JP2014237733A - Polymer compound and organic semiconductor element prepared using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound useful for the production of an organic transistor having excellent field-effect mobility.SOLUTION: A polymer compound comprises a structural unit represented by formula (1-1) and/or a structural unit represented by formula (1-2), where Zand Zindependently represent a group represented by formula (Z).

Description

  The present invention relates to a polymer compound and an organic semiconductor element using the same.

  Since organic transistors using organic semiconductor materials are expected to be lighter, have lower manufacturing costs and can be manufactured at lower temperatures than conventional transistors using inorganic semiconductor materials, they are actively researched and developed. Has been done.

  The field effect mobility, which is one of the performances of organic transistors, largely depends on the field effect mobility of the organic semiconductor material used for the active layer. ing.

  As an organic semiconductor material used for an organic transistor, for example, a polymer compound represented by the following formula has been proposed (Patent Document 1).

International Publication No. 2012/146504

  However, an organic transistor using the above polymer compound for an active layer does not necessarily have sufficient field effect mobility.

  Then, an object of this invention is to provide a high molecular compound useful for manufacture of the organic transistor excellent in a field effect mobility.

  The present invention provides the following polymer compound, a compound as a raw material of the polymer compound, and an organic semiconductor material, an organic semiconductor element, and an organic transistor containing the polymer compound.

〔式中、
ＡおよびＣは、それぞれ独立に、３価の芳香族炭化水素基または３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。
Ｂは、４価の基を表し、この基は置換基を有していてもよい。
Ｚ^１およびＺ^２は、それぞれ独立に、式（Ｚ）で表される基を表す。〕

〔式中、
Ｒ^１は、水素原子、アルキル基、アリール基または１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。〕
［２］ 前記Ａおよび前記Ｃが、３価の複素環基である、［１］に記載の高分子化合物。
［３］ 前記Ｂが、４価の芳香族炭化水素基または４価の複素環基である、［１］または［２］に記載の高分子化合物。
［４］ 前記式（１−１）で表される構造単位が、式（２−１）で表される構造単位であり、前記式（１−２）で表される構造単位が、式（２−２）で表される構造単位である、［１］〜［３］のいずれか一項に記載の高分子化合物。

〔式中、
Ｚ^１およびＺ^２は、前記と同じ意味を表す。
Ｘ^１およびＸ^２は、それぞれ独立に、酸素原子、硫黄原子またはセレン原子を表す。
Ｙ^１およびＹ^２は、それぞれ独立に、窒素原子または−ＣＨ＝で表される基を表す。
Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立に、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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。〕
［５］ 前記高分子化合物が、共役高分子化合物である、［１］〜［４］のいずれか一項に記載の高分子化合物。
［６］ 式（３−１）で表される化合物または式（３−２）で表される化合物。

〔式中、
Ｗ^１およびＷ^２は、それぞれ独立に、水素原子またはハロゲン原子を表す。
Ｘ^３およびＸ^４は、それぞれ独立に、酸素原子、硫黄原子またはセレン原子を表す。
Ｙ^３およびＹ^４は、それぞれ独立に、窒素原子または−ＣＨ＝で表される基を表す。
Ｚ^３およびＺ^４は、それぞれ独立に、式（Ｚ’）で表される基を表す。
Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。〕

〔式中、
Ｒ^１０は、水素原子、アルキル基、アリール基または１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。〕
［７］ ［１］〜［５］のいずれか一項に記載の高分子化合物を含有する、有機半導体材料。
［８］ ［７］に記載の有機半導体材料を含有する有機層を備える、有機半導体素子。
［９］ ソース電極、ドレイン電極、ゲート電極および活性層を有し、該活性層に［７］に記載の有機半導体材料を含有する、有機トランジスタ。 [1] A polymer compound comprising a structural unit represented by formula (1-1) and / or a structural unit represented by formula (1-2).

[Where,
A and C each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups optionally have a substituent.
B represents a tetravalent group, and this group may have a substituent.
Z ¹ and Z ² each independently represent a group represented by the formula (Z). ]

[Where,
R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]
[2] The polymer compound according to [1], wherein A and C are a trivalent heterocyclic group.
[3] The polymer compound according to [1] or [2], wherein B is a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group.
[4] The structural unit represented by the formula (1-1) is a structural unit represented by the formula (2-1), and the structural unit represented by the formula (1-2) The polymer compound according to any one of [1] to [3], which is a structural unit represented by 2-2).

[Where,
Z ¹ and Z ² represent the same meaning as described above.
X ¹ and X ² each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ and Y ² each independently represent a nitrogen atom or a group represented by —CH═.
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]
[5] The polymer compound according to any one of [1] to [4], wherein the polymer compound is a conjugated polymer compound.
[6] A compound represented by formula (3-1) or a compound represented by formula (3-2).

[Where,
W ¹ and W ² each independently represents a hydrogen atom or a halogen atom.
X ³ and X ⁴ each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ³ and Y ⁴ each independently represent a nitrogen atom or a group represented by —CH═.
Z ³ and Z ⁴ each independently represent a group represented by the formula (Z ′).
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]

[Where,
R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]
[7] An organic semiconductor material containing the polymer compound according to any one of [1] to [5].
[8] An organic semiconductor element comprising an organic layer containing the organic semiconductor material according to [7].
[9] An organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer contains the organic semiconductor material according to [7].

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the organic transistor excellent in a field effect mobility can be provided.

It is a schematic cross section which shows an example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention.

  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.

<Polymer compound>
(First structural unit)
The polymer compound of the present invention has a structural unit represented by formula (1-1) and / or a structural unit represented by formula (1-2) (hereinafter sometimes referred to as “first structural unit”). It is a high molecular compound containing. The first structural unit may be contained alone or in combination of two or more in the polymer compound. The polymer compound of this embodiment is preferably a conjugated polymer compound.

〔式中、
ＡおよびＣは、それぞれ独立に、３価の芳香族炭化水素基または３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。
Ｂは、４価の基を表し、この基は置換基を有していてもよい。
Ｚ^１およびＺ^２は、それぞれ独立に、式（Ｚ）で表される基を表す。式（Ｚ）で表される基は、左右反転していてもよい。〕

[Where,
A and C each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups optionally have a substituent.
B represents a tetravalent group, and this group may have a substituent.
Z ¹ and Z ² each independently represent a group represented by the formula (Z). The group represented by the formula (Z) may be reversed left and right. ]

〔式中、
Ｒ^１は、水素原子、アルキル基、アリール基または１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。〕

[Where,
R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]

The trivalent aromatic hydrocarbon group represented by A and C is the remaining atomic group obtained by removing three hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.
The aromatic hydrocarbon includes a compound in which two or more selected from the group consisting of benzene, a hydrocarbon condensed ring compound containing benzene, and a hydrocarbon condensed ring compound containing benzene and benzene are directly bonded.
The trivalent aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, An alkenyl group or an alkynyl group is mentioned.

  Examples of the trivalent aromatic hydrocarbon group include groups represented by formulas (101) to (113), and these groups may have a substituent.

The trivalent heterocyclic group represented by A and C is a remaining atomic group obtained by removing three hydrogen atoms directly bonded to carbon atoms constituting a ring from a heterocyclic compound. The number of carbon atoms of the heterocyclic compound is usually 2-30, preferably 3-20. The number of carbon atoms in the trivalent heterocyclic group does not include the number of carbon atoms in the substituent. The trivalent heterocyclic group is preferably a trivalent aromatic heterocyclic group.
A heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. In the ring.
The heterocyclic compound is selected from the group consisting of a monocyclic heterocyclic compound, a condensed ring compound containing a heterocyclic compound, a monocyclic heterocyclic compound and a condensed ring compound containing a heterocyclic compound. The compounds in which the above are directly bonded are included.
The trivalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom, an alkenyl group, and an alkynyl group. Can be mentioned.

  Examples of the trivalent heterocyclic group include groups represented by formulas (201) to (224), and these groups may have a substituent.

〔式中、Ｒ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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。Ｒが複数存在する場合、これらは同一でも異なっていてもよい。〕

[Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, a silyl group, an alkenyl group or an alkynyl group; These groups may have a substituent. When two or more R exists, these may be the same or different. ]

  Since the field effect mobility of the organic transistor produced using the polymer compound of the present embodiment is more excellent, A and C are preferably trivalent heterocyclic groups, and are represented by formulas (201) to (224). Is more preferably a divalent heterocyclic group represented by formula (206) to formula (214), more preferably a formula (207). The divalent heterocyclic group is particularly preferable.

  Examples of the tetravalent group represented by B include a tetravalent aromatic hydrocarbon group, a tetravalent heterocyclic group, and a group represented by the formula (B ′).

The tetravalent aromatic hydrocarbon group represented by B is the remaining atomic group obtained by removing four hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20. The carbon number of the tetravalent aromatic hydrocarbon group does not include the carbon number of the substituent.
The aromatic hydrocarbon includes a compound in which two or more selected from the group consisting of benzene, a hydrocarbon condensed ring compound containing benzene, and a hydrocarbon condensed ring compound containing benzene and benzene are directly bonded.
The tetravalent aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, An alkenyl group or an alkynyl group is mentioned.

  Examples of the tetravalent aromatic hydrocarbon group include groups represented by formulas (301) to (306), and these groups may have a substituent.

The tetravalent heterocyclic group represented by B is the remaining atomic group obtained by removing four hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound. The number of carbon atoms of the heterocyclic compound is usually 2-30, preferably 3-20. Note that the number of carbon atoms in the tetravalent heterocyclic group does not include the number of carbon atoms in the substituent. The tetravalent heterocyclic group is preferably a tetravalent aromatic heterocyclic group.
A heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. In the ring.
The heterocyclic compound is selected from the group consisting of a monocyclic heterocyclic compound, a condensed ring compound containing a heterocyclic compound, a monocyclic heterocyclic compound and a condensed ring compound containing a heterocyclic compound. The compounds in which the above are directly bonded are included.
The tetravalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom, an alkenyl group, and an alkynyl group. Can be mentioned.

  Examples of the tetravalent heterocyclic group include groups represented by formulas (401) to (417), and these groups may have a substituent.

〔式中、Ｒ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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。Ｒが複数存在する場合、これらは同一でも異なっていてもよい。〕

[Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, a silyl group, an alkenyl group or an alkynyl group; These groups may have a substituent. When two or more R exists, these may be the same or different. ]

  B is preferably a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group because the field effect mobility of the organic transistor produced using the polymer compound of this embodiment is more excellent. It is more preferably a valent aromatic hydrocarbon group, further preferably a tetravalent aromatic hydrocarbon group represented by the formula (301) to the formula (306), and the formula (301) or the formula (302). And a tetravalent aromatic hydrocarbon group represented by the formula (301) is particularly preferred.

Z ¹ and Z ² each independently represent a group represented by the formula (Z). The group represented by the formula (Z) may be reversed left and right.

R ¹ in Formula (Z) is preferably an alkyl group because the organic transistor produced using the polymer compound of the present embodiment has better field effect mobility.
In addition, R ¹ in the formula (Z) is preferably an alkyl group having 8 or more carbon atoms and an alkyl group having 16 or more carbon atoms because the polymer compound of the present embodiment has excellent solubility in a solvent. The group is more preferably a branched alkyl group having 16 or more carbon atoms.

  Since the field effect mobility of the organic transistor produced using the polymer compound of the present embodiment is more excellent, the structural unit represented by the formula (1-1) is a structure represented by the formula (2-1). It is preferable that it is a unit, and it is preferable that the structural unit represented by Formula (1-2) is a structural unit represented by Formula (2-2).

〔式中、
Ｚ^１およびＺ^２は、前記と同じ意味を表す。
Ｘ^１およびＸ^２は、それぞれ独立に、酸素原子、硫黄原子またはセレン原子を表す。
Ｙ^１およびＹ^２は、それぞれ独立に、窒素原子または−ＣＨ＝で表される基を表す。
Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立に、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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。〕

[Where,
Z ¹ and Z ² represent the same meaning as described above.
X ¹ and X ² each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ and Y ² each independently represent a nitrogen atom or a group represented by —CH═.
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]

X ¹ and X ² are preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom, in order to facilitate the synthesis of the polymer compound of the present embodiment.

In order to facilitate the synthesis of the polymer compound of the present embodiment, Y ¹ and Y ² are preferably —CH═. Moreover, since the atmospheric stability of the polymer compound of this embodiment becomes high, it is preferable that it is a nitrogen atom.

In the present specification, the alkyl group may be a linear alkyl group or a branched alkyl group, and may be a cycloalkyl group. The number of carbon atoms in the linear alkyl group is usually 1-30, and the number of carbon atoms in the branched alkyl group and cycloalkyl group is usually 3-30. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in the substituent.
Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group and n-hexadecyl group, isopropyl Group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, etc. Cycloalkyl groups such as a group, a cyclopentyl group, and a cyclohexyl group.
The alkyl group may have a substituent, and examples of the substituent include an alkoxy group, an aryl group, and a halogen atom. Examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

In the present specification, the alkoxy group may be either a linear alkoxy group or a branched alkoxy group, and may be a cycloalkoxy group. The straight-chain alkoxy group usually has 1 to 30 carbon atoms, and the branched alkoxy group and cycloalkoxy group usually have 3 to 30 carbon atoms. The number of carbon atoms of the alkoxy group does not include the number of carbon atoms of the substituent.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, and an n-hexadecyloxy group. Linear alkoxy group, isopropyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, 2-hexyldecyloxy group, 2-octyldodecyloxy group Groups, branched alkoxy groups such as 2-decyltetradecyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.
The alkoxy group may have a substituent, and examples of the substituent include an alkoxy group, an aryl group, and a halogen atom.

In this specification, the alkylthio group may be either a linear alkylthio group or a branched alkylthio group, or a cycloalkylthio group. The straight-chain alkylthio group usually has 1 to 30 carbon atoms, and the branched alkylthio group and cycloalkylthio group usually have 3 to 30 carbon atoms. The number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent.
Examples of the alkylthio group include a straight chain alkylthio group such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-hexadecylthio group, isopropyl Thio group, isobutylthio group, sec-butylthio group, tert-butylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group, 2-hexyldecylthio group, 2-octyldodecylthio group, 2-decyltetra Examples thereof include a branched alkylthio group such as a decylthio group, a cycloalkylthio group such as a cyclopentylthio group, and a cyclohexylthio group.
The alkylthio group may have a substituent, and examples of the substituent include an alkoxy group, an aryl group, and a halogen atom.

In the present specification, an aryl group is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20. The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.
The aromatic hydrocarbon includes a compound in which two or more selected from the group consisting of benzene, a hydrocarbon condensed ring compound containing benzene, and a hydrocarbon condensed ring compound containing benzene and benzene are directly bonded.
As the aryl group, for example, 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, Examples include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, and 4-phenylphenyl group.
The aryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, an alkenyl group, and an alkynyl group. Illustrative are alkyl groups.

In this specification, the carbon atom number of an aryloxy group is 6-60 normally, Preferably it is 6-20. The number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent.
Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.
The aryloxy group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

In this specification, the carbon atom number of an arylthio group is 6-60 normally, Preferably it is 6-20. The number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent.
Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.
The arylthio group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

In this specification, the monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from a heterocyclic compound. The number of carbon atoms of the heterocyclic compound is usually 2-30, preferably 3-20. The number of carbon atoms in the monovalent heterocyclic group does not include the number of carbon atoms in the substituent. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.
A heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. In the ring.
The heterocyclic compound is selected from the group consisting of a monocyclic heterocyclic compound, a condensed ring compound containing a heterocyclic compound, a monocyclic heterocyclic compound and a condensed ring compound containing a heterocyclic compound. The compounds in which the above are directly bonded are included.
The monovalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom, an alkenyl group, and an alkynyl group. Illustrative are alkyl groups.
Examples of the monovalent heterocyclic group include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a 2-oxazolyl group, and a 2-thiazolyl group. 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group, 4- (2,1,3-benzothiadiazolyl) ) Group.

  In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the present specification, the silyl group may have a substituent, and examples of the substituent include an alkyl group and an aryl group.
Examples of the silyl group having a substituent include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a phenylsilyl group, and a triphenylsilyl group.

In the present specification, the alkenyl group may be either a linear alkenyl group or a branched alkenyl group, or a cycloalkenyl group. The straight-chain alkenyl group usually has 2 to 30 carbon atoms, and the branched alkenyl group and the cycloalkenyl group usually have 3 to 30 carbon atoms. The number of carbon atoms in the alkenyl group does not include the number of carbon atoms in the substituent.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-hexenyl group, 1-dodecenyl group, 1-hexadecenyl group, and 1-cyclohexenyl group.
The alkenyl group may have a substituent, and examples of the substituent include an aryl group, a halogen atom, and a silyl group.

In the present specification, the alkynyl group may be a linear alkynyl group or a branched alkynyl group. The straight-chain alkynyl group usually has 2 to 30 carbon atoms, and the branched alkynyl group usually has 3 to 30 carbon atoms. The number of carbon atoms in the alkynyl group does not include the number of carbon atoms in the substituent.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-hexynyl group, 1-dodecynyl group, and 1-hexadecynyl group.
The alkynyl group may have a substituent, and examples of the substituent include an aryl group, a halogen atom, and a silyl group.

In order to facilitate the synthesis of the polymer compound of the present embodiment, R ² , R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms. Furthermore, the solubility is excellent in the solvent of the polymer compound of this ^{embodiment, R 2, R 3, R} 4 and R ⁵ are alkyl group, alkoxy group, alkylthio group, preferably an alkenyl or alkynyl group . Further, since the air stability of the polymer compound of this embodiment is ^{high, R 2, R 3, R} 4 and R ⁵ is preferably a fluorine atom.

  Examples of the structural unit represented by formula (1-1) include structural units represented by formula (1101) to formula (1120), and these structural units may have a substituent. . Since the field effect mobility of the organic transistor manufactured using the polymer compound of this embodiment is more excellent, the structural unit represented by Formula (1-1) is represented by Formula (1101) to Formula (1112). The structural unit is preferably a structural unit represented by formula (1101) or formula (1102), and more preferably a structural unit represented by formula (1101).

〔式中、Ｒ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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していもてよい。複数存在するＲは、互いに同一でも異なっていてもよい。〕

[Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, a silyl group, an alkenyl group or an alkynyl group; These groups may have a substituent. A plurality of R may be the same or different from each other. ]

  Examples of the structural unit represented by Formula (1-2) include structural units represented by Formula (1201) to Formula (1220), and these structural units may have a substituent. . Since the field effect mobility of the organic transistor produced using the polymer compound of the present embodiment is more excellent, the structural unit represented by the formula (1-2) is represented by the formula (1201) to the formula (1212). The structural unit is preferably a structural unit represented by formula (1201) or formula (1202), and more preferably a structural unit represented by formula (1201).

〔式中、Ｒ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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、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は、互いに同一でも異なっていてもよい。〕

[Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, a silyl group, an alkenyl group or an alkynyl group; These groups may have a substituent. A plurality of R may be the same or different from each other. ]

(Second structural unit)
In addition to the structural unit represented by the formula (1-1) and / or the structural unit represented by the formula (1-2), the polymer compound of the present embodiment further has a structure represented by the formula (4). It preferably includes a unit (hereinafter sometimes referred to as “second structural unit”).

-D- (4)
[Wherein, D represents a vinylene group, an ethynylene group, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, D is different from the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2). ]

When the polymer compound of the present embodiment includes the second structural unit, the structural unit represented by the formula (1-1) and / or the structural unit represented by the formula (1-2), and the formula (4) It is preferable that the structural unit represented forms a conjugate.
In this specification, “conjugate” is chained in the order of unsaturated bond-single bond-unsaturated bond, two π bonds of π orbitals are adjacent to each other, and each π electron is arranged in parallel. In this case, the π electrons are not localized but the π electrons spread on the adjacent single bond and the π electrons are delocalized. Here, the unsaturated bond refers to a double bond or a triple bond.

The arylene group represented by D is an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20. The carbon number of the arylene group does not include the carbon number of the substituent.
The aromatic hydrocarbon includes a compound in which two or more selected from the group consisting of benzene, a hydrocarbon condensed ring compound containing benzene, and a hydrocarbon condensed ring compound containing benzene and benzene are directly bonded.
The arylene group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, an alkenyl group, and an alkynyl group. Can be mentioned.

  As an arylene group, the group represented by Formula 1-12 is illustrated, for example, These groups may have a substituent.

The divalent heterocyclic group represented by D is the remaining atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound. The number of carbon atoms of the heterocyclic compound is usually 2-30, preferably 3-20. The number of carbon atoms in the divalent heterocyclic group does not include the number of carbon atoms in the substituent. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.
A heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. In the ring.
The heterocyclic compound is selected from the group consisting of a monocyclic heterocyclic compound, a condensed ring compound containing a heterocyclic compound, a monocyclic heterocyclic compound and a condensed ring compound containing a heterocyclic compound. The compounds in which the above are directly bonded are included.
The divalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom, an alkenyl group, and an alkynyl group. Can be mentioned.

  As a bivalent heterocyclic group, the bivalent heterocyclic group represented by Formula 13-63 is illustrated, for example, These groups may have a substituent.

〔式中、
Ｒ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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。Ｒ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。
ａおよびｂは、それぞれ独立に、０〜５の整数である。〕

[Where,
R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a halogen atom, a silyl group, an alkenyl group or an alkynyl group, and these groups are It may have a substituent. When a plurality of R are present, they may be the same or different.
a and b are each independently an integer of 0 to 5; ]

  a and b are preferably integers of 0 to 3, and more preferably 0 or 1.

  Since the field effect mobility of the organic transistor produced using the polymer compound of the present embodiment is more excellent, D is preferably a divalent heterocyclic group, and is represented by formula 26, formula 36, formula 38 to formula 38. More preferably, it is a divalent heterocyclic group represented by Formula 40, Formula 49 to Formula 54, Formula 57 to Formula 60, Formula 62 or Formula 63, and is represented by Formula 38, Formula 51 or Formula 54. The heterocyclic group is more preferably.

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 ⁷ . From the viewpoint of forming a good thin film during thin film production, the number average molecular weight is preferably 3 × 10 ³ or more. The number average molecular weight is preferably 1 × 10 ⁶ or less from the viewpoint of increasing the solubility in a solvent and facilitating the production of a thin film.

  The polymer compound of the present invention is highly soluble in a solvent (preferably an organic solvent). Specifically, the polymer compound of the present invention is 0.1% by weight (hereinafter referred to as “wt%”). It is preferable to have a solubility capable of producing a solution containing the above, and more preferably a solubility capable of producing a solution containing 0.4 wt% or more.

  In the polymer compound of the present invention, at least one content of the structural unit represented by the formula (1-1) and / or the structural unit represented by the formula (1-2) is included in the polymer compound. However, preferably, 3 or more are contained in the polymer compound, and more preferably 5 or more are contained in the polymer compound.

  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. Since the field effect mobility of the organic transistor produced using the polymer compound of the present embodiment is more excellent, the structural unit represented by the formula (1-1) and / or the formula (1-2) is used. The copolymer is preferably a copolymer of a structural unit and a structural unit represented by formula (4), and is represented by a structural unit represented by formula (1-1) and / or formula (1-2). More preferred is an alternating copolymer of the structural unit and the structural unit represented by the formula (4).

  In the polymer compound of the present invention, when a group active in the polymerization reaction remains at the molecular chain terminal, the field effect mobility of an organic transistor produced using the polymer compound may be lowered. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent aromatic heterocyclic group.

<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.

A ¹¹ represents a structural unit represented by the formula (1-1) and / or a structural unit represented by the formula (1-2), and A ¹² represents a structural unit represented by the formula (4). . 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 (a group represented by —B (OH) ₂ ), and a stannyl group substituted with three alkyl groups.

  Examples of the halogen atom that is a 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 a polymerization reactive group include a group represented by the following formula.

  Examples of the stannyl group substituted with three alkyl groups that are polymerization reactive groups include a stannyl group substituted with three methyl groups and a stannyl group substituted with three butyl groups.

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

The polymerization reactive group is preferably a halogen atom, a boric acid ester residue or a boric acid residue when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used. A bromine atom, an iodine atom or a borate residue is more preferable.
When the polymer compound of the present invention is polymerized by Suzuki coupling reaction, the total number of moles of bromine atom and iodine atom as the polymerization reactive group and the total mole of boric acid ester residue as the polymerization reactive group. The ratio to the number is preferably 0.7 to 1.3, and more preferably 0.8 to 1.2.

When a palladium catalyst such as a Stille coupling reaction is used, the polymerization reactive group is preferably a halogen atom or a stannyl group substituted with three alkyl groups. A stannyl group substituted with an atom, an iodine atom, or three alkyl groups is more preferable.
When the polymer compound of the present invention is polymerized by Stille coupling reaction, it is substituted with the total number of moles of bromine atom and iodine atom which are the above-mentioned polymerization reactive groups, and three alkyl groups which are the above-mentioned polymerization reactive groups. The ratio with the total number of moles of the stannyl group is preferably 0.7 to 1.3, more preferably 0.8 to 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 polymerization include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabromide. Organic bases such as butylammonium, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide are listed.

  Examples of the catalyst used for the polymerization include transition metal complexes such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphinepalladium, and other transition metal complexes, and if necessary, A catalyst comprising a ligand such as phenylphosphine, tri-tert-butylphosphine, or tricyclohexylphosphine is preferable. 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 still more 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, and examples thereof include a method of adding a reaction solution obtained by the above polymerization to a lower alcohol such as methanol and filtering and drying the deposited precipitate.

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

<Compound>
The compound of the present invention is a compound represented by the formula (3-1) or a compound represented by the formula (3-2), and as a raw material of the polymer compound of the present invention, a method for producing the above-described polymer compound Can be suitably used.

〔式中、
Ｗ^１およびＷ^２は、それぞれ独立に、水素原子またはハロゲン原子を表す。
Ｘ^３およびＸ^４は、それぞれ独立に、酸素原子、硫黄原子またはセレン原子を表す。
Ｙ^３およびＹ^４は、それぞれ独立に、窒素原子または−ＣＨ＝で表される基を表す。
Ｚ^３およびＺ^４は、それぞれ独立に、式（Ｚ’）で表される基を表し、式（Ｚ’）で表される基は左右反転していてもよい。
Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、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、アリールオキシ基、アリールチオ基、１価の複素環基、ハロゲン原子、シリル基、アルケニル基またはアルキニル基を表し、これらの基は置換基を有していてもよい。〕

[Where,
W ¹ and W ² each independently represents a hydrogen atom or a halogen atom.
X ³ and X ⁴ each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ³ and Y ⁴ each independently represent a nitrogen atom or a group represented by —CH═.
Z ³ and Z ⁴ each independently represent a group represented by the formula (Z ′), and the group represented by the formula (Z ′) may be horizontally reversed.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]

〔式中、
Ｒ^１０は、水素原子、アルキル基、アリール基または１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。〕

[Where,
R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

X ³ and X ⁴ are preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom, because the synthesis of the compound of this embodiment is facilitated.

Since it is easy to synthesize the compound of this embodiment, Y ³ and Y ⁴ are preferably —CH═, and since the atmospheric stability of the compound of this embodiment is higher, Y ³ and Y ⁴ are And preferably a nitrogen atom.

In order to facilitate the synthesis of the compound of the present embodiment, R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably hydrogen atoms, and the polymer compound of the present embodiment has excellent solubility in a solvent. R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group or an alkynyl group. In addition, since the polymer compound of the present embodiment is excellent in atmospheric stability, R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably fluorine atoms.

Z ³ and Z ⁴ each independently represent a group represented by the formula (Z ′), and the group represented by the formula (Z ′) may be horizontally reversed.

R ¹⁰ in the formula (Z ′) is preferably an alkyl group having 8 or more carbon atoms, and an alkyl group having 16 or more carbon atoms, since the compound of the present embodiment has excellent solubility in a solvent. It is more preferable that the branched alkyl group has 16 or more carbon atoms.

<Method for producing compound>
Next, the manufacturing method of the compound of this invention is demonstrated.
Although the compound of this invention may be manufactured by what kind of method, it is compoundable by the method shown below, for example.

As a manufacturing method of the compound represented by Formula (3-1), for example,
A first step of reacting a compound represented by formula (S1), a compound represented by formula (S2), and a compound represented by formula (S3) by a Suzuki coupling reaction;
A compound represented by the formula (S4) obtained in the first step, a compound represented by the formula: R ¹⁰ -Hal and a base such as potassium carbonate, and a metal salt such as copper iodide are added as necessary. A second step of reacting;
The compound represented by the formula (S5) obtained in the second step can be produced by a third step of halogenating with a halogenating agent such as N-bromosuccinimide. The compound obtained in this case is a compound represented by the formula (S6).

〔式中、
Ｒ^６、Ｒ^７、Ｒ^１０、Ｘ^３、Ｘ^４、Ｙ^３およびＹ^４は、前記と同じ意味を表す。
Ｍは、ホウ酸エステル残基または式：−Ｂ（ＯＨ）_２で表される基を表す。複数存在するＭは、互いに同一でも異なっていてもよい。
Ｈａｌは、ハロゲン原子を表す。複数存在するＨａｌは、互いに同一でも異なっていてもよい。
Ａｋは、アルキル基を表す。〕

[Where,
R ⁶ , R ⁷ , R ¹⁰ , X ³ , X ⁴ , Y ³ and Y ⁴ represent the same meaning as described above.
M represents a boric acid ester residue or a group represented by the formula: —B (OH) ₂ . A plurality of M may be the same as or different from each other.
Hal represents a halogen atom. Plural Hals may be the same as or different from each other.
Ak represents an alkyl group. ]

As a manufacturing method of the compound represented by Formula (3-2), for example,
A first step of reacting a compound represented by formula (S7), a compound represented by formula (S8) and a compound represented by formula (S9) by a Suzuki coupling reaction;
A compound represented by the formula (S10) obtained in the first step, a compound represented by the formula: R ¹⁰ -Hal and a base such as potassium carbonate, and a metal salt such as copper iodide as necessary are added. A second step of reacting;
The compound represented by the formula (S11) obtained in the second step can be produced by a third step of halogenating with a halogenating agent such as N-bromosuccinimide. The compound obtained in this case is a compound represented by the formula (S12).

〔式中、
Ｒ^８、Ｒ^９、Ｒ^１０、Ｘ^３、Ｘ^４、Ｙ^３およびＹ^４は、前記と同じ意味を表す。
Ｍは、ホウ酸エステル残基または式：−Ｂ（ＯＨ）_２で表される基を表す。複数存在するＭは、互いに同一でも異なっていてもよい。
Ｈａｌは、ハロゲン原子を表す。複数存在するＨａｌは、互いに同一でも異なっていてもよい。
Ａｋは、アルキル基を表す。〕

[Where,
R ⁸ , R ⁹ , R ¹⁰ , X ³ , X ⁴ , Y ³ and Y ⁴ represent the same meaning as described above.
M represents a boric acid ester residue or a group represented by the formula: —B (OH) ₂ . A plurality of M may be the same as or different from each other.
Hal represents a halogen atom. Plural Hals may be the same as or different from each other.
Ak represents an alkyl group. ]

<Organic semiconductor materials>
The organic semiconductor material of the present invention may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds. In addition to the polymer compound of the present invention, the organic semiconductor material of the present embodiment may further contain a compound having a carrier transport property or a polymer compound. When the organic semiconductor material of this embodiment contains components other than the polymer compound of the present invention, the polymer compound of the present invention is preferably contained in an amount of 30% by weight or more, more preferably 50% by weight or more, and 70 More preferably, it is contained by weight% or more.

  Compounds having carrier transport properties include arylamine derivatives, stilbene derivatives, oligothiophene and derivatives thereof, low molecular compounds such as oxadiazole derivatives, fullerenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polyaniline and derivatives thereof, polythiophene And derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.

  The organic semiconductor material may contain a polymer compound material different from the polymer compound of the present invention as a polymer binder in order to improve the characteristics. As the polymer binder, those that do not excessively lower the carrier transportability are preferable.

  Examples of polymer binders 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 , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

<Organic semiconductor element>
Since the polymer compound of the present invention has high mobility, when an organic thin film containing the polymer compound of the present invention is used for an organic semiconductor element, it is generated by electrons or holes injected from the electrode or light absorption. Can be transported. Taking advantage of these characteristics, the polymer compound of the present invention can be suitably used for various organic semiconductor elements such as a photoelectric conversion element, an organic transistor, and an organic electroluminescence element. Hereinafter, these elements will be described individually.

(Photoelectric conversion element)
The photoelectric conversion element containing the polymer compound of the present invention has one or more active layers containing the polymer compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.
A preferable form of the photoelectric conversion element containing the polymer compound of the present invention is formed from a composition of a pair of electrodes, at least one of which is transparent or translucent, and a p-type organic semiconductor and an n-type organic semiconductor. Has an active layer. The polymer compound of the present invention is preferably used as a p-type organic semiconductor. The operation mechanism of the photoelectric conversion element of this embodiment will be described. Light energy incident from a transparent or translucent electrode is an electron-accepting compound (n-type organic semiconductor) such as a fullerene derivative and / or an electron-donating compound (p-type organic semiconductor) such as a polymer compound of the present invention. Absorbed, producing excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface, Electric charges (electrons and holes) that can move independently are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

  The photoelectric conversion element manufactured using the polymer compound of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  In another aspect of the photoelectric conversion element having the polymer compound of the present invention, the first active layer containing the polymer compound of the present invention is interposed between a pair of electrodes, at least one of which is transparent or translucent, and the first A photoelectric conversion element including a second active layer containing an electron accepting compound such as a fullerene derivative adjacent to the active layer.

  Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, conductive materials composed of indium oxide, zinc oxide, tin oxide, and indium tin oxide (hereinafter referred to as “ITO”), indium, zinc oxide, and the like, which are composites thereof. A film prepared using, NESA, gold, platinum, silver, copper, or the like is used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  One electrode may not be transparent, and a metal, a conductive polymer, etc. can be used as an electrode material of the electrode. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  An additional intermediate layer other than the active layer may be used as a means for improving the photoelectric conversion efficiency. Examples of the material used for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).

  The active layer may contain the polymer compound of the present invention alone or in combination of two or more. In addition, a compound other than the polymer compound of the present invention can be mixed and used as the electron donating compound and / or the electron accepting compound in the active layer. The electron donating compound and the electron accepting compound are relatively determined from the energy levels of these compounds.

  Examples of the electron-donating compound include, in addition to the polymer compound of the present invention, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof. And polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

  Examples of the electron accepting compound include, in addition to the polymer compound of the present invention, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and Derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinolines and derivatives thereof, polyquinoxalines and Derivatives thereof, polyfluorene and derivatives thereof, phenanthrene derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerene, fullerene Derivatives and the like, preferably, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.

Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. Specific examples of the fullerene derivative include the following.

  Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C70 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C70 butyric acid methyl ester), [6,6] phenyl-C84 butyric acid methyl ester, [6,6] -thienyl- Examples thereof include C60 butyric acid methyl ester ([6,6] -Thienyl C60 butyric acid methyl ester).

  When the active layer contains the polymer compound of the present invention and the fullerene derivative, the ratio of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is 500 parts by weight.

  The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and more preferably 20 nm to 200 nm.

  The method for producing the active layer may be produced by any method, and examples thereof include film formation from a solution containing the polymer compound of the present invention and film formation by vacuum deposition.

  A preferred method for producing a photoelectric conversion element is a method for producing a photoelectric conversion element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode. Then, a step of forming an active layer by applying a solution (ink) containing the polymer compound of the present invention and a solvent on the first electrode by a coating method, and forming a second electrode on the active layer It is the manufacturing method of the element which has a process.

  The solvent used for film formation from a solution may be any one that dissolves the polymer compound of the present invention. Examples of the solvent include saturated hydrocarbon solvents such as decalin and bicyclohexyl, and unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, and cyclohexylbenzene. Solvents, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, and other halogenated saturated hydrocarbon solvents, chlorobenzene, dichlorobenzene, tri Examples thereof include halogenated unsaturated hydrocarbon solvents such as chlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Coating methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, capillary coating, etc. can be used, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet printing method, and a spin coating method are preferable.

  From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

(Organic thin film solar cell)
The photoelectric conversion element using the polymer compound of the present invention is operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. Can do. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  Further, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, a photocurrent flows and the organic light sensor can be operated. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  The organic thin film solar cell can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The organic thin film solar cell produced using the polymer compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

In a typical super straight type or substrate type module, cells are placed at regular intervals between support substrates that are transparent on one or both sides and treated with antireflection, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency. Also, when used in places where there is no need to cover the surface with a hard material, such as where there is little impact from the outside, the surface protective layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin It is possible to eliminate the supporting substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and a sealing material is hermetically sealed between the support substrate and the frame. Further, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. A module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 can also be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

(Organic electroluminescence device)
The polymer compound of the present invention can also be used in an organic electroluminescence element (hereinafter sometimes referred to as “organic EL element”). The organic EL element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent. The organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer. The polymer compound of the present invention is contained in any one of the light emitting layer, the hole transport layer, and the electron transport layer. In addition to the polymer compound of the present invention, the light emitting layer may contain a charge transport material (which means a generic term for an electron transport material and a hole transport material). As an organic EL element, an element having an anode, a light emitting layer, and a cathode, and further having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer, A device having an electron transport layer and a cathode, and further having a hole transport layer containing a hole transport material adjacent to the light emitting layer between the anode and the light emitting layer, the anode, the hole transport layer, the light emitting layer, and the cathode And an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

(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 with 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 A drain electrode 6 formed on the active layer 2 with an interval, an insulating layer 3 formed on the active layer 2 and the drain electrode 6, and an insulating layer on a 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. An 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 a part of the drain electrode 6 so as to cover part of the drain electrode 6, the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below. 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 another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 170 shown in FIG. 8 has a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, an active layer 2 formed on the insulating layer 3, and a predetermined interval on the active layer 2. A source electrode 5 and a drain electrode 6 formed in the above manner. In this case, the gate electrode 4 also serves as the substrate 1.

  FIG. 9 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 180 shown in FIG. 9 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval, The active layer 2 is formed on the insulating layer 3 so as to cover a part of the source electrode 5 and the drain electrode 6.

  In the organic transistor of the present invention described above, the active layer 2 and / or the active layer 2a is constituted by a 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 a field effect transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Accordingly, the state of this interface greatly affects the field effect 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, and fluorinated alkylalkoxysilanes. And silylamine compounds such as 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 higher field effect 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).

  A 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 the field effect transistor of this embodiment mentioned above contains the high molecular compound of this invention as an active layer, and since it is equipped with the active layer excellent in the mobility by that, the field effect mobility is high. It will be a thing. 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.

(Mass spectrometry)
Mass spectrometry was performed using AccuTOF TLC JMS-T100TD (manufactured by JEOL Ltd.).

(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.

Synthesis example 1
(Synthesis of Compound 2)

反応容器内に、化合物１を１２．１ｇ（５８．４ｍｍｏｌ）、濃硫酸を１０ｍL、メタノールを２５０ｍＬ加え、６時間還流させた。得られた反応液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を濃縮することで得られた液体を、シリカゲルカラムを用いて精製し、化合物２を得た。得量は１２．８ｇであり、収率は９９％であった。

In a reaction vessel, 12.1 g (58.4 mmol) of Compound 1, 10 mL of concentrated sulfuric acid, and 250 mL of methanol were added and refluxed for 6 hours. The resulting reaction solution was poured into water and extracted with toluene. The liquid obtained by concentrating the obtained toluene solution was purified using a silica gel column to obtain Compound 2. The yield was 12.8 g, and the yield was 99%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.36 (d, 1H), 7.22 (d, 1H), 3.88 (s, 3H).

Synthesis example 2
(Synthesis of Compound 4)

反応容器内に、２，５−ジクロロ−１，４−フェニレンジアミンを２０．０ｇ（１１３ｍｍｏｌ）、ビスピナコラートジボランを６３．１ｇ（２４９ｍｍｏｌ）、リン酸カリウムを９５．９ｇ（４５２ｍｍｏｌ）、２，２，２−トリフルオロエタノールを４５．２ｇ（４５２ｍｍｏｌ）、ＮｉＣｌ_２（ＰＭｅ_３）_２を１．６０ｇ（５．６８ｍｍｏｌ）、トルエンを５００ｍＬ加え、８時間還流させた。得れらた反応液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を水洗し、濃縮した。得られた固体をテトラヒドロフランに溶解させ、セライトろ過した。得られたろ液を濃縮し、化合物４を得た。得量は３０．５ｇであり、収率は７５％であった。

In a reaction vessel, 20.0 g (113 mmol) of 2,5-dichloro-1,4-phenylenediamine, 63.1 g (249 mmol) of bispinacolatodiborane, 95.9 g (452 mmol) of potassium phosphate, 2, 2,2-trifluoroethanol (45.2 g, 452 mmol), NiCl ₂ (PMe ₃ ) ₂ (1.60 g, 5.68 mmol) and toluene (500 mL) were added and refluxed for 8 hours. The obtained reaction solution was poured into water and extracted with toluene. The obtained toluene solution was washed with water and concentrated. The obtained solid was dissolved in tetrahydrofuran and filtered through Celite. The obtained filtrate was concentrated to obtain compound 4. The yield was 30.5 g, and the yield was 75%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.08 (s, 2H), 1.34 (s, 24H).

Example 1
(Synthesis of Compound 5)

反応容器内の気体を窒素ガスで置換した後に、化合物４を４．３０ｇ（１１．９ｍｍｏｌ）、化合物２を５．２８ｇ（２３．９ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウムを０．４３７ｇ（０．４７８ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボレートを１．７８ｇ（１．９１ｍｍｏｌ）、テトラヒドロフランを５０ｍＬ加え、撹拌した。得られた溶液に、２ｍｏｌ／Ｌの炭酸カリウム水溶液を８．３ｍＬ滴下し、８時間還流させた。得られた反応液を水に注ぎ、ろ過した。得られた固体をアセトンで洗浄し、化合物５を得た。得量は３．３０ｇであり、収率は８５％であった。

After replacing the gas in the reaction vessel with nitrogen gas, 4.30 g (11.9 mmol) of compound 4, 5.28 g (23.9 mmol) of compound 2, and 0.437 g of tris (dibenzylideneacetone) dipalladium ( 0.478 mmol), 1.78 g (1.91 mmol) of tri-tert-butylphosphonium tetrafluoroborate and 50 mL of tetrahydrofuran were added and stirred. To the obtained solution, 8.3 mL of a 2 mol / L potassium carbonate aqueous solution was dropped and refluxed for 8 hours. The resulting reaction solution was poured into water and filtered. The obtained solid was washed with acetone to obtain Compound 5. The yield was 3.30 g, and the yield was 85%.

  MS (m / z) 325.20

Example 2
(Synthesis of Compound 6)

反応容器内に、化合物５を４．２０ｇ（１２．９ｍｍｏｌ）、１−ブロモ−２−デシルテトラデカンを２７．０ｇ（６４．７ｍｍｏｌ）、炭酸カリウムを８．９５ｇ（６４．７ｍｍｏｌ）、Ｎ，Ｎ−ジメチルホルムアミドを５０ｍＬ加え、１０時間還流させた。得られた反応液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を水洗し、濃縮した。得られた液体を、シリカゲルカラムを用いて精製し、化合物６を得た。得量は１．７１ｇであり、収率は１３％であった。

In a reaction vessel, 4.20 g (12.9 mmol) of compound 5, 27.0 g (64.7 mmol) of 1-bromo-2-decyltetradecane, 8.95 g (64.7 mmol) of potassium carbonate, N, N -50 mL of dimethylformamide was added and refluxed for 10 hours. The resulting reaction solution was poured into water and extracted with toluene. The obtained toluene solution was washed with water and concentrated. The resulting liquid was purified using a silica gel column to obtain compound 6. The yield was 1.71 g, and the yield was 13%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.52 (s, 2H), 7.63 (d, 2H), 7.51 (d, 2H), 4.56 (d, 4H) ), 1.98 (m, 2H), 1.20-1.60 (m, 80H), 0.87 (m, 12H).

Example 3
(Synthesis of Compound 7)

反応容器内に、化合物６を１．３５ｇ（１．３５ｍｍｏｌ）、テトラヒドロフランを５０ｍＬ加え、−７８℃に冷却した。その後、ここへ、ｎ−ブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ、１２．３ｍＬ、１３．５ｍｍｏｌ）を滴下した。得られた反応液を−７８℃で１時間撹拌した。その後、ここへ、１，２−ジブロモ−１，１，２，２−テトラフルオロエタンを５．２７ｇ（２０．３ｍｍｏｌ）加えた。得られた反応液を室温で６時間撹拌した。得られた反応液を濃縮し、水に注ぎ、トルエンで抽出した。得られたトルエン溶液を濃縮し、得られた固体をシリカゲルカラム精製し、化合物７を得た。得量は１．４５ｇであり、収率は９３％であった。

Into the reaction vessel, 1.35 g (1.35 mmol) of compound 6 and 50 mL of tetrahydrofuran were added and cooled to −78 ° C. Then, the n-butyllithium hexane solution (1.6 mol / L, 12.3 mL, 13.5 mmol) was dripped here. The resulting reaction solution was stirred at -78 ° C for 1 hour. Then, 5.27 g (20.3 mmol) of 1,2-dibromo-1,1,2,2-tetrafluoroethane was added thereto. The resulting reaction solution was stirred at room temperature for 6 hours. The resulting reaction solution was concentrated, poured into water, and extracted with toluene. The obtained toluene solution was concentrated, and the obtained solid was purified by a silica gel column to obtain Compound 7. The yield was 1.45g, and the yield was 93%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.29 (s, 2H), 7.57 (s, 2H), 4.52 (d, 4H), 1.94 (m, 2H) ), 1.20-1.60 (m, 80H), 0.88 (t, 6H), 0.87 (t, 6H).

Synthesis example 3
(Synthesis of Compound 9)

反応容器内に、化合物８を１０．０ｇ（４６．１ｍｍｏｌ）、塩化メチレン３０ｍＬを加え、−７８℃に冷却した。その後、ここへ、三臭化ホウ素の塩化メチレン溶液（１ｍｏｌ／Ｌ、９６．８ｍＬ、９６．７ｍｍｏｌ）を滴下した。得られた反応溶液を、−７８℃で１時間、室温で５時間撹拌した。得られた反応溶液を水に注ぎ、塩化メチレンで抽出した。得られた塩化メチレン溶液を、水で洗浄した。得られた塩化メチレン溶液を濃縮し、化合物９を得た。得量は６．６０ｇであり、収率は７６％であった。

In a reaction vessel, 10.0 g (46.1 mmol) of compound 8 and 30 mL of methylene chloride were added and cooled to -78 ° C. Thereafter, a solution of boron tribromide in methylene chloride (1 mol / L, 96.8 mL, 96.7 mmol) was added dropwise thereto. The resulting reaction solution was stirred at −78 ° C. for 1 hour and at room temperature for 5 hours. The resulting reaction solution was poured into water and extracted with methylene chloride. The resulting methylene chloride solution was washed with water. The resulting methylene chloride solution was concentrated to obtain compound 9. The yield was 6.60 g, and the yield was 76%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 6.61 (s, 2H), 6.32 (s, 1H), 6.23 (s, 2H).

Synthesis example 4
(Synthesis of Compound 10)

反応容器内に、化合物９を６．６０ｇ（３４．９ｍｍｏｌ）、１−ブロモ−２−エチルヘキサンを２０．２ｇ（１０５ｍｍｏｌ）、炭酸カリウムを２４．１ｇ（１７５ｍｍｏｌ）、ジメチルホルムアミドを１００ｍＬ加え、７時間還流させた。得られた反応溶液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を、塩酸水溶液、水の順で洗浄した。得られたトルエン溶液を濃縮した。得られた液体を、シリカゲルカラムを用いて精製し、化合物１０を得た。得量は６．５０ｇであり、収率は４５％であった。

In a reaction vessel, 6.60 g (34.9 mmol) of compound 9, 20.2 g (105 mmol) of 1-bromo-2-ethylhexane, 24.1 g (175 mmol) of potassium carbonate, and 100 mL of dimethylformamide were added. Reflux for hours. The resulting reaction solution was poured into water and extracted with toluene. The obtained toluene solution was washed with an aqueous hydrochloric acid solution and then with water. The obtained toluene solution was concentrated. The resulting liquid was purified using a silica gel column to obtain compound 10. The amount obtained was 6.50 g, and the yield was 45%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 6.64 (s, 2H), 6.37 (s, 1H), 3.78 (d, 4H), 1.69 (m, 2H) ), 1.20-1.60 (m, 16H), 0.91 (t, 12H).

Synthesis example 5
(Synthesis of Compound 11)

反応容器内に、１０−ブロモデセンを４．１３ｇ（１８．９ｍｍｏｌ）、９−ボラビシクロ［３，３，１］ノナンのテトラヒドロフラン溶液を３８ｍＬ（０．５ｍｏｌ／Ｌ、１８．９ｍｍｏｌ）加え、室温で８時間撹拌した。得られた溶液に、化合物１０を６．５ｇ（１５．７ｍｍｏｌ）、［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリドを０．１２８ｇ（０．１６０ｍｍｏｌ）、水酸化ナトリウムを２．５１ｇ（６２．９ｍｍｏｌ）、水を１３ｍＬ加え、８時間還流させた。得られた反応溶液を濃縮し、水に注ぎ、トルエンで抽出した。得られたトルエン溶液を濃縮した。得られた液体を、シリカゲルカラムを用いて精製し、化合物１１を得た。得量は２．１７ｇであり、収率は２９％であった。

In a reaction vessel, 4.13 g (18.9 mmol) of 10-bromodecene and 38 mL (0.5 mol / L, 18.9 mmol) of a tetrahydrofuran solution of 9-borabicyclo [3,3,1] nonane were added at room temperature. Stir for hours. To the resulting solution, 6.5 g (15.7 mmol) of compound 10, 0.128 g (0.160 mmol) of [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, sodium hydroxide 2.51 g (62.9 mmol) and 13 mL of water were added and refluxed for 8 hours. The obtained reaction solution was concentrated, poured into water, and extracted with toluene. The obtained toluene solution was concentrated. The resulting liquid was purified using a silica gel column to obtain compound 11. The yield was 2.17 g, and the yield was 29%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 6.32 (s, 2H), 6.29 (s, 1H), 3.79 (d, 4H), 3.40 (t, 2H) ), 2.52 (t, 2H), 1.85 (m, 2H), 1.20-1.80 (m, 32H), 0.90 (m, 12H).

Example 4
(Synthesis of Compound 12)

反応容器内に、化合物５を０．７０ｇ（２．１６ｍｍｏｌ）、化合物１１を２．０７ｇ（４．３２ｍｍｏｌ）、炭酸カリウムを１．４９ｇ（１０．８ｍｍｏｌ）、ジメチルホルムアミドを３０ｍＬ加え、７時間還流させた。得られた反応溶液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を、塩酸水溶液、水の順で洗浄した。得られたトルエン溶液を濃縮した。得られた液体を、シリカゲルカラムを用いて精製し、化合物１２を得た。得量は０．０３０ｇであり、収率は１％であった。

In a reaction vessel, 0.70 g (2.16 mmol) of compound 5, 2.07 g (4.32 mmol) of compound 11, 1.49 g (10.8 mmol) of potassium carbonate, and 30 mL of dimethylformamide were added and refluxed for 7 hours. I let you. The resulting reaction solution was poured into water and extracted with toluene. The obtained toluene solution was washed with an aqueous hydrochloric acid solution and then with water. The obtained toluene solution was concentrated. The resulting liquid was purified using a silica gel column to obtain compound 12. The yield was 0.030 g, and the yield was 1%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.50 (s, 2H), 7.62 (s, 2H), 7.49 (d, 2H), 6.32 (s, 4H) ), 6.29 (s, 2H), 4.65 (t, 4H), 3.80 (d, 8H), 2.52 (t, 4H), 1.93 (m, 4H), 1.20. -1.80 (m, 64H), 0.90 (m, 24H).

Example 5
(Synthesis of Compound 13)

反応容器内に、化合物１２を０．０３０ｇ（０．０２３６ｍｍｏｌ）、テトラヒドロフランを３０ｍＬ加え、−７８℃に冷却した。その後、ここへ、ｎ−ブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ、１．０７ｍＬ、１．１８ｍｍｏｌ）を滴下した。得られた反応液を−７８℃で１時間撹拌した。その後、ここへ、１，２−ジブロモ−１，１，２，２−テトラフルオロエタンを０．４３０ｇ（１．６５ｍｍｏｌ）加えた。得られた反応液を室温で６時間撹拌した。得られた反応液を濃縮し、水に注ぎ、トルエンで抽出した。得られたトルエン溶液を濃縮し、得られた固体をシリカゲルカラム精製し、化合物１３を得た。得量は０．０１３５ｇであり、収率は４０％であった。

In the reaction vessel, 0.030 g (0.0236 mmol) of Compound 12 and 30 mL of tetrahydrofuran were added and cooled to -78 ° C. Then, the n-butyllithium hexane solution (1.6 mol / L, 1.07 mL, 1.18 mmol) was dripped here. The resulting reaction solution was stirred at -78 ° C for 1 hour. Thereafter, 0.430 g (1.65 mmol) of 1,2-dibromo-1,1,2,2-tetrafluoroethane was added thereto. The resulting reaction solution was stirred at room temperature for 6 hours. The resulting reaction solution was concentrated, poured into water, and extracted with toluene. The obtained toluene solution was concentrated, and the obtained solid was purified by a silica gel column to obtain Compound 13. The yield was 0.0135 g, and the yield was 40%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.25 (s, 2H), 7.58 (s, 2H), 6.32 (s, 4H), 6.29 (s, 2H) ), 4.60 (t, 4H), 3.80 (d, 8H), 2.53 (t, 4H), 1.91 (m, 4H), 1.20-1.80 (m, 64H) 0.90 (m, 24H).

Example 6
(Synthesis of polymer compound P1)

反応容器内の気体を窒素ガスで置換した後に、化合物７を０．１５０ｇ（０．１３０ｍｍｏｌ）、化合物１４を０．０６７０ｇ（０．１３６ｍｍｏｌ）、トルエンを３０ｍＬ、トリス（ジベンジリデンアセトン）ジパラジウムを２．４ｍｇ、トリオルトトリルホスフィンを３．２ｍｇ加え、５時間還流させた。得られた反応液に、ブロモベンゼンを３０ｍｇ加えて、１時間還流させた。得られた反応液をアセトンに滴下したところ、析出物が得られた。得られた析出物をろ取し、トルエンと水とＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物を加えて、３時間還流させた。その後、トルエン層を抽出した。得られたトルエン溶液を、酢酸水溶液および水で洗浄した後、シリカゲルカラムを用いて精製した。得られたトルエン溶液をアセトンに滴下したところ、析出物が得られた。得られた析出物を、アセトンを溶媒として用いてソックスレー洗浄し、高分子化合物Ｐ１を得た。得量は９０ｍｇであり、ポリスチレン換算の数平均分子量は２．０×１０^４であり、重量平均分子量は８．４×１０^４であった。

After replacing the gas in the reaction vessel with nitrogen gas, 0.150 g (0.130 mmol) of compound 7, 0.0670 g (0.136 mmol) of compound 14, 30 mL of toluene, tris (dibenzylideneacetone) dipalladium were added. 2.4 mg and 3.2 mg of triorthotolylphosphine were added and refluxed for 5 hours. 30 mg of bromobenzene was added to the obtained reaction solution and refluxed for 1 hour. When the obtained reaction solution was added dropwise to acetone, a precipitate was obtained. The obtained precipitate was collected by filtration, toluene, water, and sodium N, N-diethyldithiocarbamate trihydrate were added and refluxed for 3 hours. Thereafter, the toluene layer was extracted. The obtained toluene solution was washed with an acetic acid aqueous solution and water, and then purified using a silica gel column. When the obtained toluene solution was dropped into acetone, a precipitate was obtained. The resulting precipitate was Soxhlet washed using acetone as a solvent to obtain a polymer compound P1. The yield was 90 mg, the polystyrene-equivalent number average molecular weight was 2.0 × 10 ⁴ , and the weight average molecular weight was 8.4 × 10 ⁴ .

Example 7
(Synthesis of polymer compound P2)

反応容器内の気体を窒素ガスで置換した後に、化合物７を０．１５０ｇ（０．１３０ｍｍｏｌ）、化合物１５を０．０５０９ｇ（０．１３０ｍｍｏｌ）、テトラヒドロフランを３０ｍＬ、トリス（ジベンジリデンアセトン）ジパラジウムを４．８ｍｇ、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボレートを６．０ｍｇ加え、撹拌した。得られた溶液に、２ｍｏｌ／Ｌの炭酸カリウム水溶液を０．６０ｍＬ滴下し、５時間還流させた。
得られた反応溶液に、フェニルボロン酸を１０．０ｍｇ加えて、１時間還流させた。得られた反応溶液にＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物を０．１ｇ加えて、３時間還流させた。得られた反応液を水に注ぎ、トルエンを加え、トルエン層を抽出した。得られたトルエン溶液を酢酸水溶液および水で洗浄した後、シリカゲルカラムを用いて精製した。得られたトルエン溶液をアセトンに滴下したところ、析出物が得られた。
得られた析出物を、アセトンを溶媒として用いてソックスレー洗浄し、高分子化合物Ｐ２を得た。得量は１０５ｍｇであり、ポリスチレン換算の数平均分子量は２．１×１０^４であり、重量平均分子量は７．４×１０^４であった。

After replacing the gas in the reaction vessel with nitrogen gas, 0.150 g (0.130 mmol) of compound 7, 0.0509 g (0.130 mmol) of compound 15, 30 mL of tetrahydrofuran, tris (dibenzylideneacetone) dipalladium were added. 4.8 mg and 6.0 mg of tri-tert-butylphosphonium tetrafluoroborate were added and stirred. To the obtained solution, 0.60 mL of a 2 mol / L potassium carbonate aqueous solution was dropped and refluxed for 5 hours.
To the obtained reaction solution, 10.0 mg of phenylboronic acid was added and refluxed for 1 hour. 0.1 g of sodium N, N-diethyldithiocarbamate trihydrate was added to the resulting reaction solution, and the mixture was refluxed for 3 hours. The obtained reaction liquid was poured into water, toluene was added, and the toluene layer was extracted. The obtained toluene solution was washed with an acetic acid aqueous solution and water, and then purified using a silica gel column. When the obtained toluene solution was dropped into acetone, a precipitate was obtained.
The obtained precipitate was Soxhlet washed with acetone as a solvent to obtain a polymer compound P2. The yield was 105 mg, the polystyrene-equivalent number average molecular weight was 2.1 × 10 ⁴ , and the weight average molecular weight was 7.4 × 10 ⁴ .

Example 8
(Synthesis of polymer compound P3)

実施例７の化合物１５にかえて化合物１６を０．０５０４ｇ（０．１３０ｍｍｏｌ）を用いた以外は、実施例７と同様にして、高分子化合物Ｐ３を合成した。得量は８５ｍｇであり、ポリスチレン換算の数平均分子量は１．７×１０^４であり、重量平均分子量は３．３×１０^４であった。

A polymer compound P3 was synthesized in the same manner as in Example 7, except that 0.0504 g (0.130 mmol) of Compound 16 was used instead of Compound 15 of Example 7. The yield was 85 mg, the polystyrene-equivalent number average molecular weight was 1.7 × 10 ⁴ , and the weight average molecular weight was 3.3 × 10 ⁴ .

Example 9
(Synthesis of polymer compound P4)

実施例６の化合物１４にかえて化合物１７を０．０８９４ｇ（０．１４３ｍｍｏｌ）を用いた以外は、実施例６と同様にして、高分子化合物Ｐ４を合成した。得量は２２ｍｇであり、ポリスチレン換算の数平均分子量は６．７×１０^３であり、重量平均分子量は１．３×１０^４であった。

A polymer compound P4 was synthesized in the same manner as in Example 6, except that 0.0894 g (0.143 mmol) of Compound 17 was used instead of Compound 14 of Example 6. The yield was 22 mg, the polystyrene-equivalent number average molecular weight was 6.7 × 10 ³ , and the weight average molecular weight was 1.3 × 10 ⁴ .

Example 10
(Synthesis of polymer compound P5)

実施例６の化合物１４にかえて化合物１８を０．０６８１ｇ（０．１０４ｍｍｏｌ）を用いた以外は、実施例６と同様にして、高分子化合物Ｐ５を合成した。得量は７７ｍｇであり、ポリスチレン換算の数平均分子量は７．４×１０^３であり、重量平均分子量は１．８×１０^４であった。

A polymer compound P5 was synthesized in the same manner as in Example 6, except that 0.0681 g (0.104 mmol) of Compound 18 was used instead of Compound 14 of Example 6. The yield was 77 mg, the polystyrene-equivalent number average molecular weight was 7.4 × 10 ³ , and the weight average molecular weight was 1.8 × 10 ⁴ .

Example 11
(Synthesis of polymer compound P6)

実施例６の化合物１４にかえて化合物１９を０．１５５ｇ（０．１３０ｍｍｏｌ）を用いた以外は、実施例６と同様にして、高分子化合物Ｐ６を合成した。得量は１０３ｍｇであり、ポリスチレン換算の数平均分子量は１．７×１０^４であり、重量平均分子量は３．４×１０^４であった。

A polymer compound P6 was synthesized in the same manner as in Example 6, except that 0.155 g (0.130 mmol) of Compound 19 was used instead of Compound 14 of Example 6. The yield was 103 mg, the polystyrene-equivalent number average molecular weight was 1.7 × 10 ⁴ , and the weight average molecular weight was 3.4 × 10 ⁴ .

Example 12
(Synthesis of polymer compound P7)

実施例６の化合物１４にかえて化合物２０を０．０８６０ｇ（０．１３０ｍｍｏｌ）を用いた以外は、実施例６と同様にして、高分子化合物Ｐ７を合成した。得量は８４ｍｇであり、ポリスチレン換算の数平均分子量は７．６×１０^４であり、重量平均分子量は１．３×１０^５であった。

A polymer compound P7 was synthesized in the same manner as in Example 6, except that 0.0860 g (0.130 mmol) of Compound 20 was used instead of Compound 14 of Example 6. The yield was 84 mg, the polystyrene-equivalent number average molecular weight was 7.6 × 10 ⁴ , and the weight average molecular weight was 1.3 × 10 ⁵ .

Example 13
(Synthesis of polymer compound P8)

実施例６の化合物１４にかえて化合物２１を０．０７８７ｇ（０．１３０ｍｍｏｌ）を用いた以外は、実施例６と同様にして、高分子化合物Ｐ８を合成した。得量は９０ｍｇであり、ポリスチレン換算の数平均分子量は４．１×１０^４であり、重量平均分子量は１．２×１０^５であった。

A polymer compound P8 was synthesized in the same manner as in Example 6 except that 0.0787 g (0.130 mmol) of Compound 21 was used instead of Compound 14 of Example 6. The yield was 90 mg, the polystyrene-equivalent number average molecular weight was 4.1 × 10 ⁴ , and the weight average molecular weight was 1.2 × 10 ⁵ .

Example 14
(Synthesis of polymer compound P9)

反応容器内の気体を窒素ガスで置換した後に、化合物１３を０．０１３５ｇ（０．００９５ｍｍｏｌ）、化合物１４を０．００４７ｇ（０．００９５ｍｍｏｌ）、トルエンを３０ｍＬ、トリス（ジベンジリデンアセトン）ジパラジウムを１．７ｍｇ、トリオルトトリルホスフィンを２．３ｍｇ加え、５時間還流させた。得られた反応液に、ブロモベンゼンを３０ｍｇ加えて、１時間還流させた。得られた反応液をアセトンに滴下したところ、析出物が得られた。得られた析出物をろ取し、トルエンと水とＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物を加えて、３時間還流させた。その後、トルエン層を抽出した。得られたトルエン溶液を、酢酸水溶液および水で洗浄した後、シリカゲルカラムを用いて精製した。得られたトルエン溶液をアセトンに滴下したところ、析出物が得られた。得られた析出物を、アセトンを溶媒として用いてソックスレー洗浄し、高分子化合物Ｐ９を得た。得量は１０ｍｇであり、ポリスチレン換算の数平均分子量は７．０×１０^３であり、重量平均分子量は８．５×１０^３であった。

After replacing the gas in the reaction vessel with nitrogen gas, 0.0135 g (0.0095 mmol) of compound 13, 0.0047 g (0.0095 mmol) of compound 14, 30 mL of toluene, tris (dibenzylideneacetone) dipalladium were added. 1.7 mg and 2.3 mg of triorthotolylphosphine were added and refluxed for 5 hours. 30 mg of bromobenzene was added to the obtained reaction solution and refluxed for 1 hour. When the obtained reaction solution was added dropwise to acetone, a precipitate was obtained. The obtained precipitate was collected by filtration, toluene, water, and sodium N, N-diethyldithiocarbamate trihydrate were added and refluxed for 3 hours. Thereafter, the toluene layer was extracted. The obtained toluene solution was washed with an acetic acid aqueous solution and water, and then purified using a silica gel column. When the obtained toluene solution was dropped into acetone, a precipitate was obtained. The resulting precipitate was Soxhlet washed using acetone as a solvent to obtain a polymer compound P9. The yield was 10 mg, the polystyrene-equivalent number average molecular weight was 7.0 × 10 ³ , and the weight average molecular weight was 8.5 × 10 ³ .

Example 15
(Production and Evaluation of Organic Transistor 1)
An organic transistor 1 having a structure shown in FIG. 9 was produced using a solution containing the polymer compound P1.
The surface of the heavily doped n-type silicon substrate to be the gate electrode was 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 were formed on the thermal oxide film by a photolithography process. The source electrode and the drain electrode had a chromium (Cr) layer and a gold (Au) layer from the thermal oxide film side, and had 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 thus obtained were formed was subjected to ultrasonic cleaning with acetone, and UV ozone treatment was performed with an ozone UV cleaner. Thereafter, the surface of the thermal oxide film was modified with β-phenethyltrichlorosilane, and the surfaces of the source electrode and the drain electrode were modified with pentafluorobenzenethiol. Next, the surface-treated thermal oxide film, the source electrode and the drain electrode are spin-coated with an orthodichlorobenzene solution of 0.5% by weight of the polymer compound P1 at a rotational speed of 1000 rpm, and an organic semiconductor layer (active layer) ) Was formed. Thereafter, the organic semiconductor layer was heated in the atmosphere at 170 ° C. for 30 minutes to manufacture the organic transistor 1.

The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 1 obtained. The field effect mobility was 4.5 × 10 ⁻³ cm ² / Vs.

Example 16
(Production and evaluation of organic transistor 2)
Organic transistor 2 was produced in the same manner as in Example 15 except that polymer compound P2 was used instead of polymer compound P1 in Example 15.

The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 2 obtained. The field effect mobility was 4.3 × 10 ⁻³ cm ² / Vs.

Example 16
(Production and evaluation of organic transistor 3)
Organic transistor 3 was produced in the same manner as in Example 15 except that polymer compound P3 was used instead of polymer compound P1 in Example 15.

The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 3 obtained. The field effect mobility was 4.1 × 10 ⁻³ cm ² / Vs.

1 ... substrate,
2, 2a ... active layer,
3. Insulating layer,
4 ... Gate electrode,
5 ... Source electrode,
6 ... drain electrode,
100, 110, 120, 130, 140, 150, 160, 170, 180... Organic transistor.

Claims (9)

A polymer compound comprising a structural unit represented by formula (1-1) and / or a structural unit represented by formula (1-2).

[Where,
A and C each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups optionally have a substituent.
B represents a tetravalent group, and this group may have a substituent.
Z ¹ and Z ² each independently represent a group represented by the formula (Z). ]

[Where,
R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]   The polymer compound according to claim 1, wherein A and C are a trivalent heterocyclic group.   The polymer compound according to claim 1 or 2, wherein B is a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group. The structural unit represented by the formula (1-1) is a structural unit represented by the formula (2-1), and the structural unit represented by the formula (1-2) is represented by the formula (2-2). The high molecular compound as described in any one of Claims 1-3 which is a structural unit represented by this.

[Where,
Z ¹ and Z ² represent the same meaning as described above.
X ¹ and X ² each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ¹ and Y ² each independently represent a nitrogen atom or a group represented by —CH═.
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]   The polymer compound according to any one of claims 1 to 4, wherein the polymer compound is a conjugated polymer compound. A compound represented by formula (3-1) or a compound represented by formula (3-2).

[Where,
W ¹ and W ² each independently represents a hydrogen atom or a halogen atom.
X ³ and X ⁴ each independently represents an oxygen atom, a sulfur atom or a selenium atom.
Y ³ and Y ⁴ each independently represent a nitrogen atom or a group represented by —CH═.
Z ³ and Z ⁴ each independently represent a group represented by the formula (Z ′).
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, halogen atom, silyl Represents a group, an alkenyl group or an alkynyl group, and these groups optionally have a substituent. ]

[Where,
R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]   The organic-semiconductor material containing the high molecular compound as described in any one of Claims 1-5.   An organic semiconductor element provided with the organic layer containing the organic-semiconductor material of Claim 7.   The organic transistor which has a source electrode, a drain electrode, a gate electrode, and an active layer, and contains the organic-semiconductor material of Claim 7 in this active layer.

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