JP6247568B2 - Organic thin-film transistors, organic semiconductor materials for non-emissive organic semiconductor devices and their applications - Google Patents

Description

  The present invention relates to an organic thin film transistor, an organic semiconductor material for a non-luminescent organic semiconductor device, and an application thereof. Specifically, the present invention relates to a compound having a condensed ring skeleton structure containing two heterocycles, an organic thin film transistor, an organic semiconductor material for a non-light-emitting organic semiconductor device, a material for an organic thin-film transistor, a coating solution for a non-light-emitting organic semiconductor device, The present invention relates to an organic semiconductor thin film for a non-light-emitting organic semiconductor device and a compound that is an intermediate for synthesizing the compound.

  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 has a condensed ring skeleton structure including two heterocycles such as benzobisbenzothiophene (hereinafter also referred to as BBBT), and has a hydrogen atom, a halogen atom, and 1 to 12 carbon atoms in the side chain. It is disclosed that a compound into which at least one selected from the aliphatic hydrocarbon groups is introduced as an organic thin film transistor material.
Patent Documents 2 and 3 disclose that a compound having a condensed ring skeleton structure containing two heterocycles and having an ethynyl group introduced in the side chain is used as an organic thin film transistor material.
Patent Document 4 describes a method for producing a tetrahaloterphenyl derivative, which is a precursor of a heteroacene derivative used as an organic thin film semiconductor, and illustrates a skeleton of a heteroacene derivative. However, Patent Document 4 does not describe a benzobisbenzothiophene skeleton and has not studied a substituent of a heteroacene derivative.

  On the other hand, Patent Documents 5 and 6 describe examples of benzobisbenzothiophene and benzofuranodibenzofuran substituted at the terminal with a substituent having at least one of an aryl group, a heteroaryl group and a cycloalkyl group. It is described that when these are used as organic electroluminescent (organic EL or organic Electro-Luminescence) element materials, the luminous efficiency is high and the lifetime is long. However, these documents have not studied application to organic thin film transistors.

Japanese Patent No. 5160078 International Publication WO2008 / 131835 A1 US8101776 B2 publication EP2067782 A1 publication EP2067782 A1 publication EP2067782 A1 publication

  What is useful as an organic EL element material cannot be immediately said to be useful as a semiconductor material for organic thin film transistors. 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.

  Under such circumstances, the present inventors examined using the compounds described in these documents for the semiconductor active layer of the organic thin film transistor, and found that most of them have low carrier mobility.

  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 an organic thin film transistor having high carrier mobility.

As a result of diligent studies to solve the above problems, a condensed ring skeleton formed by the condensation of three benzene rings and two hetero 5-membered rings, that is, the type of substituents on the mother nucleus, The divalent linking group represented by —CR ′ ₂ — is not directly linked to the mother nucleus, and the group represented by the following general formula (W) having a specific structure is substituted with a substituent in the molecular major axis direction (this At least one of R ² , R ³ , R ⁶ and R ^{7 in} the general formula (1) of the invention and a substituent in the molecular minor axis direction (R ¹ , R ⁴ in the general formula (1) of the present invention) , R ⁵ and R ^{8 to} R ¹⁰ ), it is found that carrier mobility is increased when used in a semiconductor active layer of an organic thin film transistor by limiting to a specific substituent, and the present invention has been achieved. .
The present invention, which is a specific means for solving the above problems, has the following configuration.

一般式（１）中、
Ｘはそれぞれ独立にＯ原子、Ｓ原子またはＳｅ原子を表し、
Ｒ¹、Ｒ⁴、Ｒ⁵およびＲ⁸〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表し、
Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷はそれぞれ独立に水素原子、アルキル基、ハロゲン原子または下記一般式（Ｗ）で表される置換基を表し、かつ、Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷のうち少なくとも一つは一般式（Ｗ）で表される置換基である；
−Ｌ−Ｒ 一般式（Ｗ）
一般式（Ｗ）中、
Ｌは下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表し、ただしＲ¹〜Ｒ¹⁰が結合する３つのベンゼン環と２つのヘテロ５員環とが縮合してなる母核に一般式（Ｌ−１）で表される２価の連結基は直接連結せず、
Ｒは置換または無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、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、シロキサン基、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トリアルキルシリル基を表す；

一般式（Ｌ−１）〜（Ｌ−２５）中、
一般式（Ｌ−１）で表される２価の連結基における波線部分は別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、一般式（Ｌ−２）〜（Ｌ−２５）で表される２価の連結基における波線部分は母核との結合位置または別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、
一般式（Ｌ−１３）におけるｍは４を表し、一般式（Ｌ−１４）および（Ｌ−１５）におけるｍは３を表し、一般式（Ｌ−１６）〜（Ｌ−２０）におけるｍは２を表し、一般式（Ｌ−２１）におけるｍは０または１の整数を表し、一般式（Ｌ−２２）におけるｍは６を表し、
一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−６）および（Ｌ−１３）〜（Ｌ−２４）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し、
Ｒ^Nは水素原子または置換基を表し、
Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。
［２］ ［１］に記載の有機薄膜トランジスタは、一般式（１）中、ＸがいずれもＳ原子であることが好ましい。
［３］ ［１］または［２］に記載の有機薄膜トランジスタは、一般式（１）中、Ｌが、
母核に直接結合し、かつ、一般式（Ｌ−２）〜（Ｌ−２５）のいずれかで表される２価の連結基であるＬ⁰と、
一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基、または、一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であるＬ¹と、
からなることが好ましい。
［４］ ［３］に記載の有機薄膜トランジスタは、Ｌ⁰が一般式（Ｌ−２）および（Ｌ−１３）〜（Ｌ−２４）のいずれかで表されることが好ましい。
［５］ ［３］または［４］に記載の有機薄膜トランジスタは、Ｌ⁰が一般式（Ｌ−２）、（Ｌ−１３）、（Ｌ−１７）および（Ｌ−１８）のいずれかで表される２価の連結基であることが好ましい。
［６］ ［３］〜［５］のいずれかに記載の有機薄膜トランジスタは、Ｌ⁰が一般式（Ｌ−２）、（Ｌ−１３）、（Ｌ−１７）および（Ｌ−１８）のいずれかで表される２価の連結基であり、
Ｌ¹が一般式（Ｌ−１）〜（Ｌ−４）のいずれかで表される２価の連結基、または、一般式（Ｌ−１）〜（Ｌ−４）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であることが好ましい。
［７］ ［１］〜［６］のいずれかに記載の有機薄膜トランジスタは、一般式（１）中、Ｒが置換または無置換のアルキル基、シロキサン基、あるいは、ケイ素原子数が２〜５のオリゴシロキサン基であることが好ましい。
［８］ ［１］〜［７］のいずれかに記載の有機薄膜トランジスタは、一般式（１）中、Ｒ²およびＲ⁶のうち少なくとも一方が一般式（Ｗ）で表される置換基であり、かつ、
Ｒ¹、Ｒ³〜Ｒ⁵およびＲ⁷〜Ｒ¹⁰がすべて水素原子であることが好ましい。
［９］ ［８］に記載の有機薄膜トランジスタは、Ｒ²とＲ⁶が同一の基であることが好ましい。
［１０］ 下記一般式（１）で表される化合物。

一般式（１）中、
Ｘはそれぞれ独立にＯ原子、Ｓ原子またはＳｅ原子を表し、
Ｒ¹、Ｒ⁴、Ｒ⁵およびＲ⁸〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表し、
Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷はそれぞれ独立に水素原子、アルキル基、ハロゲン原子または下記一般式（Ｗ）で表される置換基を表し、かつ、Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷のうち少なくとも一つは一般式（Ｗ）で表される置換基である；
−Ｌ−Ｒ 一般式（Ｗ）
一般式（Ｗ）中、
Ｌは下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表し、ただしＲ¹〜Ｒ¹⁰が結合する３つのベンゼン環と２つのヘテロ５員環とが縮合してなる母核に一般式（Ｌ−１）で表される２価の連結基は直接連結せず、
Ｒは置換または無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、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、シロキサン基、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トリアルキルシリル基を表す；

一般式（Ｌ−１）〜（Ｌ−２５）中、
一般式（Ｌ−１）で表される２価の連結基における波線部分は別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、一般式（Ｌ−２）〜（Ｌ−２５）で表される２価の連結基における波線部分は母核との結合位置または別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、
一般式（Ｌ−１３）におけるｍは４を表し、一般式（Ｌ−１４）および（Ｌ−１５）におけるｍは３を表し、一般式（Ｌ−１６）〜（Ｌ−２０）におけるｍは２を表し、一般式（Ｌ−２１）におけるｍは０または１の整数を表し、一般式（Ｌ−２２）におけるｍは６を表し、
一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−６）および（Ｌ−１３）〜（Ｌ−２４）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し、
Ｒ^Nは水素原子または置換基を表し、
Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。
［１１］ ［１０］に記載の化合物は、一般式（１）中、ＸがいずれもＳ原子であることが好ましい。
［１２］ ［１０］または［１１］に記載の化合物は、一般式（１）中、Ｌが、
母核に直接結合し、かつ、一般式（Ｌ−２）〜（Ｌ−２５）のいずれかで表される２価の連結基であるＬ⁰と、
一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基、または、一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であるＬ¹と、
からなることが好ましい。
［１３］ ［１２］に記載の化合物は、Ｌ⁰が一般式（Ｌ−２）および（Ｌ−１３）〜（Ｌ−２４）のいずれかで表されることが好ましい。
［１４］ ［１２］または［１３］に記載の化合物は、Ｌ⁰が一般式（Ｌ−２）、（Ｌ−１３）、（Ｌ−１７）および（Ｌ−１８）のいずれかで表される２価の連結基であることが好ましい。
［１５］ ［１２］〜［１４］のいずれかに記載の化合物は、Ｌ⁰が一般式（Ｌ−２）、（Ｌ−１３）、（Ｌ−１７）および（Ｌ−１８）のいずれかで表される２価の連結基であり、
Ｌ¹が一般式（Ｌ−１）〜（Ｌ−４）のいずれかで表される２価の連結基、または、一般式（Ｌ−１）〜（Ｌ−４）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基であることが好ましい。
［１６］ ［１０］〜［１５］のいずれかに記載の化合物は、一般式（１）中、Ｒが置換または無置換のアルキル基、シロキサン基、あるいは、ケイ素原子数が２〜５のオリゴシロキサン基であることが好ましい。
［１７］ ［１０］〜［１６］のいずれかに記載の化合物は、一般式（１）中、Ｒ²およびＲ⁶のうち少なくとも一方が一般式（Ｗ）で表される置換基であり、かつ、
Ｒ¹、Ｒ³〜Ｒ⁵およびＲ⁷〜Ｒ¹⁰がすべて水素原子であることが好ましい。
［１８］ ［１７］に記載の化合物は、Ｒ²とＲ⁶が同一の基であることが好ましい。
［１９］ ［１０］〜［１８］のいずれかに記載の化合物を含有する非発光性有機半導体デバイス用有機半導体材料。
［２０］ ［１０］〜［１８］のいずれかに記載の化合物を含有する有機薄膜トランジスタ用材料。
［２１］ ［１０］〜［１８］のいずれかに記載の化合物を含有する非発光性有機半導体デバイス用塗布溶液。
［２２］ ［１０］〜［１８］のいずれかに記載の化合物とポリマーバインダーを含有する非発光性有機半導体デバイス用塗布溶液。
［２３］ ［１０］〜［１８］のいずれかに記載の化合物を含有する非発光性有機半導体デバイス用有機半導体薄膜。
［２４］ ［１０］〜［１８］のいずれかに記載の化合物とポリマーバインダーを含有する非発光性有機半導体デバイス用有機半導体薄膜。
［２５］ ［２３］または［２４］に記載の非発光性有機半導体デバイス用有機半導体薄膜は、溶液塗布法により作製されたことが好ましい。
［２６］ 下記一般式（Ｍ１）で表される化合物；
一般式（Ｍ１）

一般式（Ｍ１）中、
Ｘ¹およびＸ²はそれぞれ独立にＯ原子、Ｓ原子、Ｓｅ原子、−Ｎ（−Ｒ^N1）−、−Ｎ＝Ｃ−および−Ｃ（Ｒ^M3）＝Ｃ（Ｒ^M3）−のいずれか一つを表し、
Ｒ^N1は水素原子または置換基を表し、
Ｒ^M3はそれぞれ独立に水素原子または置換基を表し、
Ｒ^M1およびＲ^M2はそれぞれ独立に直鎖または分枝のアルキル基を表し、
ｒ１およびｒ２はそれぞれ独立に０〜２の整数を表し、
ｒ３およびｒ４はそれぞれ独立に０以上の整数を表し、かつ、ｒ３＋ｒ４が１以上であり、
Ｒはそれぞれ独立に置換または無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、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、シロキサン基、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トリアルキルシリル基を表す。
［２７］ ［２６］に記載の化合物は、［１０］〜［１８］のいずれかに記載の化合物の中間体化合物であることが好ましい。 [1] An organic thin film transistor comprising a compound represented by the following general formula (1) in a semiconductor active layer;
General formula (1)

In general formula (1),
Each X independently represents an O atom, an S atom or a Se atom;
R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a halogen atom;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and At least one of R ⁷ is a substituent represented by formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) each independently represents a hydrogen atom or a substituent,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
[2] In the organic thin film transistor according to [1], in general formula (1), it is preferable that all Xs are S atoms.
[3] In the organic thin film transistor according to [1] or [2], in the general formula (1), L is
L ⁰ which is a divalent linking group directly bonded to the mother nucleus and represented by any one of the general formulas (L-2) to (L-25);
A divalent linking group represented by any one of general formulas (L-1) to (L-25) or a divalent represented by any one of general formulas (L-1) to (L-25). L ¹ which is a divalent linking group in which two or more of the linking groups are bonded;
Preferably it consists of.
[4] In the organic thin film transistor according to [3], L ⁰ is preferably represented by any one of the general formulas (L-2) and (L-13) to (L-24).
[5] In the organic thin film transistor according to [3] or [4], L ⁰ is represented by any one of the general formulas (L-2), (L-13), (L-17), and (L-18). It is preferable that it is a divalent linking group.
[6] In the organic thin film transistor according to any one of [3] to [5], L ⁰ is any one of general formulas (L-2), (L-13), (L-17), and (L-18). A divalent linking group represented by:
L ¹ is represented by any of the divalent linking groups represented by any ^one of the general formulas (L-1) to (L-4) or any one of the general formulas (L-1) to (L-4). The divalent linking group is preferably a divalent linking group in which two or more divalent linking groups are bonded.
[7] In the organic thin film transistor according to any one of [1] to [6], R is a substituted or unsubstituted alkyl group, a siloxane group, or a silicon atom number of 2 to 5 in the general formula (1). An oligosiloxane group is preferred.
[8] The organic thin film transistor according to any one of [1] to [7] is a substituent in which at least one of R ² and R ⁶ is represented by the general formula (W) in the general formula (1). ,And,
R ¹ , R ^{3 to} R ⁵ and R ^{7 to} R ¹⁰ are preferably all hydrogen atoms.
[9] In the organic thin film transistor according to [8], R ² and R ⁶ are preferably the same group.
[10] A compound represented by the following general formula (1).

In general formula (1),
Each X independently represents an O atom, an S atom or a Se atom;
R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a halogen atom;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and At least one of R ⁷ is a substituent represented by formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) each independently represents a hydrogen atom or a substituent,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
[11] In the compound according to [10], in general formula (1), X is preferably an S atom.
[12] In the compound of [10] or [11], in the general formula (1), L is
L ⁰ which is a divalent linking group directly bonded to the mother nucleus and represented by any one of the general formulas (L-2) to (L-25);
A divalent linking group represented by any one of general formulas (L-1) to (L-25) or a divalent represented by any one of general formulas (L-1) to (L-25). L ¹ which is a divalent linking group in which two or more of the linking groups are bonded;
Preferably it consists of.
[13] In the compound according to [12], L ⁰ is preferably represented by any one of the general formulas (L-2) and (L-13) to (L-24).
[14] In the compound according to [12] or [13], L ⁰ is represented by any one of the general formulas (L-2), (L-13), (L-17) and (L-18). And a divalent linking group.
[15] In the compound according to any one of [12] to [14], L ⁰ is any one of general formulas (L-2), (L-13), (L-17), and (L-18). A divalent linking group represented by:
L ¹ is represented by any of the divalent linking groups represented by any ^one of the general formulas (L-1) to (L-4) or any one of the general formulas (L-1) to (L-4). The divalent linking group is preferably a divalent linking group in which two or more divalent linking groups are bonded.
[16] In the compound according to any one of [10] to [15], in the general formula (1), R is a substituted or unsubstituted alkyl group, a siloxane group, or an oligo having 2 to 5 silicon atoms. A siloxane group is preferred.
[17] The compound according to any one of [10] to [16] is a substituent in which at least one of R ² and R ⁶ is represented by the general formula (W) in the general formula (1), And,
R ¹ , R ^{3 to} R ⁵ and R ^{7 to} R ¹⁰ are preferably all hydrogen atoms.
[18] In the compound according to [17], R ² and R ⁶ are preferably the same group.
[19] An organic semiconductor material for a non-light-emitting organic semiconductor device containing the compound according to any one of [10] to [18].
[20] A material for an organic thin film transistor containing the compound according to any one of [10] to [18].
[21] A coating solution for a non-luminous organic semiconductor device containing the compound according to any one of [10] to [18].
[22] A coating solution for a non-light-emitting organic semiconductor device, comprising the compound according to any one of [10] to [18] and a polymer binder.
[23] An organic semiconductor thin film for a non-light-emitting organic semiconductor device containing the compound according to any one of [10] to [18].
[24] An organic semiconductor thin film for a non-light-emitting organic semiconductor device, comprising the compound according to any one of [10] to [18] and a polymer binder.
[25] The organic semiconductor thin film for a non-light-emitting organic semiconductor device according to [23] or [24] is preferably produced by a solution coating method.
[26] A compound represented by the following general formula (M1);
General formula (M1)

In general formula (M1),
X ¹ and X ² are each independently any one of O atom, S atom, Se atom, —N (—R ^N1 ) —, —N═C— and —C (R ^M3 ) ═C (R ^M3 ) —. Represents
R ^N1 represents a hydrogen atom or a substituent,
R ^M3 each independently represents a hydrogen atom or a substituent,
R ^M1 and R ^M2 each independently represent a linear or branched alkyl group,
r1 and r2 each independently represents an integer of 0 to 2,
r3 and r4 each independently represents an integer of 0 or more, and r3 + r4 is 1 or more,
R is independently a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, and a silicon atom number of 2 The above oligosiloxane group or a substituted or unsubstituted trialkylsilyl group is represented.
[27] The compound according to [26] is preferably an intermediate compound of the compound according to any one of [10] to [18].

  According to the present invention, an organic thin film transistor having high carrier mobility can be provided.

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.

一般式（１）中、
Ｘはそれぞれ独立にＯ原子、Ｓ原子またはＳｅ原子を表し、
Ｒ¹、Ｒ⁴、Ｒ⁵およびＲ⁸〜Ｒ¹⁰はそれぞれ独立に水素原子またはハロゲン原子を表し、
Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷はそれぞれ独立に水素原子、アルキル基、ハロゲン原子または下記一般式（Ｗ）で表される置換基を表し、かつ、Ｒ²、Ｒ³、Ｒ⁶およびＲ⁷のうち少なくとも一つは一般式（Ｗ）で表される置換基である；
−Ｌ−Ｒ 一般式（Ｗ）
一般式（Ｗ）中、
Ｌは下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基または下記一般式（Ｌ−１）〜（Ｌ−２５）のいずれかで表される２価の連結基が２つ以上結合した２価の連結基を表し、ただしＲ¹〜Ｒ¹⁰が結合する３つのベンゼン環と２つのヘテロ５員環とが縮合してなる母核に一般式（Ｌ−１）で表される２価の連結基は直接連結せず、
Ｒは置換または無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、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、シロキサン基、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トリアルキルシリル基を表す；

一般式（Ｌ−１）〜（Ｌ−２５）中、
一般式（Ｌ−１）で表される２価の連結基における波線部分は別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、一般式（Ｌ−２）〜（Ｌ−２５）で表される２価の連結基における波線部分は母核との結合位置または別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、
一般式（Ｌ−１３）におけるｍは４を表し、一般式（Ｌ−１４）および（Ｌ−１５）におけるｍは３を表し、一般式（Ｌ−１６）〜（Ｌ−２０）におけるｍは２を表し、一般式（Ｌ−２１）におけるｍは０または１の整数を表し、一般式（Ｌ−２２）におけるｍは６を表し、
一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−６）および（Ｌ−１３）〜（Ｌ−２４）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し、
Ｒ^Nは水素原子または置換基を表し、
Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。 [Organic thin film transistor]
The organic thin-film transistor of this invention contains the compound represented by following General formula (1) in a semiconductor active layer.
General formula (1)

In general formula (1),
Each X independently represents an O atom, an S atom or a Se atom;
R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a halogen atom;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and At least one of R ⁷ is a substituent represented by formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) each independently represents a hydrogen atom or a substituent,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

By including the compound represented by the general formula (1) having such a structure in the semiconductor active layer, the organic thin film transistor of the present invention has high carrier mobility.
Here, Japanese Patent No. 5160078 focuses on unsubstituted BBBT and BBBT compounds into which a substituted or unsubstituted alkyl substituent is introduced, and introduces a substituent in which no alkyl group is directly bonded to the mother nucleus. There is no description about the compound. It has been reported that such a compound can provide only an undesirable crystal structure as an organic thin film transistor material. For example, K.K. Muellen, Chem. Commun. 2008, 1548-1550; Takimiya, Org. Lett. As described in 2007, 9, 4499-4502, different crystal polymorphs are described, the non-substituted product is unstable due to the presence of crystal polymorphs, and tilt (vertical displacement of molecules when crystallized). In addition, it is disadvantageous for charge transport because sufficient HOMO orbital overlap cannot be obtained between molecules when crystallized. K.K. Muellen, Chem. Commun. According to 2008, 1548-1550, the alkyl (C4) substitution product of BBBT has stable crystal polymorphism that is not desirable as an organic thin film transistor material, and has a large tilt (longitudinal shift of molecules when crystallized). This is disadvantageous for charge transport because sufficient HOMO orbital overlap cannot be obtained between molecules. Actually, the carrier mobility of benzobisbenzothiophene having a relatively short chain length and a substituted or unsubstituted alkyl group reported in Japanese Patent No. 5160078 is as low as about 10 ⁻³ cm ² / Vs.
International Publication WO 2008/131835 A1 describes a compound in which an ethynyl group is introduced laterally (R ⁹ and R ¹⁰ in the general formula (1) of the present invention) in the short axis direction of the BBBT molecule. A compound cannot take a desirable crystal structure as an organic thin film transistor material. Actually, the carrier mobility of the organic thin film transistor described in International Publication WO2008 / 131835 A1 is as low as about 0.5 cm ² / Vs at the maximum, and it is used for a backplane or the like which is a driving circuit of a pixel of an organic electroluminescence element. It is insufficient for application to organic thin film transistors.
In contrast, the compound represented by the general formula (1) of the present invention devised the type of substituents to the mother nucleus so that sufficient HOMO orbital overlap is obtained between molecules when crystallized, In particular, a divalent linking group represented by —CR ′ ₂ — is not directly bonded to the mother nucleus, and a group represented by the following general formula (W) having a specific structure is substituted with a substituent in the molecular long axis direction ( At least one of R ² , R ³ , R ⁶ and R ^{7 in} the general formula (1) of the present invention and a substituent in the molecular minor axis direction (R ¹ , R in the general formula (1) of the present invention) ⁴ , R ⁵ and R ^{8 to} R ¹⁰ ), the crystal structure is greatly changed by limiting to specific substituents, and the carrier mobility is drastically improved when used in the semiconductor active layer of organic thin film transistors. I found an effect. When the compound represented by the general formula (1) of the present invention is crystallized, the crystal structure largely changes from the crystal structure of the compound described in Japanese Patent No. 5160078 or the compound described in International Publication WO2008 / 131835 A1. However, it is difficult for experts in the field of organic thin film transistor materials to predict that the polycrystal system desirable as an organic thin film transistor material has a crystal structure in which the tilt is eliminated and the crystal structure analysis is performed by the present inventors. Found as a repeated result.

  Furthermore, the organic thin film transistor of the present invention using the compound represented by the general formula (1) 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. Since the compound represented by the general formula (1) 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.

  Moreover, it is preferable that the compound represented by General formula (1) of this invention also has high solubility with respect to a general purpose organic solvent. The relatively simple alkyl group described in Japanese Patent No. 5160078 is insufficient to provide solubility in general-purpose solvents. The compound represented by the general formula (1) of the present invention has a variety of substituents, has a substituent represented by the general formula (W) described later, and greatly improves the solubility in general-purpose organic solvents. It is preferable that it is improved.

  Hereinafter, preferred embodiments of the compound of the present invention and the organic thin film transistor of the present invention will be described.

<Compound represented by the general formula (1)>
The organic thin-film transistor of this invention contains the compound represented by General formula (1) in the semiconductor active layer mentioned later. The compound represented by the general formula (1) is a novel compound and is also referred to as a compound of the present invention. The compound represented by the general formula (1) can be used as a material for an organic thin film transistor.

General formula (1)

  In general formula (1), X represents an O atom, S atom, or Se atom each independently. X is preferably independently an O atom or an S atom, and at least one of X is preferably an S atom, more preferably from the viewpoint of increasing carrier mobility. X is preferably the same linking group. It is particularly preferable that all Xs are S atoms from the viewpoint of improving carrier mobility, thermal stability, threshold voltage after repeated driving, and coating film quality.

In general formula (1), R < ¹ >, R < ⁴ >, R < ⁵ > and R < ⁸ > -R < ¹⁰ > represent a hydrogen atom or a halogen atom each independently.
Examples of the halogen atom represented by R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and may be a fluorine atom, a chlorine atom or a bromine atom. Preferably, it is a fluorine atom or a chlorine atom, more preferably a fluorine atom.
In the compound represented by the general formula (1), among R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ , the halogen atom is preferably 0 to 6, and 0 to 2 Is more preferable, 0 or 1 is particularly preferable, and 0 is particularly preferable.

一般式（Ｌ−１）〜（Ｌ−２５）中、
一般式（Ｌ−１）で表される２価の連結基における波線部分は別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、一般式（Ｌ−２）〜（Ｌ−２５）で表される２価の連結基における波線部分は母核との結合位置または別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、
一般式（Ｌ−１３）におけるｍは４を表し、一般式（Ｌ−１４）および（Ｌ−１５）におけるｍは３を表し、一般式（Ｌ−１６）〜（Ｌ−２０）におけるｍは２を表し、一般式（Ｌ−２１）におけるｍは０または１の整数を表し、一般式（Ｌ−２２）におけるｍは６を表し、
一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−６）および（Ｌ−１３）〜（Ｌ−２４）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し、
Ｒ^Nは水素原子または置換基を表し、
Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。 In the general formula (1), R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and R ⁷ are each a substituent represented by the general formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) each independently represents a hydrogen atom or a substituent,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

In general formula (1), the alkyl group represented by R ² , R ³ , R ⁶ and R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 5 to 15 carbon atoms, 8-12 alkyl groups are particularly preferred. The alkyl group represented by R ² , R ³ , R ⁶ and R ⁷ may be linear, branched or cyclic, but is preferably linear from the viewpoint of mobility.
Among the compounds represented by the general formula (1), among R ² , R ³ , R ⁶ and R ⁷ , the alkyl group is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is particularly preferable, and 0 is particularly preferable.

In the general formula (1), examples of the halogen atom represented by R ² , R ³ , R ⁶ and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A fluorine atom, a chlorine atom or a bromine atom It is preferably a fluorine atom or a chlorine atom, particularly preferably a fluorine atom.
In the compound represented by the general formula (1), among R ² , R ³ , R ⁶ and R ⁷ , the halogen atom is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is particularly preferable, and 0 is particularly preferable.

一般式（Ｌ−１）〜（Ｌ−２５）中、
一般式（Ｌ−１）で表される２価の連結基における波線部分は別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、一般式（Ｌ−２）〜（Ｌ−２５）で表される２価の連結基における波線部分は母核との結合位置または別の一般式（Ｌ−１）〜（Ｌ−２５）で表される２価の連結基の＊との結合位置を表し、
一般式（Ｌ−１３）におけるｍは４を表し、一般式（Ｌ−１４）および（Ｌ−１５）におけるｍは３を表し、一般式（Ｌ−１６）〜（Ｌ−２０）におけるｍは２を表し、一般式（Ｌ−２１）におけるｍは０または１の整数を表し、一般式（Ｌ−２２）におけるｍは６を表し、
一般式（Ｌ−１）、（Ｌ−２）、（Ｌ−６）および（Ｌ−１３）〜（Ｌ−２４）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し、
Ｒ^Nは水素原子または置換基を表し、
Ｒ^siはそれぞれ独立に水素原子、アルキル基、アルケニル基またはアルキニル基を表す。 A group represented by the general formula (W) represented by R ² , R ³ , R ⁶ and R ^{7 in the} general formula (1) will be described.
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) each independently represents a hydrogen atom or a substituent,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

In the general formula (W), L is a divalent linking group represented by any one of the following general formulas (L-1) to (L-25) or the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, provided that three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero 5-membered rings are condensed. The divalent linking group represented by the general formula (L-1) is not directly linked to the mother nucleus.

In general formulas (L-1) to (L-25), wavy lines in the divalent linking group represented by general formula (L-1) are different from general formulas (L-1) to (L-25). The bond position with * of the bivalent coupling group represented by these is represented.
In the general formulas (L-1) to (L-25), the wavy line in the divalent linking group represented by the general formulas (L-2) to (L-25) represents the bonding position with the mother nucleus or another The bond position with * of the bivalent coupling group represented by general formula (L-1)-(L-25) is represented.
In the general formulas (L-1) to (L-25), * represents a bonding position with either the wavy portion of the divalent linking group represented by the general formulas (L-1) to (L-25) and R. Indicates.
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 and m in (L-22) represents 6.
In the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24), R ′ each independently represents a hydrogen atom or a substituent.
In general formulas (L-1) to (L-25), R ^N represents a hydrogen atom or a substituent.
In the general formulas (L-1) to (L-25), R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
R ′ in general formulas (L-1) and (L-2) may be bonded to R adjacent to L to form a condensed ring.
The divalent linking groups represented by the general formulas (L-19) to (L-21), (L-23) and (L-24) are represented by the following general formulas (L-19A) to (L-21A). , (L-23A) and (L-24A) are more preferred.

また、一般式（Ｗ）で表される置換基が炭素数８のアルコキシ基である場合、−Ｏ−である一般式（Ｌ−４）で表される連結基１個と、２個のＲ’が水素原子である一般式（Ｌ−１）で表される連結基１個と、炭素数７のｎ−ヘプチル基とが結合した置換基として解釈する。一般式（Ｗ）で表される置換基がアルキル基以外の場合におけるＬとＲの分け方は次のとおりであり、Ｌは「一般式（Ｌ−１）で表される連結基以外の２価の連結基」と「一般式（Ｌ−１）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。

Here, a substituted or unsubstituted alkyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group. When the substituted trialkylsilyl group is present at the terminal of the substituent represented by the general formula (W), it can be interpreted as -R alone in the general formula (W), and -L in the general formula (W). It can also be interpreted as -R.
In the present invention, when a substituted or unsubstituted alkyl group having N carbon atoms in the main chain is present at the terminal of the substituent represented by the general formula (W), the substituent represented by the general formula (W) The linking group represented by —CR ^R ₂ — as much as possible from the end of the compound is included in R, and is interpreted as —LR in the general formula (W), and is not interpreted as —R alone. R ^R represents a hydrogen atom or a substituent. Specifically, “one (L-1) corresponding to L in the general formula (W)” and “the main chain corresponding to R in the general formula (W) is substituted or unsubstituted having N−1 carbon atoms. It is interpreted as a substituent to which “alkyl group” is bonded. For example, when an n-octyl group, which is an alkyl group having 8 carbon atoms, is present at the terminal of the substituent, two R ′ are hydrogen atoms (L-1), and n-heptyl having 7 carbon atoms. Interpreted as a substituent bonded to a group. In the case where the substituent represented by the general formula (W) is an alkyl group, L and R are separated as in the following examples, and L is a divalent linking group represented by the general formula (L-1). Represents.

In addition, when the substituent represented by the general formula (W) is an alkoxy group having 8 carbon atoms, one linking group represented by the general formula (L-4) which is —O— and two R It is interpreted as a substituent in which one linking group represented by the general formula (L-1) where 'is a hydrogen atom and an n-heptyl group having 7 carbon atoms are bonded. When the substituent represented by the general formula (W) is other than an alkyl group, L and R are separated as follows, and L represents “2 other than the linking group represented by the general formula (L-1)”. A divalent linking group to which “a valent linking group” and “a divalent linking group represented by formula (L-1)” are bonded.

On the other hand, in the present invention, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. In the case where the group is present at the terminal of the substituent represented by the general formula (W), after adding as many linking groups as possible from the terminal of the substituent represented by the general formula (W) to R, In the formula (W), it is interpreted as -R alone, and is not interpreted as -LR. For example, when a — (OCH ₂ CH ₂ ) — (OCH ₂ CH ₂ ) —OCH ₃ group is present at the end of a substituent, it is interpreted as a substituent of an oligooxyethylene group having a repeating number v of oxyethylene units of 2 alone. To do. An oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more of oxyethylene units, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group is represented by the general formula (W The method for separating L and R when present at the end of the substituent represented by

As the substituent R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24), a halogen atom, an alkyl group (methyl group, ethyl) Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and other alkyl groups having 1 to 40 carbon atoms However, 2,6-dimethyloctyl group, 2-decyltetradecyl group, 2-hexyldecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2- An ethyloctyl group, a 2-octyltetradecyl group, a 2-ethylhexyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, etc.), an alkenyl group (1 -Including pentenyl group, cycloalkenyl group, bicycloalkenyl group, etc.), alkynyl group (1-pentynyl group, trimethylsilylethynyl group, triethylsilylethynyl group, tri-i-propylsilylethynyl group, 2-p-propylphenylethynyl group) Etc.), aryl groups (phenyl group, naphthyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, 3,4-diheptoxyphenyl group having 6 to 20 carbon atoms) Aryl groups, etc.), heterocyclic groups (also referred to as heterocyclic groups, including 2-hexylfuranyl group), cyano groups, hydroxyl groups, nitro groups, acyl groups (hexanoyl groups, benzoyl groups, etc.) ), Alkoxy groups (including butoxy groups, etc.), aryloxy groups, silyloxy groups, heterocyclic oxy groups Acyloxy group, carbamoyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group (including ureido group), alkoxy and aryloxycarbonylamino group, alkyl and arylsulfonylamino group, mercapto group, alkyl and arylthio Group (including methylthio group, octylthio group, etc.), heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl 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, silyl group (ditrimethylsiloxymethylbutoxy group, etc.), hydra Amino group, a ureido group, a boronic acid group (-B (OH) _2), phosphato group (-OPO (OH) _2), a sulfato group (-OSO ₃ H), and other known substituents.
Moreover, these substituents may further have the above substituents. Moreover, when the compound represented by General formula (1) is a high molecular compound which has a repeating structure, R < ¹ > -R < ⁸ > may have group derived from a polymeric group.
Among them, the substituent R ′ in the general formula (L-6) is preferably an alkyl group, and when R ′ in (L-6) is an alkyl group, the alkyl group has 1 to 1 carbon atoms. 9 is preferable, 4-9 is more preferable from the viewpoint of chemical stability and carrier transportability, and 5-9 is still more preferable. When R ′ in (L-6) is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
R ^N represents a hydrogen atom or a substituent, examples of R ^N, may be mentioned those exemplified as the substituent which the above R 'may take. Among them a hydrogen atom or a methyl group is preferable as also R ^N.
R ^si each independently represents a hydrogen atom, an alkyl group or an alkenyl group, preferably an alkyl group. The alkyl group that R ^si can take is not particularly limited, but the preferred range of the alkyl group that R ^si can take is the same as the preferred range of the alkyl group that the silyl group can take when R is a silyl group. The alkenyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group has 2 to 3 carbon atoms. preferable. The alkynyl group that R ^si can take is not particularly limited, but a substituted or unsubstituted alkynyl group is preferable, a branched alkynyl group is more preferable, and the alkynyl group has 2 to 3 carbon atoms. preferable.

In the present invention, L is a divalent linking group represented by any one of the general formulas (L-1) to (L-25) or any one of the general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded to each other, provided that a mother nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings. The divalent linking group represented by formula (L-1) is not directly linked. The compound represented by the general formula (1) is represented by the general formula (L-1) in the mother nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero 5-membered rings. Since the divalent linking group has a structure that is not directly connected, it is excellent in that it can eliminate crystal polymorphism and stabilize a more desirable crystal structure (Herringbone structure).

In the present invention, L preferably represents a divalent linking group in which two or more divalent linking groups represented by any one of the general formulas (L-1) to (L-25) are bonded.
When L forms a linking group to which a divalent linking group represented by any one of formulas (L-1) to (L-25) is bonded, formulas (L-1) to (L-25) The number of bonds of the divalent linking group represented by any of the above is preferably 2-8, more preferably 2-4, and particularly preferably 2 or 3.

In the present invention, L is attached directly to the mother nucleus, and the general formula (L-2) ~ (L -25) L 0 is a divalent linking group represented by any one of formulas ( A divalent linking group represented by any one of L-1) to (L-25) or a divalent linking group represented by any one of the general formulas (L-1) to (L-25). Is more preferably composed of L ¹ which is a divalent linking group in which two or more are bonded.
L ⁰ is preferably represented by any one of the general formulas (L-2) and (L-13) to (L-24), and the general formulas (L-2), (L-13), (L It is more preferably a divalent linking group represented by any of -17) and (L-18), and particularly preferably a divalent linking group represented by the general formula (L-13). .
L ¹ is a divalent linking group represented by any one of general formulas (L-1) to (L-4) and (L-25), or general formulas (L-1) to (L-4). ) And (L-25) are preferably divalent linking groups in which two or more divalent linking groups are bonded. L ¹ is a divalent linking group represented by any ^one of the general formulas (L-1) to (L-4) or any one of the general formulas (L-1) to (L-4). More preferably, the divalent linking group is a divalent linking group in which two or more divalent linking groups are bonded. L ¹ is a divalent linking group represented by formula (L-1) or a divalent linking group in which two or more divalent linking groups represented by formula (L-1) are bonded. It is particularly preferred that
L is a divalent linking group in which L ⁰ is represented by any one of the general formulas (L-2) and (L-13) to (L-24), and L ¹ is the general formula (L-1). Or a divalent linking group represented by any one of (L-4) and (L-25), or any one of general formulas (L-1) to (L-4) and (L-25) The divalent linking group represented by two or more of the divalent linking groups represented is preferable. L is, L ⁰ is formula (L-2), a divalent linking group represented by any one of the (L-13), (L -17) and (L-18), L ¹ is generally A divalent linking group represented by any one of formulas (L-1) to (L-4) or a divalent linking group represented by any one of general formulas (L-1) to (L-4); It is more preferably a divalent linking group in which two or more linking groups are bonded. L is a divalent linking group in which L ⁰ is represented by the general formula (L-13), and L ¹ is a divalent linking group represented by the general formula (L-1), or A divalent linking group in which two or more divalent linking groups represented by L-1) are bonded is particularly preferred.
L is preferably a divalent linking group including a divalent linking group represented by Formula (L-1) from the viewpoints of chemical stability and carrier transportability.

In general formula (W), R represents a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having 2 or more repeating oxyethylene units, a siloxane group, and a silicon atom. It represents an oligosiloxane group having a number of 2 or more, or a substituted or unsubstituted silyl group.
In the present invention, in general formula (W), R is preferably a substituted or unsubstituted alkyl group, a siloxane group, or an oligosiloxane group having 2 to 5 silicon atoms, and a substituted or unsubstituted alkyl group. It is more preferable that

When R is a substituted or unsubstituted alkyl group, the number of carbon atoms is preferably 4-18, more preferably 6-15, more preferably 6-12 in terms of chemical stability and carrier transportability. More preferably. R is preferably a long-chain alkyl group in the above-mentioned range, particularly a long-chain straight-chain alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
When R represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. From the viewpoint of being able to.
On the other hand, from the viewpoint of increasing the solubility in an organic solvent, R is preferably a branched alkyl group.
Examples of the substituent when R is an alkyl group having a substituent include a halogen atom (in this case, R is a haloalkyl group), 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. However, R is preferably an unsubstituted alkyl group.

Wherein R is an ethylene group or, if the repetition number of oxyethylene groups is 2 or oligoethyleneoxy group, herein the R represents "oligooxyethylene _{group", - (OCH 2 CH 2)} v It refers to a group represented by OY (the repeating number v of oxyethylene units 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 a siloxane group or an oligosiloxane group having 2 or more silicon atoms, the “siloxane group” represented by R is a group represented by * —O—SiZ ₃ in the present specification. In the present specification, “oligosiloxane group” refers to a group represented by — (O—Si) _w —O—SiZ ₃ (* in the description of the siloxane group is a bond connected to a Si atom). The repeating number w of the oligosiloxane unit represents an integer of 1 or more, and the terminal Z represents a hydrogen atom or a substituent. The number of repeating siloxane units is preferably 1 to 4, 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 L adjacent to R is a divalent linking group represented by the general formula (L-3), it is also preferable that R is a substituted or unsubstituted silyl group. Among them, when R is a substituted or unsubstituted silyl group, R is preferably a substituted silyl group. Although there is no restriction | limiting in particular as a substituent of a silyl group, A substituted or unsubstituted alkyl group is preferable and it is more preferable that it is a branched alkyl group. When R is a trialkylsilyl group, the alkyl group bonded to the Si atom preferably has 1 to 3 carbon atoms, and for example, a methyl group, an ethyl group, or an isopropyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups may be bonded thereto. When R is a trialkylsilyl group further having a substituent on the alkyl group, the substituent is not particularly limited.

  The total number of carbon atoms contained in the group represented by the general formula (W), that is, the total number of carbon atoms contained in L and R is not particularly limited, and the lower limit can be set to 2 or more, for example, 12 or more. Preferably, it is 13 or more, more preferably 14 or more. When the total number of carbon atoms contained in L and R is not less than the lower limit of the above range, the carrier mobility is increased and the solubility is increased. The total number of carbon atoms contained in the group represented by the general formula (W), that is, the upper limit value of the total number of carbon atoms contained in L and R can be, for example, 20 or less, preferably 19 or less, More preferably, it is 18 or less. When the total number of carbon atoms contained in L and R is not more than the upper limit of the above range, the driving voltage is lowered.

  As a combination of R and L in the general formula (W), when L includes a divalent linking group represented by the general formulas (L-13) to (L-24), R is an alkyl group, Any one of the divalent linking groups represented by the general formulas (L-13) to (L-24) is represented by R through the divalent linking group represented by the general formula (L-1); It is preferable that it is connected with.

In the compound represented by the general formula (1), among R ² , R ³ , R ⁶ and R ⁷ , the number of groups represented by the general formula (W) is 1 to 4, and the carrier mobility is It is preferable from the viewpoint of enhancing the solubility in an organic solvent, more preferably 1 or 2, and particularly preferably 2 from the viewpoint of improving the thermal stability and the quality of the coating film.
There is no restriction | limiting in particular in the position of group represented by general formula (W) among R < ² >, R < ³ >, R < ⁶ > and R < ⁷ >. Among them, in the present invention, in the general formula (1), it is preferable that at least one of R ² and R ⁶ is a substituent represented by formula (W), both R ² and R ⁶ are generally more preferably a substituent represented by formula (W), the substituents R ² and R ⁶ are represented by even general formula both R ² and R ⁶ (W) and is the same group It is particularly preferred.
In the present invention, at least one of R ² and R ⁶ is a substituent represented by the general formula (W), and R ¹ , R ^{3 to} R ⁵ and R ^{7 to} R ¹⁰ are all hydrogen atoms. It is preferable from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent.
In the present invention, R ² and R ⁶ are all substituents represented by the general formula (W), and R ¹ , R ^{3 to} R ⁵ and R ^{7 to} R ¹⁰ are all hydrogen atoms. More preferred.
In the present invention, a substituent and the same radicals R ² and R ⁶ are represented both R ² and R ⁶ in the general formula (W), and, R ^1, R ³ ~R ⁵ and R ⁷ ~ It is particularly preferred that all R ¹⁰ are hydrogen atoms.

In the general formula (1), two or more R ^{1 to} R ¹⁰ may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but they are not bonded to each other to form a ring. Is preferred.

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is limitedly interpreted by these specific examples. It shouldn't be.

General formula (1 ')

X, R ² , R ³ , R ⁶ and R ⁷ in the general formula (1 ′) are as shown in the following table. In the table below, Ph represents a phenylene group. In the following table, an alkylene group or an alkyl group is linear unless otherwise specified.

The compound represented by the general formula (1) may have a repeating structure, and may be a low molecule or a polymer. When the compound represented by the general formula (1) is a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and 850 or less. It is particularly preferred. It is preferable to make the molecular weight not more than the above upper limit value because the solubility in a solvent can be increased.
On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and further preferably 500 or more.
When the compound represented by the general formula (1) is a polymer compound having a repeating structure, the weight average molecular weight is preferably 30,000 or more, more preferably 50,000 or more, and 100,000 or more. More preferably. When the compound represented by the general formula (1) is a polymer compound having a repeating structure, the intermolecular interaction can be increased by setting the weight average molecular weight to be equal to or higher than the above lower limit, and high mobility is achieved. Since it is obtained, it is preferable.
Examples of the polymer compound having a repeating structure include a π-conjugated polymer in which the compound represented by the general formula (1) represents at least one arylene group or heteroarylene group (thiophene, bithiophene) and exhibits a repeating structure, A pendant polymer in which a compound represented by the formula (1) is bonded to a polymer main chain through a side chain is exemplified. As the polymer main chain, polyacrylate, polyvinyl, polysiloxane, and the like are preferable. Is preferably an alkylene group or a polyethylene oxide group.

The compound represented by the general formula (1) is described in Scheme 1 or 2 described later, Document A (K. Muellen, Chem. Commun. 2008, 1548-1550.), Document B (K. Takimiya, Org. Lett. 2007, 9, 4499-4502.).
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. Optimum reaction conditions vary depending on the structure of the target compound, but can be set with reference to specific reaction conditions described in the above-mentioned documents.

<Intermediate compound>
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, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

<< Compound Represented by Formula (M1) >>
The present invention also relates to a compound represented by the following general formula (M1). The compound represented by the general formula (M1) is preferably an intermediate compound of the compound represented by the general formula (1). The compound represented by the above general formula (1) can be synthesized according to Scheme 1 described below via the compound represented by the general formula (M1) as a synthetic intermediate compound.

一般式（Ｍ１）中、
Ｘ¹およびＸ²はそれぞれ独立にＯ原子、Ｓ原子、Ｓｅ原子、−Ｎ（−Ｒ^N1）−、−Ｎ＝Ｃ−および−Ｃ（Ｒ^M3）＝Ｃ（Ｒ^M3）−のいずれか一つを表し、
Ｒ^N1は水素原子または置換基を表し、
Ｒ^M3はそれぞれ独立に水素原子または置換基を表し、
Ｒ^M1およびＲ^M2はそれぞれ独立に直鎖または分枝のアルキル基を表し、
ｒ１およびｒ２はそれぞれ独立に０〜２の整数を表し、
ｒ３およびｒ４はそれぞれ独立に０以上の整数を表し、かつ、ｒ３＋ｒ４が１以上であり、
Ｒはそれぞれ独立に置換または無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、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、シロキサン基、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トリアルキルシリル基を表す。 General formula (M1)

In general formula (M1),
X ¹ and X ² are each independently any one of O atom, S atom, Se atom, —N (—R ^N1 ) —, —N═C— and —C (R ^M3 ) ═C (R ^M3 ) —. Represents
R ^N1 represents a hydrogen atom or a substituent,
R ^M3 each independently represents a hydrogen atom or a substituent,
R ^M1 and R ^M2 each independently represent a linear or branched alkyl group,
r1 and r2 each independently represents an integer of 0 to 2,
r3 and r4 each independently represents an integer of 0 or more, and r3 + r4 is 1 or more,
R is independently a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, and a silicon atom number of 2 The above oligosiloxane group or a substituted or unsubstituted trialkylsilyl group is represented.

X ¹ and X ^{2 in} formula (M1) are each independently an O atom, an S atom, a Se atom, —N (—R ^N1 ) —, —N═C— and —C (R ^M3 ) ═C (R ^M3 ) ^-represents one of the following. X ¹ and X ² are each independently any one of O atom, S atom, —N (—R ^N1 ) —, —N═C— and —C (R ^M3 ) ═C (R ^M3 ) —. It is more preferable that —N═C— and —C (R ^M3 ) ═C (R ^M3 ) — are more preferable, and —C (R ^M3 ) = C (R ^M3 ) —. It is particularly preferred.
R ^N1 is a hydrogen atom or a substituent, examples of the substituent R ^N1 represents are the same as the examples of the substituents R ^N in the general formula (L-24) represents. R ^N1 is preferably a hydrogen atom.
R ^M3 independently represents a hydrogen atom or a substituent, and examples of the substituent represented by R ^M3 are the same as the examples of the substituent represented by R ′ in General Formula (L-13). R ^M3 is preferably a hydrogen atom.

R ^M1 and R ^M2 in the general formula (M1) each independently represent a linear or branched alkyl group. In addition, a methyl group is contained in a linear alkyl group. R ^M1 and R ^M2 are preferably linear alkyl groups.
The number of carbon atoms of the alkyl group represented by R ^M1 and R ^M2 is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

R1 and r2 in the general formula (M1) each independently represents an integer of 0 to 2, preferably 1 or 2, and more preferably 1.
R3 and r4 in the general formula (M1) each independently represent an integer of 0 or more, and r3 + r4 is 1 or more. r3 + r4 is preferably from 1 to 4, more preferably r3 + r4 is from 1 to 2, and particularly preferably r3 + r4 is 2.

  R in the general formula (M1) is each independently a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more, and siloxane Group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. The preferable range of R in the general formula (M1) is the same as the preferable range of R in the general formula (W).

<< Compounds Represented by General Formulas (M2) and (M3) >>
Next, the compounds represented by the following general formulas (M2) and (M3) will be described.
The compounds represented by the general formulas (M2) and (M3) are preferably intermediate compounds of the compound represented by the above general formula (1). The compound represented by the general formula (1) is obtained by using the compound represented by the general formula (M2) as a synthetic intermediate compound, and then further using the compound represented by the general formula (M3) as a synthetic intermediate compound. Then, it can be synthesized according to the following scheme 2.

一般式（Ｍ２）中、Ｙ¹〜Ｙ⁴はそれぞれ独立にハロゲン原子、アルコキシ基、アシルオキシ基またはスルホネート基である。
一般式（Ｍ２）中、＊および＊２はそれぞれＹ³およびＹ⁴の置換位置を表す。
一般式（Ｍ２）中、ｒ１およびｒ２はそれぞれ独立に０〜２の整数である。 General formula (M2)

In General Formula (M2), Y ^{1 to} Y ⁴ each independently represent a halogen atom, an alkoxy group, an acyloxy group, or a sulfonate group.
In general formula (M2), * and * 2 represent the substitution positions of Y ³ and Y ⁴ , respectively.
In general formula (M2), r1 and r2 are each independently an integer of 0-2.

一般式（Ｍ３）中、Ｙ³およびＹ⁴はそれぞれ独立にハロゲン原子、アルコキシ基、アシルオキシ基またはスルホネート基である。
一般式（Ｍ３）中、＊および＊２はそれぞれＹ³およびＹ⁴の置換位置を表す。
一般式（Ｍ３）中、ｒ１およびｒ２はそれぞれ独立に０〜２の整数である。 General formula (M3)

In formula (M3), Y ³ and Y ⁴ each independently represent a halogen atom, an alkoxy group, an acyloxy group, or a sulfonate group.
In general formula (M3), * and * 2 represent the substitution positions of Y ³ and Y ⁴ , respectively.
In general formula (M3), r1 and r2 are each independently an integer of 0-2.

In the general formulas (M2) and (M3), Y ^{1 to} Y ⁴ are each independently a halogen atom, an alkoxy group, an acyloxy group, or a sulfonate group.
Examples of the halogen atom represented by Y ^{1 to} Y ⁴ include an iodine atom, a bromine atom, and a chlorine atom.
Examples of the alkoxy group represented by Y ^{1 to} Y ⁴ include an alkoxy group having 1 to 4 carbon atoms.
Examples of the acyloxy group represented by Y ^{1 to} Y ⁴ include an acyloxy group having 1 to 4 carbon atoms.

  In the general formulas (M2) and (M3), r1 and r2 are each independently an integer of 0 to 2, preferably 1.

<Structure of organic thin film transistor>
The organic thin-film transistor of this invention has a semiconductor active layer containing the compound represented by General formula (1).
The organic thin film transistor of the present invention may further contain 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 a board | substrate, A well-known material can be used, For example, polyester films, such as a polyethylene naphthalate (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, and silicon is preferable.

<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 conductivity. Any known conductive material such as a 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 represented by the general formula (1), that is, the compound of the present invention.
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, and still more preferably. It is used within a range of 20 to 80% by mass, and particularly preferably within a 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 also relates to a compound represented by the general formula (1), that is, an organic semiconductor material for a non-light-emitting organic semiconductor device containing the compound of the present invention.

(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-transporting) organic semiconductor materials that conduct holes as carriers and n-type (electron-transporting) organic semiconductor materials 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 is preferably high, preferably 1 × 10 ⁻³ cm ² / Vs or more, more preferably 5 × 10 ⁻³ cm ² / Vs or more, and 1 × 10 ⁻² cm ^2. / Vs or higher is particularly preferable, 5 × 10 ⁻² cm ² / Vs or higher is more preferable, 1 × 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 also relates to a compound represented by the above general formula (1), that is, an organic semiconductor thin film for a non-light-emitting organic semiconductor device containing the compound of the present invention.
The aspect which the organic-semiconductor thin film for nonluminous organic-semiconductor devices of this invention contains the compound represented by General formula (1), ie, the compound of this invention, and does not contain a polymer binder is also preferable.
Moreover, the organic-semiconductor thin film for nonluminous organic-semiconductor devices of this invention may contain the compound represented by General formula (1), ie, the compound of this invention, and a polymer binder.

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 their co-polymers. Examples thereof include photoconductive polymers such as coalescence, polyvinyl carbazole, and polysilane, conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and semiconductor polymers.
The polymer binder may be used alone or in combination.
In addition, the organic semiconductor material and the polymer binder may be uniformly mixed, or part or all of them may be phase-separated, but from the viewpoint of charge mobility, A structure in which the binder is 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, 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.

[Coating solution for non-luminescent organic semiconductor devices]
The present invention also relates to a coating solution for a non-light-emitting organic semiconductor device containing the compound represented by the general formula (1), that is, the compound of the present invention.
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, hydrocarbon solvents, halogenated hydrocarbon solvents or ether solvents are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole are more preferable, and toluene, xylene, tetralin and anisole are particularly preferable. The concentration of the compound represented by the general formula (1) in the coating solution is preferably 0.1 to 80% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 10% by weight. By setting the ratio to%, a film having an arbitrary thickness can be formed.

  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 represented by the general formula (1) is excellent in that crystallization (aggregation) hardly occurs.

The coating solution for non-light-emitting organic semiconductor devices of the present invention is also preferably an embodiment containing the compound represented by the general formula (1), that is, the compound of the present invention and not containing a polymer binder.
Moreover, the coating solution for nonluminous organic semiconductor devices of this invention may contain the compound represented by General formula (1), ie, the compound of this invention, and a polymer binder. 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 301]
<Synthesis Example 1>
According to the specific synthesis procedure shown in the following scheme 1, compound 4 and intermediate compound (a), which are compounds represented by general formula (1), were synthesized.

Details of the synthesis of compound 4 will be shown below.
First, the synthesis method of the intermediate compound a is shown below.

Intermediate compound a is described in J. Org. Am. Chem. Soc. 4'-octyl-4-biphenylboronic acid (form B) synthesized by the method described in 2009, 131 (5), 1780-1786, and 1 synthesized by the method described in Macromolecules, 1999, 32, 3146-3149. , 4-Dibromo-2,5-bis (methylsulfinyl) benzene (Br) was synthesized by Suzuki coupling.
In a 25 ml Schlenk tube, stirring bar, Br isomer (1.2 g, 3.2 mmol), B isomer (2.1 g, 6.8 mmol), palladium acetate (36 mg, 0.16 mmol), SPhos (99 mg, 0.24 mmol), K ₃ PO ₄ (1.6 g, 12.8 mmol) was added and vacuum deaeration was performed, followed by replacement with nitrogen, degassed THF (6 ml) and water (2 ml) were added under a nitrogen flow, and the mixture was heated for 3 hours. Reflux was performed. Ethyl acetate and dilute hydrochloric acid were added to the reaction mixture for extraction, and ethyl acetate was distilled off under reduced pressure to obtain a crude product containing intermediate a as a solid. This crude product was purified by silica gel column chromatography using chloroform as a developing solvent, and the solid obtained by distilling off chloroform under reduced pressure was further ultrasonically washed with isopropyl alcohol to obtain the desired intermediate compound a In 1.0 g (43% yield).
The structure of intermediate compound a was identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ )
δ: 8.15 (2H, s), 7.72 (4H, d), 7.59 (4H, d), 7.52 (4H, d), 7.30 (4H, d), 2.67 (4H, t), 2.53 (6H, s), 1.66 (4H, m), 1.42-1.25 (20H, m), 0.89 (6H, t)

  Then, according to the above-mentioned scheme 1, compound 4 which is a compound represented by general formula (1) was synthesized from intermediate compound a.

Further, in a synthesis method similar to the synthesis method of each compound described above, according to the above-described scheme 1, the compounds 8, 22, 36, 63, 120, 148, 162 represented by the other general formula (1) 184 was synthesized.
The obtained compound represented by the general formula (1) was identified by elemental analysis, NMR and MASS spectrum.

The compounds used for the comparative elements 1, 3 and 4 were synthesized according to the method described in Japanese Patent No. 5160078.
The compound used in Comparative Element 2 was synthesized according to the method described in Document A (K. Muellen, Chem. Commun. 2008, 1548-1550.).
Comparative compound 2 used for comparative element 5 was synthesized according to the method described in EP2067882A1.

[Examples 1 to 9 and Comparative Examples 1 to 5]
<Device fabrication and evaluation>
All materials used for device fabrication were subjected to sublimation purification, and it was confirmed by high performance liquid chromatography (Tosoh TSKgel ODS-100Z) that the purity (absorption intensity area ratio at 254 nm) was 99.5% or more.

<Forming a semiconductor active layer (organic semiconductor layer) with a compound alone>
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. This coating solution is cast on an FET characteristic measurement substrate heated to 90 ° C. in a nitrogen atmosphere to form an organic semiconductor thin film for a non-light-emitting organic semiconductor device, and the organic thin film transistor of Example 2 for FET characteristic measurement An element was obtained. 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 gate / bottom contact structure (a schematic diagram of the structure is shown in FIG. 2) was used.

[Evaluation]
The FET characteristics of the organic thin film transistor elements of Examples 1 to 9 and Comparative Examples 1 to 5 were measured at normal pressure and nitrogen using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semiauto prober (Vector Semicon, AX-2000). The evaluation was performed in terms of carrier mobility, thermal stability, threshold shift, and coating film quality under an atmosphere.
The obtained results are shown in Table 1 below.
(A) Carrier mobility A voltage of −80 V is applied between the source electrode and the drain electrode of each organic thin film transistor element (FET element), the gate voltage is changed in the range of 20 V to −100 V, and the drain current I _d is expressed below. The carrier mobility μ was calculated using the formula.
I _d = (w / 2L) μC _i (V _g −V _th ) ²
In the formula, 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, and V _th is the threshold voltage.
A: It was 1.0 cm ² / Vs or more.
B: 0.5 cm ² / Vs or more and less than 1.0 cm ² / Vs.
C: It was 0.1 cm ² / Vs or more and less than 0.5 cm ² / Vs.
D: 0.05cm ² / Vs or more, was less than 0.1 cm ² / Vs.
E: It was less than 0.05 cm ² / Vs.

(B) Thermal stability (heat resistance)
Each organic thin film transistor element was heated on a hot plate at 150 ° C. for 30 minutes to evaluate the decrease in mobility.
A: The decrease in mobility was less than 10%.
B: The decrease in mobility was 10% or more and less than 15%.
C: The decrease in mobility was 15% or more and less than 20%.
D: The decrease in mobility was 20% or more and less than 30%.
E: The decrease in mobility was 30% or more.

(C) Threshold shift (change in threshold voltage 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), the gate voltage is repeated 100 times in the range of +20 V to −100 V, the same measurement as in (a) is performed, and the driving is repeated. The difference between the previous threshold voltage V and the threshold voltage V after repeated driving (| after V and before V) 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 | ≦ 1V
B: 1V <| V after -V before | ≦ 5V
C: 5 V <| V after −V before | ≦ 10 V
D: 10V <| V after −V before | ≦ 15V
E: | After V-Before V |> 15V

(D) Quality of coating film The quality of the coating film was evaluated by the following method.
About the semiconductor active layer of the organic thin-film transistor element of Example 2, the domain size was measured in the range of 1 mm square using a polarizing microscope, and the average domain size was calculated. The obtained results were evaluated in the following three stages. In practice, there is no problem even with D evaluation, but A, B or C evaluation is preferable, A or B evaluation is more preferable, and A evaluation is particularly preferable.
A: The average domain size exceeds 10 micrometers.
B: The average domain size exceeds 5 micrometers and is 10 micrometers or less.
C: The average domain size exceeds 1 micrometer and is 5 micrometers or less.
D: The average domain size exceeds 0.5 micrometers and is 1 micrometer or less.
E: The average domain size is 0.5 micrometers or less.

From the above results, it was found that 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 comparative elements 1 to 5 have low carrier mobility.
In addition, the organic thin-film transistor element using the compound of the present invention has high thermal stability, small change in threshold voltage after repeated driving, and good coating film quality.

<(E) Crystal polymorph>
About the compound 4 which is a compound represented by General formula (1), the crystal structure was examined by the single-crystal X-ray crystal structure analysis method. As a result, it was found that the desired crystal system, specifically herringbone type, is stable.
On the other hand, the crystal structure of Comparative Compound 2, which is an unsubstituted product used in Comparative Example 2, was examined by single crystal X-ray crystal structure analysis. As a result, it was found that a polycrystal system exists and is unstable, and the tilt (longitudinal shift of molecules) is large, which is disadvantageous for charge transport. The results are shown in Reference A (K. Muellen, Chem. Commun. 2008, 1548-1550.) And Reference B (K. Takimiya, Org. Lett. 2007, 9, 4499-4502.) As a reference for the synthesis method. It agrees well with the results described in.
In addition, the crystal structure of Comparative Compound 3 which is a disubstituted product of the —C ₄ H ₉ group used in Comparative Example 3 was examined by single crystal X-ray crystal structure analysis. As a result, it was found that an undesirable polycrystal system, specifically, a -stack type, is stable, and a tilt (longitudinal shift of molecules) is large, which is disadvantageous for charge transport. This result also agrees well with the contents described in the above-mentioned document A (K. Muellen, Chem. Commun. 2008, 1548-1550.) As a reference for the synthesis method.

[Examples 101 to 109 and Comparative Examples 101 to 105]
<Forming a semiconductor active layer (organic semiconductor layer) using a compound together with a binder>
The same compounds of the present invention or comparative compounds (1 mg each) as in Examples 1 to 9 and Comparative Examples 1 to 5, PαMS (poly (α-methylstyrene, Mw = 300,000), manufactured by Aldrich) 1 mg, toluene (1 mL) ), And heated to 100 ° C., except that the coating solutions were used in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 5 in Examples 101 to 109 and Comparative Examples 101 to 105 for measuring FET characteristics. Organic thin-film transistor elements were produced and evaluated in the same manner as in Examples 1-9 and Comparative Examples 1-5.
As a result, it turned out that it is the same tendency as Examples 1-9 and Comparative Examples 1-5.

[Examples 201 to 209 and Comparative Examples 201 to 205]
<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.
The same compounds of the present invention or comparative compounds (1 mg each) and toluene (1 mL) as in Examples 1 to 9 and Comparative Examples 1 to 5 were mixed and heated to 100 ° C., and applied to a non-luminescent organic semiconductor device It was set as the solution. 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 Examples 201 to 209 of the bottom gate / top contact structure having a gate width W = 5 mm and a gate length L = 80 μm and comparison Organic thin film transistor elements of Examples 201 to 205 were obtained (a schematic diagram of the structure is shown in FIG. 1).
The FET characteristics of the organic thin film transistor elements of Examples 201-221 and Comparative Examples 201-206 were measured at normal pressure and nitrogen using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (Vector Semicon, AX-2000). Under the atmosphere, the same evaluations as in Examples 1 to 9 and Comparative Examples 1 to 5 were performed.
As a result, it turned out that it is the same tendency as Examples 1-9 and Comparative Examples 1-5.

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 (26)

An organic thin film transistor comprising a compound represented by the following general formula (1) in a semiconductor active layer;
General formula (1)

In general formula (1),
Each X independently represents an O atom, an S atom or a Se atom;
Two or more R ^{1 to} R ¹⁰ are not bonded to each other to form a ring;
R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a halogen atom;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and At least one of R ⁷ is a substituent represented by formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
Formula (L-1), it represents a (L-2) Contact and (L-13) ~ (L -24) R 'in each independently represents a hydrogen atom or a substituent,
R ′ in the general formula (L-6) represents a linear alkyl group,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.   2. The organic thin film transistor according to claim 1, wherein in the general formula (1), X is an S atom. In the general formula (1), L is
L ⁰ which is a divalent linking group directly bonded to the mother nucleus and represented by any one of the general formulas (L-2) to (L-25);
The divalent linking group represented by any one of the general formulas (L-1) to (L-25) or any one of the general formulas (L-1) to (L-25). L ¹ which is a divalent linking group in which two or more divalent linking groups are bonded;
The organic thin-film transistor of Claim 1 or 2 consisting of. The organic thin-film transistor according to claim 3, wherein L ⁰ is represented by any one of the general formulas (L-2) and (L-13) to (L-24). The L ⁰ is a divalent linking group represented by any one of the general formulas (L-2), (L-13), (L-17), and (L-18). Organic thin film transistor. L ⁰ is a divalent linking group represented by any one of the general formulas (L-2), (L-13), (L-17) and (L-18),
L ¹ is a divalent linking group represented by any one of the general formulas (L-1) to (L-4), or any one of the general formulas (L-1) to (L-4). The organic thin film transistor according to any one of claims 3 to 5, which is a divalent linking group in which two or more divalent linking groups are bonded.   In the general formula (1), R is a substituted or unsubstituted alkyl group, a siloxane group, or an oligosiloxane group having 2 to 5 silicon atoms, The organic according to any one of claims 1 to 6. Thin film transistor. In the general formula (1), at least one of R ² and R ⁶ is a substituent represented by the general formula (W), and
R ^1, an organic thin film transistor according to any one of claims 1 to 7 R ³ to R ⁵ and R ⁷ to R ¹⁰ are all hydrogen atoms. The organic thin film transistor according to claim 8, wherein R ² and R ⁶ are the same group. A compound represented by the following general formula (1).

In general formula (1),
Each X independently represents an O atom, an S atom or a Se atom;
Two or more R ^{1 to} R ¹⁰ are not bonded to each other to form a ring;
R ¹ , R ⁴ , R ⁵ and R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a halogen atom;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a halogen atom or a substituent represented by the following general formula (W), and R ² , R ³ , R ⁶ and At least one of R ⁷ is a substituent represented by formula (W);
-LR General Formula (W)
In general formula (W),
L is represented by any one of the following general formulas (L-1) to (L-25) or a divalent linking group represented by any one of the following general formulas (L-1) to (L-25). Represents a divalent linking group in which two or more divalent linking groups are bonded, provided that the parent nucleus formed by condensation of three benzene rings to which R ^{1 to} R ¹⁰ are bonded and two hetero five-membered rings has a general formula The divalent linking group represented by (L-1) is not directly linked,
R is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligo having 2 or more silicon atoms Represents a siloxane group or a substituted or unsubstituted trialkylsilyl group;

In general formulas (L-1) to (L-25),
The wavy line part in the divalent linking group represented by the general formula (L-1) is the bonding position of the divalent linking group represented by another general formula (L-1) to (L-25) with *. In the divalent linking groups represented by the general formulas (L-2) to (L-25), the wavy line part represents the bonding position with the mother nucleus or another general formula (L-1) to (L-25). ) Represents the bonding position with * of the divalent linking group represented by
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 in the general formula (L-21) represents an integer of 0 or 1, m in the general formula (L-22) represents 6.
Formula (L-1), it represents a (L-2) Contact and (L-13) ~ (L -24) R 'in each independently represents a hydrogen atom or a substituent,
R ′ in the general formula (L-6) represents a linear alkyl group,
R ^N represents a hydrogen atom or a substituent,
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.   The compound according to claim 10, wherein in the general formula (1), X is an S atom. In the general formula (1), L is
L ⁰ which is a divalent linking group directly bonded to the mother nucleus and represented by any one of the general formulas (L-2) to (L-25);
The divalent linking group represented by any one of the general formulas (L-1) to (L-25) or any one of the general formulas (L-1) to (L-25). L ¹ which is a divalent linking group in which two or more divalent linking groups are bonded;
The compound according to claim 10 or 11, which comprises: The compound according to claim 12, wherein L ⁰ is represented by any one of the general formulas (L-2) and (L-13) to (L-24). The L ⁰ is a divalent linking group represented by any one of the general formulas (L-2), (L-13), (L-17) and (L-18). Compound. L ⁰ is a divalent linking group represented by any one of the general formulas (L-2), (L-13), (L-17) and (L-18),
L ¹ is a divalent linking group represented by any one of the general formulas (L-1) to (L-4), or any one of the general formulas (L-1) to (L-4). The compound according to any one of claims 12 to 14, which is a divalent linking group in which two or more divalent linking groups are bonded.   The compound according to any one of claims 10 to 15, wherein, in the general formula (1), R is a substituted or unsubstituted alkyl group, a siloxane group, or an oligosiloxane group having 2 to 5 silicon atoms. . In the general formula (1), at least one of R ² and R ⁶ is a substituent represented by the general formula (W), and
R ^1, R ³ ~R ⁵ and a compound according to any one of claims 10 to 16 R ⁷ to R ¹⁰ are all hydrogen atoms. The compound according to claim 17, wherein R ² and R ⁶ are the same group.   The organic-semiconductor material for nonluminous organic-semiconductor devices containing the compound as described in any one of Claims 10-18.   The material for organic thin-film transistors containing the compound as described in any one of Claims 10-18.   The coating solution for nonluminous organic-semiconductor devices containing the compound as described in any one of Claims 10-18.   The coating solution for nonluminous organic-semiconductor devices containing the compound and polymer binder as described in any one of Claims 10-18.   The organic-semiconductor thin film for nonluminous organic-semiconductor devices containing the compound as described in any one of Claims 10-18.   The organic-semiconductor thin film for nonluminous organic-semiconductor devices containing the compound and polymer binder as described in any one of Claims 10-18.   The organic-semiconductor thin film for nonluminous organic-semiconductor devices of Claim 23 or 24 produced by the solution apply | coating method. Represented by the following general formula (M1) ,
Intermediate compound der Ru compound of a compound according to any one of claims 10 to 18;
General formula (M1)

In general formula (M1),
X ¹ and X ² are each independently any one of O atom, S atom, Se atom, —N (—R ^N1 ) —, —N═C— and —C (R ^M3 ) ═C (R ^M3 ) —. Represents
R ^N1 represents a hydrogen atom or a substituent,
R ^M3 each independently represents a hydrogen atom or a substituent,
R ^M1 and R ^M2 each independently represent a linear or branched alkyl group,
r1 and r2 each independently represents an integer of 0 to 2,
r3 and r4 each independently represents an integer of 0 or more, and r3 + r4 is 1 or more,
R is independently a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, and a silicon atom number of 2 The above oligosiloxane group or a substituted or unsubstituted trialkylsilyl group is represented.

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