JP6174404B2 - Organic thin film transistor, organic semiconductor thin film and organic semiconductor material - Google Patents

Description

  The present invention relates to an organic thin film transistor, an organic semiconductor thin film, an organic semiconductor material, and the like. Specifically, the present invention relates to a compound having a repeating unit composed of at least two cyclopentadienone fused ring structures and a linking group capable of hydrogen bonding, an organic thin film transistor containing the compound, a composition containing the compound, and the compound Organic semiconductor material for non-emissive organic semiconductor device, containing organic compound for organic thin film transistor, coating solution for non-emissive organic semiconductor device characterized by containing the compound, non-comprising containing the compound The present invention relates to an organic semiconductor thin film for a light-emitting organic semiconductor device.

  Devices using organic semiconductor materials are attracting a great deal of attention because they are expected to have various advantages over conventional devices using inorganic semiconductor materials such as silicon. Examples of a device using an organic semiconductor material include a photoelectric conversion element such as an organic thin film solar cell or a solid-state imaging device using the organic semiconductor material as a photoelectric conversion material, and a non-light emitting organic transistor. A device using an organic semiconductor material may be capable of manufacturing a large-area element at a lower temperature and lower cost than a device using an inorganic semiconductor material. Furthermore, since the material characteristics can be easily changed by changing the molecular structure, there are a wide variety of materials, and it is possible to realize functions and elements that could not be achieved with inorganic semiconductor materials.

For example, Patent Document 1 describes a polycyclic fused-ring polymer in which a 5-membered ring is condensed at the end of a linear polyacene. By using this polymer for an organic light-emitting device, high charge transportability and solvent solubility are described. It is described that it can be realized.
Non-Patent Document 1 describes that molecular orbital calculations of various isomers of pentalendione, which is a low-molecular compound, show that the 1,5-dione isomer is the most stable.

JP 2012-177104 A

THEOCHEM, (2002), 589-590, 459-464.

Patent Document 1 describes a polycyclic condensed ring polymer in which a 5-membered ring is condensed at the end of a linear polyacene, but a polycyclic condensed polymer in which a 5-membered ring is condensed at the end of a linear polyacene described in Patent Document 1. In the ring polymer, since there is no interaction between the linked rings and the planarity is lowered, sufficient HOMO orbital overlap cannot be obtained, and sufficient transistor characteristics (low carrier mobility) cannot be obtained. In fact, when the inventors manufactured an organic thin film transistor element having a bottom-gate / bottom-contact structure using the polycyclic fused-ring polymer described in the example of Patent Document 1, the transistor characteristics of 10 ⁻³ units were obtained. It was found that the mobility was low.
Non-Patent Document 1 describes a low molecular compound in which cyclopentadienone is condensed, but there is no example of using the low molecular compound described in the same document in an organic transistor, and the present inventors have disclosed the same document. When the low molecular weight compounds described in 1) were used, sufficient transistor characteristics (low carrier mobility) could not be obtained.

  Therefore, the present inventors proceeded with studies in order to solve such problems of the prior art. The problem to be solved by the present invention is to provide a compound having high carrier mobility and high solubility in an organic solvent when used in a semiconductor active layer of an organic thin film transistor, and an organic thin film transistor using the compound. is there.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the present invention has been developed on the two cyclopentadienone condensed ring structures fused to the end of polyacene or the condensed structure of two cyclopentadienones. A repeating unit structure in which a heteroarylene group or an arylene group is introduced as a linking group at a position adjacent to the carbonyl group, respectively, and the atoms on the ring of the heteroarylene group or the arylene group adjacent to the carbonyl group of the cyclopentadienone condensed ring structure It was found that an intramolecular hydrogen bond is formed between the two layers and the planarity is increased, so that sufficient HOMO orbital overlap is obtained and the carrier mobility is increased. In general, a compound having high planarity and high carrier mobility is known to have low solubility, but unexpectedly, this compound exhibits high solubility in a solvent. From this, it was found that both high carrier mobility and high solubility can be achieved, leading to the present invention.
The present invention, which is a specific means for solving the above problems, has the following configuration.

（一般式（１−１）において、Ｒ¹およびＲ²はそれぞれ独立に水素原子または置換基を表す。Ａｒ¹およびＡｒ²はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表し、Ｖ¹は２価の連結基を表す。ｍは０〜６の整数を表し、ｍが２以上のとき、２つ以上のＶ¹は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）

（一般式（１−２）において、Ｃｙはナフタレン環、またはアントラセン環を表し、Ｒ³およびＲ⁴はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）
［２］ 一般式（１−２）が下記一般式（２−１）、（２−２）、（２−３）、（２−４）または（２−５）で表されるｎ個の繰り返し単位からなる化合物である、［１］の有機薄膜トランジスタ。

（一般式（２−１）〜（２−５）中、Ｒ³、Ｒ⁴、およびＲ¹⁰〜Ｒ³³はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）
［３］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ｖ¹およびＶ²がそれぞれ独立に下記一般式（Ｖ−１）〜（Ｖ−１７）のいずれかで表される２価の連結基である、［１］または［２］の有機薄膜トランジスタ。

（一般式（Ｖ−１）〜（Ｖ−１７）中、＊はｍまたはｐが１のときはＡｒ¹〜Ａｒ⁴のいずれかとの結合位置を示し、ｍまたはｐが２以上のときはＡｒ¹〜Ａｒ⁴および一般式（Ｖ−１）〜（Ｖ−１７）で表される２価の連結基のいずれかとの結合位置を示す。一般式（Ｖ−１）、（Ｖ−２）、（Ｖ−５）、（Ｖ−６）、（Ｖ−９）〜（Ｖ−１１）、（Ｖ−１３）〜（Ｖ−１５）および（Ｖ−１７）中のＲはそれぞれ独立に水素原子またはアルキル基を表し、互いに隣り合うＲは結合して環を形成しても良い。一般式（Ｖ−４）、（Ｖ−７）、（Ｖ−８）および（Ｖ−１２）中のＺはそれぞれ独立に水素原子、アルキル基またはアルコキシ基を表し、互いに隣り合うＺは結合して環を形成しても良い。一般式（Ｖ−１６）中のＹはそれぞれ独立に水素原子、アルキル基、アルコキシ基、ＣＮ基またはＦ原子を表し、互いに隣り合うＹは結合して環を形成しても良い。）
［４］ 一般式（１−１）〜（１−２）および（２−１）〜（２−５）において、Ｖ¹およびＶ²が下記一般式（Ｖ−１）〜（Ｖ−８）および（Ｖ−１１）〜（Ｖ−１５）のいずれかで表される２価の連結基である、［３］の有機薄膜トランジスタ。
［５］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ａｒ¹〜Ａｒ⁴がそれぞれ独立に下記一般式（４−１）、（４−２）または（４−３）で表される２価の連結基である、［１］〜［４］のいずれかの有機薄膜トランジスタ。

（一般式（４−１）〜（４−３）において、ＸはＳ原子、Ｏ原子またはＳｅ原子を表し、Ｃｙ²は１〜４個の環が縮環した構造を表し、Ｒ⁵〜Ｒ⁹はそれぞれ独立に水素原子または置換基を表す。ｑは０〜６の整数を表し、ｑが２以上のとき、２以上のＲ⁶はそれぞれ同一であっても異なっていても良い。波線部分は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。）
［６］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ａｒ¹〜Ａｒ⁴がそれぞれ独立に前記一般式（４−１）または（４−２）で表される２価の連結基である、［５］の有機薄膜トランジスタ。
［７］ 一般式（４−２）で表される２価の連結基が、下記一般式（５−１）〜（５−８）のいずれかで表される２価の連結基である、［５］または［６］のいずれかの有機薄膜トランジスタ。

（一般式（５−１）〜（５−８）中、Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、２個以上のＲ⁶は同一であっても、異なっていても良い。波線は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。）
［８］ 一般式（１−１）において、Ｒ¹およびＲ²の少なくとも１つ、一般式（１−２）において、Ｒ³およびＲ⁴の少なくとも１つ、一般式（２−１）において、Ｒ³、Ｒ⁴、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、およびＲ¹³の少なくとも１つ、一般式（２−２）において、Ｒ³、Ｒ⁴、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、およびＲ¹⁷の少なくとも１つ、一般式（２−３）において、Ｒ³、Ｒ⁴、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、およびＲ²¹の少なくとも１つ、一般式（２−４）において、Ｒ³、Ｒ⁴、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、およびＲ²⁷の少なくとも１つ、ならびに前記一般式（２−５）において、Ｒ³、Ｒ⁴、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、およびＲ³³の少なくとも１つが、下記一般式（Ｗ）で表される基である、［１］〜［６］のいずれかの有機薄膜トランジスタ。
−Ｌ−Ｒ 一般式（Ｗ）
（一般式（Ｗ）において、Ｌは下記一般式（Ｌ−１）〜（Ｌ−１２）のいずれかで表される２価の連結基または２以上の下記一般式（Ｌ−１）〜（Ｌ−１２）のいずれかで表される２価の連結基が結合した２価の連結基を表す。Ｒは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、またはケイ素原子数が２以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。また、Ｒが置換または無置換のシリル基を表すのは、Ｒに隣接するＬが下記一般式（Ｌ−１）〜（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１２）において、波線部分はシクロペンタジエノン骨格との結合位を表す。＊は（Ｌ−１）〜（Ｌ−１２）で表される２価の連結基およびＲのいずれかの結合位置を表す。一般式（Ｌ−１０）におけるｍは４であり、一般式（Ｌ−１１）および（Ｌ−１２）におけるｍは２である。一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−１０）、（Ｌ−１１）および（Ｌ−１２）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。）
［９］ 一般式（Ｗ）において、Ｌが一般式（Ｌ−１）、（Ｌ−４）または（Ｌ−８）のいずれかで表される２価の連結基またはこれらの２価の連結基が２以上結合した２価の連結基であることを特徴とする、［８］の有機薄膜トランジスタ。
［１０］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、ｎが１０以上であることを特徴とする、［１］〜［９］のいずれかの有機薄膜トランジスタ。
［１１］ 下記一般式（１−１）または（１−２）で表されるｎ個の繰り返し単位からなる化合物。

（一般式（１−１）において、Ｒ¹およびＲ²はそれぞれ独立に水素原子または置換基を表す。Ａｒ¹およびＡｒ²はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表し、Ｖ¹は２価の連結基を表す。ｍは０〜６の整数を表し、ｍが２以上のとき、２つ以上のＶ¹は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）

（一般式（１−２）において、Ｃｙはナフタレン環、またはアントラセン環を表し、Ｒ³およびＲ⁴はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）
［１２］ 一般式（１−２）が下記一般式（２−１）、（２−２）、（２−３）、（２−４）または（２−５）で表されるｎ個の繰り返し単位からなることを特徴とする、［１１］の化合物。

（一般式（２−１）〜（２−５）中、Ｒ³、Ｒ⁴、およびＲ¹⁰〜Ｒ³³はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）
［１３］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ｖ¹およびＶ²がそれぞれ独立に下記一般式（Ｖ−１）〜（Ｖ−１７）のいずれかで表される２価の連結基である、［１１］または［１２］の化合物。

（一般式（Ｖ−１）〜（Ｖ−１７）中、＊はｍまたはｐが１のときはＡｒ¹〜Ａｒ⁴のいずれかとの結合位置を示し、ｍまたはｐが２以上のときはＡｒ¹〜Ａｒ⁴および一般式（Ｖ−１）〜（Ｖ−１７）で表される２価の連結基のいずれかとの結合位置を示す。一般式（Ｖ−１）、（Ｖ−２）、（Ｖ−５）、（Ｖ−６）、（Ｖ−９）〜（Ｖ−１１）、（Ｖ−１３）〜（Ｖ−１５）および（Ｖ−１７）中のＲはそれぞれ独立に水素原子またはアルキル基を表し、互いに隣り合うＲは結合して環を形成しても良い。一般式（Ｖ−４）、（Ｖ−７）、（Ｖ−８）および（Ｖ−１２）中のＺはそれぞれ独立に水素原子、アルキル基またはアルコキシ基を表し、互いに隣り合うＺは結合して環を形成しても良い。一般式（Ｖ−１６）中のＹはそれぞれ独立に水素原子、アルキル基、アルコキシ基、ＣＮ基またはＦ原子を表し、互いに隣り合うＹは結合して環を形成しても良い。）
［１４］ 一般式（１−１）〜（１−２）および（２−１）〜（２−５）において、Ｖ¹およびＶ²が下記一般式（Ｖ−１）〜（Ｖ−８）および（Ｖ−１１）〜（Ｖ−１５）のいずれかで表される２価の連結基である、［１３］に記載の化合物。
［１５］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ａｒ¹〜Ａｒ⁴がそれぞれ独立に下記一般式（４−１）、（４−２）または（４−３）で表される２価の連結基である、［１１］〜［１４］のいずれかの化合物。

（一般式（４−１）〜（４−３）において、ＸはＳ原子、Ｏ原子またはＳｅ原子を表し、Ｃｙ²は１〜４個の環が縮環した構造を表し、Ｒ⁵〜Ｒ⁹はそれぞれ独立に水素原子または置換基を表す。ｑは０〜６の整数を表し、ｑが２以上のとき、２以上のＲ⁶はそれぞれ同一であっても異なっていても良い。波線部分は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。）
［１６］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、Ａｒ¹〜Ａｒ⁴がそれぞれ独立に前記一般式（４−１）または（４−２）で表される２価の連結基である、［１５］の化合物。
［１７］ 一般式（４−２）で表される２価の連結基が、下記一般式（５−１）〜（５−８）のいずれかで表される２価の連結基である、［１５］または［１６］の化合物。

（一般式（５−１）〜（５−８）中、Ｒ⁶は水素原子または置換基を表し、２個以上のＲ⁶は同一であっても、異なっていても良い。波線は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。）
［１８］ 一般式（１−１）において、Ｒ¹およびＲ²の少なくとも１つ、一般式（１−２）において、Ｒ³およびＲ⁴の少なくとも１つ、一般式（２−１）において、Ｒ³、Ｒ⁴、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、およびＲ¹³の少なくとも１つ、一般式（２−２）において、Ｒ³、Ｒ⁴、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、およびＲ¹⁷の少なくとも１つ、一般式（２−３）において、Ｒ³、Ｒ⁴、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、およびＲ²¹の少なくとも１つ、一般式（２−４）において、Ｒ³、Ｒ⁴、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、およびＲ²⁷の少なくとも１つ、ならびに前記一般式（２−５）において、Ｒ³、Ｒ⁴、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、およびＲ³³の少なくとも１つが、下記一般式（Ｗ）で表される基である、［１１］〜［１７］のいずれかの化合物。
−Ｌ−Ｒ 一般式（Ｗ）
（一般式（Ｗ）において、Ｌは下記一般式（Ｌ−１）〜（Ｌ−１２）のいずれかで表される２価の連結基または２以上の下記一般式（Ｌ−１）〜（Ｌ−１２）のいずれかで表される２価の連結基が結合した２価の連結基を表す。Ｒは置換または無置換のアルキル基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、またはケイ素原子数が２以上のオリゴシロキサン基、あるいは、置換または無置換のシリル基を表す。また、Ｒが置換または無置換のシリル基を表すのは、Ｒに隣接するＬが下記一般式（Ｌ−１）〜（Ｌ−３）で表される２価の連結基である場合に限る。）

（一般式（Ｌ−１）〜（Ｌ−１２）において、波線部分はシクロペンタジエノン骨格との結合位を表す。＊は（Ｌ−１）〜（Ｌ−１２）で表される２価の連結基およびＲのいずれかの結合位置を表す。一般式（Ｌ−１０）におけるｍは４であり、一般式（Ｌ−１１）および（Ｌ−１２）におけるｍは２である。一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−１０）、（Ｌ−１１）および（Ｌ−１２）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。）
［１９］ 一般式（Ｗ）において、Ｌが一般式（Ｌ−１）、（Ｌ−４）または（Ｌ−８）のいずれかで表される２価の連結基またはこれらの２価の連結基が２以上結合した２価の連結基であることを特徴とする、［１８］の化合物。
［２０］ 一般式（１−１）、（１−２）および（２−１）〜（２−５）において、ｎが１０以上であることを特徴とする、［１１］〜［１９］のいずれかの化合物。
［２１］ ［１１］〜［２０］のいずれかの化合物と有機溶媒を含有することを特徴とする組成物。
［２２］ 前記有機溶媒が、芳香族炭化水素系溶媒、エーテル系溶媒またはケトン系溶媒である、［２１］の組成物。
［２３］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物を含有することを特徴とする非発光性有機半導体デバイス用有機半導体材料。
［２４］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物を含有することを特徴とする有機薄膜トランジスタ用材料。
［２５］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物を含有することを特徴とする非発光性有機半導体デバイス用塗布溶液。
［２６］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物とポリマーバインダーとを含有することを特徴とする非発光性有機半導体デバイス用塗布溶液。
［２７］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物を含有することを特徴とする非発光性有機半導体デバイス用有機半導体薄膜。
［２８］ ［１１］〜［２０］のいずれかの化合物または［２１］もしくは［２２］に記載の組成物とポリマーバインダーとを含有することを特徴とする非発光性有機半導体デバイス用有機半導体薄膜。
［２９］ 溶液塗布法により作製されたことを特徴とする［２７］または［２８］の非発光性有機半導体デバイス用有機半導体薄膜。 [1] An organic thin film transistor comprising a compound comprising n repeating units represented by the following general formula (1-1) or (1-2) in a semiconductor active layer.

(In General Formula (1-1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. Ar ¹ and Ar ² each independently represent a heteroarylene group or an arylene group, and V ¹ represents a divalent group. M represents an integer of 0 to 6, and when m is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more. .)

(In general formula (1-2), Cy represents a naphthalene ring or an anthracene ring, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ each independently represent a heteroarylene group. Or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² are the same or different. (N represents an integer of 2 or more.)
[2] n pieces of general formula (1-2) represented by the following general formula (2-1), (2-2), (2-3), (2-4) or (2-5) The organic thin film transistor of [1], which is a compound composed of repeating units.

(In the general formulas (2-1) to (2-5), R ³ , R ⁴ , and R ^{10 to} R ³³ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ are each independently heterogeneous. Represents an arylene group or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² may be the same or different (N represents an integer of 2 or more.)
[3] In the general formulas (1-1), (1-2) and (2-1) to (2-5), V ¹ and V ² are each independently represented by the following general formulas (V-1) to (V The organic thin-film transistor of [1] or [2] which is a bivalent coupling group represented by any of -17).

(In the general formulas (V-1) to (V-17), * represents a bonding position with any ^one of Ar ^{1 to} Ar ⁴ when m or p is 1, and Ar or m when p is 2 or more. ^{1 to} Ar ⁴ and a bonding position with any of the divalent linking groups represented by the general formulas (V-1) to (V-17) are represented by the general formulas (V-1), (V-2), R in (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and (V-17) each independently represents a hydrogen atom Or an alkyl group, and Rs adjacent to each other may combine to form a ring, and Z in the general formulas (V-4), (V-7), (V-8) and (V-12) Each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other may combine to form a ring, and Y in formula (V-16) is independently Represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring.)
[4] In general formulas (1-1) to (1-2) and (2-1) to (2-5), V ¹ and V ² are the following general formulas (V-1) to (V-8). And the organic thin film transistor of [3], which is a divalent linking group represented by any one of (V-11) to (V-15).
[5] In the general formulas (1-1), (1-2) and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the following general formulas (4-1) and (4). -2) or the organic thin film transistor according to any one of [1] to [4], which is a divalent linking group represented by (4-3).

(In General Formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, Cy ² represents a structure in which 1 to 4 rings are condensed, and R ^{5 to} R ⁹ each independently represents a hydrogen atom or a substituent, q represents an integer of 0 to 6, and when q is 2 or more, 2 or more R ^{6 s} may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. )
[6] In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently the general formula (4-1) or (4). The organic thin film transistor of [5], which is a divalent linking group represented by -2).
[7] The divalent linking group represented by the general formula (4-2) is a divalent linking group represented by any one of the following general formulas (5-1) to (5-8). The organic thin-film transistor in any one of [5] or [6].

(In the general formulas (5-1) to (5-8), R ⁶ each independently represents a hydrogen atom or a substituent, and two or more R ⁶ may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. )
[8] In the general formula (1-1), in at least one of R ¹ and R ² , in the general formula (1-2), in at least one of R ³ and R ⁴ , in the general formula (2-1), In general formula (2-2), at least one of R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ , R ³ , R ⁴ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ In general formula (2-3), at least one of R ³ , R ⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ , in general formula (2-4), R ³ , R ⁴ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ , and the general formula (2-5), R ³ , R ⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ are groups represented by the following general formula (W), and the organic thin film transistor according to any one of [1] to [6] Jista.
-LR General Formula (W)
(In General Formula (W), L is a divalent linking group represented by any one of the following General Formulas (L-1) to (L-12) or two or more General Formulas (L-1) to ( L-12) represents a divalent linking group to which a divalent linking group represented by any one of R-12) is bonded, wherein R represents a substituted or unsubstituted alkyl group, and an oligooxy having a repeating number v of oxyethylene units of 2 or more. Represents an ethylene group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted silyl group, and R represents a substituted or unsubstituted silyl group. (Only when it is a divalent linking group represented by the general formulas (L-1) to (L-3).)

(In the general formulas (L-1) to (L-12), the wavy line represents the bonding position with the cyclopentadienone skeleton. * Is a divalent group represented by (L-1) to (L-12). In the general formula (L-10), m is 4 and m in the general formulas (L-11) and (L-12) is 2. (R ′ in (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represents a hydrogen atom or a substituent))
[9] In the general formula (W), L is a divalent linking group represented by any one of the general formulas (L-1), (L-4), or (L-8) or a divalent linking group thereof. [8] The organic thin film transistor according to [8], wherein the organic thin film transistor is a divalent linking group in which two or more groups are bonded.
[10] In the general formulas (1-1), (1-2), and (2-1) to (2-5), n is 10 or more, [1] to [9] Any organic thin film transistor.
[11] A compound comprising n repeating units represented by the following general formula (1-1) or (1-2).

(In General Formula (1-1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. Ar ¹ and Ar ² each independently represent a heteroarylene group or an arylene group, and V ¹ represents a divalent group. M represents an integer of 0 to 6, and when m is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more. .)

(In general formula (1-2), Cy represents a naphthalene ring or an anthracene ring, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ each independently represent a heteroarylene group. Or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² are the same or different. (N represents an integer of 2 or more.)
[12] n number of the general formula (1-2) is represented by the following general formula (2-1), (2-2), (2-3), (2-4) or (2-5) The compound according to [11], comprising a repeating unit.

(In the general formulas (2-1) to (2-5), R ³ , R ⁴ , and R ^{10 to} R ³³ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ are each independently heterogeneous. Represents an arylene group or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² may be the same or different (N represents an integer of 2 or more.)
[13] In the general formulas (1-1), (1-2), and (2-1) to (2-5), V ¹ and V ² are each independently represented by the following general formulas (V-1) to (V The compound of [11] or [12] which is a divalent linking group represented by any one of -17).

(In the general formulas (V-1) to (V-17), * represents a bonding position with any ^one of Ar ^{1 to} Ar ⁴ when m or p is 1, and Ar or m when p is 2 or more. ^{1 to} Ar ⁴ and a bonding position with any of the divalent linking groups represented by the general formulas (V-1) to (V-17) are represented by the general formulas (V-1), (V-2), R in (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and (V-17) each independently represents a hydrogen atom Or an alkyl group, and Rs adjacent to each other may combine to form a ring, and Z in the general formulas (V-4), (V-7), (V-8) and (V-12) Each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other may combine to form a ring, and Y in formula (V-16) is independently Represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring.)
[14] In the general formulas (1-1) to (1-2) and (2-1) to (2-5), V ¹ and V ² are represented by the following general formulas (V-1) to (V-8). And the compound according to [13], which is a divalent linking group represented by any one of (V-11) to (V-15).
[15] In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the following general formulas (4-1) and (4). -2) The compound in any one of [11]-[14] which is a bivalent coupling group represented by (4-3).

(In General Formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, Cy ² represents a structure in which 1 to 4 rings are condensed, and R ^{5 to} R ⁹ each independently represents a hydrogen atom or a substituent, q represents an integer of 0 to 6, and when q is 2 or more, 2 or more R ^{6 s} may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. )
[16] In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the general formula (4-1) or (4). The compound of [15] which is a bivalent coupling group represented by -2).
[17] The divalent linking group represented by the general formula (4-2) is a divalent linking group represented by any one of the following general formulas (5-1) to (5-8). [15] or [16] compound.

(In the general formulas (5-1) to (5-8), R ⁶ represents a hydrogen atom or a substituent, and two or more R ^{6 s} may be the same or different. The bond position with the pentadienone fused ring portion is represented, and # represents the bond position with V ¹ or V ^2. )
[18] In general formula (1-1), in at least one of R ¹ and R ² , in general formula (1-2), in at least one of R ³ and R ⁴ , in general formula (2-1), In general formula (2-2), at least one of R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ , R ³ , R ⁴ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ In general formula (2-3), at least one of R ³ , R ⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ , in general formula (2-4), R ³ , R ⁴ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ , and the general formula (2-5), R ³ , R ⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ are the compounds represented by any one of [11] to [17], which is a group represented by the following general formula (W).
-LR General Formula (W)
(In General Formula (W), L is a divalent linking group represented by any one of the following General Formulas (L-1) to (L-12) or two or more General Formulas (L-1) to ( L-12) represents a divalent linking group to which a divalent linking group represented by any one of R-12) is bonded, wherein R represents a substituted or unsubstituted alkyl group, and an oligooxy having a repeating number v of oxyethylene units of 2 or more. Represents an ethylene group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted silyl group, and R represents a substituted or unsubstituted silyl group. (Only when it is a divalent linking group represented by the general formulas (L-1) to (L-3).)

(In the general formulas (L-1) to (L-12), the wavy line represents the bonding position with the cyclopentadienone skeleton. * Is a divalent group represented by (L-1) to (L-12). In the general formula (L-10), m is 4 and m in the general formulas (L-11) and (L-12) is 2. (R ′ in (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represents a hydrogen atom or a substituent))
[19] In the general formula (W), L is a divalent linking group represented by any one of the general formulas (L-1), (L-4), or (L-8) or a divalent linking group thereof. [18] The compound according to [18], which is a divalent linking group in which two or more groups are bonded.
[20] In the general formulas (1-1), (1-2), and (2-1) to (2-5), n is 10 or more, [11] to [19] Any compound.
[21] A composition comprising the compound of any one of [11] to [20] and an organic solvent.
[22] The composition of [21], wherein the organic solvent is an aromatic hydrocarbon solvent, an ether solvent or a ketone solvent.
[23] An organic semiconductor material for a non-light-emitting organic semiconductor device, comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22].
[24] An organic thin film transistor material comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22].
[25] A coating solution for a non-luminescent organic semiconductor device comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22].
[26] A coating solution for a non-light-emitting organic semiconductor device, comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22] and a polymer binder.
[27] An organic semiconductor thin film for a non-luminescent organic semiconductor device, comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22].
[28] An organic semiconductor thin film for a non-light-emitting organic semiconductor device comprising the compound according to any one of [11] to [20] or the composition according to [21] or [22] and a polymer binder. .
[29] The organic semiconductor thin film for non-light-emitting organic semiconductor devices according to [27] or [28], which is produced by a solution coating method.

  ADVANTAGE OF THE INVENTION According to this invention, when it uses for the semiconductor active layer of an organic thin-film transistor, the carrier mobility is high and can provide the organic thin-film transistor using the compound which has high solubility to an organic solvent, and this compound.

FIG. 1 is a schematic view showing a cross section of an example of the structure of the organic thin film transistor of the present invention. FIG. 2 is a schematic view showing a cross section of the structure of an organic thin film transistor manufactured as a substrate for measuring FET characteristics in an example of the present invention.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, a hydrogen atom when used without being particularly distinguished in the description of each general formula represents that it also contains an isotope (such as a deuterium atom). Furthermore, the atom which comprises a substituent represents that the isotope is also included.
In the present specification, a compound consisting of n repeating units represented by the general formula (1-1) or (1-2) is a compound represented by the general formula (1-1) or (1-2). It is synonymous with.

（一般式（１−１）において、Ｒ¹およびＲ²はそれぞれ独立に水素原子または置換基を表す。Ａｒ¹およびＡｒ²はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表し、Ｖ¹は２価の連結基を表す。ｍは０〜６の整数を表し、ｍが２以上のとき、２つ以上のＶ¹は同一であっても、異なっていても良い。ｎは２以上の整数を表す。）

（一般式（１−２）において、Ｃｙはナフタレン環、またはアントラセン環を表し、Ｒ³およびＲ⁴はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。） [Organic thin film transistor]
The organic thin film transistor of the present invention is characterized in that a semiconductor active layer contains a compound composed of n repeating units represented by the following general formula (1-1) or (1-2).

(In General Formula (1-1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. Ar ¹ and Ar ² each independently represent a heteroarylene group or an arylene group, and V ¹ represents a divalent group. M represents an integer of 0 to 6, and when m is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more. .)

(In general formula (1-2), Cy represents a naphthalene ring or an anthracene ring, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ each independently represent a heteroarylene group. Or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² are the same or different. (N represents an integer of 2 or more.)

A compound comprising n repeating units represented by the general formula (1-1) or (1-2) has high carrier mobility when used in a semiconductor active layer of an organic thin film transistor, and high solubility in an organic solvent. Therefore, the organic thin film transistor of the present invention has high carrier mobility by including the compound in the semiconductor active layer.
The compound consisting of n repeating units represented by the general formula (1-1) or (1-2) has a sufficient HOMO orbital overlap because the condensed cyclopentadienone skeleton has a carbonyl group. can get. Thereby, an organic thin film transistor with high carrier mobility can be obtained. Unexpectedly, the effect of high solubility in organic solvents can also be obtained. As a mechanism for obtaining such an effect, a compound composed of n repeating units represented by the general formula (1-1) or (1-2) is a cyclopentadienone skeleton having a condensed ring as a mother skeleton. In the film, the hydrogen bond is maintained in the plane by having a hydrogen bond between the double bond oxygen and the hydrogen atom of the adjacent arylene group or heteroarylene group on both sides of the condensed cyclopentadienone skeleton. Therefore, the intermolecular distance between polymer molecules can be shortened to increase the carrier mobility, and in the solution, the hydrogen bond can be dissociated and freely rotated to increase the solubility in an organic solvent.

  In addition, it is conventionally known that a polycyclic condensed compound containing an aromatic heterocycle is useful as an organic EL device material. However, it cannot be said that what is useful as an organic EL element material is immediately useful as a semiconductor material for an organic thin film transistor. This is because organic EL elements and organic thin film transistors have different characteristics required for organic compounds. In the organic EL element, it is usually necessary to transport charges in the film thickness direction (usually several nm to several hundred nm), whereas in the organic thin film transistor, the long distance between the electrodes in the thin film surface direction (usually several μm to several hundred μm). It is necessary to transport charges (carriers). For this reason, the required carrier mobility is remarkably high. Therefore, as a semiconductor material for an organic thin film transistor, an organic compound having high molecular order and high crystallinity is required. In order to develop high carrier mobility, the π conjugate plane is preferably upright with respect to the substrate. On the other hand, in order to increase the light emission efficiency, an organic EL element is required to have a high light emission efficiency and uniform light emission in the surface. In general, organic compounds with high crystallinity cause light emission defects such as in-plane electric field strength non-uniformity, light emission non-uniformity, and light emission quenching, so organic EL device materials have low crystallinity and are amorphous. High material is desired. For this reason, even if the organic compound constituting the organic EL element material is directly transferred to the organic semiconductor material, good transistor characteristics cannot be obtained immediately.

Further, the organic thin film transistor of the present invention using the compound composed of n repeating units represented by the general formula (1-1) or (1-2) preferably has a small threshold voltage change after repeated driving. . In order to reduce the threshold voltage change after repeated driving, HOMO of the organic semiconductor material is neither too shallow nor too deep, the chemical stability of the organic semiconductor material (particularly air oxidation resistance, redox stability), There is a need for thermal stability in a thin film state, high film density that does not allow air and moisture to enter, film quality that prevents charges from accumulating, and has few defects. In addition, an oligomer or a polymer compound having a repeating unit such as a compound consisting of n repeating units represented by the general formula (1-1) or (1-2) can be used as an organic solvent during film formation. The higher the solubility, the smaller the threshold voltage change after repeated driving when used in the semiconductor active layer of the organic thin film transistor. Since the compound consisting of n repeating units represented by the general formula (1-1) or (1-2) satisfies these, it is considered that the threshold voltage change after repeated driving is small. That is, in an organic thin film transistor having a small threshold voltage change after repeated driving, the semiconductor active layer has high chemical stability, film density, etc., and can function effectively as a transistor for a long period of time.
Hereinafter, preferred embodiments of the compound of the present invention and the organic thin film transistor of the present invention will be described.

<Compound consisting of n repeating units represented by the general formula (1-1) or (1-2)>
The compound of the present invention is characterized by comprising n repeating units represented by the following general formula (1-1) or (1-2). The compound of this invention is contained in the below-mentioned semiconductor active layer in the organic thin-film transistor of this invention. That is, the compound of the present invention can be used as a material for an organic thin film transistor.
Hereinafter, the compound which consists of n repeating units represented by general formula (1-1) or (1-2) is demonstrated.

（一般式（１−１）において、Ｒ¹およびＲ²はそれぞれ独立に水素原子または置換基を表す。Ａｒ¹およびＡｒ²はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表し、Ｖ¹は２価の連結基を表す。ｍは０〜６の整数を表し、ｍが２以上のとき、２つ以上のＶ¹は同一であっても、異なっていても良い。ｎは２以上の整数を表す。） << Compound Composed of n Repeating Units Represented by General Formula (1-1) >>
The compound consisting of n repeating units represented by the general formula (1-1) is represented by the following general formula.

(In General Formula (1-1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. Ar ¹ and Ar ² each independently represent a heteroarylene group or an arylene group, and V ¹ represents a divalent group. M represents an integer of 0 to 6, and when m is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more. .)

（一般式（Ｌ−１）〜（Ｌ−１２）において、波線部分はシクロペンタジエノン骨格との結合位を表す。＊は（Ｌ−１）〜（Ｌ−１２）で表される２価の連結基およびＲのいずれかの結合位置を表す。一般式（Ｌ−１０）におけるｍは４であり、一般式（Ｌ−１１）および（Ｌ−１２）におけるｍは２である。一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−１０）、（Ｌ−１１）および（Ｌ−１２）におけるＲ’はそれぞれ独立に水素原子または置換基を表す。） In General Formula (1-1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. The substituent that R ¹ and R ² can take is not particularly limited, and examples thereof include the same substituents as those represented by the following general formula (W) and examples of substituents that can be adopted by R ^{5 to} R ⁹ described below. A group represented by the following general formula (W) is preferable, and at least one of R ¹ and R ² is more preferably a group represented by the following general formula (W). preferable.
-LR General Formula (W)
(In General Formula (W), L is a divalent linking group represented by any one of the following General Formulas (L-1) to (L-12) or two or more General Formulas (L-1) to ( L-12) represents a divalent linking group to which a divalent linking group represented by any one of R-12) is bonded, wherein R represents a substituted or unsubstituted alkyl group, and an oligooxy having a repeating number v of oxyethylene units of 2 or more. Represents an ethylene group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted silyl group, and R represents a substituted or unsubstituted silyl group. (Only when it is a divalent linking group represented by the general formulas (L-1) to (L-3).)

(In the general formulas (L-1) to (L-12), the wavy line represents the bonding position with the cyclopentadienone skeleton. * Is a divalent group represented by (L-1) to (L-12). In the general formula (L-10), m is 4 and m in the general formulas (L-11) and (L-12) is 2. (R ′ in (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represents a hydrogen atom or a substituent))

  In the general formula (W), L is a divalent linking group represented by any one of the general formulas (L-1) to (L-12) or two or more general formulas (L-1) to (L-12). ) Represents a divalent linking group to which a divalent linking group represented by any of the above is bonded. When L forms a linking group to which a divalent linking group represented by any one of the general formulas (L-1) to (L-12) is bonded, the general formulas (L-1) to (L- The number of bonds of the divalent linking group represented by any one of 12) is preferably 2 to 4, and more preferably 2 or 3.

The substituents R ′ in the general formulas (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represent a hydrogen atom or a substituent. Examples of the substituent that R ′ can take include an alkyl group having 5 to 15 carbon atoms (preferably an alkyl group having 6 to 15 carbon atoms), and an alkoxy group having 5 to 15 carbon atoms (preferably an alkoxy group having 6 to 15 carbon atoms). ).
M in the general formula (L-10) represents 4, and m in the general formulas (L-11) and (L-12) represents 2.

  L is a divalent linking group represented by any one of the general formulas (L-1), (L-4), and (L-8), or a divalent linking of two or more of these divalent linking groups. The divalent linking group represented by the general formula (L-1) or (L-4) or a divalent linking group in which two or more of these divalent linking groups are bonded. The linking group is more preferably a divalent linking group represented by formula (L-1) or a divalent linking group in which two or more divalent linking groups are bonded.

  In the general formula (W), R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, an oligosiloxane group having 2 or more silicon atoms, or a substituted group. Or an unsubstituted silyl group is represented. However, R represents a substituted or unsubstituted silyl group only when a hydrogen atom is present when L adjacent to R is a divalent linking group represented by the following general formula (L-3). Is limited to the case where L adjacent to R is a divalent linking group represented by the following general formulas (L-1) to (L-3).

As a substituted or unsubstituted alkyl group which R can take, when L is represented by the said general formula (L-1), it is preferable that it is a C3 or more alkyl group, and C3-C40 The alkyl group is more preferably an alkyl group having 10 to 30 carbon atoms, more preferably from the viewpoint of chemical stability and carrier transportability, and an alkyl group having 15 to 30 carbon atoms. Particularly preferred. Moreover, as the substituted or unsubstituted alkyl group which R can take, when L is represented with the said general formula (L-1), it is preferable that it is a linear or branched alkyl group, and a branched alkyl group is A group is more preferable from the viewpoint of improving carrier mobility and solubility in a solvent without reducing intramolecular hydrogen bonding.
When L is represented by the general formulas (L-2) to (L-3), the alkyl group that R can take is preferably an alkyl group having 2 or more carbon atoms, and having 3 to 3 carbon atoms. It is preferably an 18 alkyl group, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly preferably an alkyl group having 4 to 10 carbon atoms.
When L is represented by the general formulas (L-4) to (L-12), the alkyl group that R can take is preferably an alkyl group having 4 or more carbon atoms, and having 4 to 4 carbon atoms. It is preferably an 18 alkyl group, more preferably an alkyl group having 4 to 12 carbon atoms, and particularly preferably an alkyl group having 4 to 10 carbon atoms.

In the general formula (W), when the LR includes an alkyl group, the carrier mobility is increased when the alkyl group represented by R is not less than the lower limit of the above range. In addition, when L includes the general formula (L-1) adjacent to R, an alkyl group formed by combining an alkylene group represented by the general formula (L-1) and an alkyl group represented by R When the number of carbon atoms is equal to or greater than the lower limit of the above range, the carrier mobility is increased.
Examples of the substituent when R is an alkyl group having a substituent include a halogen atom, and a fluorine atom is preferable. In addition, when R is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group.

When R is an oligoethyleneoxy group having a repeating number v of oxyethylene group of 2 or more, the “oxyethylene group” represented by R is a group represented by — (CH ₂ CH ₂ ) _v OY in the present specification. (The repeating number v of the oxyethylene unit represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The repeating number v of oxyethylene units is preferably 2 to 4, and more preferably 2 to 3. The terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is particularly preferable.

  When R is an oligosiloxane group having 2 or more silicon atoms, the number of repeating siloxane units is preferably 2 to 4, and more preferably 2 to 3. Further, it is preferable that a hydrogen atom or an alkyl group is bonded to the Si atom. When the alkyl group is bonded to the Si atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded to it. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same. When R is a substituted or unsubstituted silyl group, examples of the silyl group that R can take include a trialkylsilyl group having 3 to 15 carbon atoms and a silyl group substituted with 1 to 3 trialkylsilyloxy groups (monoalkyldi ( Trialkylsilyloxy) silyl group, dialkylmono (trialkylsilyloxy) silyl group, tri (trialkylsilyloxy) silyl group) are preferred.

Examples of the group represented by the general formula (W) include 2,6-dimethyloctyl group, 2-decyltetradecyl group, 2-hexyldecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2 -Butyldecyl, 2-octylnonyl, 2-ethyloctyl, 2-octyltetradecyl, 2-hexyldecyloxy, ditrimethylsiloxymethylbutoxy, hexyl, heptyl, octyl, nonyl, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and the like. The substituent that can be taken by R ¹ and R ² is preferably a branched substituent further having a substituent on the linear substituent.

（一般式（４−１）〜（４−３）において、ＸはＳ原子、Ｏ原子またはＳｅ原子を表し、Ｃｙ²は１〜４個の環が縮環した構造を表し、Ｒ⁵〜Ｒ⁹はそれぞれ独立に水素原子または置換基を表す。ｑは０〜６の整数を表し、ｑが２以上のとき、２以上のＲ⁶はそれぞれ同一であっても異なっていても良い。波線部分は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。） Ar ¹ and Ar ² each independently represents a heteroarylene group or an arylene group. Ar ¹ is preferably not bonded to R ² to form a condensed ring from the viewpoint of enhancing solubility, and Ar ² is preferably bonded to R ¹ to form a condensed ring from the viewpoint of increasing solubility. The heteroarylene group or arylene group that Ar ¹ and Ar ² can take is not particularly limited, and examples thereof include a heteroarylene group having 4 to 30 carbon atoms or an arylene group having 6 to 30 carbon atoms. The heteroarylene group or the arylene group that Ar ¹ and Ar ² can take is a divalent linking group represented by the following general formula (4-1), (4-2), or (4-3). A divalent linking group represented by the following general formula (4-1) or (4-2) is more preferable. Ar ¹ and Ar ² preferably represent the same heteroarylene group or arylene group.

(In General Formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, Cy ² represents a structure in which 1 to 4 rings are condensed, and R ^{5 to} R ⁹ each independently represents a hydrogen atom or a substituent, q represents an integer of 0 to 6, and when q is 2 or more, 2 or more R ^{6 s} may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. )

  In the general formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, preferably an S atom or Se atom, and more preferably an S atom.

In General Formulas (4-1) to (4-3), R ^{5 to} R ⁹ each independently represent a hydrogen atom or a substituent. The substituent that R ^{5 to} R ⁹ can take is not particularly limited, and examples thereof include halogen atoms, alkyl groups (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, C1-C40 alkyl groups (preferably C3-C40 alkyl groups, more preferably C10-30 carbon atoms) such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc. Alkyl group), 2,6-dimethyloctyl group, 2-decyltetradecyl group, 2-hexyldecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2-ethyloctyl group, 2-octyltetradecyl group, etc.), alkenyl group (1-pentenyl group, cycloalkenyl group, biphenyl) Alkenyl group (including 1-pentynyl group, trimethylsilylethynyl group, triethylsilylethynyl group, tri-i-propylsilylethynyl group, 2-p-propylphenylethynyl group, etc.), aryl group (including A phenyl group, a naphthyl group, a p-pentylphenyl group, a 3,4-dipentylphenyl group, a p-heptoxyphenyl group, a 3,4-diheptoxyphenyl group having 6 to 20 carbon atoms, and the like), A heterocyclic group (also referred to as a heterocyclic group, including a 2-hexylfuranyl group), a cyano group, a hydroxyl group, a nitro group, an acyl group (including a hexanoyl group, a benzoyl group, etc.), an aryloxy group, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including anilino group), acyl Amino group, aminocarbonylamino group (including ureido group), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptoxy group, octoxy group, nonyloxy group, decyloxy group, 2-hexylde C1-C40 alkoxy groups (preferably C3-C40 alkoxy groups, more preferably C10-C10, such as siloxy groups, undecyloxy groups, dodecyloxy groups, tridecyloxy groups, tetradecyloxy groups, pentadecyloxy groups, etc. 30 alkoxy groups)), aryloxycarbonylamino groups, alkyl and arylsulfonylamino groups, mercapto groups, alkyl and arylthio groups (including methylthio groups, octylthio groups, etc.), heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyls And ants Rusulfinyl group, alkyl and arylsulfonyl group, alkyl and aryloxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group , A silyl group (ditrimethylsiloxymethylbutoxy group), a hydrazino group, and other known substituents. Among these, an alkyl group and an alkoxy group are preferable.
The alkyl group that can be taken by R ^{5 to} R ⁹ is more preferably an alkyl group having 3 to 40 carbon atoms, and an alkyl group having 10 to 30 carbon atoms is chemically stable and carrier transportable. In view of the above, the alkyl group is more preferably an alkyl group having 15 to 30 carbon atoms. In addition, the alkyl group that R ^{5 to} R ⁹ can take is preferably a linear or branched alkyl group, and the branched alkyl group is capable of transferring carriers without reducing intramolecular hydrogen bonding. It is more preferable from the viewpoint of improving the solubility in the solvent and the solvent.
The alkoxy group that can be taken by R ^{5 to} R ⁹ is more preferably an alkoxy group having 3 to 40 carbon atoms, and an alkoxy group having 10 to 30 carbon atoms is chemical stability and carrier transportability. In view of the above, it is more preferably an alkoxy group having 15 to 30 carbon atoms. The alkoxy group that can be taken by R ^{5 to} R ⁹ is preferably a straight-chain or branched alkoxy group, and the branched alkoxy group is a carrier mobility without reducing intramolecular hydrogen bonding. And more preferable from the viewpoint of increasing the solubility in a solvent.
Moreover, these substituents may further have the above substituents.
Further, these substituents may have a group derived from a polymerizable group.

  In General formula (4-2), q represents the integer of 0-6, the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and the integer of 0-1 is more preferable.

（一般式（５−１）〜（５−８）中、Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、２個以上のＲ⁶は同一であっても、異なっていても良い。波線は、シクロペンタジエノン縮環部位との結合位を表し、＃はＶ¹またはＶ²との結合位を表す。） In the general formula (4-2), Cy ² represents a structure in which 1 to 4 rings are condensed, and is preferably a structure in which 1 to 4 aromatic rings or heteroaromatic rings are condensed, More preferably, it is a structure in which 1-4 aromatic rings having 6 to 10 carbon atoms or heteroaromatic rings having 4 to 6 carbon atoms are condensed, and a benzene ring or thiophene ring having 1 to 4 carbon atoms is preferable. A fused ring structure is particularly preferred.
The divalent linking group represented by the general formula (4-2) is preferably a divalent linking group represented by any one of the following general formulas (5-1) to (5-8). It is more preferably a divalent linking group represented by the general formula (5-1).

(In the general formulas (5-1) to (5-8), R ⁶ each independently represents a hydrogen atom or a substituent, and two or more R ⁶ may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. )

In General Formulas (5-1) to (5-8), R ⁶ independently represents a hydrogen atom or a substituent, and two or more R ⁶ may be the same or different. Examples of the substituent that R ⁶ can adopt include those exemplified as the substituent that R ^{5 to} R ^{9 in} the above general formulas (4-1) to (4-3) can adopt, and a preferable range is also included. It is the same.

（一般式（Ｖ−１）〜（Ｖ−１７）中、＊はｍまたはｐが１のときはＡｒ¹〜Ａｒ²のいずれかとの結合位置を示し、ｍまたはｐが２以上のときはＡｒ¹〜Ａｒ²および一般式（Ｖ−１）〜（Ｖ−１７）で表される２価の連結基のいずれかとの結合位置を示す。一般式（Ｖ−１）、（Ｖ−２）、（Ｖ−５）、（Ｖ−６）、（Ｖ−９）〜（Ｖ−１１）、（Ｖ−１３）〜（Ｖ−１５）および（Ｖ−１７）中のＲはそれぞれ独立に水素原子またはアルキル基を表し、互いに隣り合うＲは結合して環を形成しても良い。一般式（Ｖ−４）、（Ｖ−７）、（Ｖ−８）および（Ｖ−１２）中のＺはそれぞれ独立に水素原子、アルキル基またはアルコキシ基を表し、互いに隣り合うＺは結合して環を形成しても良い。一般式（Ｖ−１６）中のＹはそれぞれ独立に水素原子、アルキル基、アルコキシ基、ＣＮ基またはＦ原子を表し、互いに隣り合うＹは結合して環を形成しても良い。） In General Formula (1-1), V ¹ represents a divalent linking group. From the viewpoint of enhancing solubility, it is preferable that V ¹ does not form a condensed ring with Ar ¹ or Ar ² . No particular restriction on the divalent linking group V ¹ is can take, it is preferably represented by any one of the following formulas (V-1) ~ (V -17).

(In the general formulas (V-1) to (V-17), * represents a bonding position with Ar ^{1 to} Ar ² when m or p is 1, and Ar when m or p is 2 or more. ^{1 to} Ar ² and a bonding position with any of the divalent linking groups represented by the general formulas (V-1) to (V-17) are represented by the general formulas (V-1), (V-2), R in (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and (V-17) each independently represents a hydrogen atom Or an alkyl group, and Rs adjacent to each other may combine to form a ring, and Z in the general formulas (V-4), (V-7), (V-8) and (V-12) Each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other may combine to form a ring, and Y in formula (V-16) is independently Represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring.)

General formulas (V-1), (V-2), (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and R in (V-17) independently represents a hydrogen atom or an alkyl group, and Rs adjacent to each other may be bonded to form a ring. Examples of the alkyl group that R can take include the alkyl groups that R ^{5 to} R ^{9 in} the general formulas (4-1) to (4-3) can take, and the preferred range of the alkyl group that R can take. is the same as the preferred ranges of the alkyl group R ⁵ to R ⁹ may take.

Z in the general formulas (V-4), (V-7), (V-8) and (V-12) each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other are bonded. To form a ring. Examples of the alkyl group or alkoxy group that can be taken by Z include alkyl groups and alkoxy groups that can be taken by R ^{5 to} R ^{9 in} the above general formulas (4-1) to (4-3). The preferable range of the alkyl group and alkoxy group that can be used is the same as the preferable range of the alkyl group and alkoxy group that can be adopted by R ^{5 to} R ⁹ .

Y in general formula (V-16) each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring, an alkyl group, Alkoxy groups are preferred. Examples of the alkyl group or alkoxy group that Y can take include the alkyl groups and alkoxy groups exemplified as the substituents that R ^{5 to} R ^{9 in} the general formulas (4-1) to (4-3) can take. The preferable range is also the same.

  Among the divalent linking groups represented by general formulas (V-1) to (V-17), general formulas (V-1) to (V-8) and (V-11) to (V-15) The bivalent coupling group represented by General formula (V-1)-(V-3) is more preferable.

In General Formula (1-1), m represents an integer of 0 to 6, and when m is 2 or more, two or more V ^{1 s} may be the same or different. m is preferably an integer of 0 to 5, and more preferably 0 to 3.
In General Formula (1-1), n represents an integer of 2 or more, preferably 10 or more, more preferably 30 or more, and particularly preferably 50 or more. As n increases, the interaction between the π-conjugated polymer chains can be increased, and the carrier mobility can be increased. Although there is no restriction | limiting in particular about the upper limit of n, It is preferable that it is 1000 or less, and it is more preferable that it is 500 or less.

（一般式（１−２）において、Ｃｙはナフタレン環、またはアントラセン環を表し、Ｒ³およびＲ⁴はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。） << Compound Composed of n Repeating Units Represented by General Formula (1-2) >>
The compound consisting of n repeating units represented by the general formula (1-2) is represented by the following general formula.

(In general formula (1-2), Cy represents a naphthalene ring or an anthracene ring, R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ each independently represent a heteroarylene group. Or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² are the same or different. (N represents an integer of 2 or more.)

In General Formula (1-2), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. The substituents that R ³ and R ⁴ can take are the same as the substituents that R ¹ and R ^{2 in} formula (1-1) can take, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl Group, aryl group, alkenyl group, alkynyl group, heterocyclic group, alkoxy group, alkylthio group and group represented by the general formula (W) are preferable, a hydrogen atom, an alkyl having 1 to 12 carbon atoms More preferably any one of a group and an alkoxy group having 1 to 11 carbon atoms, and R ³ and any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. It is particularly preferred from the viewpoint that high carrier mobility can be obtained without suppressing the bulkiness of R ⁴ and lowering the intermolecular interaction, and more preferably a hydrogen atom, a methyl group or an ethoxy group. The hydrogen atom is most preferred.
In the general formula (1-2), Ar ³ and Ar ⁴ each independently represent a heteroarylene group or an arylene group. Ar ³ is preferably not bonded to R ⁴ to form a condensed ring from the viewpoint of enhancing the solubility, and Ar ⁴ is preferably bonded to R ³ to form a condensed ring from the viewpoint of increasing the solubility. The heteroarylene group or arylene group that Ar ³ and Ar ⁴ can adopt is the same as the heteroarylene group or arylene group that Ar ¹ and Ar ² in general formula (1-1) can adopt, and the preferred range is also the same. is there.
In the general formula (1-2), V ² represents a divalent linking group. From the viewpoint of enhancing solubility, it is preferable that V ² does not form a condensed ring with Ar ³ or Ar ⁴ . The divalent linking group that can be taken by V ² is the same as the divalent linking group that can be taken by V ¹ in formula (1-1), and the preferred range is also the same. However, * in the general formulas (V-1) to (V-17) indicates a bonding position with any of Ar ^{3 to} Ar ⁴ when m or p is 1, and when m or p is 2 or more. The bonding position with any of the divalent linking groups represented by Ar ^{3 to} Ar ⁴ and general formulas (V-1) to (V-17) is shown.
In the general formula (1-2), p represents an integer of 0 to 6, and when p is 2 or more, two or more V ^{2 s} may be the same or different. p has the same meaning as m in formula (1-1), and the preferred range is also the same.
In General formula (1-2), n represents an integer greater than or equal to 2, is synonymous with n in General formula (1-1), and its preferable range is also the same.

（一般式（２−１）〜（２−５）中、Ｒ³、Ｒ⁴、およびＲ¹⁰〜Ｒ³³はそれぞれ独立に水素原子または置換基を表す。Ａｒ³およびＡｒ⁴はそれぞれ独立にヘテロアリーレン基またはアリーレン基を表す。Ｖ²は２価の連結基を表す。ｐは０〜６の整数を表し、ｐが２以上のとき、２つ以上のＶ²は同一であっても、異なっていても良い。ｎは２以上の整数を表す。） In general formula (1-2), Cy represents a naphthalene ring or an anthracene ring. There is no particular limitation on the site where the naphthalene ring and the anthracene ring are condensed with the cyclopentadienone ring. Specifically, the naphthalene ring or anthracene ring may be condensed so that a compound composed of n repeating units represented by the general formula (1-2) is a compound having a rotationally symmetric skeleton. Preferably, the compound is composed of n repeating units represented by the following general formula (2-1), (2-2), (2-3), (2-4) or (2-5). More preferably, it is condensed.

(In the general formulas (2-1) to (2-5), R ³ , R ⁴ , and R ^{10 to} R ³³ each independently represent a hydrogen atom or a substituent. Ar ³ and Ar ⁴ are each independently heterogeneous. Represents an arylene group or an arylene group, V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ² may be the same or different (N represents an integer of 2 or more.)

In General Formulas (2-1) to (2-5), R ³ , R ⁴ , and R ^{10 to} R ³³ each independently represent a hydrogen atom or a substituent.
The substituents that R ³ and R ^{4 in the} general formulas (2-1) to (2-5) can take are the same as the substituents that R ³ and R ^{4 in} the general formula (1-2) can take, which is preferable. The range is the same.
The substituents that R ^{10 to} R ^{33 in the} general formulas (2-1) to (2-5) can take are the same as the substituents that R ¹ and R ^{2 in} the general formula (1-1) can take. R ^{10 to} R ³³ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, a heterocyclic group, an alkylthio group, an amino group, or a group represented by the general formula (W). And preferably a hydrogen atom, an alkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or 3 to 3 carbon atoms. 40 alkoxy groups, C5-C12 heterocyclic groups, C1-C12 alkylthio groups, amino groups substituted with C1-C12 alkyl groups, and groups represented by general formula (W) It is more preferable that it is either. R ^{10 to} R ³³ are preferably branched substituents further having a substituent on the linear substituent.
The alkyl group that can be taken by R ^{10 to} R ³³ is more preferably an alkyl group having 3 to 40 carbon atoms, and an alkyl group having 10 to 30 carbon atoms is chemically stable and carrier transportable. In view of the above, the alkyl group is more preferably an alkyl group having 15 to 30 carbon atoms. Further, the alkyl group that R ^{10 to} R ³³ can take is preferably a linear or branched alkyl group, and the branched alkyl group is a carrier transfer without reducing the intramolecular hydrogen bondability. It is more preferable from the viewpoint of increasing the degree of solubility in the solvent.
The alkoxy group that can be taken by R ^{10 to} R ³³ is more preferably an alkoxy group having 3 to 40 carbon atoms, and an alkoxy group having 10 to 30 carbon atoms is chemical stability and carrier transportability. In view of the above, it is more preferably an alkoxy group having 15 to 30 carbon atoms. Further, the alkoxy group that can be taken by R ^{10 to} R ³³ is preferably a linear or branched alkoxy group, and the branched alkoxy group is capable of transferring carriers without deteriorating intramolecular hydrogen bonding. It is more preferable from the viewpoint of increasing the degree of solubility in the solvent.
In the general formula (2-1), it is preferable that at least one of R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ is a group represented by the general formula (W), R ³ , 0 and of R ^4, more preferably ^{R 10, R 11, R 12} , and R ¹³ at least one of a group represented by the general formula (W), 0 of R ^3, R ⁴ More preferably, one or two of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are groups represented by the general formula (W), and 0 of R ³ and R ⁴ , and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are particularly preferably groups represented by the general formula (W).
In the general formula (2-2), at least one of R ³ , R ⁴ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ is preferably a group represented by the general formula (W), R ³ , 0 and of R ^4, more preferably ^{R 14, R 15, R 16} , and R ¹⁷ at least one is a group represented by the general formula (W), 0 of R ^3, R ⁴ More preferably, one or two of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are a group represented by the general formula (W), and 0 of R ³ and R ⁴ and R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are particularly preferably groups represented by the general formula (W).
In the general formula (2-3), at least one of R ³ , R ⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ is preferably a group represented by the general formula (W), R ³ , 0 and of R ^4, more preferably ^{R 18, R 19, R 20} , and R ²¹ at least one is a group represented by the general formula (W), 0 of R ^3, R ⁴ More preferably, one of R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is a group represented by the general formula (W), and 0 of R ³ and R ⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are particularly preferably groups represented by the general formula (W).
In the general formula (2-4), at least one of R ³ , R ⁴ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ is a group represented by the general formula (W). And at least one of R ³ , R ^{4 and} at least one of R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ is a group represented by the general formula (W) More preferably, 0 of R ³ and R ⁴ and 2 to ⁴ of R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are groups represented by the general formula (W). More preferably, 0 of R ³ and R ⁴ and two of R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are groups represented by the general formula (W). It is particularly preferred.
In the general formula (2-5), at least one of R ³ , R ⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ is a group represented by the general formula (W). And at least one of R ³ , R ^{4 and} at least one of R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ is a group represented by the general formula (W) More preferably, 0 of R ³ and R ⁴ and 2 to ⁴ of R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ are groups represented by the general formula (W). More preferably, 0 of R ³ and R ⁴ and two of R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , and R ³³ are groups represented by the general formula (W). It is particularly preferred.
In General Formulas (2-1) to (2-5), Ar ³ and Ar ⁴ each independently represent a heteroarylene group or an arylene group. The heteroarylene group or an arylene group Ar ³ and Ar ⁴ may take the general formula (1-2) is the same as the heteroarylene group or an arylene group Ar ³ and Ar ⁴ may take in the preferable range is also the same is there.
In general formulas (2-1) to (2-5), V ² represents a divalent linking group. Examples of the divalent linking group V ² may take the general formula (1-2) is the same as the divalent linking group V ² may take in, and preferred ranges are also the same.
In general formulas (2-1) to (2-5), p represents an integer of 0 to 6, and when p is 2 or more, two or more V ^{2 s} may be the same or different. P in the general formulas (2-1) to (2-5) has the same meaning as p in the general formula (1-2), and the preferred range is also the same.
In the general formulas (2-1) to (2-5), n represents an integer of 2 or more, and is synonymous with n in the general formula (1-2), and a preferable range is also the same.

  The compound consisting of n repeating units represented by the general formula (1-2) is a compound consisting of n repeating units represented by the general formulas (2-1) to (2-2). Is preferable from the viewpoint of high carrier mobility and high solubility in a solvent.

  Specific examples of the compound consisting of n repeating units represented by the above general formula (1-1) or (1-2) are shown below, but the general formula (1-1) that can be used in the present invention is shown below. ) Or a compound composed of n repeating units represented by (1-2) should not be construed as being limited by these specific examples. In the specific examples of the following compounds, the number of repeating units n is omitted, and only the repeating units are shown.

The compound consisting of n repeating units represented by the general formula (1-1) or (1-2) is a compound having two or more repeating structures, and an oligomer having 2 to 9 repeating units, It may be a polymer having a repeating unit number n of 10 or more.
When the compound represented by the general formula (1-1) or (1-2) is an oligomer having 2 to 9 repeating units, the molecular weight is preferably 2000 or more, more preferably 5000 or more. preferable.
When the compound represented by the general formula (1-1) or (1-2) is a polymer compound, the weight average molecular weight is preferably 30000 or more, more preferably 50000 or more, and 100000 or more. It is particularly preferred that Although there is no restriction | limiting in particular about an upper limit, It is preferable that it is 1000000 or less, and it is more preferable that it is 750,000 or less. By setting the molecular weight to the upper limit or less, it is preferable because intermolecular interaction can be enhanced, carrier transmission is advantageous, and solubility in a solvent can be maintained.
The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) using a high-speed GPC (HLC-8220GPC) manufactured by Tosoh after dissolving the polymer in tetrahydrofuran (THF). The weight average molecular weight in the present invention is a value using polystyrene as a standard substance.

The compound consisting of n repeating units represented by the general formula (1-1) or (1-2) can be synthesized with reference to US Pat. No. 7928249 and the like.
Any reaction conditions may be used in the synthesis of the compounds of the invention. Any solvent may be used as the reaction solvent. In order to promote the ring formation reaction, it is preferable to use an acid or a base, and it is particularly preferable to use a base. The optimum reaction conditions vary depending on the structure of the desired condensed cyclopentadienone, but can be set with reference to the specific reaction conditions described in the above-mentioned documents.

  Synthetic intermediates having various substituents can be synthesized by combining known reactions. Each substituent may be introduced at any intermediate stage. After the synthesis of the intermediate, purification by column chromatography, recrystallization or the like is preferable.

<Structure of organic thin film transistor>
The organic thin film transistor of the present invention has a semiconductor active layer containing a compound composed of n repeating units represented by the general formula (1-1) or (1-2).
The organic thin film transistor of the present invention may further include other layers in addition to the semiconductor active layer.
The organic thin film transistor of the present invention is preferably used as an organic field effect transistor (FET), and more preferably as an insulated gate FET in which a gate-channel is insulated.
Hereinafter, although the aspect of the preferable structure of the organic thin-film transistor of this invention is demonstrated in detail using drawing, this invention is not limited to these aspects.

(Laminated structure)
There is no restriction | limiting in particular as a laminated structure of an organic field effect transistor, It can be set as the thing of various well-known structures.
As an example of the structure of the organic thin film transistor of the present invention, a structure in which an electrode, an insulator layer, a semiconductor active layer (organic semiconductor layer), and two electrodes are sequentially arranged on the upper surface of the lowermost substrate (bottom gate / top contact type) ). In this structure, the electrode on the upper surface of the lowermost substrate is provided on a part of the substrate, and the insulator layer is disposed so as to be in contact with the substrate at a portion other than the electrode. Further, the two electrodes provided on the upper surface of the semiconductor active layer are arranged separately from each other.
The structure of the bottom gate / top contact type element is shown in FIG. FIG. 1 is a schematic view showing a cross section of an example of the structure of the organic thin film transistor of the present invention. The organic thin film transistor of FIG. 1 has a substrate 11 disposed in the lowermost layer, an electrode 12 is provided on a part of the upper surface thereof, further covers the electrode 12 and is in contact with the substrate 11 at a portion other than the electrode 12. 13 is provided. Further, the semiconductor active layer 14 is provided on the upper surface of the insulator layer 13, and the two electrodes 15a and 15b are disposed separately on a part of the upper surface.
In the organic thin film transistor shown in FIG. 1, the electrode 12 is a gate, and the electrodes 15a and 15b are drains or sources, respectively. The organic thin film transistor shown in FIG. 1 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

An example of the structure of the organic thin film transistor of the present invention is a bottom gate / bottom contact type element.
The structure of the bottom gate / bottom contact type element is shown in FIG. FIG. 2 is a schematic view showing a cross section of the structure of an organic thin film transistor manufactured as a substrate for measuring FET characteristics in an example of the present invention. In the organic thin film transistor of FIG. 2, the substrate 31 is disposed in the lowermost layer, the electrode 32 is provided on a part of the upper surface thereof, and the insulator layer is further covered with the electrode 32 and in contact with the substrate 31 at a portion other than the electrode 32 33 is provided. Further, the semiconductor active layer 35 is provided on the upper surface of the insulator layer 33, and the electrodes 34 a and 34 b are below the semiconductor active layer 35.
In the organic thin film transistor shown in FIG. 2, the electrode 32 is a gate, and the electrode 34a and the electrode 34b are a drain or a source, respectively. The organic thin film transistor shown in FIG. 2 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

  As the structure of the organic thin film transistor of the present invention, a top gate / top contact type element having an insulator and a gate electrode above the semiconductor active layer, and a top gate / bottom contact type element can also be preferably used.

(thickness)
When the organic thin film transistor of the present invention needs to be a thinner transistor, for example, the thickness of the entire transistor is preferably 0.1 to 0.5 μm.

(Sealing)
In order to shield the organic thin film transistor element from the air and moisture and improve the storage stability of the organic thin film transistor element, the entire organic thin film transistor element is made of a metal sealing can, glass, an inorganic material such as silicon nitride, a polymer material such as parylene, It may be sealed with a low molecular material or the like.
Hereinafter, although the preferable aspect of each layer of the organic thin-film transistor of this invention is demonstrated, this invention is not limited to these aspects.

<Board>
(material)
The organic thin film transistor of the present invention preferably includes a substrate.
There is no restriction | limiting in particular as a material of the said board | substrate, For example, a well-known material can be used, For example, polyester films, such as a polyethylene naphthoate (PEN) and a polyethylene terephthalate (PET), a cycloolefin polymer film, a polycarbonate film, a triacetyl cellulose (TAC) film, polyimide film, and those obtained by bonding these polymer films to ultrathin glass, ceramic, silicon, quartz, glass, and the like can be mentioned, and silicon is preferred.

<Electrode>
(material)
The organic thin film transistor of the present invention preferably includes an electrode.
Examples of the constituent material of the electrode include metal materials such as Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, In, Ni, and Nd, alloy materials thereof, carbon materials, and conductive materials. Any known conductive material such as a conductive polymer can be used without particular limitation.

(thickness)
The thickness of the electrode is not particularly limited, but is preferably 10 to 50 nm.
There is no particular limitation on the gate width (or channel width) W and the gate length (or channel length) L, but the ratio W / L is preferably 10 or more, more preferably 20 or more.

<Insulating layer>
(material)
The material constituting the insulating layer is not particularly limited as long as the necessary insulating effect can be obtained. For example, fluorine polymer insulating materials such as silicon dioxide, silicon nitride, PTFE, CYTOP, polyester insulating materials, polycarbonate insulating materials, acrylic polymers Insulating material, epoxy resin insulating material, polyimide insulating material, polyvinylphenol resin insulating material, polyparaxylylene resin insulating material, and the like.
The upper surface of the insulating layer may be surface-treated. For example, an insulating layer whose surface is treated by applying hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS) to the silicon dioxide surface can be preferably used.

(thickness)
The thickness of the insulating layer is not particularly limited, but when thinning is required, the thickness is preferably 10 to 400 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm. .

<Semiconductor active layer>
(material)
The organic thin film transistor of the present invention is characterized in that the semiconductor active layer contains a compound composed of n repeating units represented by the general formula (1-1) or (1-2), that is, the compound of the present invention. To do.
The semiconductor active layer may be a layer made of the compound of the present invention, or may be a layer further containing a polymer binder described later in addition to the compound of the present invention. Moreover, the residual solvent at the time of film-forming may be contained.
The content of the polymer binder in the semiconductor active layer is not particularly limited, but is preferably used in the range of 0 to 95% by mass, more preferably in the range of 10 to 90% by mass, Preferably it is used within the range of 20 to 80% by mass, and particularly preferably within the range of 30 to 70% by mass.

(thickness)
Although there is no restriction | limiting in particular in the thickness of a semiconductor active layer, When thinning is calculated | required, it is preferable to set thickness to 10-400 nm, It is more preferable to set it as 10-200 nm, It is especially preferable to set it as 10-100 nm. preferable.

[Organic semiconductor materials for non-luminescent organic semiconductor devices]
The present invention provides a compound comprising n repeating units represented by the general formula (1-1) or (1-2), that is, an organic semiconductor material for a non-luminescent organic semiconductor device containing the compound of the present invention. Also related.

(Non-luminescent organic semiconductor devices)
In the present specification, the “non-light emitting organic semiconductor device” means a device not intended to emit light. The non-light-emitting organic semiconductor device is preferably a non-light-emitting organic semiconductor device using an electronic element having a thin film layer structure. Non-light-emitting organic semiconductor devices include organic thin film transistors, organic photoelectric conversion elements (solid-state imaging elements for optical sensors, solar cells for energy conversion, etc.), gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. The The organic photoelectric conversion element can be used for both optical sensor applications (solid-state imaging elements) and energy conversion applications (solar cells). An organic photoelectric conversion element and an organic thin film transistor are preferable, and an organic thin film transistor is more preferable. That is, the organic semiconductor material for a non-light-emitting organic semiconductor device of the present invention is preferably an organic thin film transistor material as described above.

(Organic semiconductor materials)
In the present specification, the “organic semiconductor material” is an organic material exhibiting semiconductor characteristics. Similar to semiconductors made of inorganic materials, there are p-type (hole transportable) organic semiconductors that conduct holes as carriers, and n-type (electron-transport) organic semiconductors that conduct electrons as carriers.
The compound of the present invention may be used as either a p-type organic semiconductor material or an n-type organic semiconductor material, but is more preferably used as a p-type. The ease of carrier flow in the organic semiconductor is represented by carrier mobility μ. The carrier mobility μ should be high, preferably 1 × 10 ⁻² cm ² / Vs or more, more preferably 5 × 10 ⁻² cm ² / Vs or more, and more preferably 1 × 10 ⁻¹ cm ^2. / Vs or higher is particularly preferable, and 2 × 10 ⁻¹ cm ² / Vs or higher is even more preferable. The carrier mobility μ can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.

[Organic semiconductor thin film for non-luminescent organic semiconductor devices]
(material)
The present invention provides a compound consisting of n repeating units represented by the above general formula (1-1) or (1-2), that is, an organic semiconductor thin film for a non-luminescent organic semiconductor device containing the compound of the present invention. Also related.
The organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention contains a compound composed of n repeating units represented by the general formula (1-1) or (1-2), that is, the compound of the present invention. Also preferred is an embodiment containing no polymer binder.
Further, the organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention comprises a compound comprising n repeating units represented by the general formula (1-1) or (1-2), that is, the compound of the present invention. A polymer binder may be contained.

Examples of the polymer binder include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and co-polymers thereof. Examples thereof include a polymer, a photoconductive polymer such as polyvinyl carbazole and polysilane, a conductive polymer such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and a semiconductor polymer.
The polymer binders may be used alone or in combination.
In addition, the organic semiconductor material and the polymer binder may be uniformly mixed, or a part or all of them may be phase-separated, but from the viewpoint of charge mobility, A structure in which the binder and the binder are phase-separated is most preferable because the binder does not hinder the charge transfer of the organic semiconductor.
In consideration of the mechanical strength of the thin film, a polymer binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a polymer binder, a photoconductive polymer, or a conductive polymer having a structure containing no polar group is preferable.
Although there is no restriction | limiting in particular in the usage-amount of a polymer binder, Preferably it uses in the range of 0-95 mass% in the organic-semiconductor thin film for nonluminous organic-semiconductor devices of this invention, More preferably, it is 10-90 mass% Is more preferably used within a range of 20 to 80% by mass, and particularly preferably within a range of 30 to 70% by mass.

  Furthermore, in the present invention, an organic thin film with good film quality can be obtained by the compound having the structure described above. Specifically, since the compound obtained by the present invention has good crystallinity, a sufficient film thickness can be obtained, and the obtained organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention has a good quality. Become.

(Film formation method)
Any method may be used for forming the compound of the present invention on the substrate.
During film formation, the substrate may be heated or cooled, and the film quality and molecular packing in the film can be controlled by changing the temperature of the substrate. Although there is no restriction | limiting in particular as temperature of a board | substrate, It is preferable that it is between 0 degreeC and 200 degreeC, It is more preferable that it is between 15 degreeC-100 degreeC, It is especially between 20 degreeC-95 degreeC. preferable.
When the compound of the present invention is formed on a substrate, it can be formed by a vacuum process or a solution process, both of which are preferable.

  Specific examples of film formation by a vacuum process include physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, molecular beam epitaxy (MBE), and chemical vapor deposition (CVD) such as plasma polymerization. ) Method, and it is particularly preferable to use a vacuum deposition method.

Here, film formation by a solution process refers to a method in which an organic compound is dissolved in a solvent that can be dissolved and a film is formed using the solution. Specifically, it is applied using the composition of the present invention containing a compound composed of n repeating units represented by the general formula (1-1) or (1-2) and an organic solvent. Specifically, coating methods such as casting method, dip coating method, die coater method, roll coater method, bar coater method, spin coating method, ink jet method, screen printing method, gravure printing method, flexographic printing method, offset printing Various printing methods such as micro contact printing, micro contact printing, and ordinary methods such as Langmuir-Blodgett (LB) can be used. Casting, spin coating, ink jet, gravure printing, flexographic printing, offset It is particularly preferable to use a printing method or a microcontact printing method.
The organic semiconductor thin film for a non-luminescent organic semiconductor device of the present invention is preferably produced by a solution coating method. Further, when the organic semiconductor thin film for a non-light-emitting organic semiconductor device of the present invention contains a polymer binder, the material for forming the layer and the polymer binder are dissolved or dispersed in an appropriate solvent to form a coating solution. It is preferably formed by a coating method.
Hereinafter, the coating solution for non-light-emitting organic semiconductor devices of the present invention that can be used for film formation by a solution process will be described.

[Composition, coating solution for non-luminescent organic semiconductor device]
The present invention relates to a compound comprising n repeating units represented by the general formula (1-1) or (1-2), that is, a composition containing the compound of the present invention, a coating for a non-light-emitting organic semiconductor device. Also related to the solution.
When a film is formed on a substrate using a solution process, a material for forming the layer is selected from hydrocarbons such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, and 1-methylnaphthalene. Solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene and the like Solvent, for example, ester solvent such as ethyl acetate, butyl acetate, amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl Alcohol solvents such as rosolve, ethyl cellosolve, ethylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2- An amide / imide solvent such as pyrrolidone, 1-methyl-2-imidazolidinone, a sulfoxide solvent such as dimethyl sulfoxide, a nitrile solvent such as acetonitrile) and / or water is dissolved or dispersed into a coating solution. A thin film can be formed by various coating methods. A solvent may be used independently and may be used in combination of multiple. Among these, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, or a ketone solvent is preferable, and an aromatic hydrocarbon solvent, an ether solvent, or a ketone solvent is more preferable. Specifically, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, anisole, isophorone, diisopropylbenzene, s-butylbenzene are more preferable, and toluene, xylene, tetralin, chlorobenzene, dichlorobenzene, diisopropylbenzene, s-butyl. Benzene is particularly preferred. The concentration of the compound consisting of n repeating units represented by the general formula (1-1) or (1-2) in the coating solution is preferably 0.1 to 80% by mass, more preferably 0.00. By setting the content to 1 to 10% by mass, particularly preferably 0.5 to 10% by mass, a film having an arbitrary thickness can be formed.
Among these, as the organic solvent, n solvents represented by the general formula (1-1) or (1-2), which are aromatic solvents having a boiling point of 150 ° C. or more and do not contain active hydrogen. From the viewpoint of increasing the solubility with a compound comprising the repeating unit and carrier mobility. Examples of such a solvent include tetralin, dichlorobenzene, anisole, isophorone, diisopropylbenzene, s-butylbenzene, and the like. As the organic solvent used in the present invention, dichlorobenzene, tetralin, diisopropylbenzene, and s-butylbenzene are preferable, and tetralin, diisopropylbenzene, and s-butylbenzene are more preferable.

  In order to form a film by a solution process, it is necessary that the material is dissolved in the above-described solvent or the like, but it is not sufficient to simply dissolve the material. Usually, even a material for forming a film by a vacuum process can be dissolved in a solvent to some extent. However, in the solution process, there is a process in which after the material is dissolved in a solvent and applied, the solvent evaporates to form a thin film, and many materials that are not suitable for solution process film formation have high crystallinity. It is difficult to form a good thin film due to inappropriate crystallization (aggregation) in the process. The compound consisting of n repeating units represented by the general formula (1-1) or (1-2) is excellent in that such crystallization (aggregation) hardly occurs.

The coating solution for a non-luminescent organic semiconductor device of the present invention comprises a compound comprising n repeating units represented by the general formula (1-1) or (1-2), that is, a compound of the present invention, and a polymer. An embodiment containing no binder is also preferred.
The coating solution for a non-luminescent organic semiconductor device of the present invention is a compound comprising n repeating units represented by the general formula (1-1) or (1-2), that is, the compound of the present invention and a polymer. A binder may be contained. In this case, the material for forming the layer and the polymer binder can be dissolved or dispersed in the aforementioned appropriate solvent to form a coating solution, and a thin film can be formed by various coating methods. The polymer binder can be selected from those described above.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Synthesis Example 1: Synthesis of Compound 2>
In accordance with a specific synthesis procedure shown in the following scheme, Compound 2, which is a compound composed of n repeating units represented by the general formula (1-1), is synthesized.

  The obtained compound was identified by elemental analysis and NMR.

  Compounds composed of n repeating units represented by formula (1-1) used in other examples are also synthesized in the same manner as compound 2.

[Example 2]
<Synthesis Example 2: Synthesis of Compound 34>
Compound 34, which is a compound represented by the general formula (1-2), is synthesized according to the specific synthesis procedure shown in the following scheme.

The obtained compound was identified by elemental analysis and NMR.
Moreover, when the molecular weight of each compound was measured by the method as described in this specification, it turned out that the weight average molecular weight of each compound is the range of 50000-200000. That is, it was found that the number n of repeating units of each compound represented by the general formula (1-1) or (1-2) was in the range of 50 to 200.

  The compound represented by formula (1-2) used in other examples is also synthesized in the same manner as compound 34.

Comparative compound 1 described in JP 2012-177104 A and the THEOCHEM, (2002), 589-590, 459-464. Comparative compound 2 described in 1 was synthesized with reference to each literature. The structures of comparative compounds 1 and 2 are shown below.

<Device fabrication and evaluation>
[Example 3]
<Preparation of coating solution for non-luminescent organic semiconductor device>
The non-luminescent organic semiconductor device coating solution was prepared by mixing the compound of the present invention or the comparative compound (each 10 mg) and toluene (1 mL) and heating to 100 ° C. Those not completely dissolved were filtered using a 0.2 μm filter.

<Forming a semiconductor active layer (organic semiconductor layer) with a compound alone>
The organic semiconductor thin film for non-light-emitting organic semiconductor devices was formed by spin-coating the coating solution for non-light-emitting organic semiconductor devices in the atmosphere to obtain an organic thin film transistor element of Example 3 for measuring FET characteristics. As a substrate for FET characteristic measurement, a bottom provided with chromium / gold (gate width W = 100 mm, gate length L = 100 μm) disposed in a comb shape as source and drain electrodes, and SiO ₂ (film thickness 200 nm) as an insulating film. A silicon substrate having a contact structure (a schematic diagram of the structure is shown in FIG. 2) was used.
The FET characteristics of the organic thin film transistor element of Example 3 are as follows. The carrier mobility was measured under a normal pressure / nitrogen atmosphere using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (Vector Semicon, AX-2000). Evaluation was performed from the viewpoint of threshold voltage change and film-forming property after repeated driving.
Moreover, the coating solution for nonluminous organic semiconductor devices of Example 3 was evaluated from the viewpoint of solubility.
The results obtained are shown in the table below.

(A) Solubility evaluation The compound of the present invention or the comparative compound (each 10 mg) and toluene (1 mL) were mixed, heated to 100 ° C., allowed to stand at room temperature for 30 minutes, and the solubility was determined according to the amount of precipitated solid. It was evaluated in three stages.
A: No precipitation B: Precipitation amount is less than 30% C: Precipitation amount is 30% or more

(B) Carrier mobility An equation representing drain current I _d by applying a voltage of −50 V between the source electrode and the drain electrode of each organic thin film transistor element (FET element) and changing the gate voltage in the range of 20 V to −100 V. I _d = (w / 2L) μC _i (V _g −V _th ) ² (where L is the gate length, W is the gate width, C _i is the capacitance per unit area of the insulating layer, V _g is the gate voltage, Carrier mobility μ was calculated using _Vth (threshold voltage). In addition, since the characteristic is too low for the carrier mobility below 1 × 10 ⁻⁵ cm ² / Vs, evaluation of the threshold voltage change after the subsequent (c) repeated driving is not performed.

(C) Threshold voltage change after repeated driving A voltage of −80 V is applied between the source electrode and the drain electrode of each organic thin film transistor element (FET element), and the gate voltage is repeated 100 times in the range of +20 V to −100 V (a The difference between the threshold voltage V before the repeated driving and the threshold voltage V after the repeated driving (| V after −V before |) was evaluated in the following three stages. The smaller this value, the higher the repeated driving stability of the element, which is preferable.
A: | After V and before V | ≦ 5V
B: 5 V <| V after −V before | ≦ 10 V
C: | After V and before V |> 10V

(D) Film-formability evaluation About each obtained organic thin-film transistor element, observation with the naked eye and optical microscope observation were performed. Ten elements were manufactured by the above method, and the ratio of film repelling on the source electrode and the drain electrode was evaluated.
The results were evaluated in the following three stages.
A: Less than 10%.
B: 10% or more and less than 30%.
C: 30% or more.

(E) Element variation The mobility of 30 fabricated elements was measured, and the coefficient of variation was calculated. The results were evaluated in the following three stages.
A: Less than 30% B: 30% or more and less than 50% C: 50% or more

From the above table, it was found that the compound of the present invention has good solubility in an organic solvent, and the organic thin film transistor element using the compound of the present invention has high carrier mobility. Therefore, it turned out that the compound of this invention is preferably used as an organic-semiconductor material for nonluminous organic-semiconductor devices.
On the other hand, the organic thin-film transistor element using the comparative compounds 1 and 2 had a low carrier mobility.
The organic thin film transistor element using the compound of the present invention had a small threshold voltage change after repeated driving. In addition, it was found that any organic thin film transistor element using the compound of the present invention has very high film smoothness and uniformity and good film forming properties.

[Example 4]
<Semiconductor active layer (organic semiconductor layer) formation>
A silicon wafer provided with SiO ₂ (thickness: 370 nm) as a gate insulating film was used, and surface treatment was performed with octyltrichlorosilane.
A non-luminescent organic semiconductor device coating solution was prepared by mixing the compound of the present invention or a comparative compound (each 1 mg) and toluene (1 mL) and heating to 100 ° C. The coating solution was cast on an octylsilane surface-treated silicon wafer heated to 90 ° C. in a nitrogen atmosphere to form an organic semiconductor thin film for a non-light-emitting organic semiconductor device.
Further, gold was deposited on the surface of the thin film to produce source and drain electrodes, and an organic thin film transistor element having a bottom gate / top contact structure having a gate width W = 5 mm and a gate length L = 80 μm was obtained ( FIG. 1 shows a schematic diagram of the structure).
The FET characteristics of the organic thin film transistor element of Example 4 are as follows. The carrier mobility was measured under a normal pressure / nitrogen atmosphere using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (Vector Semicon, AX-2000). Evaluation was performed from the viewpoint of threshold voltage change and film-forming property after repeated driving.
Moreover, the coating solution for nonluminous organic semiconductor devices of Example 4 was evaluated from the viewpoint of solubility.
The results obtained are shown in the table below.

From the above table, it was found that the compound of the present invention has good solubility in an organic solvent, and the organic thin film transistor element using the compound of the present invention has high carrier mobility. Therefore, it turned out that the compound of this invention is preferably used as an organic-semiconductor material for nonluminous organic-semiconductor devices.
On the other hand, the organic thin-film transistor element using Comparative Compounds 1 and 2 had a low carrier mobility.
The organic thin film transistor element using the compound of the present invention had a small threshold voltage change after repeated driving. In addition, it was found that any organic thin film transistor element using the compound of the present invention has very high film smoothness and uniformity and good film forming properties.

11 Substrate 12 Electrode 13 Insulator Layer 14 Semiconductor Active Layer (Organic Material Layer, Organic Semiconductor Layer)
15a, 15b Electrode 31 Substrate 32 Electrode 33 Insulator layer 34a, 34b Electrode 35 Semiconductor active layer (organic material layer, organic semiconductor layer)

Claims (29)

An organic thin film transistor comprising a semiconductor active layer containing a compound composed of n repeating units represented by the following general formula (1-1) or (1-2).

(In the general formula (1-1), R ¹ and R ² each independently represents a hydrogen atom or a substituent. The substituent that R ¹ and R ² can take is a linear substituent further substituted with a substituent. is a branched substituent having. Ar ¹ and Ar ² each independently represent a hetero arylene group or an arylene group, V ¹ is .m which represents a divalent linking group represents an integer of Less than six, m When 2 is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more.)

(In General Formula (1-2), Cy represents a naphthalene ring or an anthracene ring, and the substituent that Cy can take is a branched substituent further having a substituent on a linear substituent. R ³ and R ⁴ .V ² represent each .Ar ³ and Ar ⁴ independently heteroarylene group or an arylene group each independently represents a hydrogen atom may represent a divalent linking group .p is 0 to 6 Represents an integer, and when p is 2 or more, two or more V ^{2 s} may be the same or different, and n represents an integer of 2 or more.) N repeating units in which the general formula (1-2) is represented by the following general formula (2-1), (2-2), (2-3), (2-4) or (2-5) The organic thin-film transistor of Claim 1 which is a compound which consists of.

(In the general formula (2-1) ~ (2-5), R 3, R 4 each independently represent a hydrogen atom. R ¹⁰ to R ³³ is table a hydrogen atom or a substituent independently, R ¹⁰ substituent to R ³³ may take represents a straight-chain, respectively more .Ar ³ and Ar ⁴ is a branched substituent having a substituent group in a substituent independently heteroarylene group or an arylene group .V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ^{2 s} may be the same or different, and n is 2 or more. Represents an integer.) In the general formulas (1-1), (1-2), and (2-1) to (2-5), V ¹ and V ² are each independently represented by the following general formulas (V-1) to (V-17). The organic thin-film transistor of Claim 1 or 2 which is a bivalent coupling group represented by either.

(In the general formulas (V-1) to (V-17), * represents a bonding position with any ^one of Ar ^{1 to} Ar ⁴ when m or p is 1, and Ar or m when p is 2 or more. ^{1 to} Ar ⁴ and a bonding position with any of the divalent linking groups represented by the general formulas (V-1) to (V-17) are represented by the general formulas (V-1), (V-2), R in (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and (V-17) each independently represents a hydrogen atom Or an alkyl group, and Rs adjacent to each other may combine to form a ring, and Z in the general formulas (V-4), (V-7), (V-8) and (V-12) Each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other may combine to form a ring, and Y in formula (V-16) is independently Represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring.) In the general formulas (1-1) to (1-2) and (2-1) to (2-5), V ¹ and V ² are represented by the following general formulas (V-1) to (V-8) and ( The organic thin-film transistor of Claim 3 which is a bivalent coupling group represented by either V-11)-(V-15). In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the following general formulas (4-1) and (4-2). ) Or the organic thin film transistor according to any one of claims 1 to 4, which is a divalent linking group represented by (4-3).

(In General Formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, Cy ² represents a structure in which 1 to 4 rings are condensed, and R ^{5 to} R ⁹ each independently represents a hydrogen atom or a substituent, q represents an integer of 0 to 6, and when q is 2 or more, 2 or more R ^{6 s} may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. ) In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the general formula (4-1) or (4-2). The organic thin-film transistor of Claim 5 which is a bivalent coupling group represented by this. The divalent linking group represented by the general formula (4-2) is a divalent linking group represented by any one of the following general formulas (5-1) to (5-8). 5. The organic thin film transistor according to 5 or 6.

(In the general formulas (5-1) to (5-8), R ⁶ each independently represents a hydrogen atom or a substituent, and two or more R ⁶ may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. ) In the general formula (1-1), at least one of R ¹ and R ² ;
Prior following general formula (2-1), at least one of ^{R 10, R 11, R 12} , and R ^13,
In the general formula (2-2), at least one of R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ ,
In the general formula (2-3), at least one of R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ ,
In the general formula (2-4), at least one of R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ , and in the general formula (2-5) , R ²⁸ , R ²⁹ , ^{R 30, R 31, R 32} , and at least one of R ^33, a group represented by the following general formula (W), an organic thin film transistor according to any one of claims 1-7.
-LR General Formula (W)
(In General Formula (W), L is a divalent linking group represented by any one of the following General Formulas (L-1) to (L-12) or two or more General Formulas (L-1) to ( L-12) represents a divalent linking group to which a divalent linking group represented by any one of R-12) is bonded, wherein R represents a substituted or unsubstituted alkyl group, and an oligooxy having a repeating number v of oxyethylene units of 2 or more. Represents an ethylene group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted silyl group, and R represents a substituted or unsubstituted silyl group. (Only when it is a divalent linking group represented by the general formulas (L-1) to (L-3).)

(In the general formulas (L-1) to (L-12), the wavy line represents the bonding position with the cyclopentadienone skeleton. * Is a divalent group represented by (L-1) to (L-12). In the general formula (L-10), m is 4 and m in the general formulas (L-11) and (L-12) is 2. (R ′ in (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represents a hydrogen atom or a substituent))   In the general formula (W), L is a divalent linking group represented by any one of the general formulas (L-1), (L-4), or (L-8) or a divalent linking group thereof. The organic thin film transistor according to claim 8, wherein the organic thin film transistor is a divalent linking group in which two or more are bonded.   The general formulas (1-1), (1-2), and (2-1) to (2-5), wherein n is 10 or more, 10. The organic thin film transistor as described in 1. A compound comprising n repeating units represented by the following general formula (1-1) or (1-2).

(In the general formula (1-1), R ¹ and R ² each independently represents a hydrogen atom or a substituent. The substituent that R ¹ and R ² can take is a linear substituent further substituted with a substituent. is a branched substituent having. Ar ¹ and Ar ² each independently represent a hetero arylene group or an arylene group, V ¹ is .m which represents a divalent linking group represents an integer of Less than six, m When 2 is 2 or more, two or more V ^{1 s} may be the same or different, and n represents an integer of 2 or more.)

(In General Formula (1-2), Cy represents a naphthalene ring or an anthracene ring, and the substituent that Cy can take is a branched substituent further having a substituent on a linear substituent. R ³ and R ⁴ .V ² represent each .Ar ³ and Ar ⁴ independently heteroarylene group or an arylene group each independently represents a hydrogen atom may represent a divalent linking group .p is 0 to 6 Represents an integer, and when p is 2 or more, two or more V ^{2 s} may be the same or different, and n represents an integer of 2 or more.) N repeating units in which the general formula (1-2) is represented by the following general formula (2-1), (2-2), (2-3), (2-4) or (2-5) 12. A compound according to claim 11, characterized in that it consists of:

(In the general formula (2-1) ~ (2-5), R 3, R 4 each independently represent a hydrogen atom. R ¹⁰ to R ³³ is table a hydrogen atom or a substituent independently, R ¹⁰ substituent to R ³³ may take represents a straight-chain, respectively more .Ar ³ and Ar ⁴ is a branched substituent having a substituent group in a substituent independently heteroarylene group or an arylene group .V ² represents a divalent linking group, p represents an integer of 0 to 6, and when p is 2 or more, two or more V ^{2 s} may be the same or different, and n is 2 or more. Represents an integer.) In the general formulas (1-1), (1-2), and (2-1) to (2-5), V ¹ and V ² are each independently represented by the following general formulas (V-1) to (V-17). The compound of Claim 11 or 12 which is a bivalent coupling group represented by either.

(In General Formulas (V-1) to (V-17), * represents a bonding position with any of Ar ^{2 to} Ar ⁴ when m or p is 1, and Ar when m or p is 2 or more. ^{1 to} Ar ⁴ and a bonding position with any of the divalent linking groups represented by the general formulas (V-1) to (V-17) are represented by the general formulas (V-1), (V-2), R in (V-5), (V-6), (V-9) to (V-11), (V-13) to (V-15) and (V-17) each independently represents a hydrogen atom Or an alkyl group, and Rs adjacent to each other may combine to form a ring, and Z in the general formulas (V-4), (V-7), (V-8) and (V-12) Each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and Zs adjacent to each other may combine to form a ring, and Y in formula (V-16) is independently Represents a hydrogen atom, an alkyl group, an alkoxy group, a CN group or an F atom, and Ys adjacent to each other may combine to form a ring.) In the general formulas (1-1) to (1-2) and (2-1) to (2-5), V ¹ and V ² are represented by the following general formulas (V-1) to (V-8) and ( The compound according to claim 13, which is a divalent linking group represented by any one of V-11) to (V-15). In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the following general formulas (4-1) and (4-2). The compound of any one of Claims 11-14 which is a bivalent coupling group represented by (4-3).

(In General Formulas (4-1) to (4-3), X represents an S atom, an O atom or a Se atom, Cy ² represents a structure in which 1 to 4 rings are condensed, and R ^{5 to} R ⁹ each independently represents a hydrogen atom or a substituent, q represents an integer of 0 to 6, and when q is 2 or more, 2 or more R ^{6 s} may be the same or different. Represents a bonding position with a cyclopentadienone fused ring site, and # represents a bonding position with V ¹ or V ^2. ) In the general formulas (1-1), (1-2), and (2-1) to (2-5), Ar ^{1 to} Ar ⁴ are each independently represented by the general formula (4-1) or (4-2). The compound of Claim 15 which is a bivalent coupling group represented by this. The divalent linking group represented by the general formula (4-2) is a divalent linking group represented by any one of the following general formulas (5-1) to (5-8). The compound according to 15 or 16.

(In the general formulas (5-1) to (5-8), R ⁶ represents a hydrogen atom or a substituent, and two or more R ^{6 s} may be the same or different. The bond position with the pentadienone fused ring portion is represented, and # represents the bond position with V ¹ or V ^2. ) In the general formula (1-1), at least one of R ¹ and R ² ;
Prior following general formula (2-1), at least one of ^{R 10, R 11, R 12} , and R ^13,
In the general formula (2-2), at least one of R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ ,
In the general formula (2-3), at least one of R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ ,
In the general formula (2-4), at least one of R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ , and in the general formula (2-5) , R ²⁸ , R ²⁹ , The compound according to any one of claims 11 to 17, wherein at least one of R ³⁰ , R ³¹ , R ³² , and R ³³ is a group represented by the following general formula (W).
-LR General Formula (W)
(In General Formula (W), L is a divalent linking group represented by any one of the following General Formulas (L-1) to (L-12) or two or more General Formulas (L-1) to ( L-12) represents a divalent linking group to which a divalent linking group represented by any one of R-12) is bonded, wherein R represents a substituted or unsubstituted alkyl group, and an oligooxy having a repeating number v of oxyethylene units of 2 or more. Represents an ethylene group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted silyl group, and R represents a substituted or unsubstituted silyl group. (Only when it is a divalent linking group represented by the general formulas (L-1) to (L-3).)

(In the general formulas (L-1) to (L-12), the wavy line represents the bonding position with the cyclopentadienone skeleton. * Is a divalent group represented by (L-1) to (L-12). In the general formula (L-10), m is 4 and m in the general formulas (L-11) and (L-12) is 2. (R ′ in (L-1), (L-2), (L-10), (L-11) and (L-12) each independently represents a hydrogen atom or a substituent))   In the general formula (W), L is a divalent linking group represented by any one of the general formulas (L-1), (L-4), or (L-8) or a divalent linking group thereof. The compound according to claim 18, wherein the compound is a divalent linking group in which two or more are bonded.   The general formulas (1-1), (1-2), and (2-1) to (2-5), wherein n is 10 or more, 20. Compound described in 1.   A composition comprising the compound according to any one of claims 11 to 20 and an organic solvent.   The composition according to claim 21, wherein the organic solvent is an aromatic hydrocarbon solvent, an ether solvent or a ketone solvent.   An organic semiconductor material for a non-light-emitting organic semiconductor device, comprising the compound according to any one of claims 11 to 20 or the composition according to claim 21 or 22.   An organic thin film transistor material comprising the compound according to any one of claims 11 to 20 or the composition according to claim 21 or 22.   A coating solution for a non-light-emitting organic semiconductor device, comprising the compound according to any one of claims 11 to 20 or the composition according to claim 21 or 22.   A coating solution for a non-light-emitting organic semiconductor device, comprising the compound according to any one of claims 11 to 20, or the composition according to claim 21 or 22, and a polymer binder.   An organic semiconductor thin film for a non-light-emitting organic semiconductor device, comprising the compound according to any one of claims 11 to 20 or the composition according to claim 21 or 22.   An organic semiconductor thin film for a non-light-emitting organic semiconductor device, comprising the compound according to any one of claims 11 to 20, or the composition according to claim 21 or 22, and a polymer binder. It is a manufacturing method of the organic-semiconductor thin film for nonluminous organic-semiconductor devices of Claim 27 or 28, Comprising:
The non-luminescent organic manufacturing method of non-luminescent organic semiconductor device for an organic semiconductor thin characterized in that to produce the organic semiconductor thin film for a semiconductor device by a solution coating method.

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