromethyl) -2- (2'-pyridyl) pyrrolate) iridium (III), bis (4 ', 6'-difluorophenylpyridinato) (3- (tri Fluoromethyl) -5- (2-pyridyl) -1,2,4-triazolate) iridium (III), (Z) -6-mesityl-N- (6-mesitylquinoline-2 (1H) -ylidene) quinoline 2-amine _{-BF 2, (E) -2- (} 2- (4- ( dimethylamino) styryl) -6- Til-4H-pyran-4-ylidene) malononitrile, 4- (dicyanomethylene) -2-methyl-6-julolidyl-9-enyl-4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (1 , 1,7,7-Tetramethyljulolidyl-9-enyl) -4H-pyran, 4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7,7-tetramethyljulolidine -4-yl-vinyl) -4H-pyran, tris (dibenzoylmethane) phenanthroline europium (III), 5,6,11,12-tetraphenylnaphthacene, bis (2-benzo [b] thiophen-2-yl -Pyridine) (acetylacetonate) iridium (III), tris (1-phenylisoquinoline) iridium (III), bis (1-phenylisoquinoline) (acetylacetonate) iridium (III), bis [1- (9,9 - Til-9H-fluoren-2-yl) -isoquinoline] (acetylacetonate) iridium (III), bis [2- (9,9-dimethyl-9H-fluoren-2-yl) quinoline] (acetylacetonate) iridium (III), tris [4,4′-di-t-butyl- (2,2 ′)-bipyridine] ruthenium (III) bis (hexafluorophosphate), tris (2-phenylquinoline) iridium (III), Bis (2-phenylquinoline) (acetylacetonate) iridium (III), 2,8-di-t-butyl-5,11-bis (4-t-butylphenyl) -6,12-diphenyltetracene, bis ( 2-Phenylbenzothiazolate) (acetylacetonate) iridium (III), 5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, osmium (II) bis (3-trifluoromethyl-5- (2- Pyridine ) -Pyrazolate) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (4-tert-butylpyridyl) -1,2,4-triazolate) diphenylmethylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (2-pyridyl) -1,2,4-triazole) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (4-t- Butylpyridyl) -1,2,4-triazolate) dimethylphenylphosphine, bis [2- (4-n-hexylphenyl) quinoline] (acetylacetonate) iridium (III), tris [2- (4-n-hexyl) Phenyl) quinoline] iridium (III), tris [2-phenyl-4-methylquinoline] iridium (III), bis (2-phenylquinoline) (2- (3-methylphenyl) pyridinate) irid (III), bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H-benzo [d] imidazolato) (acetylacetonate) iridium (III), bis (2-phenyl) Pyridine) (3- (pyridin-2-yl) -2H-chromen-2-onate) iridium (III), bis (2-phenylquinoline) (2,2,6,6-tetramethylheptane-3,5- Diate) iridium (III), bis (phenylisoquinoline) (2,2,6,6-tetramethylheptane-3,5-dionate) iridium (III), iridium (III) bis (4-phenylthieno [3,2 -c] pyridinato -N, C ²⁾ acetylacetonate, (E) -2- (2- t- butyl-6- (2- (2,6,6-trimethyl-2,4,5,6-tetrahydro -1H-pyrrolo [3,2,1-ij] quinolin-8-yl) vinyl) -4H-pyran-4-ylide ) Malononitrile, bis (3-trifluoromethyl-5- (1-isoquinolyl) pyrazolate) (methyldiphenylphosphine) ruthenium, bis [(4-n-hexylphenyl) isoquinoline] (acetylacetonate) iridium (III), platinum (II) octaethylporphine, bis (2-methyldibenzo [f, h] quinoxaline) (acetylacetonate) iridium (III), tris [(4-n-hexylphenyl) xoquinoline] iridium (III), etc. .

  As a material for forming the electron transport layer / hole blocking layer, 8-hydroxyquinolinolate-lithium, 2,2 ′, 2 ″-(1,3,5-benztolyl) -tris (1-phenyl-1 -H-benzimidazole), 2- (4-biphenyl) 5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10 -Phenanthroline, 4,7-diphenyl-1,10-phenanthroline, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum, 1,3-bis [2- (2,2'-bipyridine) -6-yl) -1,3,4-oxadiazo-5-yl] benzene, 6,6′-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2, 2'-bipyridine, 3- (4-biphenyl) -4-phenyl-5-t-butyl Phenyl-1,2,4-triazole, 4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole, 2,9-bis (naphthalen-2-yl) -4 , 7-Diphenyl-1,10-phenanthroline, 2,7-bis [2- (2,2′-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] -9,9-dimethylfluorene 1,3-bis [2- (4-t-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene, tris (2,4,6-trimethyl-3- (pyridin-3-yl) Phenyl) borane, 1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5f] [1,10] phenanthroline, 2- (naphthalen-2-yl) -4, 7-diphenyl-1,10-phenanthroline, phenyl-dipyrenylphosphine oxide, 3,3 ′ , 5,5′-Tetra [(m-pyridyl) -phen-3-yl] biphenyl, 1,3,5-tris [(3-pyridyl) -phen-3-yl] benzene, 4,4′-bis (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl, 1,3-bis [3,5-di (pyridin-3-yl) phenyl] benzene, bis (10-hydroxybenzo [ h] quinolinato) beryllium, diphenylbis (4- (pyridin-3-yl) phenyl) silane, 3,5-di (pyren-1-yl) pyridine and the like.

Materials for forming the electron injection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride ( MgF ₂ ), cesium fluoride (CsF), strontium fluoride (SrF ₂ ), molybdenum trioxide (MoO ₃ ), aluminum, Li (acac), lithium acetate, lithium benzoate and the like.

  Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.

  Examples of the material for forming the electron blocking layer include tris (phenylpyrazole) iridium.

  Although the manufacturing method of the PLED element using the charge transportable varnish of this invention is not specifically limited, The following methods are mentioned.

  In the preparation of the OLED element, instead of performing the vacuum deposition operation of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, the hole transport polymer layer and the light emitting polymer layer are sequentially formed. A PLED element having a charge transporting thin film formed by the charge transporting varnish of the invention can be produced.

  Specifically, the charge transporting varnish of the present invention is applied on the anode substrate to prepare a hole injection layer by the above method, and a hole transporting polymer layer and a light emitting polymer layer are sequentially formed thereon. Then, a cathode electrode is vapor-deposited to obtain a PLED element.

  As the cathode and anode material to be used, the same materials as those used in the production of the OLED element can be used, and the same cleaning treatment and surface treatment can be performed.

  As a method for forming the hole transporting polymer layer and the light emitting polymer layer, a hole transporting polymer material or a light emitting polymer material, or a material in which a dopant is added to these materials are added and dissolved, The method of forming into a film by disperse | distributing uniformly and apply | coating on a positive hole injection layer or a positive hole transportable polymer layer, and baking each is mentioned.

  As the hole transporting polymer material, poly [(9,9-dihexylfluorenyl-2,7-diyl) -co- (N, N′-bis {p-butylphenyl} -1,4-diamino Phenylene)], poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (N, N′-bis {p-butylphenyl} -1,1′-biphenylene-4,4- Diamine)], poly [(9,9-bis {1'-penten-5'-yl} fluorenyl-2,7-diyl) -co- (N, N'-bis {p-butylphenyl} -1, 4-diaminophenylene)], poly [N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) -benzidine] -endcapped with polysilsesquioxane, poly [(9, 9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (p-butylphenyl)) diphenylamine)] and the like.

  Examples of the light emitting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH). -PPV) and the like, polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

  Examples of the solvent include toluene, xylene, chloroform and the like. Examples of the dissolution or uniform dispersion method include methods such as stirring, heating and stirring, and ultrasonic dispersion.

  The application method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating method. The application is preferably performed under an inert gas such as nitrogen or argon.

  As a method of baking, the method of heating with an oven or a hotplate in inert gas or in a vacuum is mentioned.

  In addition to the charge transporting thin film obtained from the above charge transporting varnish, the deposited film obtained from the thiophene derivative of the present invention is also excellent in charge transporting properties. May be used.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the apparatus used is as follows.
(1) Liquid chromatography: Agilent Technologies, Agilent 1260 Infinity Binary LC System (2) NMR: JEOL Ltd., JNM-ECP300 FT NMR SYSTEM
(3) Substrate cleaning: manufactured by Choshu Sangyo Co., Ltd.
(4) Varnish application: Mikasa Co., Ltd., spin coater MS-A100
(5) Film thickness measurement: Kosaka Laboratory Co., Ltd., micro shape measuring machine Surfcorder ET-4000
(6) Manufacture of EL element: Choshu Sangyo Co., Ltd., multifunctional vapor deposition system C-E2L1G1-N
(7) Measurement of EL element brightness, etc .: (Technical) manufactured by Tech World, IVL measurement system (8) Lifetime measurement of EL element: ELC Sea, Inc., organic EL brightness life evaluation system PEL -105S

[1] Synthesis of Compound [Synthesis Example 1]
Based on the following reaction formula, 3-methoxy-2- (tri-n-butylstannyl) thiophene (9) was synthesized.

Into the flask, 5.01 g of 3-methoxythiophene (8) was put and nitrogen substitution was performed. Thereto, 100 mL of diisopropyl ether was added and cooled to 0 ° C., and 29.5 mL of a hexane solution (concentration 1.64 M) of n-butyllithium was further added dropwise thereto. After the dropwise addition, the mixture was stirred for 30 minutes while maintaining the temperature at 0 ° C, and then 14.5 mL of tri-n-butylstannyl chloride was added dropwise, and further stirred for 3 hours while maintaining the temperature at 0 ° C.
After stirring, the solvent was distilled off under reduced pressure, n-hexane was added to the obtained residue, the resulting insoluble material was filtered off, the solvent was distilled off under reduced pressure and dried again, and 3-methoxy-2- A mixture containing (tri-n-butylstannyl) thiophene was obtained.
This mixture was used for the reaction with compound (10) in the next step without further purification. In addition, using ¹ H-NMR and liquid chromatography, it was confirmed that the content of 3-methoxy-2- (tri-n-butylstannyl) thiophene in the mixture was 90.46%.

[Example 1]
The thiophene derivative (11) was synthesized by the following method.

In the flask, 0.5 g of 2,3,4,5-tetrabromothiophene (10) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3-methoxy-2- (tri-n-butylstannyl) thiophene (9) 2 0.7 g (4.8 equivalents, purity 90.46%) was placed in a reaction vessel and purged with nitrogen. Thereto, 10 mL of xylene and 0.073 g (5 mol%) of Pd (PPh ₃ ) ₄ were added and stirred for 23 hours under heating and refluxing conditions. After completion of the stirring, the reaction solution was cooled to room temperature.
Chloroform and ion-exchanged water were added to the cooled reaction solution for separation, and the resulting organic layer was washed twice with ion-exchanged water, and then the washed organic layer was dried over sodium sulfate. Then, the solvent was distilled off under reduced pressure. And the n-hexane was added to the obtained residue, the slurry washing | cleaning was performed, it filtered, and the residue was collect | recovered.
Thereafter, the filtrate and 5 mL of toluene were placed in the flask, stirred under heating and refluxing conditions to confirm that the filtrate was dissolved, and then the solution was allowed to cool to room temperature.
After allowing to cool, the precipitate was collected by filtration and dried well to obtain the thiophene derivative (11) (yield 0.40 g, yield 60%). The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (300MHz, CDCl ₃ ) δ [ppm]: 7.20 (d, 2H, J = 6.0Hz), 7.02 (d, 2H, J = 6.0Hz), 6.80 (d, 2H, J = 5.4Hz) , 6.74 (d, 2H, J = 5.4Hz), 3.94 (s, 6H), 3.64 (s, 6H).

[2] Preparation of charge transporting varnish [Example 2]
0.052 g of thiophene derivative (11) and 0.258 g of phosphotungstic acid (manufactured by Kanto Chemical Co., Inc.) were dissolved in 3.0 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere. To the resulting solution, 0.0009 g of pentafluorophenyltriethoxysilane was added and stirred, and 5.0 g of diethylene glycol dimethyl ether and 2 g of butanediol were further added thereto and stirred to prepare a charge transporting varnish.

[3] Manufacture and characteristic evaluation of organic EL element [Example 3]
The varnish obtained in Example 2 was applied to an ITO substrate using a spin coater, then dried at 50 ° C. for 5 minutes, and further baked at 230 ° C. for 10 minutes in an air atmosphere. A uniform thin film was formed. As the ITO substrate, a glass substrate of 25 mm × 25 mm × 0.7 t with indium tin oxide (ITO) patterned to a thickness of 150 nm on the surface is used, and an O ₂ plasma cleaning device (150 W, 30 seconds) before use. To remove impurities on the surface.
Next, a thin film of α-NPD, Alq ₃ , lithium fluoride and aluminum is sequentially laminated on the ITO substrate on which the thin film is formed using a vapor deposition apparatus (degree of vacuum 1.0 × 10 ⁻⁵ Pa), and an organic EL element Got. At this time, the deposition rate was 0.2 nm / second for α-NPD, Alq ₃ and aluminum, and 0.02 nm / second for lithium fluoride, and the film thicknesses were 30 nm, 40 nm and 0.5 nm, respectively. And 120 nm.
In addition, in order to prevent the characteristic deterioration by the influence of oxygen in the air, water, etc., after sealing the organic EL element with the sealing substrate, the characteristic was evaluated. Sealing was performed according to the following procedure.
In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -85 ° C or less, the organic EL element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (XNR5516Z-B1 manufactured by Nagase ChemteX Corporation). It was. At this time, a water catching agent (manufactured by Dynic Co., Ltd., HD-071010W-40) was placed in a sealing substrate together with the organic EL element. The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm ² ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.

[Comparative Example 1]
Example 3 except that PEDOT / PSS (AI4083 manufactured by HC Starck) was used instead of the varnish obtained in Example 2 and baked at 150 ° C. for 30 minutes instead of baked at 230 ° C. for 10 minutes. A device was fabricated in the same manner.

Measurements of current density and luminance at a driving voltage of 5 V and a durability test were performed on the fabricated devices. Table 1 shows the measurement results and the half life of the luminance (initial luminance of 5,000 cd / m ² ).

  As shown in Table 1, the organic EL device (Example 3) having a hole injection layer obtained from the varnish of the present invention uses PEDOT / PSS which is a general charge transporting material (Comparative Example) It was found that it has far superior durability compared to 1).

Claims (12)

A thiophene derivative represented by the following formula (1):

(Wherein, R ¹ to R ⁴ are each independently, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹ , Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms in Z ^1, Z ¹ is optionally carbon atoms, which may 2 substituted with 20 alkenyloxy group, alkynyloxy group which may C2-20 optionally substituted by Z ^1, alkylthio group with carbon atoms which may have from 1 to 20 substituted by Z ^1, be substituted with Z ¹ An alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms that may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms that may be substituted with Z ² , Z ² carbon atoms which may be substituted with 2-20 heteroaryl of Aryloxy group, a heteroarylthio group arylthio group or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2,
R ⁵ to R ⁸ are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , an aryloxy group having 6 to 20 carbon atoms which may be substituted with Z ² , Z carbon atoms which may be substituted with ² to 20 heteroar- of Aryloxy group, a heteroarylthio group arylthio group or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ^2,
When R ^{5 to} R ⁸ are not hydrogen atoms, R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ and / or R ⁴ and R ⁸ are bonded to each other to form a divalent group. May be formed,
R ⁹ to R ¹² are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, Z ¹ in the optionally substituted alkynyl group having 2 to 20 carbon atoms, an alkoxy group having carbon atoms which may be have 1-20 substituted with Z ^1, Z ¹ carbon atoms which may be substituted with 2-20 alkenyloxy group, an alkynyloxy group which may C2-20 optionally substituted by Z ^1, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, optionally substituted by Z ¹ A good alkenylthio group having 2 to 20 carbon atoms, an alkynylthio group having 2 to 20 carbon atoms which may be substituted with Z ¹ , or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² ;
Z ¹ is a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkenylthio group, C2-C20 alkynylthio group, C6-C20 aryl group, C6-C20 aryloxy group, C2-C20 heteroaryloxy group, C6-C20 An arylthio group or a C2-C20 heteroarylthio group,
Z ² is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. Oxy group, alkynyloxy group having 2-20 carbon atoms, alkylthio group having 1-20 carbon atoms, alkenylthio group having 2-20 carbon atoms, alkynylthio group having 2-20 carbon atoms, aryloxy having 6-20 carbon atoms Group, a C2-C20 heteroaryloxy group, a C6-C20 arylthio group, or a C2-C20 heteroarylthio group is represented. ) R ¹ to R ⁴ are each independently, Z ¹ in the optionally substituted alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group optionally 2 to 20 carbon atoms optionally substituted by Z ^1, Z ¹ in good C2-20 substituted alkynyloxy group, an optionally substituted alkylthio group having 1 to 20 carbon atoms in Z ^1, Z ¹ which may be 2-20 carbons substituted with alkenylthio group, alkynylthio group Z ¹ may C2-20 optionally substituted with, aryloxy group carbon atoms which may be have 6-20 substituted with Z ^2, optionally substituted by Z ² heteroaryl group having 2 to 20 carbon atoms, in heteroarylthio groups arylthio groups or Z ² optionally 2 to 20 carbon atoms optionally substituted by from 6 to 20 carbon atoms which may be substituted with Z ² The thiophene derivative according to claim 1. R ⁵ to R ⁸ are each independently a hydrogen atom, Z ¹ in the optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ^1, thiophene derivative according to claim 1 or 2, wherein optionally substituted alkoxy group which may having 1 to 20 carbon atoms in the alkynyl group or Z ¹ good 2 to 20 carbon atoms optionally substituted by Z ^1. R ⁹ to R ¹² are each independently a hydrogen atom, an alkyl group of Z ¹ is carbon atoms and optionally 1 to 20 substituted by an alkenyl group which may C2-20 optionally substituted by Z ¹ or The thiophene derivative according to any one of claims 1 to 3, which is an alkynyl group having 2 to 20 carbon atoms which may be substituted with Z ¹ . The thiophene according to claim 1, wherein the thiophene compound represented by the following formula (2) and the trialkylstannyl thiophene compound represented by the formulas (3) to (6) are reacted in the presence of a catalyst. A method for producing a derivative.

(In the formula, each Hal independently represents a halogen atom or a pseudohalogen group, and each R ^a independently represents an alkyl group having 1 to 20 carbon atoms. R ^{1 to} R ¹² are the same as above.)   A charge transporting substance comprising the thiophene derivative according to any one of claims 1 to 4.   A charge transporting varnish comprising the thiophene derivative according to any one of claims 1 to 4, a dopant, and an organic solvent.   A charge transporting thin film produced using the charge transporting varnish according to claim 7.   A charge transporting thin film comprising the thiophene derivative according to any one of claims 1 to 4.   An electronic device comprising at least one charge transporting thin film according to claim 8 or 9.   An organic electroluminescence device comprising at least one charge transporting thin film according to claim 8 or 9.   The organic electroluminescence device according to claim 11, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.