JP2013181071A - Polymer compound, composition including the same, ink composition, thin film and element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound capable of obtaining high charge mobility; a thin film and an ink composition including the polymer compound; an organic thin film transistor equipped with the thin film; and an image sensor equipped with the organic thin film transistor.SOLUTION: This polymer compound has structural units represented by formulae (1-1), (1-2) and (1-3) and a structural unit comprising a bivalent heterocyclic group or the like. in formulae, Erepresents -S- or the like.

Description

  The present invention relates to a polymer compound, a composition containing the same, an ink composition, a thin film and an element (an organic thin film transistor and a photoelectric conversion element), and an image sensor including the element.

  Organic thin film transistors are low in cost and have characteristics such as flexibility and bendability, and thus can be suitably used for applications such as electronic paper and flexible displays, and have attracted attention in recent years.

  An organic thin film transistor includes a layer having a charge transporting property (herein, charge means holes and electrons; the same shall apply hereinafter) composed of an organic substance. As the organic substance, an organic semiconductor material is mainly used. Used. As such an organic semiconductor material, a high molecular compound capable of forming a layer (that is, an organic semiconductor layer and generally also referred to as an active layer) by a coating method in a state dissolved in a solvent has been studied. A polymer compound having a thiophene skeleton has been proposed (Non-patent Document 1).

Organic Electronics 6 (2005) p. 142-146

  The characteristics of the organic thin film transistor mainly depend on the charge mobility in the organic semiconductor layer, and the higher the charge mobility, the better the field effect mobility of the organic thin film transistor and the better the characteristics. In recent years, applications of organic thin film transistors have been diversified, and higher field effect mobility is required than ever before. However, when the conventional polymer compound as described above is used for the organic semiconductor layer, it has been difficult to obtain sufficient high mobility as required in recent years.

  Therefore, the present invention has been made in view of such circumstances, and an object of the present invention is to provide a polymer compound that can obtain high charge mobility when used in an organic semiconductor layer. Another object of the present invention is to provide a composition containing the polymer compound, an ink composition, a thin film and an element (an organic thin film transistor, a photoelectric conversion element), and an image sensor including the element.

〔式中、
Ｅ^１は、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＳＯ−又は−Ｓｅ−を表す。複数存在するＥ^１は、同一でも異なっていてもよい。
Ｒ^１は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、フッ素原子、アシル基、アシルオキシ基、アミド基、カルボキシル基、ニトロ基又はシアノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^１は、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環状構造を形成していてもよい。〕
で表される構造単位と、
式：

〔式中、
Ａｒは、アリーレン基、２価の複素環基、−ＣＲ^ｇ＝ＣＲ^ｇ−又は−Ｃ≡Ｃ−を表し、これらの基は置換基を有していてもよい。Ｒ^ｇは、水素原子、アルキル基、アリール基、１価の芳香族複素環基又はシアノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^ｇは、同一でも異なっていてもよい。〕
で表される構造単位と、を有する高分子化合物を提供する。 To achieve the above objective, the present invention provides a compound of the formula:

[Where,
E ¹ represents —O—, —S—, —SO ₂ —, —SO— or —Se—. A plurality of E ¹ may be the same or different.
R ¹ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, fluorine atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. A plurality of R ¹ may be the same or different, and may be bonded to each other to form a cyclic structure together with the carbon atom to which each is bonded. ]
A structural unit represented by
formula:

[Where,
Ar represents an arylene group, a divalent heterocyclic group, —CR ^g ═CR ^g — or —C≡C—, and these groups optionally have a substituent. R ^g represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a cyano group, and these groups may have a substituent. A plurality of R ^g may be the same or different. ]
And a polymer unit having a structural unit represented by:

  The polymer compound of the present invention has a structural unit represented by the formula (1-1), (1-2) or (1-3), so that it has a high charge when used in an organic semiconductor layer. The mobility of can be demonstrated. Although the cause is not necessarily clear, a plurality of aromatic rings are condensed, and the structure of the condensed structure is highly symmetric, so that the main chains of the polymer compound are easy to overlap (easy to pack). It is thought that. In addition, since the polymer compound of the present invention has the specific structural unit described above, it tends to be highly soluble in a solvent, and an organic semiconductor layer is formed by a coating method as a state of an ink composition described later. It also tends to be relatively easy.

In the structural units represented by formulas (1-1) to (1-3), E ¹ is —O— (oxygen atom), —S— (sulfur atom), or —Se— (selenium atom). -S- or -O- is more preferable, and -S- is particularly preferable. By using a polymer compound having such a structure for the organic semiconductor layer, higher charge mobility can be obtained.

In the structural units represented by formulas (1-1) to (1-3), R ¹ is a hydrogen atom, an aryl group, a monovalent aromatic heterocyclic group, an alkyl group, a halogen atom, an acyl group, or acyloxy. A group is preferred, and an alkyl group is more preferred. This is because it becomes easy to synthesize a monomer as a raw material of the polymer compound of the present invention.

  The polymer compound of the present invention has a structural unit represented by the formula (2) in addition to the structural unit represented by the formula (1-1), (1-2) or (1-3). Thus, when used in the organic semiconductor layer, high charge mobility can be exhibited.

  Ar in the structural unit represented by the formula (2) is preferably a divalent heterocyclic group having a 5-membered ring (2 to 12 carbon atoms) or a monocyclic arylene group having 6 to 18 carbon atoms. . The divalent heterocyclic group may be monocyclic or polycyclic (that is, a divalent heterocyclic group in which a plurality of monocycles are directly bonded). By so doing, higher charge mobility can be obtained when used in an organic semiconductor layer.

  In addition, since higher charge mobility can be obtained when used in the organic semiconductor layer, Ar in the structural unit represented by Formula (2) is represented by Formula (3-1) to Formula (3-14). A group represented by formula (3-1), formula (3-2), or formula (3-6) to (3-13), and more preferably a group represented by formula (3- 6) is more preferable.

〔式中、
Ｅ^２は、−Ｏ−、−Ｓ−又は−Ｓｅ−を表す。Ｅ^２が複数存在する場合、それらは同一でも異なっていてもよい。
Ｒ^２は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アシル基、アシルオキシ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^２が複数存在する場合、それらは同一でも異なっていてもよい。
ｎは、０〜１の整数を表す。
Ｘは、式（Ｚ−１）〜（Ｚ−７）で表される２価の基を表す。
Ｙは、−Ｃ（Ｒ^３）_２−、−Ｎ（Ｒ^３）−、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。Ｙが複数存在する場合、それらは同一でも異なっていてもよい。Ｒ^３は、水素原子、アルキル基、アリール基又は１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^３が複数存在する場合、それらは同一でも異なっていてもよい。］

［式中、
Ｒ^４は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、アミド基、カルボキシル基、ニトロ基又はシアノ基を表し、これらの基は置換基を有していてもよい。Ｒ^４が複数存在する場合、それらは同一でも異なっていてもよい。
Ｅ^３は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）−、−ＳＯ_２−、−Ｓｉ（Ｒ^５）（Ｒ^５）−、−Ｎ（Ｒ^５）−、−Ｂ（Ｒ^５）−、−Ｐ（Ｒ^５）−又は−Ｐ（＝Ｏ）（Ｒ^５）−を表す。Ｒ^５は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、アミド基、カルボキシル基、ニトロ基又はシアノ基を表し、これらの基は置換基を有していてもよい。〕

[Where,
E ² represents —O—, —S— or —Se—. When ^two or more E2 exists, they may be the same or different.
R ² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an acyl group, an acyloxy group, or a halogen atom, and these groups have a substituent. Also good. When a plurality of R ² are present, they may be the same or different.
n represents an integer of 0 to 1.
X represents a divalent group represented by formulas (Z-1) to (Z-7).
Y represents —C (R ³ ) ₂ —, —N (R ³ ) —, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When a plurality of Y are present, they may be the same or different. R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. When a plurality of R ³ are present, they may be the same or different. ]

[Where:
R ⁴ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. When a plurality of R ⁴ are present, they may be the same or different.
E ³ represents —O—, —S—, —C (═O) —, —S (═O) —, —SO ₂ —, —Si (R ⁵ ) (R ⁵ ) —, —N (R ^{5 ) -, - B (R 5} ) -, - P (R 5) - or ^{-P (= O) (R 5} ) - represents a. R ⁵ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. ]

  The present invention also provides a composition comprising the polymer compound of the present invention, an ink composition comprising the polymer compound of the present invention and a solvent, and an ink composition comprising the composition of the present invention and a solvent. . Such an ink composition is effective for forming an organic semiconductor layer or the like by a coating method because the polymer compound is uniformly dispersed or dissolved in a solvent.

  The present invention also provides a thin film containing the polymer compound of the present invention. Since the thin film of the present invention contains the polymer compound of the present invention, it can exhibit high charge mobility when used in an organic semiconductor layer.

  The present invention also includes a first electrode and a second electrode, an active layer between the first electrode and the second electrode, and the polymer compound of the present invention in the active layer. An element comprising: The element is preferably an organic thin film transistor, a photoelectric conversion element, or an image sensor. In particular, since the organic thin film transistor of the present invention has high charge mobility in the active layer, high field effect mobility can be obtained.

  The present invention further provides an image sensor comprising the element of the present invention. This image sensor can exhibit excellent characteristics because the charge mobility of the active layer is high.

  When the polymer compound of the present invention is used in an organic semiconductor layer, high charge mobility can be obtained, and such an organic semiconductor layer can be easily formed. According to the present invention, a composition containing such a polymer compound, an ink composition advantageous for the formation of a thin film, and a high charge suitably obtained by such an ink composition and used in an organic semiconductor layer A thin film having the mobility can be provided.

  The present invention also provides an organic transistor that includes the organic semiconductor layer containing the polymer compound of the present invention and can obtain excellent field effect mobility, and a planar light source and a display device including the organic transistor. be able to. Specifically, the organic transistor of the present invention includes a driving circuit for a liquid crystal display and electronic paper, a switch circuit for a curved or flat light source for illumination, a segment type display element, and a dot matrix flat panel. It is also useful for driving circuits such as displays.

  Furthermore, the polymer compound of the present invention can also be used as a material for an organic semiconductor layer of a photoelectric conversion element, and a photoelectric conversion element including such an organic semiconductor layer is useful as a solar cell module or an image sensor.

1 is a schematic cross-sectional view of an organic transistor according to a first embodiment. It is a schematic cross section of the organic transistor which concerns on 2nd Embodiment. It is a schematic cross section of the organic transistor which concerns on 3rd Embodiment. It is a schematic cross section of the organic transistor which concerns on 4th Embodiment. It is a schematic cross section of the organic transistor which concerns on 5th Embodiment. It is a schematic cross section of the organic transistor which concerns on 6th Embodiment. It is a schematic cross section of the organic transistor which concerns on 7th Embodiment. It is a schematic cross section of the photoelectric conversion element which concerns on embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  In the present specification, the “structural unit” means a unit structure present in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure present in two or more in the polymer compound).

<Polymer compound>
(First structural unit)
The polymer compound of the present invention includes structural units represented by the above formulas (1-1) to (1-3) (hereinafter sometimes referred to as first structural units). The first structural unit may be contained alone or in combination of two or more in the polymer compound.

  Suitable groups and atoms that these formulas (1-1) to (1-3) may have are as follows.

In formulas (1-1) to (1-3), E ¹ represents —O—, —S—, —SO ₂ —, —SO— or —Se—. A plurality of E ¹ may be the same or different.

E ¹ is preferably -S- or -O-, and more preferably -S-, because a higher charge mobility can be obtained by using the polymer compound of the present invention for the organic semiconductor layer.

In formulas (1-1) to (1-3), R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an aryloxy group, an arylthio group, or an alkenyl. Represents a group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. A plurality of R ¹ may be the same or different, and may be bonded to each other to form a cyclic structure together with the carbon atom to which each is bonded.

Here, the alkyl group may be linear or branched, and may be a cycloalkyl group. The number of carbon atoms (not including the number of carbon atoms of the substituent described below) of the linear alkyl group and the branched alkyl group is usually 1 to 60, and preferably 1 to 20. The number of carbon atoms of the cycloalkyl group (not including the number of carbon atoms of the substituent described later) is usually 3 to 60, and preferably 3 to 20. Among the alkyl groups, a linear alkyl group or a branched alkyl group is preferable, and a linear alkyl group is more preferable.
Specific examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group, Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, and 3,7-dimethyloctyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.
The alkyl group may have a substituent, and examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The alkoxy group may be linear or branched, and may be a cycloalkoxy group. The straight-chain alkoxy group and the branched alkoxy group usually have 1 to 20 carbon atoms (not including the carbon atoms of the substituents described later). The number of carbon atoms of the cycloalkoxy group (not including the number of carbon atoms of the substituents described later) is usually 3-20.
Specific examples of the alkoxy group include n-butyloxy group, n-hexyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, n-dodecyloxy group, and the like. A straight-chain alkyloxy group such as -hexyloxy group, n-dodecyloxy group, n-hexadecyloxy is preferable.
The alkoxy group may have a substituent, and examples of the substituent that the alkoxy group may have include an aryl group and a halogen atom.

The alkylthio group may be linear or branched, and may be a cycloalkylthio group. The number of carbon atoms of the straight chain alkylthio group and the branched alkylthio group (not including the number of carbon atoms of the substituent described later) is usually 1-20. The number of carbon atoms of the cycloalkylthio group (not including the number of carbon atoms of the substituents described later) is usually 3-20.
Specific examples of the alkylthio group include n-butylthio group, n-hexylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group, n-dodecylthio group, n-hexadecylthio group and the like, and n-butylthio group , N-hexylthio group, n-dodecylthio group, n-hexadecylthio and other linear alkylthio groups are preferable.
The alkylthio group may have a substituent, and examples of the substituent that the alkylthio group may have include an aryl group and a halogen atom.

An aryl group is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon which may have a substituent, a group having a benzene ring, a condensed group It includes a group in which two or more selected from a group having a ring, an independent benzene ring and a condensed ring are directly bonded. The number of carbon atoms of the aryl group (not including the number of carbon atoms of the substituents described below) is usually 6 to 60, and preferably 6 to 20.
Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group. 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 4-phenylphenyl group and the like.
The aryl group may have a substituent, and examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, an alkylthio group, a monovalent aromatic heterocyclic group, and a halogen atom. It is done. Examples of the aryl group having a substituent include 4-hexylphenyl group, 3,5-dimethoxyphenyl group, and pentafluorophenyl group. When the aryl group has a substituent, the substituent is preferably an alkyl group.

The monovalent aromatic heterocyclic group is the remainder obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the aromatic ring from the aromatic compound which may have a substituent. It is an atomic group and includes a group in which two or more selected from a group having a condensed ring, an independent aromatic heterocyclic ring and a condensed ring are directly bonded. The number of carbon atoms of the monovalent aromatic heterocyclic group (not including the number of carbon atoms of the substituent described later) is usually 2 to 60, and preferably 3 to 20.
Specific examples of the monovalent aromatic heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2 -Thiazolyl group, 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like.
The monovalent aromatic heterocyclic group may have a substituent, and examples of the substituent that the monovalent aromatic heterocyclic group may have include an alkyl group, an alkoxy group, an alkylthio group, and an aryl group. And halogen atoms. Examples of the monovalent aromatic heterocyclic group having a substituent include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group. When the monovalent aromatic heterocyclic group has a substituent, the substituent is preferably an alkyl group.

The aryloxy group may have a substituent, and the number of carbon atoms of the aryloxy group excluding the substituent is usually 6-20.
Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

The arylthio group may have a substituent, and the number of carbon atoms of the arylthio group excluding the substituent is usually 6 to 20.
Specific examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

The alkenyl group may have a substituent, and the number of carbon atoms of the alkenyl group excluding the substituent is usually 2-20.
Specific examples of the alkenyl group include a vinyl group and a 1-octenyl group.

The alkynyl group may have a substituent, and the alkynyl group excluding the substituent usually has 2 to 20 carbon atoms.
Specific examples of the alkynyl group include ethynyl group, 1-octynyl group, 2-phenylethynyl group, trimethylsilylethynyl group and the like.

The amino group may have a substituent, and the number of carbon atoms of the amino group that may have a substituent is usually 1 to 40.
Specific examples of the amino group which may have a substituent include a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a dicyclohexylamino group, a pyrrolidyl group, a piperidyl group, a phenylamino group, a diphenylamino group, Examples include 1-naphthylamino group, 2-naphthylamino group, pyridylamino group and the like.

The silyl group may have a substituent, and the number of carbon atoms of the silyl group that may have a substituent is usually 1 to 60.
Specific examples of the silyl group which may have a substituent include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a tribenzylsilyl group. , Diphenylmethylsilyl group, dimethylphenylsilyl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The acyl group may have a substituent, and the number of carbon atoms of the acyl group that may have a substituent is usually 1-20.
Specific examples of the acyl group that may have a substituent include an acetyl group, a propionyl group, a butyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The acyloxy group may have a substituent, and the number of carbon atoms of the acyloxy group that may have a substituent is usually 1 to 20.
Specific examples of the acyloxy group which may have a substituent include an acetoxy group, a propionyloxy group, a butyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The amide group may have a substituent.
Specific examples of the amide group which may have a substituent include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, And dibenzamide group.

R ¹ is a hydrogen atom, an alkyl group, an alkylthio group, an acyl group, an acyloxy group, a halogen atom, an aryl group, a monovalent fragrance from the viewpoint of ease of synthesis of the monomer that is a raw material for the polymer compound of the present invention. A group heterocyclic group is more preferable, and a hydrogen atom, an alkyl group, an acyl group, an acyloxy group, and a halogen atom are more preferable.

By making the main chains of the polymer compound easily overlap each other (by facilitating packing), when used in the organic semiconductor layer, higher charge mobility can be exhibited, so that the formulas (1-1) to (1 R- ^{1 of the} structural unit represented by -3) is selected so that each structural unit is point-symmetric (that is, the corresponding R ¹ when the structural units are rotated by 180 ° are the same group). It is preferred that

  As the first structural unit, structural units represented by formula (1-1) to formula (1-12) are preferable, and formula (1-1) to formula (1-5), formula (1-11) and The structural unit represented by Formula (1-12) is more preferable, and the structural unit represented by Formula (1-1), Formula (1-5), and Formula (1-11) is more preferable.

(Second structural unit)
The polymer compound of the present invention includes a structural unit represented by the formula (2) (hereinafter sometimes referred to as “second structural unit”). The second structural unit may be contained alone or in combination of two or more in the polymer compound.

In formula (2), Ar represents an arylene group, a divalent heterocyclic group, a group represented by —CR ^g ═CR ^g — or —C≡C—, which may have a substituent. Good. R ^g represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a cyano group, and these groups may have a substituent. A plurality of R ^g may be the same or different.

An arylene group is a remaining atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon which may have a substituent, a group having a benzene ring, a condensed group It includes a group in which two or more selected from a group having a ring, an independent benzene ring and a condensed ring are directly bonded. The number of carbon atoms of the arylene group (not including the number of carbon atoms of the substituents described later) is usually 6 to 60, and preferably 6 to 20.
Examples of the substituent that the arylene group has include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, and a halogen atom. Definition of alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group and halogen atom, specific examples are alkyl group, alkoxy group, alkylthio group, aryl group, monovalent represented by R ¹ The definition and specific examples of the aromatic heterocyclic group and halogen atom are the same.
Specific examples of the arylene group include a phenylene group, naphthalenediyl group, anthracenediyl group, phenanthenediyl group, tetracenediyl group, pyrenediyl group, pentacenediyl group, perylenediyl group, and fluorenediyl group.

  As the arylene group, groups represented by formulas (9a) to (9f) are preferable, and groups represented by formulas (9a) and (9f) are more preferable.

In formulas (9a) to (9f), R ⁹³ , R ⁹⁴ and R ⁹⁶ are each independently a hydrogen atom or a monovalent group, and R ⁹⁵ is a monovalent group. U is an integer of 0 or more. Examples of the monovalent group include those similar to R ¹ . In the structure represented by the above formula, when a plurality of R ⁹³ , R ⁹⁴ or R ⁹⁵ are included, the groups represented by the same reference numerals may be the same or different. In addition, when two groups out of R ⁹³ , R ⁹⁴ , R ⁹⁵ and R ⁹⁶ or groups represented by the same symbol are bonded to the same carbon atom or an adjacent carbon atom, this relationship is established. Certain groups may form a cyclic structure together with the carbon atoms to which they are bonded. The cyclic structure formed in this case may be a single ring or a condensed ring, and may be a hydrocarbon ring or a heterocyclic ring. Moreover, these rings may have a substituent. As the cyclic structure formed, a monocyclic hydrocarbon ring or a monocyclic heterocycle containing an oxygen atom or a sulfur atom as a hetero atom is preferable.

The divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting an aromatic ring from an optionally substituted heterocyclic compound, and forming a condensed ring. And a group in which two or more selected from an independent heterocyclic ring and a condensed ring are directly bonded. The number of carbon atoms of the divalent heterocyclic group (not including the number of carbon atoms of the substituent described later) is usually 2 to 60, and preferably 3 to 20.
Examples of the substituent that the divalent heterocyclic group has include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, and a halogen atom. Definition of alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group and halogen atom, specific examples are alkyl group, alkoxy group, alkylthio group, aryl group, monovalent represented by R ¹ The definition and specific examples of the aromatic heterocyclic group and halogen atom are the same.
Specific examples of the divalent heterocyclic group include oxadiazole diyl group, thiadiazole diyl group, oxazole diyl group, thiazole diyl group, thiophene diyl group, bithiophene diyl group, terthiophene diyl group, quaterthiophene diyl group, Pyrrole diyl group, furandyl group, selenophene diyl group, pyridine diyl group, pyrazine diyl group, pyrimidine diyl group, triazine diyl group, benzothiophene diyl group, benzopyrrole diyl group, benzofuran diyl group, quinoline diyl group, isoquinoline diyl group, thienothiophene Examples thereof include a diyl group, a benzodithiophene diyl group, a benzothiadiazole diyl group, and a quinoxaline diyl group.

  Examples of the divalent heterocyclic group include groups represented by formulas (10a) to (10h).

［式中、Ｒ^ｆは、水素原子又は１価の基を表す。複数存在するＲ^ｆは、同一でも異なっていてもよい。］

[Wherein, R ^f represents a hydrogen atom or a monovalent group. A plurality of R ^f may be the same or different. ]

^Examples of the monovalent group represented by R ^f include the same groups as R ¹ .

Preferably, when Ar forms a polymer compound together with the structural units represented by formulas (1-1) to (1-3), in the skeleton that becomes the main chain of the polymer compound, And a group selected to form a π-conjugated system in which multiple bonds and single bonds are alternately repeated. Examples of such a π-conjugated system include a structure shown within a dotted line in the formula (E1).

  Ar is preferably an arylene group or a divalent heterocyclic group, more preferably a divalent heterocyclic group, from the viewpoint of further improving the charge mobility when a polymer compound is used in the organic semiconductor layer. A valent aromatic heterocyclic group is more preferable, and structural units represented by formula (3-1) to formula (3-14) are particularly preferable. Among these, the structural unit represented by Formula (3-1), Formula (3-2), and Formula (3-6) to (3-13) is preferable, and the structural unit represented by Formula (3-6) Is more preferable.

［式中、
Ｅ^２は、−Ｏ−、−Ｓ−又は−Ｓｅ−を表す。Ｅ^２が複数存在する場合、それらは同一でも異なっていてもよい。
Ｒ^２は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アシル基、アシルオキシ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。
ｎは０〜１の整数を表す。
Ｘは、式（Ｚ−１）〜（Ｚ−７）で表される２価の基を表す。
Ｙは、−Ｃ（Ｒ^３）_２−、−Ｎ（Ｒ^３）−、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^３は、水素原子、アルキル基、アリール基又は１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^３が複数存在する場合、それらは同一でも異なっていてもよい。］

[Where:
E ² represents —O—, —S— or —Se—. When ^two or more E2 exists, they may be the same or different.
R ² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an acyl group, an acyloxy group, or a halogen atom, and these groups have a substituent. Also good.
n represents an integer of 0 to 1.
X represents a divalent group represented by formulas (Z-1) to (Z-7).
Y represents —C (R ³ ) ₂ —, —N (R ³ ) —, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. When a plurality of R ³ are present, they may be the same or different. ]

［式中、
Ｒ^４は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、アミド基、カルボキシル基、ニトロ基又はシアノ基を表し、これらの基は置換基を有していてもよい。Ｒ^４が複数存在する場合、それらは同一でも異なっていてもよい。
Ｅ^３は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）−、−ＳＯ_２−、−Ｓｉ（Ｒ^５）（Ｒ^５）−、−Ｎ（Ｒ^５）−、−Ｂ（Ｒ^５）−、−Ｐ（Ｒ^５）−又は−Ｐ（＝Ｏ）（Ｒ^５）−を表す。Ｒ^５は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、１価の芳香族複素環基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、アミド基、カルボキシル基、ニトロ基又はシアノ基を表し、これらの基は置換基を有していてもよい。〕

[Where:
R ⁴ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. When a plurality of R ⁴ are present, they may be the same or different.
E ³ represents —O—, —S—, —C (═O) —, —S (═O) —, —SO ₂ —, —Si (R ⁵ ) (R ⁵ ) —, —N (R ^{5 ) -, - B (R 5} ) -, - P (R 5) - or ^{-P (= O) (R 5} ) - represents a. R ⁵ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. ]

R is represented by ^2, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an acyl group, an acyloxy group, the definition of a halogen atom, specific examples are represented by the aforementioned R ¹ The definition of alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, acyl group, acyloxy group, halogen atom, and specific examples are the same.

Definition of alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ³ , specific examples are the alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ¹ described above. Definitions and specific examples are the same.

An alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, represented by R ⁴ and R ⁵ Definitions of halogen atom, acyl group, acyloxy group, amide group, carboxyl group, specific examples are the alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group represented by R ¹ described above, Definitions and specific examples of aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group, and carboxyl group are the same as in the specific examples.

  The definition and specific examples of the arylene group and divalent heterocyclic group represented by Y are the same as the definition and specific examples of the arylene group and divalent heterocyclic group represented by Ar described above.

From the viewpoint of further improving the charge mobility when the polymer compound of the present invention is used in the organic semiconductor layer, in the structural units represented by the formulas (3-1) to (3-14), R ² Is preferably a hydrogen atom or an alkyl group.

From the viewpoint of further improving the charge mobility when the polymer compound of the present invention is used in the organic semiconductor layer, in the structural units represented by the formulas (3-1) to (3-14), R ³ Is preferably a hydrogen atom or an alkyl group.

From the viewpoint of further improving the charge mobility when the polymer compound of the present invention is used in the organic semiconductor layer, the structural unit represented by the formula (3-6) is represented by the formula (Z- In 1) to formula (Z-6), R ⁴ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a monovalent aromatic heterocyclic group, and more preferably a hydrogen atom or an alkyl group.

From the viewpoint of further improving the charge mobility when the polymer compound of the present invention is used in the organic semiconductor layer, R ⁵ is preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and an aryl group Or an alkyl group is more preferable.

  Examples of the structural unit including two or more second structural units include structural units represented by formula (4-1) to formula (4-9). Among these structural units, from the viewpoint of further improving the charge mobility when the polymer compound is used in the organic semiconductor layer, the formula (4-1), the formula (4-5), the formula (4-7) Or a polymer compound containing a structural unit represented by formula (4-9).

(Other structural units)
The polymer compound of the present invention may contain a structural unit other than the first structural unit and the second structural unit (hereinafter sometimes referred to as “other structural unit”). Other structural units may be contained alone or in combination of two or more in the polymer compound.

Examples of the other structural unit include a group represented by the formula —CR ^h ₂ —, a group represented by the formula —C (═O) —, and a group represented by the formula —C (═O) O—. Can be mentioned. R ^h represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a halogen atom, and these groups optionally have a substituent.
Definitions and specific examples of the alkyl group, aryl group, monovalent aromatic heterocyclic group and halogen atom represented by R ^h are the alkyl group, aryl group, monovalent aromatic represented by the aforementioned R ^1. The definition and specific examples of the heterocyclic group and the halogen atom are the same.

(Polymer compound)
The polymer compound of the present invention is preferably a conjugated polymer compound from the viewpoint of further improving the charge mobility when the polymer compound is used in the organic semiconductor layer.

  From the viewpoint of further improving the charge mobility when the polymer compound of the present invention is used in the organic semiconductor layer, the first structural unit and the second structural unit are compared with the total of the structural units of the polymer compound. The total is preferably 50 mol% or more, and more preferably 70 mol% or more.

  Specific examples of the polymer compound of the present invention include polymer compounds represented by formula (5-1) to formula (5-22).

  In the polymer compound of the present invention, if a group showing activity in the polymerization reaction remains at the end of the molecular chain, the charge mobility may be reduced when the polymer compound is used in the organic semiconductor layer. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent aromatic heterocyclic group.

  The polymer compound of the present invention may be any type of copolymer, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer.

The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present invention is usually 1 × 10 ³ to 1 × 10 ⁸ . From the viewpoint of forming a good thin film during thin film production, the number average molecular weight is preferably 1.5 × 10 ³ or more. From the viewpoints of solubility and film formability, the number average molecular weight is preferably 1 × 10 ⁶ or less.

<Method for producing polymer compound>
Next, a method for producing the polymer compound of the present invention will be described.
The polymer compound of the present invention may be produced by any method. For example, the polymer compound represented by the formula: X ¹¹ -A ¹¹ -X ¹² and the formula: X ¹³ -A ¹² -X ¹⁴ The compound can be dissolved in an organic solvent as necessary, a base is added as necessary, and the compound can be synthesized by a known polymerization method such as aryl coupling using an appropriate catalyst.

In the above formula, A ¹¹ represents a structural unit represented by the formulas (1-1), (1-2) and (1-3), and A ¹² represents a structure represented by the formula (2). Indicates the unit. In the above formula, X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a polymerization reactive group.

Examples of the polymerization reactive group include a halogen atom, a boric acid ester residue, a boric acid residue (—B (OH) ₂ ), a trialkylstannyl group, and the like.

  Examples of the halogen atom that is the polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the boric acid ester residue that is the polymerization reactive group include groups represented by the following formulae.

  Examples of the trialkylstannyl group that is the polymerization reactive group include a trimethylstannyl group and a tributylstannyl group.

  Examples of the polymerization method such as aryl coupling include polymerization by Suzuki coupling reaction (Chemical Review, 1995, 95, 2457-2483), polymerization by Stille coupling reaction (European Polymer Journal, 2005). Year 41, 2923-2933).

The polymerization reactive group is a halogen atom, a boric acid ester residue, a boric acid residue, or the like when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used. From the viewpoint of simplicity of the polymerization reaction, a bromine atom, an iodine atom, and a boric acid ester residue are preferable.
When the polymer compound of the present invention is polymerized by a Suzuki coupling reaction, the ratio of the total moles of bromine and iodine atoms and the total moles of boric acid ester residues, which are the polymerization reactive groups, is 0.00. It is preferable to set it as 7-1.3, and it is more preferable to set it as 0.8-1.2.

The polymerization reactive group is a halogen atom, a trialkylstannyl group or the like when a palladium catalyst such as Stille coupling reaction is used. From the viewpoint of simplicity of the polymerization reaction, a bromine atom, an iodine atom, and a trialkylstannyl group are preferable.
When the polymer compound of the present invention is polymerized by Stille coupling reaction, the ratio of the total number of moles of bromine atom and iodine atom and the total number of moles of trialkylstannyl group, which are the polymerization reactive groups, is 0.00. It is preferable to set it as 7-1.3, and it is more preferable to set it as 0.8-1.2.

  Examples of the organic solvent used for the polymerization include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, and dioxane. These organic solvents may be used alone or in combination of two or more.

  Examples of the base used for the polymerization include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, and tetrabutyl bromide. Organic bases such as ammonium, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide are listed.

  As the catalyst used for the polymerization, transition metal complexes such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphinepalladium and the like, and if necessary, It is a catalyst comprising a ligand such as triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine. As these catalysts, those synthesized in advance may be used, or those prepared in the reaction system may be used as they are. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.

  The polymerization reaction temperature is preferably 0 to 200 ° C, more preferably 0 to 150 ° C, and further preferably 0 to 120 ° C.

  The reaction time of the polymerization is usually 1 hour or longer, preferably 2 to 500 hours.

  The post-treatment of the polymerization can be performed by a known method, for example, a method of adding a reaction solution obtained by the polymerization to a lower alcohol such as methanol and filtering and drying the precipitate. .

  When the purity of the polymer compound of the present invention is low, it may be purified by a method such as recrystallization, continuous extraction with a Soxhlet extractor, or column chromatography.

<Composition>
The polymer compound of the present invention can also be used as a light emitting material or a charge transport material as a composition containing other components. Examples of such a composition include those containing the polymer compound of the present invention and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material. As the hole transport material and the electron transport material, the same materials as those exemplified in the description of the thin film described later can be applied.

  The content ratio of the polymer compound of the present invention to at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material may be determined according to the use of the composition, but the entire composition The polymer compound of the present invention is preferably 20 to 99 parts by weight and more preferably 40 to 95 parts by weight with respect to 100 parts by weight.

The number average molecular weight (Mn) in terms of polystyrene by GPC of the composition containing the polymer compound of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁸ , and 5 × 10 ³ to 1 × 10 ⁶ . More preferably. In addition, the weight average molecular weight (Mw) in terms of polystyrene is preferably 1 × 10 ³ to 1 × 10 ⁸ , good film formability is obtained, and high mobility is obtained when used for device fabrication. Since it is obtained, it is more preferable in it being 1 * 10 < ⁴ > -5 * 10 < ⁶ >. Here, the average molecular weight of the composition containing the polymer compound of the present invention refers to a value obtained by analyzing this composition by GPC.

  The composition of the present invention can also be a solution containing a solvent such as an organic solvent (hereinafter referred to as “ink composition”), as will be described later. Hereinafter, a suitable form of the ink composition will be described.

<Ink composition>
The ink composition containing the polymer compound of the present invention contains the polymer compound of the present invention and a solvent. Further, the ink composition may contain the above-described composition of the present invention and a solvent. This ink composition is mainly in the form of a solution and is useful for forming a thin film by a printing method or the like. Components other than the polymer compound and solvent of the present invention contained in the ink composition include hole transport materials, electron transport materials, light emitting materials, stabilizers, thickeners (high molecular weight compounds for increasing viscosity and poor solvents ), Low molecular weight compounds for lowering viscosity, surfactants (for lowering surface tension), antioxidants, and the like.

  The ink composition may contain only one kind of the polymer compound of the present invention, or may contain two or more kinds in combination.

  The ratio of the polymer compound of the present invention in the ink composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total amount of the ink composition. 1 to 20 parts by weight is more preferable. By including the polymer compound at such a ratio, the coating method can be performed satisfactorily, and a thin film or the like that can exhibit the excellent characteristics of the polymer compound of the present invention can be easily formed.

  The viscosity of the ink composition may be adjusted depending on the type of printing method to be used. In order to prevent this, it is preferable that it is the range of 1-20 mPa * s in 25 degreeC.

  The solvent used in the ink composition is preferably one that can dissolve or uniformly disperse the solid components in the ink composition. Solvents include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, ether solvents such as tetrahydrofuran, dioxane, anisole, toluene, xylene, etc. Aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, Ketone solvents such as cyclohexanone, benzophenone and acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and its derivatives such as monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol And alcohol solvents such as cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more.

  Among these, since the solubility, viscosity characteristics, and uniformity during film formation of the polymer compound are improved, aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketones System solvents are preferred. Specifically, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, Tetralin, anisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin, methyl benzoate, cyclohexanone, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone, acetophenone, and benzophenone are preferred.

  As a solvent, since film formability and device characteristics are improved, it is preferable to use a combination of two or more types, more preferably a combination of two to three types, and particularly preferably a combination of two types. .

  When combining two types of solvents, one of the solvents may be in a solid state at 25 ° C. In order to obtain good film formability, the boiling point of at least one kind of solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. Moreover, since favorable viscosity is obtained, it is preferable that both of the two types of solvents are those capable of dissolving 1% by weight or more of the polymer compound of the present invention at 60 ° C., and particularly among the two types of solvents. It is preferable that the one kind of solvent dissolves 1% by weight or more of the polymer compound of the present invention at 25 ° C.

  Furthermore, when two or more types of solvents are combined, good viscosity and film formability can be obtained. Therefore, among the combined solvents, the solvent having the highest boiling point should be 40 to 90% by weight of the total solvent weight. Is preferable, it is more preferable that it is 50 to 90 weight%, and it is more preferable that it is 65 to 85 weight%.

  When the ink composition contains a high molecular weight compound as a thickener, this compound is soluble in the same solvent as the polymer compound of the present invention and does not inhibit charge transport when a device is formed. It is preferable. Examples of such thickeners include high molecular weight polystyrene and high molecular weight polymethyl methacrylate. These high molecular weight compounds preferably have a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more.

  Moreover, as a thickener, the poor solvent with respect to solid content in the component of an ink composition can also be used. The viscosity can be increased moderately by adding a small amount of such a poor solvent. When a poor solvent is added for this purpose, the type and amount of the solvent may be selected as long as the solid content in the ink composition does not precipitate. Considering the stability during storage of the ink composition, the amount of the poor solvent is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the entire ink composition. .

  The antioxidant is for improving the storage stability of the ink composition. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit charge transport when the element is formed, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants. Is done.

  Further, the ink composition may contain water, metal, or a salt thereof in a range of 1 to 1000 ppm on a weight basis. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. In addition, the ink composition may contain silicon, phosphorus, fluorine, chlorine, bromine and the like in a range of 1 to 1000 ppm on a weight basis.

<Thin film>
The thin film containing the polymer compound of the present invention can be applied as an organic semiconductor thin film, for example.

When the thin film is an organic semiconductor thin film, the larger one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / Vs or more, and more preferably 10 ⁻³ cm ² / Vs or more. Preferably, it is more preferably 10 ⁻¹ cm ² / Vs or more. An organic transistor as described later can be formed using such an organic semiconductor thin film.

  In the case of an organic semiconductor thin film, the film thickness is preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 3 nm to 500 nm, and particularly preferably 5 nm to 200 nm.

  The organic semiconductor thin film may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds in combination.

  As the hole transport material, known materials can be used, such as pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, side chains or main chains. Examples thereof include polysiloxane derivatives having an aromatic amine, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

As the electron transport material, known materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodi. methane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, such as C ₆₀ Examples include fullerenes and derivatives thereof.

Moreover, the thin film of this embodiment may contain the charge generation material in order to generate an electric charge with the light absorbed by the said thin film depending on a use. As the charge generation material, known materials can be used, azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone series compounds and their derivatives, squarylium compounds and their derivatives, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes and derivatives thereof such as C ₆₀ is illustrated.

  Furthermore, the thin film of this embodiment may contain other materials necessary for expressing various functions. Examples of such materials include sensitizers for sensitizing the function of generating charges by absorbed light, stabilizers for increasing stability, and UV absorbers for absorbing UV light. The

  Further, since the mechanical properties of the thin film are improved, a polymer compound other than the polymer compound of the present invention may be included as a polymer binder. As the polymer binder, those not extremely disturbing the electron transport property or hole transport property are preferable, and those having no strong absorption against visible light are preferably used.

  Examples of such a polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. Examples include derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  Examples of the method for producing a thin film according to the present embodiment include a method of using the polymer compound of the present invention as it is, or a method of forming a film using the above-described composition (for example, an ink composition). For example, it is a method by film formation using a solution in which an electron transport material, a hole transport material, a polymer binder or the like is added to the polymer compound of the present invention as necessary. In addition, when the polymer compound of the present invention is in an oligomer state, a thin film can be formed by vacuum deposition.

  Thin film formation methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, and flexographic printing. Method, offset printing method, ink jet printing method, capillary coating method, nozzle coating method, dispenser printing method, etc., screen printing method, flexographic printing method, offset printing method, ink jet printing method, dispenser printing method are preferable. A printing method, an inkjet printing method, and a dispenser printing method are more preferable.

  When forming a film using a solution (for example, an ink composition) or the like, as a solvent to be used, in addition to the polymer compound of the present invention, components to be mixed (electron transport material, hole transport material, polymer binder, etc.) are dissolved. It is preferable to use what is to be used.

  As the solvent, the solvent used in the ink composition described above can be applied, and unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc. Solvent, halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene And halogenated unsaturated hydrocarbon solvents such as tetrahydrofuran, and ether solvents such as tetrahydrofuran and tetrahydropyran. Although the polymer compound of the present invention depends on its structure and molecular weight, it can often be dissolved in these solvents in an amount of 0.1% by weight or more.

  When manufacturing the organic-semiconductor thin film containing the high molecular compound of this invention, the process of orientating a high molecular compound may be included in the manufacturing process. In the organic semiconductor thin film in which the polymer compound is oriented by this process, the main chain molecules or the side chain molecules are arranged in one direction, and therefore the charge mobility is further increased.

  As a method of aligning the polymer compound, a method known as a liquid crystal alignment method can be used. Of these, the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.

<Organic semiconductor element>
Since the high molecular compound of the present invention has high charge mobility when used in an organic semiconductor layer, it is used as an organic semiconductor material, for example, in an organic layer of an element (for example, an organic semiconductor element). it can. Examples of the organic semiconductor element include an organic transistor, a photoelectric conversion element, and an organic electroluminescence element. The polymer compound of the present invention is particularly useful as a charge transport material for organic transistors.

<Organic transistor>
The organic transistor has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path The thing which has is mentioned. Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.

  A field effect organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path. The organic transistor having an active layer and an insulating layer disposed between the gate electrode. In particular, an organic transistor in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.

  The electrostatic induction organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path And the gate electrode is provided in the active layer. In particular, an organic transistor in which a source electrode, a drain electrode, and the gate electrode are provided in contact with the active layer is preferable.

  The gate electrode has only to have a structure in which a current path flowing from the source electrode to the drain electrode can be formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode, for example, a comb electrode.

  FIG. 1 is a schematic cross-sectional view showing an example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 at a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the active layer 2 formed on the insulating layer 3, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 on the region between the source electrode 5 and the drain electrode 6. The gate electrode 4 is provided.

  FIG. 2 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5, and a predetermined electrode The drain electrode 6 formed on the active layer 2 with an interval, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer on the region between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to cover 3.

  FIG. 3 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 120 shown in FIG. 3 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to cover a part of the region of the insulating layer 3 formed, and a part of the source electrode 5 and the drain electrode 6 And an active layer 2 formed on the insulating layer 3 so as to cover the surface.

  FIG. 4 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 130 shown in FIG. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The source electrode 5 formed on the insulating layer 3 so as to cover a part of the region of the insulating layer 3 formed on the active layer 3 and the active formed on the insulating layer 3 so as to cover a part of the source electrode 5 A layer 2 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to cover a part of the active layer 2 are provided.

  FIG. 5 is a schematic cross-sectional view showing another example of the organic transistor (static induction organic transistor) of the present invention. The organic transistor 140 shown in FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality of active transistors 2 with a predetermined interval on the active layer 2. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a is the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

  FIG. 6 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 150 shown in FIG. 6 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and an insulating layer 3 formed on the active layer 2 so as to cover a part of the drain electrode 6, a region of the insulating layer 3 in which the source electrode 5 is formed in the lower portion, and a drain electrode 6 are formed in the lower portion. And a gate electrode 4 formed on the insulating layer 3 so as to partially cover each region of the insulating layer 3.

  FIG. 7 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 160 shown in FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. An active layer 2 formed so as to cover the region of the insulating layer 3 formed on the active layer 2, a source electrode 5 formed on the active layer 2 so as to cover a part of the active layer 2, and one of the active layers 2 A source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval are provided so as to cover the portion.

  FIG. 8 is a schematic cross-sectional view showing an example of the photoelectric conversion element of the present invention. A photoelectric conversion element 300 shown in FIG. 8 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the active layer 2 formed on the first electrode 7a, and the active layer 2. And a second electrode 7b.

  In the organic transistor of the present invention described above, the active layer 2 and / or the active layer 2a is formed of a thin film containing the polymer compound of the present invention, and a current path (channel) between the source electrode 5 and the drain electrode 6 is formed. ) The gate electrode 4 controls the amount of current passing through the current path (channel) by applying a voltage.

  Such a field effect organic transistor can be produced by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic transistor can be produced by a known method such as the method described in Japanese Patent Application Laid-Open No. 2004-006476.

  The material of the substrate 1 may be any material that does not hinder the characteristics of the organic transistor. As the substrate, a glass substrate, a flexible film substrate, or a plastic substrate can be used.

The material of the insulating layer 3 may be any material having high electrical insulation, and SiO _x , SiN _x , Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, and the like can be used. From the viewpoint of lowering the voltage, it is preferable to use a material having a high dielectric constant.

  When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification.

  In the case of an organic field effect transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Therefore, the state of this interface greatly affects the mobility of the transistor. Therefore, as a method for improving the interface state and improving the properties, control of the interface with a silane coupling agent has been proposed (for example, Surface Chemistry, 2007, Vol. 28, No. 5, p. 242-248). ).

Examples of silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxy. Examples thereof include silylamine compounds such as silanes and hexamethyldisilazane (HMDS). In addition, the surface of the insulating layer may be subjected to ozone UV treatment or O ₂ plasma treatment before treatment with the surface treatment agent.

  By such treatment, the surface energy of the silicon oxide film or the like used as the insulating layer can be controlled. Further, the surface treatment improves the orientation of the film constituting the active layer on the insulating layer, and high charge transportability (mobility) can be obtained.

  The gate electrode 4 includes metals such as gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low-resistance polysilicon, low-resistance amorphous silicon, tin oxide, indium oxide, indium / tin oxide. A material such as (ITO) can be used. These materials may be used alone or in combination of two or more. Note that a highly doped silicon substrate can be used as the gate electrode 4. A highly doped silicon substrate has not only the performance as a gate electrode but also the performance as a substrate. When the gate electrode 4 having such a performance as a substrate is used, the substrate 1 may be omitted in the organic transistor in which the substrate 1 and the gate electrode 4 are in contact with each other.

  The source electrode 5 and the drain electrode 6 are preferably made of a low-resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.

  In the organic transistor, a layer composed of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2. Examples of such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.

  In addition, after manufacturing the organic transistor as described above, it is preferable to form a protective film on the organic transistor in order to protect the element. Thereby, an organic transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic transistor can be suppressed. Further, when a display device to be driven is formed on an organic transistor, the protective film can also reduce the influence on the organic transistor in the formation process.

Examples of the method for forming the protective film include a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON _x film, or the like. In order to effectively block the atmosphere, it is preferable to form a protective film after the organic transistor is manufactured without exposing the organic transistor to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  An organic field effect transistor, which is a kind of organic transistor configured as described above, can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display. And since the organic field effect transistor of embodiment mentioned above is equipped with the active compound which contains the high molecular compound of this invention as an active layer, and the charge transport property improved by it, the field effect mobility is provided. Is expensive. Therefore, it is useful for manufacturing a display having a sufficient response speed.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(NMR analysis)
The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).

(Molecular weight analysis)
The number average molecular weight and the weight average molecular weight of the polymer compound were determined using gel permeation chromatography (GPC, manufactured by Waters, trade name: Alliance GPC 2000). The polymer compound to be measured was dissolved in orthodichlorobenzene and injected into GPC. Orthodichlorobenzene was used for the mobile phase of GPC. As the column, TSKgel GMHHR-H (S) HT (two linked, manufactured by Tosoh Corporation) was used. A UV detector was used as the detector.

窒素雰囲気下、シクロヘキサン溶液中、化合物１に４，４’−ジ−ｔｅｒｔ−ブチル−２，２’−ジピリジルと（１，５−シクロオクタジエン）（メトキシ）イリジウム（Ｉ）ダイマーの触媒存在下において、２当量のビス（ピナコラト）ジボロンを反応させることで化合物２を合成する。 Synthesis example 1
(Synthesis of Compound 2)

In the presence of a catalyst of 4,4′-di-tert-butyl-2,2′-dipyridyl and (1,5-cyclooctadiene) (methoxy) iridium (I) dimer in compound 1 in a cyclohexane solution under a nitrogen atmosphere In this method, compound 2 is synthesized by reacting 2 equivalents of bis (pinacolato) diboron.

アルゴン雰囲気下で、化合物２及び化合物３をトルエンに溶解させる。相間移動触媒としてメチルトリアルキルアンモニウムクロリド（シグマアルドリッチ社製、商品名Ａｌｉｑｕａｔ３３６（登録商標））をトルエンに対して加えた後、溶液にアルゴンをバブリングして脱気を行う。その後、化合物２に対して酢酸パラジウム及びトリス（ｏ−メトキシフェニル）ホスフィンを加え、さらに飽和炭酸ナトリウム水溶液をトルエンに対して加え、還流下で反応を行う。反応後、ジエチルジチオカルバミン酸ナトリウムの水溶液をトルエンの体積の半分の量加え、還流下で攪拌を行う。水層を除去後、水で２回、酢酸水溶液で２回、さらに水で２回洗浄し、メタノールに注いで固体を析出させる。固体をろ過後、乾燥し、得られた固体をｏ−ジクロロベンゼンに溶解させて溶液を調製し、アルミナ／シリカゲルカラムを通し、得られた溶液をメタノールに注いで固体を析出させ、固体をろ過後、乾燥して高分子化合物４を得る。 Example 1
(Synthesis of polymer compound 4)

Under an argon atmosphere, Compound 2 and Compound 3 are dissolved in toluene. Methyltrialkylammonium chloride (manufactured by Sigma-Aldrich, trade name Aliquat 336 (registered trademark)) as a phase transfer catalyst is added to toluene, and degassing is performed by bubbling argon through the solution. Thereafter, palladium acetate and tris (o-methoxyphenyl) phosphine are added to Compound 2, and a saturated aqueous sodium carbonate solution is further added to toluene, followed by reaction under reflux. After the reaction, an aqueous solution of sodium diethyldithiocarbamate is added in half the volume of toluene, and the mixture is stirred under reflux. After removing the aqueous layer, it is washed twice with water, twice with an aqueous acetic acid solution and twice with water, and poured into methanol to precipitate a solid. The solid is filtered and dried, and the resulting solid is dissolved in o-dichlorobenzene to prepare a solution. The solution is passed through an alumina / silica gel column, and the resulting solution is poured into methanol to precipitate the solid, and the solid is filtered. Thereafter, the polymer compound 4 is obtained by drying.

Example 2
(Production and Evaluation of Organic Transistor 1)
Using the solution containing the polymer compound 4, the organic transistor 1 having the structure shown in FIG.
The surface of the heavily doped n-type silicon substrate to be the gate electrode is thermally oxidized to form a silicon oxide film (hereinafter referred to as “thermal oxide film”). The thermal oxide film functions as an insulating layer. Next, a source electrode and a drain electrode are formed on the thermal oxide film by a photolithography process. The source electrode and the drain electrode have a chromium (Cr) layer and a gold (Au) layer from the thermal oxide film side, and have a channel length of 20 μm and a channel width of 2 mm. The substrate on which the thermal oxide film, the source electrode and the drain electrode obtained in this way are formed is ultrasonically cleaned with acetone, and UV ozone treatment is performed with an ozone UV cleaner. Thereafter, the surface of the thermal oxide film is modified with β-phenethyltrichlorosilane. Next, an orthodichlorobenzene solution of the polymer compound 4 is spin-coated on the surface-treated thermal oxide film, source electrode, and drain electrode to form an organic semiconductor layer (active layer). Thereafter, the organic semiconductor layer is heated to manufacture the organic transistor 1.

  The transistor characteristics are measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 1 obtained.

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Active layer, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode, 6 ... Drain electrode, 7a ... 1st electrode, 7b ... 2nd electrode, 100 ... Organic transistor according to the first embodiment, 110 ... Organic transistor according to the second embodiment, 120 ... Organic transistor according to the third embodiment, 130 ... Organic transistor according to the fourth embodiment, 140 ... According to the fifth embodiment Organic transistor, 150... Organic transistor according to the sixth embodiment, 160... Organic transistor according to the seventh embodiment, 300.

Claims (12)

formula:

[Where,
E ¹ represents —O—, —S—, —SO ₂ —, —SO— or —Se—. A plurality of E ¹ may be the same or different.
R ¹ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. A plurality of R ¹ may be the same or different, and may be bonded to each other to form a cyclic structure together with the carbon atom to which each is bonded. ]
A structural unit represented by
formula:

[Where,
AR represents an arylene group, a divalent heterocyclic group, —CR ^g ═CR ^g — or —C≡C—, and these groups optionally have a substituent. R ^g represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a cyano group, and these groups may have a substituent. A plurality of R ^g may be the same or different. ]
And a structural unit represented by the formula: The polymer compound according to claim 1, wherein E ¹ is —S— or —O—. The polymer compound according to claim ¹ , wherein R ¹ is a hydrogen atom, an aryl group, a monovalent aromatic heterocyclic group, an alkyl group, a halogen atom, an acyl group, or an acyloxy group. The polymer compound according to any one of claims 1 to 3, wherein Ar is any one of groups represented by formulas (3-1) to (3-14).

[Where:
E ² represents —O—, —S— or —Se—. When ^two or more E2 exists, they may be the same or different.
R ² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent aromatic heterocyclic group, an acyl group, an acyloxy group, or a halogen atom, and these groups have a substituent. Also good. When a plurality of R ² are present, they may be the same or different.
n represents an integer of 0 to 1.
X represents a divalent group represented by formulas (Z-1) to (Z-7).
Y represents —C (R ³ ) ₂ —, —N (R ³ ) —, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When a plurality of Y are present, they may be the same or different. R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. When a plurality of R ³ are present, they may be the same or different. ]

[Where:
R ⁴ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. When a plurality of R ⁴ are present, they may be the same or different.
E ³ represents —O—, —S—, —C (═O) —, —S (═O) —, —SO ₂ —, —Si (R ⁵ ) (R ⁵ ) —, —N (R ^{5 ) -, - B (R 5} ) -, - P (R 5) - or ^{-P (= O) (R 5} ) - represents a. R ⁵ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent aromatic heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, It represents an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group or a cyano group, and these groups may have a substituent. ]   The composition containing the high molecular compound as described in any one of Claims 1-4.   An ink composition comprising the polymer compound according to any one of claims 1 to 4 and a solvent.   An ink composition comprising the composition according to claim 5 and a solvent.   The thin film containing the high molecular compound as described in any one of Claims 1-4.   It has a 1st electrode and a 2nd electrode, it has an active layer between this 1st electrode and this 2nd electrode, and this active layer is any one of Claims 1-4. A device containing a polymer compound.   The device according to claim 9, which is an organic thin film transistor.   The device according to claim 9, which is a photoelectric conversion device.   An image sensor comprising the element according to claim 9.

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