JP2014031364A - Compound, method for producing compound, polymer obtained by polymerizing compound, and organic thin film and organic semiconductor element containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound used as a raw material of a polymer which is useful for manufacturing an organic transistor excellent in field effect mobility and for manufacturing an organic solar cell excellent in photoelectric conversion efficiency.SOLUTION: The compound is represented by formula (1). (In the formula, Rand Reach independently represent a C1-C30 alkyl group, a C6-C30 aryl group or a C2-C30 monovalent heterocyclic group, and these groups may have a substituent; Zand Zeach independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (a group represented by -B(OH)), or an organic tin residue; and ring A and ring B each independently represent a heterocyclic ring which may have a substituent.)

Description

  The present invention relates to a compound having a specific structure, a method for producing the compound, a polymer compound obtained by polymerizing the compound, an organic thin film containing the polymer compound, and an organic semiconductor element.

  A compound in which two heterocycles are cross-linked is fixed in planarity by cross-linking, and π conjugation spreads, and a soluble substituent can be introduced into the cross-linked site, so that a polymer compound capable of forming a thin film by a coating method can be produced. It is known that the polymer compound is useful as an organic transistor material or an organic solar cell material (Patent Document 1, Non-Patent Document 1, Non-Patent Document 2).

Special table 2009-506519

Macromolecular Chemistry and Physics 2011, 212, 428-443. Journal of Polymer Science: Part A: Polymer Chemistry, 2009, 47, 2073-2092.

  However, it cannot be said that the field effect mobility of the organic transistor using the polymer compound and the photoelectric conversion efficiency of the organic solar cell are sufficient.

  Then, an object of this invention is to provide the novel compound used as the raw material of the high molecular compound useful for manufacture of the organic transistor excellent in a field effect mobility. Another object of the present invention is to provide a novel compound that is a raw material for a polymer compound useful for the production of an organic solar cell having excellent photoelectric conversion efficiency. The present invention further provides a method for producing the compound, a polymer compound produced using the compound, an organic thin film containing the polymer compound, and an organic semiconductor element (particularly, an organic transistor and an organic solar cell). Objective.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.

（式中、
Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の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。
Ｚ^１およびＺ^２は、それぞれ独立に、水素原子、ハロゲン原子、ホウ酸エステル残基、ホウ酸残基（−Ｂ（ＯＨ）_２で表される基を意味する。）または有機スズ残基を表す。
環Ａおよび環Ｂは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。）
［２］ 前記環Ａおよび環Ｂが、同一である、[１]に記載の化合物。
［３］ 前記式（１）で表される化合物が、式（２）で表される化合物である、[１]または[２]に記載の化合物。

（式中、
Ｒ^１、Ｒ^２、Ｚ^１およびＺ^２は、前記と同じ意味を表す。
Ｘは、酸素原子、硫黄原子またはセレン原子を表す。２個存在するＸは、同一でも異なっていてもよい。
Ｙは、窒素原子または−ＣＲ^３＝を表す。２個存在するＹは、同一でも異なっていてもよい。Ｒ^３は、水素原子、フッ素原子、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の１価の複素環基または炭素原子数１〜３０のアルコキシ基を表し、これらの基は置換基を有していてもよい。Ｒ^３が２個存在する場合、それらは同一でも異なっていてもよい。）
［４］ 前記Ｙが、−ＣＨ＝である、[３]に記載の化合物。
［５］ 前記Ｘが、硫黄原子である、[３]または[４]に記載の化合物。
［６］ 前記Ｒ^１とＲ^２が、同一である、[１]〜[５]のいずれか一項に記載の化合物。
［７］ 前記Ｒ^１とＲ^２が、炭素原子数１〜３０のアルキル基である、[６]に記載の化合物。
［８］ 前記Ｚ^１とＺ^２が、同一である、[１]〜[７]のいずれか一項に記載の化合物。
［９］ 前記Ｚ^１とＺ^２が、水素原子である、[８]に記載の化合物。
［１０］ 式（３）で表される化合物と、式（４）で表される化合物および式（５）で表される化合物からなる群から選ばれる少なくとも１種の化合物と、を反応させる第一工程と、

（式中、
環Ａおよび環Ｂは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。）

Ｒ^１−Ｍｔｌ （４）
（式中、
Ｒ^１は、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、または炭素原子数２〜３０の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。
Ｍｔｌは、リチウム原子またはマグネシウムハライドを表す。）

Ｒ^２−Ｍｔｌ （５）
（式中、
Ｒ^２は、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の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。
Ｍｔｌは、前記と同じ意味を表す。）
第一工程で得られた化合物を酸の存在下にて反応させる第二工程と、
を含む、[９]に記載の化合物の製造方法。
［１１］ 式（Ａ）で表される化合物。

Ｚ^３−Ｗ^１−Ａｒ^１−Ｗ^２−Ｚ^４ （Ａ）
（式中、Ｚ^３およびＺ^４は、それぞれ独立に、水素原子、ハロゲン原子、ホウ酸エステル残基、ホウ酸残基（−Ｂ（ＯＨ）_２で表される基を意味する。）または有機スズ残基を表す。Ａｒ^１は、アリーレン基または２価の複素環基を表す。Ｗ^１は、式（Ａ−１）で表される基または式（Ａ−２）で表される基を表す。Ｗ^２は、式（Ａ−３）で表される基または式（Ａ−４）で表される基を表す。）

（式（Ａ−１）〜式（Ａ−４）中、Ｒ’、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の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。環Ｃ、環Ｄ、環Ｅ、および環Ｆは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。）
［１２］ 式（７）で表される化合物、式（８）で表される化合物、または式（９）で表される化合物である[１１]に記載の化合物。

（式（７）〜式（９）中、Ｒ’、Ｒ^４、Ｒ^５、Ｒ^６、Ｚ^３、Ｚ^４、Ａｒ^１、環Ｃ、環Ｄ、環Ｅ、および環Ｆは、前記と同じ意味を表す。）
［１３］ 式（１０）で表される化合物、式（１１）で表される化合物、または式（１２）で表される化合物である[１２]に記載の化合物。

（式（１０）〜式（１２）中、Ｒ’、Ｒ^４、Ｒ^５、Ｒ^６、Ｚ^３、およびＺ^４は、前記と同じ意味を表す。Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の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。）
［１４］ [１]〜[９]、および[１１]〜[１３]のいずれか一項に記載の化合物を、単独重合または共重合して得られる高分子化合物。
［１５］ [１４]に記載の高分子化合物を含む、有機薄膜。
［１６］ 第１の電極と第２の電極とを有し、
該第１の電極と該第２の電極との間に活性層を有し、該活性層に［１４］に記載の高分子化合物を含む、有機半導体素子。
［１７］ 光電変換素子である、［１６］に記載の有機半導体素子。
［１８］ 有機トランジスタである、［１６］に記載の有機半導体素子。 [1] A compound represented by formula (1).

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups May have a substituent.
Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or an organic tin residue. Represent.
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )
[2] The compound according to [1], wherein the ring A and the ring B are the same.
[3] The compound according to [1] or [2], wherein the compound represented by the formula (1) is a compound represented by the formula (2).

(Where
R ¹ , R ² , Z ¹ and Z ² represent the same meaning as described above.
X represents an oxygen atom, a sulfur atom or a selenium atom. Two X's may be the same or different.
Y represents a nitrogen atom or —CR ³ ═. Two Y's may be the same or different. R ³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms. These groups may have a substituent. When two R ³ are present, they may be the same or different. )
[4] The compound according to [3], wherein Y is —CH═.
[5] The compound according to [3] or [4], wherein X is a sulfur atom.
[6] The compound according to any one of [1] to [5], wherein R ¹ and R ² are the same.
[7] The compound according to [6], wherein R ¹ and R ² are alkyl groups having 1 to 30 carbon atoms.
[8] The compound according to any one of [1] to [7], wherein Z ¹ and Z ² are the same.
[9] The compound according to [8], wherein Z ¹ and Z ² are hydrogen atoms.
[10] First reaction of the compound represented by the formula (3) with at least one compound selected from the group consisting of the compound represented by the formula (4) and the compound represented by the formula (5). One process,

(Where
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )

R ¹ -Mtl (4)
(Where
R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. It may be.
Mtl represents a lithium atom or a magnesium halide. )

R ² -Mtl (5)
(Where
R ² represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. May be.
Mtl represents the same meaning as described above. )
A second step of reacting the compound obtained in the first step in the presence of an acid;
The manufacturing method of the compound as described in [9] containing.
[11] A compound represented by the formula (A).

^{Z 3 -W 1 -Ar 1 -W 2} -Z 4 (A)
(In the formula, Z ³ and Z ⁴ each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or organic. Represents a tin residue, Ar ¹ represents an arylene group or a divalent heterocyclic group, and W ¹ represents a group represented by the formula (A-1) or a group represented by the formula (A-2). W ² represents a group represented by the formula (A-3) or a group represented by the formula (A-4).

(In Formula (A-1) to Formula (A-4), R ′, R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 30 carbon atoms, or having 6 to 30 carbon atoms. Represents an aryl group or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups may have a substituent, and ring C, ring D, ring E, and ring F are each independently Represents a heterocyclic ring, which may have a substituent.
[12] The compound according to [11], which is a compound represented by formula (7), a compound represented by formula (8), or a compound represented by formula (9).

(In Formula (7) to Formula (9), R ′, R ⁴ , R ⁵ , R ⁶ , Z ³ , Z ⁴ , Ar ¹ , Ring C, Ring D, Ring E, and Ring F are the same as above. Represents meaning.)
[13] The compound according to [12], which is a compound represented by formula (10), a compound represented by formula (11), or a compound represented by formula (12).

(In the formula (10) to Formula ^{(12), R ', R} 4, R 5, R 6, Z 3, and ^{Z 4 are, .R} 7, R ⁸ represent the same meanings as defined above, R ^{9, R 10} , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or a monovalent group having 2 to 30 carbon atoms. And these groups may have a substituent.)
[14] A polymer compound obtained by homopolymerizing or copolymerizing the compound according to any one of [1] to [9] and [11] to [13].
[15] An organic thin film comprising the polymer compound according to [14].
[16] having a first electrode and a second electrode;
An organic semiconductor device comprising an active layer between the first electrode and the second electrode, wherein the active layer contains the polymer compound according to [14].
[17] The organic semiconductor element according to [16], which is a photoelectric conversion element.
[18] The organic semiconductor element according to [16], which is an organic transistor.

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound as a raw material for a polymer compound useful for the production of an organic transistor having excellent field effect mobility, and a raw material for a polymer compound useful for the production of an organic solar cell having excellent photoelectric conversion efficiency A novel compound can be provided. The present invention also provides a method for producing the compound, a polymer compound produced using the compound, an organic thin film containing the polymer compound, and an organic semiconductor element (particularly, an organic transistor and an organic solar cell). can do.
Furthermore, according to a preferred embodiment of the present invention, a polymer compound exhibiting a high ionization potential can be provided. By using the polymer compound, it is possible to provide an organic solar cell having an excellent open circuit voltage, and it is generally known that there is a correlation between the ionization potential and the atmospheric stability. Organic semiconductor elements (in particular, organic transistors and organic solar cells) are also expected.

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. It is a schematic cross section which shows an example of the photoelectric conversion element 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.

  <Compound>

（式中、
Ｒ^１およびＲ^２は、それぞれ独立に、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の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。
Ｚ^１およびＺ^２は、それぞれ独立に、水素原子、ハロゲン原子、ホウ酸エステル残基、ホウ酸残基（−Ｂ（ＯＨ）_２で表される基を意味する。）または有機スズ残基を表す。
環Ａおよび環Ｂは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。）

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups May have a substituent.
Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or an organic tin residue. Represent.
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )

R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups May have a substituent. From the viewpoint of ease of synthesis of the compound of the present invention, R ¹ and R ² are preferably the same, more preferably the same, and more preferably an alkyl group having 1 to 30 carbon atoms.

The alkyl group represented by R ¹ and R ² may be either a linear alkyl group or a branched alkyl group, or a cycloalkyl group. The number of carbon atoms of the alkyl group is usually 1 to 30 (usually 3 to 30 in the case of a cycloalkyl group), and preferably 1 to 20 (3 to 20 in the case of a cycloalkyl group). The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group, Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, and 3,7-dimethyloctyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.
The alkyl group may have a substituent, and examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The aryl group represented by R ¹ and R ² is the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the aromatic hydrocarbon which may have a substituent, and benzene It includes a group in which two or more selected from a group having a ring, a group having a condensed ring, an independent benzene ring and a condensed ring are directly bonded. The number of carbon atoms that the aryl group has is usually 6 to 30, and preferably 6 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group. 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 4-phenylphenyl group and the like, and a phenyl group is preferable.
Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, an alkylthio group, a monovalent heterocyclic group, and a halogen atom. Examples of the aryl group containing these groups include 4-hexylphenyl group, 3,5-dimethoxyphenyl group, pentafluorophenyl group and the like. When the aryl group has a substituent, the substituent is preferably an alkyl group.

The monovalent heterocyclic group represented by R ¹ and R ² is the remaining atom obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the heterocyclic compound which may have a substituent. It is a group and includes a group in which two or more selected from a group having a condensed ring, an independent heterocyclic ring and a condensed ring are directly bonded. The number of carbon atoms that the monovalent heterocyclic group has is usually 2 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the monovalent heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group. Group, 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like, and 2-thienyl group is preferable.
Examples of the substituent that the monovalent heterocyclic group may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Examples of the monovalent heterocyclic group containing these groups include 5-octyl-2-thienyl group and 5-phenyl-2-furyl group. When the monovalent heterocyclic group has a substituent, the substituent is preferably an alkyl group.

The definitions and examples of the alkyl group, aryl group and monovalent heterocyclic group as substituents are the same as the definitions and examples of the alkyl group, aryl group and monovalent heterocyclic group represented by R ¹ and R ² .

The alkoxy group as a substituent may be either a linear alkoxy group or a branched alkoxy group, or a cycloalkoxy group. The number of carbon atoms that the alkoxy group has is usually 1 to 30 (in the case of a cycloalkoxy group, usually 3 to 30).
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n- Linear alkoxy group such as dodecyloxy group, n-hexadecyloxy group, isopropoxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, 2-butyloctyloxy group, 2- Examples thereof include branched alkoxy groups such as hexyldecyloxy group and 2-octyldodecyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.

The alkylthio group as a substituent may be either a linear alkylthio group or a branched alkylthio group, or a cycloalkylthio group. The number of carbon atoms that the alkylthio group has is usually 1 to 30 (usually 3 to 30 in the case of a cycloalkylthio group).
Specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-dodecylthio group, n -Straight chain alkylthio group such as hexadecylthio group, isopropylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, 2-ethylhexylthio group, 2-butyloctylthio group, 2-hexyldecylthio group, 2- Examples thereof include branched alkylthio groups such as octyldodecylthio group, cycloalkylthio groups such as cyclopentylthio group and cyclohexylthio group.

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

Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or an organic tin residue. Represent. From the viewpoint of ease of synthesis of the compound of the present invention, Z ¹ and Z ² are preferably the same and more preferably a hydrogen atom.

Examples of the halogen atom represented by Z ¹ and Z ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the boric acid ester residue represented by Z ¹ and Z ² include the following formula:

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。）
で表される基等が挙げられる。

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
The group etc. which are represented by these are mentioned.

Examples of the organotin residue represented by Z ¹ and Z ² include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
Specific examples of the alkyl group as the monovalent organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, and n-pentyl. Group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, Examples include chain alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and adamantyl group. It is done.
Specific examples of the aryl group as the monovalent organic group include a phenyl group and a naphthyl group.
The organotin residues, preferably -SnMe _3, -SnEt _3, a -SnBu ₃ or -SnPh _3, more preferably -SnMe _3, a -SnEt ₃ or -SnBu _3.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. The number of carbon atoms in the heterocyclic ring is preferably 2 to 30, more preferably 2 to 14, and further preferably 3 to 8. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Ring A and ring B are preferably the same from the viewpoint of ease of synthesis of the compound of the present invention, and from the viewpoint of further expanding the π conjugation of the polymer compound obtained by polymerizing the compound of the present invention, 5 A 6-membered ring is preferable, and a 5-membered ring is more preferable.

  The compound represented by the formula (1) is preferably a compound represented by the formula (2).

（式中、
Ｒ^１、Ｒ^２、Ｚ^１およびＺ^２は、前記と同じ意味を表す。
Ｘは、酸素原子、硫黄原子またはセレン原子を表す。２個存在するＸは、同一でも異なっていてもよい。
Ｙは、窒素原子または−ＣＲ^３＝を表す。２個存在するＹは、同一でも異なっていてもよい。Ｒ^３は、水素原子、フッ素原子、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の１価の複素環基または炭素原子数１〜３０のアルコキシ基を表し、これらの基は置換基を有していてもよい。Ｒ^３が２個存在する場合、それらは同一でも異なっていてもよい。）

(Where
R ¹ , R ² , Z ¹ and Z ² represent the same meaning as described above.
X represents an oxygen atom, a sulfur atom or a selenium atom. Two X's may be the same or different.
Y represents a nitrogen atom or —CR ³ ═. Two Y's may be the same or different. R ³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms. These groups may have a substituent. When two R ³ are present, they may be the same or different. )

  X is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom, from the viewpoint of ease of synthesis of the compound of the present invention.

Y is preferably —CR ³ ═, more preferably —CH═, from the viewpoint of ease of synthesis of the compound of the present invention.

R ³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms. These groups may have a substituent.
Definitions and examples of the alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the monovalent heterocyclic group having 2 to 30 carbon atoms represented by R ³ are R ¹ and R ^2. Are the same as the definitions and examples of the alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the monovalent heterocyclic group having 2 to 30 carbon atoms.

Examples of the alkoxy group having 1 to 30 carbon atoms represented by R ³ include methoxy group, ethoxy group, n-propoxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, and n-heptyloxy. Group, linear alkoxy group such as n-octyloxy group, n-dodecyloxy group, n-hexadecyloxy group, isopropoxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group Branched alkoxy groups such as 2-butyloctyloxy group, 2-hexyldecyloxy group and 2-octyldodecyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.
Examples of the substituent that the alkoxy group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkoxy group having a substituent include a methoxyethoxy group, a benzyloxy group, and a trifluoromethoxy group.

R ³ preferably represents an alkyl group having 1 to 30 carbon atoms, a fluorine atom or a hydrogen atom, more preferably a hydrogen atom, from the viewpoint of the ease of synthesis of the compound of the present invention.

  Examples of the compound represented by Formula (1) or the compound represented by Formula (2) include compounds represented by Formula (1-1) to Formula (1-27).

  Among the compounds represented by the formula (1-1) to the formula (1-27), the compounds represented by the formula (1-1) to the formula (1-10) are preferable, and the formula is more preferable. It is a compound represented by (1-1) -Formula (1-3), More preferably, it is a compound represented by Formula (1-1).

The compound represented by the formula (1) in which Z ¹ and Z ² represent a halogen atom is the same as the compound represented by the formula (1 ′) which is an embodiment of the compound represented by the formula (1). Alternatively, it can be produced by reacting with N-halosuccinimide.
In addition, the compound represented by the formula (1) in which Z ¹ and Z ² represent a halogen atom is reacted with an alcoholate diborane such as pinacholate diborane in the presence of a palladium catalyst such as dichloro (diphenylphosphinoferrocene) palladium. Thus, a compound represented by the formula (1) in which Z ¹ and Z ² represent a boric acid ester residue can be produced.
In addition, a compound represented by the formula (1) in which Z ¹ and Z ² represent a halogen atom is converted into a compound such as hexamethylditine or hexabutylditine in the presence of a palladium catalyst such as dichloro (diphenylphosphinoferrocene) palladium. By reacting with an organic distin compound, a compound represented by the formula (1) in which Z ¹ and Z ² represent an organic tin residue can be produced.
Moreover, after anionizing the compound represented by the formula (1 ′) with a lithium reagent such as butyl lithium or lithium diisopropylamide, and reacting with an organic tin halide, Z ¹ and Z ² represent an organic tin residue. A compound represented by the formula (1) can be produced.
Furthermore, instead of the above organotin halide, Z ¹ and Z ² are reacted with trialkoxyborane and then hydrolyzed with an acid, whereby Z ¹ and Z ² are groups represented by a boric acid residue (—B (OH) _2. It is possible to produce a compound represented by formula (1).

（式中、Ｒ^１、Ｒ^２、環Ａおよび環Ｂは、前記と同じ意味を表す。）

(Wherein R ¹ , R ² , ring A and ring B represent the same meaning as described above.)

<Method for producing compound>
The compound represented by the above formula (1 ′) is
A first step of reacting a compound represented by formula (3) with at least one compound selected from the group consisting of a compound represented by formula (4) and a compound represented by formula (5); ,

（式中、
環Ａおよび環Ｂは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。）
Ｒ^１−Ｍｔｌ （４）
（式中、
Ｒ^１は、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の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。
Ｍｔｌは、リチウム原子またはマグネシウムハライドを表す。）
Ｒ^２−Ｍｔｌ （５）
（式中、
Ｒ^２は、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の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。
Ｍｔｌは、前記と同じ意味を表す。）
第一工程で得られた化合物を酸の存在下にて反応させる第二工程と、
を含む方法により製造することができる。

(Where
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )
R ¹ -Mtl (4)
(Where
R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. May be.
Mtl represents a lithium atom or a magnesium halide. )
R ² -Mtl (5)
(Where
R ² represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. May be.
Mtl represents the same meaning as described above. )
A second step of reacting the compound obtained in the first step in the presence of an acid;
It can manufacture by the method containing.

  Under the present circumstances, after refine | purifying the compound represented by Formula (6) manufactured at a 1st process, you may make it react on the acidic conditions of a 2nd process.

（式中、Ｒ^１、Ｒ^２、環Ａおよび環Ｂは、前記と同じ意味を表す。〕

(Wherein R ¹ , R ² , ring A and ring B represent the same meaning as described above.)

Examples of Mtl in the compound represented by formula (4) and the compound represented by formula (5) used in the first step include a lithium atom and magnesium halide.
When Mtl represents magnesium halide, specific examples of the compound represented by formula (4) or the compound represented by formula (5) include methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, propyl. Magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, hexyl magnesium bromide, octyl magnesium bromide, decyl magnesium bromide, allyl magnesium chloride, allyl magnesium bromide, benzyl magnesium chloride, phenyl magnesium bromide, naphthyl magnesium bromide, tolyl magnesium bromide Etc.

  When Mtl represents a lithium atom, specific examples of the compound represented by Formula (4) or the compound represented by Formula (5) include methyllithium, ethyllithium, propyllithium, butyllithium, phenyllithium, and naphthyllithium. , Benzyl lithium, tolyl lithium and the like.

  The reaction in the first step may be performed in an inert gas atmosphere such as nitrogen gas or argon gas, or in the presence of a solvent. The reaction temperature is not particularly limited, but the reaction is preferably performed at a temperature within the range of -80 ° C to the boiling point of the solvent.

  Solvents used in the first step reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl-t- And ethers such as butyl ether, tetrahydrofuran, tetrahydropyran and dioxane. These solvents may be used alone or in combination.

  After the reaction in the first step (for example, after the reaction is stopped by adding water), the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent to obtain the formula (6) A mixture containing a compound represented by the formula can be obtained. The mixture may be purified by chromatographic fractionation or recrystallization.

  Next, in the second step, the compound represented by the formula (1 ′) can be produced by reacting the mixture containing the compound represented by the above formula (6) in the presence of an acid. it can.

  The acid used in the reaction in the second step may be any of Lewis acid or Bronsted acid. Specific examples include hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, and oxalic acid. , Benzoic acid, boron trifluoride diethyl ether complex, aluminum chloride, tin (IV) chloride, silicon (IV) chloride, iron (III) chloride, titanium tetrachloride, zinc chloride, benzenesulfonic acid, p-toluenesulfonic acid, Examples thereof include trifluoroacetic acid, trifluoromethanesulfonic acid, and mixtures thereof.

  The reaction in the second step may be performed in the presence of an acid alone or in the presence of an acid and a solvent. The reaction temperature is not particularly limited, but the reaction is preferably performed at a temperature within the range of -80 ° C to the boiling point of the solvent.

  Solvents used in the second step reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane and chlorobutane. , Halogenated saturated hydrocarbons such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, Alcohols such as isopropanol, butanol and tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether, Le -tert- butyl ether, tetrahydrofuran, tetrahydropyran, ethers such as dioxanes, hydrochloric, hydrobromic, hydrofluoric, sulfuric acid, and inorganic acids such as nitric acid. These solvents may be used alone or in combination.

  After the reaction in the second step (for example, after adding water to stop the reaction), the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent. The compounds represented can be produced. If necessary, purification such as fractionation by chromatography or recrystallization may be further performed.

<Polymer compound>
The weight average molecular weight of the polymer compound of the present invention obtained by polymerizing the compound of the present invention is usually 3000 or more, but preferably 3000 to 1000000. If the weight average molecular weight is lower than 3000, defects may occur in the film formation during the production of the organic semiconductor element, and if it is greater than 1000000, the solubility in a solvent and the coating property during the production of the organic semiconductor element may be reduced. . The weight average molecular weight of the polymer compound of the present invention is more preferably 8,000 to 500,000, still more preferably 10,000 to 300,000.
In addition, the weight average molecular weight in the polymer compound of the present invention refers to a weight average molecular weight in terms of polystyrene calculated using gel permeation chromatography (GPC) and using a polystyrene standard sample.

  In addition, when the polymer compound of the present invention is used in an organic semiconductor element, it is preferable that the solubility in a solvent is high because the production of the organic semiconductor element becomes easier. Specifically, it preferably has a solubility capable of producing a solution containing 0.01% by weight (hereinafter sometimes referred to as “wt%”) of the polymer compound of the present invention, and is preferably 0.1% by weight or more. More preferably, it has a solubility capable of producing a solution containing it, and more preferably has a solubility capable of producing a solution containing 0.4 wt% or more.

The polymer compound of the present invention is a polymer compound obtained by homopolymerization or copolymerization of the compound of the present invention, and examples of the copolymerization partner include vinylene group, ethynylene group, arylene group or divalent group. A heterocyclic group, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid residue (meaning a group represented by —B (OH) ₂ ), a boric acid ester residue Examples thereof include compounds in which two groups selected from a group and an organic tin residue are substituted, and these substituents are appropriately selected according to the polymerization method described later.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of synthesis of the polymer compound of the present invention, a bromine atom or an iodine atom is preferable, and a bromine atom is more preferable.

Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.
Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group.
Examples of the arylalkyl sulfonate group include a benzyl sulfonate group.

  As the borate ester residue, the following formula:

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。）
で表される基等が例示される。

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
The group etc. which are represented by these are illustrated.

Examples of the organic tin residue include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
Specific examples of the alkyl group as the monovalent organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, and n-pentyl. Group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, Examples include chain alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and adamantyl group. It is done.
Specific examples of the aryl group as the monovalent organic group include a phenyl group and a naphthyl group.
The organotin residues, preferably -SnMe _3, -SnEt _3, a -SnBu ₃ or -SnPh _3, more preferably -SnMe _3, a -SnEt ₃ or -SnBu _3.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

  The arylene group that can be contained in the polymer compound of the present invention is the remaining atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon which may have a substituent. And those having a benzene ring, those having a condensed ring, those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. The number of carbon atoms constituting the ring of the arylene group is usually 6 to 60, preferably 6 to 20.

  Specific examples of the arylene group include arylene groups represented by Formulas 1 to 12.

(Where
R represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. A plurality of R may be the same or different.
The definition and examples of the alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the monovalent heterocyclic group having 2 to 30 carbon atoms represented by R are the carbons represented by R ¹ and R ^2. The definition and examples are the same as those of the alkyl group having 1 to 30 atoms, the aryl group having 6 to 30 carbon atoms, and the monovalent heterocyclic group having 2 to 30 carbon atoms.
The definition and examples of the alkoxy group having 1 to 30 carbon atoms represented by R are the same as the definition and examples of the alkoxy group having 1 to 30 carbon atoms represented by R ³ . )

  The divalent heterocyclic group that can be contained in the polymer compound of the present invention is the remaining atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound, And a group in which two or more selected from an independent heterocyclic ring and a condensed ring are directly bonded. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. The thing included in. The number of carbon atoms constituting the ring of the divalent heterocyclic group is usually 2-30, preferably 3-20. Further, the divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

  Specific examples of the divalent heterocyclic group include divalent heterocyclic groups represented by formulas 13 to 60. From the viewpoint of further expanding the π conjugation of the polymer compound of the present invention, a five-membered ring is formed. Formulas 25 to 28, Formula 36, Formula 37, Formula 43, Formula 44, Formulas 52 to 58, and Formula 60 are preferable. Further, from the viewpoint of further expanding the π conjugation of the polymer compound of the present invention, Formula 15 and Formula 18 having a 6-membered ring are preferable. Of the divalent heterocyclic group having a 5-membered ring and the divalent heterocyclic group having a 6-membered ring, a divalent heterocyclic group having a 5-membered ring is preferable. That is, Formula 25-Formula 28, Formula 36, Formula 37, Formula 43, Formula 44, Formula 52-58, and Formula 60 which have a 5-membered ring are more preferable.

(Where
R represents the same meaning as described above.
a and b each independently represent the number of repeating units, generally 1 to 5, preferably 1 to 3, and particularly preferably 1. )

（式中、Ｒは前記と同じ意味を表す。Ｒ’、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の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。） Examples of the structural unit contained in the polymer compound of the present invention include structural units represented by Formula 70 to Formula 84.

(In the formula, R represents the same meaning as described above. R ′, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or Represents a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups optionally have a substituent.)

Definition of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or a monovalent heterocyclic group having 2 to 30 carbon atoms represented by R ′, R ⁴ , R ⁵ and R6 Specific examples include the definition of the alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms, or the monovalent heterocyclic group having 2 to 30 carbon atoms represented by R ¹ described above. Same as example. From the viewpoint of ease of synthesis of the compound of the present invention, R ′, R ⁴ , R ⁵ , and R ⁶ preferably represent the same group, represent the same group, and have 1 to 30 carbon atoms. It is more preferable to represent the alkyl group.

  The polymer compound of the present invention may have a structural unit represented by Formula 70 to Formula 84 as a repeating unit, and may have a chain of the structural unit. In addition, a divalent organic group in which the structural unit is bonded through an arylene group or a divalent heterocyclic group may be included as a repeating unit, and the divalent organic group has a chain. Also good. Examples of the arylene group and the divalent heterocyclic group include groups represented by the above formulas 1 to 60.

<Method for producing polymer compound>
The method for producing the polymer compound of the present invention is not particularly limited, but a method using a Suzuki coupling reaction or a Stille coupling reaction is preferable from the viewpoint of ease of synthesis of the polymer compound.

As a method using the Suzuki coupling reaction, for example, when Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) represent a halogen atom, the compound represented by the formula (1) is used. One or more compounds (preferably, one or more compounds represented by formula (2)), one or more compounds represented by formula (100), and optionally formula (200) The manufacturing method which has the process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. As the divalent group represented by E ¹ and E ^2, the group represented by Formulas 1 to 60 described above are preferred.
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
(Where
E ¹ represents a vinylene group, an ethynylene group, an arylene group or a divalent heterocyclic group.
Q ¹⁰⁰ and Q ²⁰⁰ each independently represent a boric acid residue (meaning a group represented by —B (OH) ₂ ) or a boric acid ester residue. )
T ¹ -E ² -T ² (200)
(Where
E ² represents an arylene group or a divalent heterocyclic group.
T ¹ and T ² each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group. )

In the formula (100), the boric acid ester residue represented by Q ¹⁰⁰ and Q ²⁰⁰ is represented by the following formula:

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。）
で表される基等が挙げられる。

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
The group etc. which are represented by these are mentioned.

Examples of the halogen atom represented by T ¹ and T ² in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of synthesis of the polymer compound of the present invention, a bromine atom or an iodine atom is preferable, and a bromine atom is more preferable.

Examples of the alkyl sulfonate group represented by T ¹ and T ² in the formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.
Examples of the aryl sulfonate group represented by T ¹ and T ² in the formula (200) include a benzene sulfonate group and a p-toluene sulfonate group.
Examples of the arylalkyl sulfonate group represented by T ¹ and T ² in Formula (200) include a benzyl sulfonate group.

When Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) represent a halogen atom, one or more compounds represented by the formula (1) (preferably the formula (1) 2) one or more compounds represented by formula (2) and the total number of moles of one or more compounds represented by formula (200) and the sum of the number of moles of one or more compounds represented by formula (100) Is preferably close to 1. Specifically, one or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)) and one or more compounds represented by the formula (200) The ratio of the total number of moles of one or more compounds represented by the formula (100) to the total number of moles is preferably 0.7 to 1.4, preferably 0.8 to 1.2. More preferably it is.

On the other hand, Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) are boric acid ester residues or boric acid residues (groups represented by —B (OH) _2. Means.
), One or more compounds represented by formula (1) (preferably one or more compounds represented by formula (2)) and one or more compounds represented by formula (200) The manufacturing method which has the process of making a compound and 1 or more types of compounds represented by Formula (100) react with presence of a palladium catalyst and a base as needed is mentioned. As the divalent group represented by E ¹ and E ^2, the group represented by Formulas 1 to 60 described above are preferred.

Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) are boric acid ester residues or boric acid residues (meaning groups represented by —B (OH) _2. ), One or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)) and one or more compounds represented by the formula (100) The ratio of the total number of moles of the compound and the total number of moles of one or more compounds represented by the formula (200) is preferably close to 1. Specifically, one or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)) and one or more compounds represented by the formula (100) The ratio of the total number of moles of one or more compounds represented by formula (200) to the total number of moles is preferably 0.7 to 1.4, and preferably 0.8 to 1.2. More preferably it is.

  Specific examples of the method for carrying out the Suzuki coupling reaction include a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is performed in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (0) catalyst, Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, etc. are mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate. , Dichlorobis (triphenylphosphine) palladium, palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but one or more kinds of compounds represented by the formula (1) (preferably one kind represented by the formula (2) The total number of moles of the above compound) is usually 0.0001 to 0.5 mol%, preferably 0.0003 to 0.1 mol%.

  When using palladium acetate as the palladium catalyst used in the Suzuki coupling reaction, add phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine as ligands Can do. In this case, the addition amount of the ligand is usually 0.5 to 100 mol%, preferably 0.9 to 20 mol%, more preferably 1 to 10 mol%, based on the total number of moles of the palladium catalyst. is there.

Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide and the like. Examples of the organic base include triethylamine and tributylamine. Examples of the inorganic salt include cesium fluoride.
The addition amount of the base is usually 0.5 to 100 with respect to the total number of moles of one or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)). It is mol%, Preferably it is 0.9-20 mol%, More preferably, it is 1-10 mol%.

The Suzuki coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solvent solubility of the polymer compound of the present invention, toluene or tetrahydrofuran is preferred.
Moreover, you may make it react by a two-phase system by adding a base as aqueous solution. When an inorganic salt is used as the base, it is usually added and reacted as an aqueous solution from the viewpoint of solubility of the inorganic salt. In addition, when making it react by a two-phase system by adding a base as aqueous solution, you may add phase transfer catalysts, such as a quaternary ammonium salt, as needed.

  Although the temperature at which the Suzuki coupling reaction is carried out depends on the solvent, it is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound of the present invention. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

The Suzuki coupling reaction is preferably performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently deaerated with argon gas or nitrogen gas.
Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, dichlorobis (triphenylphosphine) palladium (II), represented by the formula (1), is added to the polymerization vessel. One or more types of compounds (preferably one or more types of compounds represented by formula (2)) and one or more types of compounds represented by formula (100) or one or more types of compounds represented by formula (200) The compound and, if necessary, one or more compounds represented by the formula (200) or one or more compounds represented by the formula (100) are charged, and the polymerization vessel is sufficiently substituted with nitrogen gas, After deaeration, a solvent (for example, toluene) deaerated by bubbling with nitrogen gas in advance is added, and then a base (for example, sodium carbonate) deaerated by bubbling with nitrogen gas is added to the solution. Was added dropwise an aqueous solution, etc.), heating, with thermal insulation (e.g., 8 hours at reflux temperature, while retaining the inert atmosphere), and may polymerize.

As a method using the Stille coupling reaction, for example, when Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) represent a halogen atom, the compound represented by the formula (1) is used. One or more compounds (preferably one or more compounds represented by the formula (2)), one or more compounds represented by the formula (300), and the above formula ( 200), and a production method having a step of reacting with one or more compounds in the presence of a palladium catalyst. As the divalent group represented by E ^3, a group represented by Formulas 1 to 60 described above are preferred.
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (300)
(Where
E ³ represents a vinylene group, an ethynylene group, an arylene group or a divalent heterocyclic group.
Q ³⁰⁰ and Q ⁴⁰⁰ each independently represent an organotin residue. )

In the formula (300), examples of the organotin residue represented by Q ³⁰⁰ and Q ⁴⁰⁰ include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
Specific examples of the alkyl group as the monovalent organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, and n-pentyl. Group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, Examples include chain alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and adamantyl group. It is done.
Specific examples of the aryl group as the monovalent organic group include a phenyl group and a naphthyl group.
The organotin residues, preferably -SnMe _3, -SnEt _3, a -SnBu ₃ or -SnPh _3, more preferably -SnMe _3, a -SnEt ₃ or -SnBu _3.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

When Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) represent a halogen atom, one or more compounds represented by the formula (1) (preferably the formula (1) 2) one or more compounds represented by formula (2) and the total number of moles of one or more compounds represented by formula (200) and the sum of the number of moles of one or more compounds represented by formula (300) Is preferably close to 1. Specifically, one or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)) and one or more compounds represented by the formula (200) The ratio of the total number of moles of one or more compounds represented by the formula (300) to the total number of moles is preferably 0.7 to 1.4, and 0.8 to 1.2. More preferably it is.

On the other hand, when Z ¹ and Z ² in the compound represented by Formula (1) or the compound represented by Formula (2) represent an organotin residue, one or more compounds represented by Formula (1) ( Preferably, one or more compounds represented by formula (2)), one or more compounds represented by formula (200), and optionally one or more compounds represented by formula (300) The manufacturing method which has a process with which a compound is made to react in presence of a palladium catalyst is mentioned.

When Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) represent an organotin residue, one or more compounds represented by the formula (1) (preferably (One or more compounds represented by formula (2)) and the total number of moles of one or more compounds represented by formula (300), and the number of moles of one or more compounds represented by formula (200) The total ratio is preferably close to 1. Specifically, one or more compounds represented by the formula (1) (preferably one or more compounds represented by the formula (2)) and one or more compounds represented by the formula (300) The ratio of the total number of moles of one or more compounds represented by formula (200) to the total number of moles is preferably 0.7 to 1.4, and preferably 0.8 to 1.2. More preferably it is.

Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specific examples include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, Palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable from the viewpoints of easy reaction (polymerization) operation and reaction (polymerization) rate.
The addition amount of the palladium catalyst used in the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but one or more compounds represented by the formula (1) (preferably the formula (2) ) Is usually 0.0001 to 0.5 mol%, preferably 0.0003 to 0.2 mol%, based on the total number of moles of one or more compounds represented by).

Further, in the Stille coupling reaction, a ligand or a cocatalyst can be used as necessary. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, triphenylarsine, and triphenoxyarsine. Examples include arsenic compounds. Examples of the cocatalyst include copper iodide, copper bromide, copper chloride, and copper (I) 2-thenoylate.
When using a ligand or a cocatalyst, the addition amount of the ligand or the cocatalyst is usually 0.5 to 100 mol%, preferably 0.9 to 20 mol%, based on the total number of moles of the palladium catalyst. More preferably, it is 1 to 10 mol%.

  The Stille coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solvent solubility of the polymer compound of the present invention, toluene or tetrahydrofuran is preferred.

The temperature at which the Stille coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound of the present invention. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for performing the reaction (reaction time) may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

The Stille coupling reaction is preferably performed in a reaction system in which the Pd catalyst is not deactivated in an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently deaerated with argon gas, nitrogen gas or the like.
Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the polymerization vessel is charged with a palladium catalyst, and one or more compounds represented by the formula (1) (preferably Is one or more compounds represented by formula (2)), one or more compounds represented by formula (300) or one or more compounds represented by formula (200), and optionally formula One or more compounds represented by (200) or one or more compounds represented by formula (300) are charged, and the polymerization vessel is sufficiently substituted with nitrogen gas, deaerated, and then preliminarily filled with nitrogen gas. After adding a solvent degassed by bubbling (for example, toluene), a ligand and a co-catalyst are added as necessary, and then heated and heated (for example, at reflux temperature for 8 hours, undisturbed Polymerization while maintaining an active atmosphere) It is below.

By reacting one or more compounds represented by formula (1) (preferably, one or more compounds represented by formula (2)) in the presence of a zerovalent nickel compound, the polymer of the present invention Compounds can also be produced. As the zero-valent nickel compound, bis (cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, or the like may be used. Also, a reducing metal such as zinc and divalent nickel such as NiCl ₂ and NiBr ₂ may be used. You may use the method of generating a zerovalent nickel compound within a reaction system by making a compound coexist.
When the reaction is carried out in the presence of a zerovalent nickel compound, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, and tetrahydrofuran. The temperature at which the reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The reaction time (reaction time) may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

In the case where Z ¹ and Z ² in the compound represented by the formula (1) or the compound represented by the formula (2) are hydrogen atoms, a production method by oxidative polymerization is also exemplified, and 1 represented by the formula (1) One or more kinds of compounds (preferably one or more kinds of compounds represented by formula (2)) and, if necessary, one or more kinds of compounds represented by formula (400) in the presence of a known oxidation polymerization catalyst. The method of making it react is mentioned. As the arylene group or a divalent heterocyclic group represented by E ^4, groups represented by Formulas 1 to 60 described above are preferred.
As the oxidation polymerization catalyst, for example, a metal halide, a mixture of a metal halide and an amine complex (metal halide / amine complex), or the like is used. Here, as the metal halide, for example, a monovalent, divalent, or trivalent halide of a metal such as copper, iron, vanadium, or chromium can be used. As the amine used for the production of the amine complex, for example, amines such as pyridine, lutidine, 2-methylimidazole, N, N, N ′, N′-tetramethylethylenediamine can be used. A metal halide / amine complex can be prepared by mixing a metal halide and an amine in a solvent in the presence of oxygen, and the molar ratio of the metal halide to the amine is usually the metal halide / amine. = 1/0. 1 to 1/200, preferably 1 / 0.3 to 1/100.
H-E ⁴ -H (400)
(In the formula, E ⁴ represents an arylene group or a divalent heterocyclic group.)

  As a catalyst in the oxidative polymerization, iron chloride can also be used (Polym. Prep. Japan, Vol. 48, 309 (1999)). Further, a polymer compound is obtained by using a copper / amine catalyst system (J. Org. Chem., 64, 2264 (1999), J. Polym. Sci. Part A, Polym. Chem., 37, 3702 (1999)). The molecular weight of can be increased.

  As the solvent in the oxidative polymerization, any solvent that does not cause poisoning of the catalyst can be used without particular limitation. Examples of the solvent include hydrocarbon solvents, ether solvents, and alcohols. Here, examples of the hydrocarbon solvent include toluene, benzene, xylene, trimethylbenzene, tetramethylbenzene, naphthalene, and tetralin. Examples of the ether solvent include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, and tert-butyl methyl ether. Examples of alcohols include methanol, ethanol, isopropanol, and 2-methoxyethanol.

  The reaction temperature in oxidative polymerization is usually -100 ° C to 100 ° C, preferably about -50 to 50 ° C.

  Furthermore, in the case of producing a polymer compound, a method of polymerizing a mixture of two or more compounds (hereinafter sometimes referred to as “monomer”) as a raw material of the polymer compound, or a single monomer. Examples thereof include a method of adding a second monomer after polymerization. By using these methods, or by combining these methods, it is possible to produce block copolymers, random copolymers, alternating copolymers, multi-block copolymers, graft copolymers, etc. is there.

  Since the terminal group of the polymer compound of the present invention, if the polymerization active group remains as it is, when used for the production of an organic semiconductor element, there is a possibility that the characteristics and life of the obtained organic semiconductor element may be reduced. It is preferably protected by a stable group. The polymer compound of the present invention preferably has a π-conjugated bond continuous with the π-conjugated structure of the main chain, and is preferably protected with an aryl group or a monovalent heterocyclic group.

（式（Ａ−１）〜式（Ａ−４）中、Ｒ’、Ｒ^４、Ｒ^５およびＲ^６は、前記と同じ意味を表す。環Ｃ、環Ｄ、環Ｅ、および環Ｆは、それぞれ独立に、複素環を表し、該複素環は置換基を有していてもよい。） The polymer compound of the present invention can also be produced using a compound represented by the formula (A).
^{Z 3 -W 1 -Ar 1 -W 2} -Z 4 (A)
(In the formula, Z ³ and Z ⁴ each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or organic. Represents a tin residue, Ar ¹ represents an arylene group or a divalent heterocyclic group, and W ¹ represents a group represented by the formula (A-1) or a group represented by the formula (A-2). W ² represents a group represented by the formula (A-3) or a group represented by the formula (A-4).

(In Formula (A-1) to Formula (A-4), R ′, R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above. Ring C, Ring D, Ring E and Ring F are Each independently represents a heterocycle, which may have a substituent.

The definitions and specific examples of ring C, ring D, ring E and ring F are the same as the definitions and specific examples of ring A and ring B described above.
Definitions and specific examples of halogen atoms, boric acid ester residues, boric acid residues (meaning groups represented by —B (OH) ₂ ) or organotin residues represented by Z ³ and Z ⁴ are as follows. Definition of the halogen atom represented by Z ¹ , borate ester residue, boric acid residue (meaning a group represented by —B (OH) ₂ ) or organotin residue, specific examples and The same. From the viewpoint of ease of synthesis of the compound of the present invention, Z ³ and Z ⁴ preferably represent the same group, and more preferably represent a hydrogen atom.

The definition and specific examples of the arylene group or divalent heterocyclic group represented by Ar ¹ are the same as the definition and specific examples of the arylene group or divalent heterocyclic group described above. From the viewpoint of spreading π conjugation of the polymer compound of the present invention, a divalent heterocyclic group is preferable, and Formulas 25 to 28, Formula 36, Formula 37, Formula 43, Formula 44, and Formula 52 having a five-membered ring are preferable. -58 and Formula 60 are more preferred.

〔式（７）〜式（９）中、Ｒ’、Ｒ^４、Ｒ^５、Ｒ^６、Ｚ^３、Ｚ^４、環Ｃ、環Ｄ、環Ｅ、環Ｆ、およびＡｒ^１は、前記と同じ意味を表す。〕 Examples of the compound represented by the formula (A) include a compound represented by the formula (7), a compound represented by the formula (8), and a compound represented by the formula (9).

[In the formulas (7) to (9), R ′, R ⁴ , R ⁵ , R ⁶ , Z ³ , Z ⁴ , ring C, ring D, ring E, ring F, and Ar ¹ are the same as above. Represents meaning. ]

（式（１０）〜式（１２）中、Ｒ’、Ｒ^４、Ｒ^５、Ｒ^６、Ｚ^３及びＺ^４は前記と同じ意味を表す。Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ独立に、水素原子、フッ素原子、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の１価の複素環基または炭素原子数１〜３０のアルコキシ基を表し、これらの基は置換基を有していてもよい。） As a compound represented by Formula (7), the compound represented by Formula (10) is preferable.
As a compound represented by Formula (8), the compound represented by Formula (11) is preferable.
As a compound represented by Formula (9), the compound represented by Formula (12) is preferable.

(In the formula (10) to Formula ^{(12), R ', R} 4, R 5, .R 7 R 6, Z 3 and ^{Z 4} represent the same meanings as defined ^{above, R 8, R 9, R} 10, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 1 having 2 to 30 carbon atoms. A valent heterocyclic group or an alkoxy group having 1 to 30 carbon atoms, which may have a substituent.)

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and the number of carbon atoms The definition and specific examples of the monovalent heterocyclic group having 2 to 30 carbon atoms or the alkoxy group having 1 to 30 carbon atoms include the alkyl group having 1 to 30 carbon atoms represented by the aforementioned R ³ , and 6 to 6 carbon atoms. Definitions and specific examples of 30 aryl groups, monovalent heterocyclic groups having 2 to 30 carbon atoms, or alkoxy groups having 1 to 30 carbon atoms are the same as those described above. From the viewpoint of ease of synthesis of the compound of the present invention, an alkyl group having 1 to 30 carbon atoms and a fluorine atom are preferable, and a hydrogen atom is more preferable.

（式中、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２は前記と同じ意味を表す。） The compound represented by formula (10), the compound represented by formula (11), and the compound represented by formula (12) are, for example, compounds represented by formula (2), wherein Z ¹ is bromine. A compound that is an atom and Z ² is a hydrogen atom, or a compound that Z ¹ is a hydrogen atom and Z ² is a bromine atom, and a compound represented by the formula (13), It can be obtained by reacting with a Stille coupling method.

(Wherein R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² represent the same meaning as described above.)

The compound represented by the formula (10) in which Z ³ and Z ⁴ are hydrogen atoms, the compound represented by the formula (11), and the compound represented by the formula (12) are increased in molecular weight by oxidation polymerization or the like. It is also possible to do. Z ³ and Z ⁴ are the same or different and are a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or an organotin residue formula (10 ), The compound represented by formula (11), and the compound represented by formula (12) can be made high molecular weight using the above-described Suzuki coupling or Stille coupling reaction. .

<Organic semiconductor materials>
The organic semiconductor material may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds. Moreover, in order to improve carrier transport property, the organic-semiconductor material may further contain the low molecular compound or polymer compound which has carrier transport property in addition to the polymer compound of this invention. When the organic semiconductor material contains a component 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.

  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 other than 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 charge mobility, when an organic thin film containing the polymer compound of the present invention is used for an organic semiconductor element, it means charges (electrons and holes) injected from the electrode. ) Or charge generated by light absorption can be efficiently transported. Taking advantage of these characteristics, the polymer compound of the present invention can be suitably used for various organic semiconductor elements such as photoelectric conversion elements (particularly, organic solar cells), organic transistors, and organic electroluminescence elements. Hereinafter, these organic semiconductor 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 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, etc. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples thereof include alloys with metals, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. 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.

  As a means for improving the photoelectric conversion efficiency, an additional intermediate layer other than the above active layer may be used. 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. The electron donating compound and the electron accepting compound are relatively determined from the energy levels of these compounds.

  As the electron-donating compound, 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, Examples thereof include 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, polythienylene vinylene and derivatives thereof, and the like.

  As the electron-accepting compound, in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof Derivatives, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof Derivatives, polyfluorenes and derivatives thereof, phenanthrene derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine), fullerenes, fullerene derivatives Body and the like, preferably, titanium oxide, carbon nanotubes, a fullerene or a fullerene derivative, more preferably a fullerene or a fullerene derivative.

Examples of fullerene or 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 (C84PCBM, [6,6] -Phenyl C84 butyric acid methyl ester), [6,6] 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 preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  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. A step of forming an active layer on the first electrode by a coating method using a solution containing the polymer compound of the present invention and a solvent (sometimes referred to as “ink”), a second on the active layer. It is a manufacturing method including the process of forming this electrode.

  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 unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene, carbon tetrachloride, chloroform, and dichloromethane. Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene Examples of the solvent include ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the above solvent at 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 solar cell)
The photoelectric conversion element using the polymer compound of the present invention can be operated as an organic solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. it can. It can also be used as an organic solar cell module by accumulating a plurality of organic 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 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 solar battery produced using the polymer compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, place of use and environment.

In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one side or both sides and have been subjected to antireflection treatment. 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. In addition, when used in places where it is not necessary to cover the surface with a hard material, such as where there is little impact from the outside, the protective function can be achieved by configuring the surface protective layer with a transparent plastic film or curing the filling resin. It is possible to eliminate the supporting substrate on one side. The periphery of the support substrate can be fixed in a sandwich with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame can be hermetically sealed with a sealing material. 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, an electron transport layer, and the like 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 transporting layer containing an electron transporting material adjacent to the light emitting layer between the cathode and the light emitting layer, the anode, the light emitting layer, and the electron An element having a 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 only needs 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 in the current path can be controlled by a voltage applied to the gate electrode. It is done.

  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.

  FIG. 10 is a schematic cross-sectional view of the photoelectric conversion element of the present invention. The photoelectric conversion element 300 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 formed on the first electrode 7a, and a second electrode formed on the active layer 2. The electrode 7b is provided.

  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. Therefore, the state of this interface greatly affects the mobility of the transistor. Therefore, as a method for improving the interface state and improving the properties, control of the interface with a silane coupling agent has been proposed (for example, Surface Chemistry, 2007, Vol. 28, No. 5, p. 242-248). ).

Examples of silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, 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 made 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 the organic transistor is manufactured, it is preferable to form a protective film on the organic transistor in order to protect the organic transistor. 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. The field effect transistor according to the present embodiment described above includes the polymer compound of the present invention as an active layer, and thereby includes an active layer excellent in carrier mobility. The degree will be high. 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 or deuterated acetone and using an NMR apparatus (manufactured by 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.

(Ionization potential analysis)
The ionization potential of the organic thin film containing the polymer compound was measured using a photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). Specifically, a coating solution was prepared by dissolving a polymer compound in o-dichlorobenzene at a concentration of 0.5% by weight, and the coating solution was measured by spin coating on a quartz substrate as a sample. . Each process was performed at room temperature and in the atmosphere.

１００ｍＬ三口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物１（０．４ｇ，１．８ｍｍｏｌ）および乾燥ＴＨＦ（５．４ｍＬ）を加え、８０℃に加熱した。その後、ｎ−ペンタデシルマグネシウムブロミド−ＴＨＦ溶液（１０．９ｍＬ，５．４ｍｍｏｌ）を同温で加え、２時間攪拌した。続いて、水（１０ｍＬ）を加えることで反応を終了させ、反応溶液をクロロホルムで２回抽出した。得られた有機層を飽和塩化アンモニウム水溶液で２回、飽和食塩水で１回洗浄し、無水硫酸ナトリウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製することで化合物２を得た。化合物２の得量は５１２ｍｇ、収率は３４％であった。 Example 1
(Synthesis of Compound 3)

After the gas in the 100 mL three-necked flask was placed in a nitrogen gas atmosphere, Compound 1 (0.4 g, 1.8 mmol) and dry THF (5.4 mL) were added and heated to 80 ° C. Thereafter, n-pentadecylmagnesium bromide-THF solution (10.9 mL, 5.4 mmol) was added at the same temperature, and the mixture was stirred for 2 hours. Subsequently, the reaction was terminated by adding water (10 mL), and the reaction solution was extracted twice with chloroform. The obtained organic layer was washed twice with saturated aqueous ammonium chloride solution and once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain compound 2. The yield of Compound 2 was 512 mg, and the yield was 34%.

¹ H-NMR (300 MHz, CO (CD ₃ ) ₂ ): δ (ppm) = 7.25 (d, 2H), 7.20 (d, 2H), 3.83 (s, 2H), 2.0 -1.0 (m, 56H), 0.93 (t, 6H).

１００ｍＬ三口フラスコ内を窒素ガス雰囲気下とした後、化合物２（０．５ｇ、０．７７ｍｍｏｌ）、酢酸（４０ｍＬ）およびトリフルオロ酢酸（２０ｍＬ）を加え、８０℃で１時間に加熱した。反応終了後、反応溶液を水３００ｍＬに注ぎ、トルエンで２回抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液で３回洗浄し、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製することで、化合物３を得た。化合物３の得量は４５１ｍｇ、収率は９３％であった。同様の方法により、化合物３をさらに合成した。

After the inside of the 100 mL three-necked flask was placed in a nitrogen gas atmosphere, Compound 2 (0.5 g, 0.77 mmol), acetic acid (40 mL) and trifluoroacetic acid (20 mL) were added, and the mixture was heated at 80 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into 300 mL of water and extracted twice with toluene. The obtained organic layer was washed three times with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain compound 3. The yield of Compound 3 was 451 mg, and the yield was 93%. Compound 3 was further synthesized by the same method.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.44 (d, 1H), 7.34 (d, 1H), 7.05 (d, 1H), 6.98 (d, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.24 (m, 52H), 0.87 (t, 6H).

１００ｍＬ三口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物３（０．８８７ｇ，１．４ｍｍｏｌ）、乾燥ＤＭＦ（１４０ｍＬ）およびＮ−ブロモ琥珀酸イミド（５５４ｍｇ，３．１１ｍｍｏｌ）を加え、６０℃で４時間加熱した。反応終了後、反応溶液を室温まで冷却した後、水（２００ｍｌ）を加え、トルエン（５０ｍＬ）で２回抽出した。
得られた有機層を飽和チオ硫酸ナトリウム水溶液（５０ｍＬ）、飽和食塩水（５０ｍＬ）で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。中圧分取カラムで精製することで化合物４を得た。化合物４の得量は１．０２ｇ，収率は９３％であった。 Example 2
(Synthesis of Compound 4)

After the gas in the 100 mL three-necked flask was put under a nitrogen gas atmosphere, Compound 3 (0.887 g, 1.4 mmol), dry DMF (140 mL) and N-bromosuccinimide (554 mg, 3.11 mmol) were added, and 60 Heat at 4 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (200 ml) was added, and the mixture was extracted twice with toluene (50 mL).
The obtained organic layer was washed with saturated aqueous sodium thiosulfate solution (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Compound 4 was obtained by purification with an intermediate pressure preparative column. The yield of Compound 4 was 1.02 g, and the yield was 93%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.40 (s, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.24 (m, 52H), 0.87 (t, 6H).

１００ｍＬ四口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（１５７ｍｇ，０．２０ｍｍｏｌ）および乾燥ＴＨＦ（５ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（９．１６ｍｇ，０．０１ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（１１．６ｍｇ，０．０４ｍｍｏｌ）、３Ｍリン酸カリウム水溶液（１ｍＬ）を加え、８０℃に加熱した。この反応溶液に対して、３０分間アルゴンガスバブリングによって脱気した化合物５（７７．６ｍｇ，０．２０ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて８０℃で滴下し、８０℃で３時間攪拌した。この反応溶液に対して、３０分間アルゴンガスバブリングによって脱気したフェニルボロン酸（１２２ｍｇ，０．４５ｍｍｏｌ）の乾燥ＴＨＦ（７ｍＬ）溶液、トリス（ジベンジリデンアセトン）ジパラジウム（９．１６ｍｇ，１μｍｏｌ）およびトリ-tert-ブチルホスホニウムテトラフルオロボラート（１１．６ｍｇ，４μｍｏｌ）を加え、８０℃で２時間攪拌した後、Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物（１．７ｇ）および水（１５ｇ）を加え、さらに８０℃で２時間攪拌した。得られた反応溶液中の水層を除去後、有機層を水（２０ｇ）で１回、１０ｗｔ％酢酸水溶液（２０ｇ）で２回、水（２０ｇ）で１回洗浄した後、アセトン（１３６ｍＬ）により再沈殿させた。得られた固体をカラムクロマトグラフィ（ＳｉＯ_２）で精製し、メタノールにより再沈殿することで、高分子化合物Ａを１１２ｍｇ得た。高分子化合物Ａのポリスチレン換算の数平均分子量は４．３×１０^４であり、ポリスチレン換算の重量平均分子量は１．３×１０^５であった。なお、高分子化合物Ａを含む有機薄膜のイオン化ポテンシャルは５．６ｅＶであった Example 3
(Synthesis of polymer compound A)

After the gas in the 100 mL four-necked flask was placed in a nitrogen gas atmosphere, Compound 4 (157 mg, 0.20 mmol) and dry THF (5 mL) were added, and degassed by argon gas bubbling for 30 minutes. Then, tris (dibenzylideneacetone) dipalladium (9.16 mg, 0.01 mmol), tri-tert-butylphosphonium tetrafluoroborate (11.6 mg, 0.04 mmol), 3M aqueous potassium phosphate solution (1 mL) were added. And heated to 80 ° C. To this reaction solution, a dry THF (5 mL) solution of Compound 5 (77.6 mg, 0.20 mmol) degassed by argon gas bubbling for 30 minutes was added dropwise at 80 ° C. over 5 minutes, and then at 80 ° C. for 3 hours. Stir. To this reaction solution, a solution of phenylboronic acid (122 mg, 0.45 mmol) dehydrated by argon gas bubbling for 30 minutes in dry THF (7 mL), tris (dibenzylideneacetone) dipalladium (9.16 mg, 1 μmol) and After adding tri-tert-butylphosphonium tetrafluoroborate (11.6 mg, 4 μmol) and stirring at 80 ° C. for 2 hours, sodium N, N-diethyldithiocarbamate trihydrate (1.7 g) and water ( 15 g) was added, and the mixture was further stirred at 80 ° C. for 2 hours. After removing the aqueous layer in the obtained reaction solution, the organic layer was washed once with water (20 g), twice with 10 wt% aqueous acetic acid (20 g) and once with water (20 g), and then with acetone (136 mL). By reprecipitation. The obtained solid was purified by column chromatography (SiO ₂ ) and reprecipitated with methanol to obtain 112 mg of polymer compound A. The number average molecular weight in terms of polystyrene of the polymer compound A was 4.3 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 1.3 × 10 ⁵ . The ionization potential of the organic thin film containing the polymer compound A was 5.6 eV.

１００ｍＬ四口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（１０６ｍｇ，０．１３５ｍｍｏｌ）および乾燥トルエン（１５ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、化合物６（７３．８ｍｇ，０．１５０ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（２．７５ｍｇ，３μｍｏｌ）およびトリス（ｏ−トルイル）ホスフィン（３．６５ｍｇ，１２μｍｏｌ）を加え、１００℃で３時間攪拌した。この反応溶液に対して、３０分間アルゴンガスバブリングによって脱気したフェニルブロマイド（７０ｍｇ，０．４５ｍｍｏｌ）の乾燥トルエン（６．２ｍＬ）溶液を１００℃で加え、１００℃で２時間攪拌し、Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物（０．８ｇ）および水（６．８ｇ）を加え、さらに８０℃で２時間攪拌した。得られた反応溶液中の水層を除去後、有機層を水（７．５ｇ）で１回、１０ｗｔ％酢酸水溶液（７．５ｇ）で２回、水（７．５ｇ）で１回洗浄した後、アセトン（１００ｍＬ）により再沈殿させた。得られた固体をカラムクロマトグラフィ（ＳｉＯ_２）で精製し、メタノールにより再沈殿することで、高分子化合物Ｂを７５ｍｇ得た。高分子化合物Ｂのポリスチレン換算の数平均分子量は２．５×１０^４であり、ポリスチレン換算の重量平均分子量は８．７×１０^４であった。なお、高分子化合物Ｂを含む有機薄膜のイオン化ポテンシャルは５．４ｅＶであった。 Example 4
(Synthesis of polymer compound B)

After the gas in the 100 mL four-necked flask was placed in a nitrogen gas atmosphere, Compound 4 (106 mg, 0.135 mmol) and dry toluene (15 mL) were added, and degassed by argon gas bubbling for 30 minutes. Then, compound 6 (73.8 mg, 0.150 mmol), tris (dibenzylideneacetone) dipalladium (2.75 mg, 3 μmol) and tris (o-toluyl) phosphine (3.65 mg, 12 μmol) were added, and at 100 ° C. Stir for 3 hours. To this reaction solution, a dry toluene (6.2 mL) solution of phenyl bromide (70 mg, 0.45 mmol) deaerated by argon gas bubbling for 30 minutes was added at 100 ° C., stirred at 100 ° C. for 2 hours, N, Sodium N-diethyldithiocarbamate trihydrate (0.8 g) and water (6.8 g) were added, and the mixture was further stirred at 80 ° C. for 2 hr. After removing the aqueous layer in the obtained reaction solution, the organic layer was washed once with water (7.5 g), twice with 10 wt% acetic acid aqueous solution (7.5 g), and once with water (7.5 g). Then, it was reprecipitated with acetone (100 mL). The obtained solid was purified by column chromatography (SiO ₂ ) and reprecipitated with methanol to obtain 75 mg of polymer compound B. The polymer compound B had a polystyrene-equivalent number average molecular weight of 2.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 8.7 × 10 ⁴ . The ionization potential of the organic thin film containing the polymer compound B was 5.4 eV.

１００ｍＬ四口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（１５７ｍｇ，０．２０ｍｍｏｌ）および乾燥ＴＨＦ（５ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（９．１６ｍｇ，１μｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（１１．６ｍｇ，４μｍｏｌ）および３Ｍリン酸カリウム水溶液（１ｍＬ）を加え、８０℃に攪拌した。この反応溶液に対して、８０℃において３０分間アルゴンガスバブリングによって脱気した化合物７（７８．４ｍｇ，０．２０ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で３時間攪拌した。この反応溶液に対して、３０分間アルゴンガスバブリングによって脱気したフェニルボロン酸（１２２ｍｇ，０．４５ｍｍｏｌ）の乾燥ＴＨＦ（７ｍＬ）溶液、トリス（ジベンジリデンアセトン）ジパラジウム（９．１６ｍｇ，１μｍｏｌ）およびトリ-tert-ブチルホスホニウムテトラフルオロボラート（１１．６ｍｇ，４μｍｏｌ）を８０℃で加え、８０℃で２時間攪拌し、Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物（１．７ｇ）および水（１５ｇ）を加え、さらに８０℃で２時間攪拌した。得られた反応溶液中の水層を除去後、有機層を水（２０ｇ）で１回、１０ｗｔ％酢酸水溶液（２０ｇ）で２回、水（２０ｇ）で１回洗浄した後、アセトン（１３６ｍＬ）により再沈殿させた。得られた固体をカラムクロマトグラフィ（ＳｉＯ_２）で精製し、メタノールにより再沈殿することで高分子化合物Ｃを１２０ｍｇ得た。高分子化合物Ｃのポリスチレン換算の数平均分子量は５．６×１０^４であり、ポリスチレン換算の重量平均分子量は１．１×１０^５であった。なお、高分子化合物Ｃを含む有機薄膜のイオン化ポテンシャルは５．４ｅＶであった。 Example 5
(Synthesis of polymer compound C)

After the gas in the 100 mL four-necked flask was placed in a nitrogen gas atmosphere, Compound 4 (157 mg, 0.20 mmol) and dry THF (5 mL) were added, and degassed by argon gas bubbling for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (9.16 mg, 1 μmol), tri-tert-butylphosphonium tetrafluoroborate (11.6 mg, 4 μmol) and 3M aqueous potassium phosphate solution (1 mL) were added, and the mixture was heated to 80 ° C. Stir. To this reaction solution, a dry THF (5 mL) solution of Compound 7 (78.4 mg, 0.20 mmol) degassed by argon gas bubbling at 80 ° C. for 30 minutes was added dropwise over 5 minutes, and then at 80 ° C. for 3 hours. Stir. To this reaction solution, a solution of phenylboronic acid (122 mg, 0.45 mmol) dehydrated by argon gas bubbling for 30 minutes in dry THF (7 mL), tris (dibenzylideneacetone) dipalladium (9.16 mg, 1 μmol) and Tri-tert-butylphosphonium tetrafluoroborate (11.6 mg, 4 μmol) was added at 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to give sodium N, N-diethyldithiocarbamate trihydrate (1.7 g) and Water (15 g) was added, and the mixture was further stirred at 80 ° C. for 2 hours. After removing the aqueous layer in the obtained reaction solution, the organic layer was washed once with water (20 g), twice with 10 wt% aqueous acetic acid (20 g) and once with water (20 g), and then with acetone (136 mL). By reprecipitation. The obtained solid was purified by column chromatography (SiO ₂ ) and reprecipitated with methanol to obtain 120 mg of polymer compound C. The number average molecular weight of polystyrene conversion of the high molecular compound C was 5.6 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 1.1 * 10 < ⁵ >. The ionization potential of the organic thin film containing the polymer compound C was 5.4 eV.

Example 6
(Production and Evaluation of Organic Transistor 1)
Using a solution containing the polymer compound A, an organic transistor 1 having the structure shown in FIG. 3 was produced.
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 with an ozone UV cleaner. Thereafter, the surface treatment of the thermal oxide film was performed with β-phenethyltrichlorosilane. 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 polymer compound A at a rotational speed of 1000 rpm, and an organic semiconductor layer (active layer) Formed. Thereafter, in a nitrogen atmosphere, the organic semiconductor layer was heated at 170 ° C. for 30 minutes to produce an 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 2.7 × 10 ⁻³ cm ² / Vs.

Example 7
(Production and evaluation of organic transistor 2)
Organic transistor 2 was produced in the same manner as in Example 6 except that polymer compound B was used in place of polymer compound A.

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 7.4 × 10 ⁻² cm ² / Vs.

Example 8
(Production and evaluation of organic transistor 3)
An organic transistor 3 was produced in the same manner as in Example 6 except that the polymer compound C was used in place of the polymer compound A.

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 3.1 × 10 ⁻² cm ² / Vs.

Example 9
(Production and Evaluation of Organic Solar Cell 1)
A glass substrate on which ITO with a thickness of about 150 nm formed by sputtering was patterned was washed with an organic solvent, an alkaline detergent and ultrapure water, and dried. Thereafter, the glass substrate was subjected to ultraviolet ozone (UV-O ₃ ) treatment using an ultraviolet ozone (UV-O ₃ ) apparatus.
Next, a suspension in which poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid is dissolved in water (trade name: Bytron P TP AI 4083, manufactured by HC Starck B-Tech Co., Ltd.) is filtered with a filter having a pore diameter of 0.45 μm. Filtered. The suspension after filtration was spin-coated on the ITO side of the substrate to form a film with a thickness of 40 nm. Subsequently, it was dried on the hot plate at 200 ° C. for 10 minutes in the air to form an organic layer.
Next, polymer compound A and fullerene C60PCBM (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name: E100)) are polymer compound A and C60PCBM (by weight ratio). Polymer Compound A / C60PCBM = 1/3) was dissolved in orthodichlorobenzene to produce Ink 1 (by weight percent, the sum of Polymer Compound A and C60PCBM was 2.0 weight percent). Next, the ink 1 was spin-coated on the organic layer side of the substrate to form an active layer with a thickness of 100 nm. The active layer thus fabricated had a light absorption edge wavelength end of 750 nm.
Next, 97% of Titanium (IV) isopropoxide purchased from SIGMA ALDRICH was mixed with isopropanol to a concentration of 1% by weight, and the mixture was spin-coated on the active layer side of the substrate to 10 nm. A hole transport layer was formed with a thickness of. Subsequently, Al was vacuum-deposited with a film thickness of about 70 nm, and the organic solar cell 1 which is a photoelectric conversion element was manufactured. The shape of the obtained organic solar cell 1 was a 2 mm × 2 mm square.
The obtained organic solar cell 1 is irradiated with a certain amount of light using a solar simulator (product name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined by measurement. Jsc (short circuit current density) is 8.88 mA / cm ² , Voc (open circuit voltage) is 1.10 V, ff (fill factor) is 0.61, and photoelectric conversion efficiency (η ) Was 6.03%.

１００ｍＬ三口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物１（５ｇ、２２．７ｍｍｏｌ）および乾燥ＴＨＦ（３００ｍＬ）を加え、８０℃に加熱した。その後、ｎ−ドデシルマグネシウムブロミドのジエチルエーテル溶液（９０．８ｍＬ、９０．８ｍｍｏｌ）を同温で加え、２．５時間攪拌した。続いて、水（３０ｍＬ）を加えることで反応を終了させ、さらに酢酸１０ｍＬを加え、反応溶液をクロロホルムで２回抽出した。得られた有機層を飽和塩化アンモニウム水溶液で２回、飽和食塩水で１回洗浄し、無水硫酸ナトリウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製することで化合物８を得た。化合物８の得量は８．５ｇ、収率は６７％であった。 Example 10
(Synthesis of Compound 9)

After the gas in the 100 mL three-neck flask was placed in a nitrogen gas atmosphere, Compound 1 (5 g, 22.7 mmol) and dry THF (300 mL) were added, and the mixture was heated to 80 ° C. Thereafter, a diethyl ether solution of n-dodecylmagnesium bromide (90.8 mL, 90.8 mmol) was added at the same temperature and stirred for 2.5 hours. Subsequently, the reaction was terminated by adding water (30 mL), 10 mL of acetic acid was further added, and the reaction solution was extracted twice with chloroform. The obtained organic layer was washed twice with saturated aqueous ammonium chloride solution and once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain compound 8. The yield of compound 8 was 8.5 g, and the yield was 67%.

１００ｍＬ三口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物８（８．５ｇ、１５．２ｍｍｏｌ）、酢酸（２００ｍＬ）およびトリフルオロ酢酸（５０ｍＬ）を加え、８０℃で１時間に加熱した。反応終了後、反応溶液を水２００ｍＬに注ぎ、トルエンで２回抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液で３回洗浄し、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィで精製することで、化合物９を得た。化合物９の得量は６．２８ｇ（１１．６ｍｍｏｌ）、収率は７６％であった。

After the gas in the 100 mL three-necked flask was placed in a nitrogen gas atmosphere, Compound 8 (8.5 g, 15.2 mmol), acetic acid (200 mL) and trifluoroacetic acid (50 mL) were added, and the mixture was heated at 80 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into 200 mL of water and extracted twice with toluene. The obtained organic layer was washed three times with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain compound 9. The yield of Compound 9 was 6.28 g (11.6 mmol), and the yield was 76%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.44 (d, 1H), 7.34 (d, 1H), 7.05 (d, 1H), 6.98 (d, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.24 (m, 40H), 0.87 (t, 6H).

５００ｍＬ三口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物９（６．２８ｇ、１１．６ｍｍｏｌ）、クロロホルム（１００ｍＬ）、酢酸（１００ｍＬ）およびＮ−ブロモ琥珀酸イミド（４．５３ｇ，２５．４ｍｍｏｌ）を加え、６５℃で１時間加熱した。反応終了後、反応溶液を室温まで冷却した後、水（３００ｍｌ）を加え、クロロホルム（１００ｍＬ）で２回抽出した。得られた有機層を飽和チオ硫酸ナトリウム水溶液（５０ｍＬ）、飽和食塩水（５０ｍＬ）で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。ヘキサン／クロロホルム混合溶媒（ヘキサン：クロロホルム＝８：１（ｖｏｌ／ｖｏｌ））を溶出溶媒として用いたシリカゲルカラムクロマトグラフィで精製することで化合物１０を得た。化合物１０の得量は６．７４ｇ、収率は８３％であった。 Example 12
(Synthesis of Compound 10)

After the gas in the 500 mL three-necked flask was placed under a nitrogen gas atmosphere, Compound 9 (6.28 g, 11.6 mmol), chloroform (100 mL), acetic acid (100 mL) and N-bromosuccinimide (4.53 g, 25.25). 4 mmol) was added and heated at 65 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature, water (300 ml) was added, and the mixture was extracted twice with chloroform (100 mL). The obtained organic layer was washed with saturated aqueous sodium thiosulfate solution (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Compound 10 was obtained by purification by silica gel column chromatography using hexane / chloroform mixed solvent (hexane: chloroform = 8: 1 (vol / vol)) as an elution solvent. The yield of compound 10 was 6.74 g, and the yield was 83%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.40 (s, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.24 (m, 40H), 0.87 (t, 6H).

１００ｍＬフラスコ内の気体を窒素ガス雰囲気下とした後、化合物１０（２．０ｇ，２．８５ｍｍｏｌ）および乾燥ＴＨＦ（８０ｍＬ）を加え、均一溶液とした。その後、反応溶液を−７８℃に冷却し、ｎ−ブチルリチウムのヘキサン溶液（７．５ｍＬ，１２ｍｍｏｌ）を同温で加えた。その後、反応溶液を１時間かけて室温まで昇温し、同温にて３時間攪拌した。その後、反応溶液を−７８℃に冷却し、トリブチルスズクロリド（３．５ｇ，１０．８ｍｍｏｌ）を加え、反応溶液を１時間かけて室温まで昇温し、同温にて１時間攪拌した。その後、水（１００ｍＬ）を加えることで反応を終了させ、酢酸エチル（５０ｍＬ）で２回抽出した。得られた有機層を水（５０ｍＬ）で１回、飽和食塩水（５０ｍＬ）で１回洗浄し、無水硫酸ナトリウムで乾燥した。得られた溶液をろ過後、得られたろ液をシリカゲルカラムに通過させ、得られた溶液をエバポレーターで濃縮した。得られた粗精製物を、クロロホルムを溶出溶媒として用いたリサイクルＧＰＣ（日本分析工業社製、ＬＣ−２５０ＨＳ）で精製することで、化合物１１を得た。化合物１１の得量は３．００g、収率は９３％であった。 Example 13
(Synthesis of Compound 11)

After the gas in the 100 mL flask was placed in a nitrogen gas atmosphere, Compound 10 (2.0 g, 2.85 mmol) and dry THF (80 mL) were added to obtain a homogeneous solution. Thereafter, the reaction solution was cooled to −78 ° C., and a hexane solution of n-butyllithium (7.5 mL, 12 mmol) was added at the same temperature. Thereafter, the reaction solution was warmed to room temperature over 1 hour and stirred at the same temperature for 3 hours. Thereafter, the reaction solution was cooled to −78 ° C., tributyltin chloride (3.5 g, 10.8 mmol) was added, the reaction solution was warmed to room temperature over 1 hour, and stirred at the same temperature for 1 hour. Thereafter, water (100 mL) was added to terminate the reaction, and the mixture was extracted twice with ethyl acetate (50 mL). The obtained organic layer was washed once with water (50 mL) and once with saturated brine (50 mL), and dried over anhydrous sodium sulfate. After the obtained solution was filtered, the obtained filtrate was passed through a silica gel column, and the obtained solution was concentrated by an evaporator. The obtained crude product was purified by recycle GPC (manufactured by Nippon Analytical Industries, LC-250HS) using chloroform as an elution solvent to obtain Compound 11. The yield of compound 11 was 3.00 g, and the yield was 93%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.47 (s, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.53 (m, 78H), 0.87 (t, 24H).

１００ｍＬフラスコ内の気体をアルゴンガス雰囲気下とした後、化合物１１（２４４ｍｇ，０．２１８ｍｍｏｌ）、Journal of Polymer Science Part A: Polymer Chemistry, Volume 47, Issue 13, pages 3399-3408, 2009に記載の方法に従って合成した化合物１２（７５ｍｇ，０．２１８ｍｍｏｌ）、トリス（２−トリル）ホスフィン（５．９７ｍｇ，０．０１９６ｍｍｏｌ）および脱水トルエン（６ｍＬ）を加え均一溶液とした後、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（２．９９ｍｇ，０．００３２７ｍｍｏｌ）を加え、１０５℃で４．５時間攪拌し、さらに、１２０℃で２時間攪拌した。その後、得られた反応溶液にフェニルブロミド（１００ｍｇ）を加え、２時間攪拌した。その後、得られた反応溶液を室温まで冷却し、該反応溶液を、メタノール（２００ｍＬ）および３７ｗｔ％の濃塩酸（２０ｍＬ）の混合溶液に注いだ。析出した固体をろ過することで回収し、得られた固体を円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。その後、円筒ろ紙内に残った残渣をトルエン（１５ｍＬ）に溶解させ、ジエチルジチオカルバミン酸ナトリウム（０．１８ｇ）および水（２．０ｍＬ）を加え、９０℃で３時間攪拌を行った。水層を分液にて除去後、得られた有機層を水（５０ｍＬ）で２回、３ｗｔ%酢酸水溶液（５０ｍＬ）で２回、水（５０ｍＬ）で２回洗浄した後、得られた溶液をメタノールに注ぐことで固体を析出させた。得られた固体をろ過後、乾燥し、得られた固体をｏ−ジクロロベンゼン（８ｍＬ）に再度溶解させた後、アルミナ／シリカゲルカラムを通過させた。得られた溶液をメタノールに注ぐことで固体を析出させ、得られた固体をろ過後、乾燥することで、高分子化合物Ｄを５２ｍｇを得た。高分子化合物Ｄのポリスチレン換算の数平均分子量は２．１×１０^４であり、ポリスチレン換算の重量平均分子量は４．１×１０^４であった。なお、高分子化合物Ｄを含む有機薄膜のイオン化ポテンシャルは５．３３ｅＶであった。 Example 14
(Synthesis of polymer compound D)

After the gas in the 100 mL flask was placed under an argon gas atmosphere, the method described in Compound 11 (244 mg, 0.218 mmol), Journal of Polymer Science Part A: Polymer Chemistry, Volume 47, Issue 13, pages 3399-3408, 2009 Compound 12 (75 mg, 0.218 mmol), tris (2-tolyl) phosphine (5.97 mg, 0.0196 mmol) and dehydrated toluene (6 mL) were added to make a homogeneous solution, and then degassed by bubbling with argon gas for 30 minutes. I worried. Thereafter, tris (dibenzylideneacetone) dipalladium (2.99 mg, 0.00327 mmol) was added, and the mixture was stirred at 105 ° C. for 4.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, phenyl bromide (100 mg) was added to the obtained reaction solution, and the mixture was stirred for 2 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of methanol (200 mL) and 37 wt% concentrated hydrochloric acid (20 mL). The precipitated solid was collected by filtration, and the obtained solid was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. Thereafter, the residue remaining in the cylindrical filter paper was dissolved in toluene (15 mL), sodium diethyldithiocarbamate (0.18 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer by liquid separation, the obtained organic layer was washed twice with water (50 mL), twice with 3 wt% aqueous acetic acid (50 mL), and twice with water (50 mL), and then the obtained solution Was poured into methanol to precipitate a solid. The obtained solid was filtered and dried, and the obtained solid was dissolved again in o-dichlorobenzene (8 mL), and then passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a solid, and the obtained solid was filtered and dried to obtain 52 mg of polymer compound D. The number average molecular weight of polystyrene conversion of the high molecular compound D was 2.1 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 4.1 * 10 < ⁴ >. The ionization potential of the organic thin film containing the polymer compound D was 5.33 eV.

１００ｍＬフラスコ内の気体を窒素ガス気流雰囲気下とした後、化合物１３（Ｌｕｍｉｎｅｓｃｅｎｃｅ Ｔｅｃｈｎｏｌｏｇｙ社製，３．７０ｇ，５．４ｍｍｏｌl）、ビス（ピナコラト）ジボロン（３．００ｇ，１１．８ｍｍｏｌ）、酢酸カリウム（２．５９ｇ，２６．４ｍｍｏｌ）、［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 ジクロロメタン付加物（０．０９ｇ，０．１ｍｍｏｌ）、１，１’−ビス（ジフェニルホスフィノ）フェロセン（０．０６ｇ，０．１ｍｍｏｌ）および無水１，４−オキサン（３００ｍＬ）を室温下にて加え、１５時間１２０℃で過熱攪拌した。得られた反応溶液をセライトろ過し、得られたセライトをクロロホルム（２００ｍＬ）を用いて、５回洗浄した。得られたろ液をエバポレータにて濃縮し、得られた残渣にクロロホルム（２００ｍＬ）を加え、８０℃にて加熱攪拌した後、アセトニトリル（４００ｍＬ）を加え、攪拌しながら室温まで放冷し、さらに室温にて１時間攪拌した。得られた固体をろ取し、アセトニトリル（１００ｍＬ）を用いて２回洗浄した後、減圧下で乾燥することにより、化合物１４を得た。化合物１４の得量は２．２５g（０．２４ｍｍｏｌ）、収率は５３．４％であった。 Synthesis example 1
(Synthesis of Compound 14)

After the gas in the 100 mL flask was placed under a nitrogen gas stream atmosphere, Compound 13 (Luminescence Technology, 3.70 g, 5.4 mmol), bis (pinacolato) diboron (3.00 g, 11.8 mmol), potassium acetate ( 2.59 g, 26.4 mmol), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.09 g, 0.1 mmol), 1,1′-bis (diphenylphosphine) Fino) ferrocene (0.06 g, 0.1 mmol) and anhydrous 1,4-oxane (300 mL) were added at room temperature, and the mixture was stirred with heating at 120 ° C. for 15 hours. The obtained reaction solution was filtered through Celite, and the obtained Celite was washed 5 times with chloroform (200 mL). The obtained filtrate was concentrated with an evaporator, chloroform (200 mL) was added to the obtained residue, and the mixture was heated and stirred at 80 ° C., then acetonitrile (400 mL) was added, and the mixture was allowed to cool to room temperature with stirring. For 1 hour. The obtained solid was collected by filtration, washed twice with acetonitrile (100 mL), and then dried under reduced pressure to obtain compound 14. The yield of compound 14 was 2.25 g (0.24 mmol), and the yield was 53.4%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 8.93 (d, 2H), 7.72 (d, 2H), 4.07 (m, 4H), 1.85 (m, 2H), 1.37 (s, 24H), 1.50-1.15 (m, 16H), 0.95-0.80 (d, 12H).

１００ｍＬの四つ口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（１５０ｍｇ，０．１９１ｍｍｏｌ）および乾燥クロロベンゼン（４ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（８．７５ｍｇ，０．００９５６ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（１１．１ｍｇ，０．０３８２ｍｍｏｌ）および３Ｍリン酸カリウム水溶液（２ｍＬ）を加え、８０℃に加熱した。この反応溶液に対して、３０分間アルゴンガスバブリングにより脱気した化合物１４（１４８ｍｇ，０．１９１ｍｍｏｌ）の乾燥ＴＨＦ（４ｍＬ）溶液を５分間かけて滴下し、８０℃で２時間攪拌した。この反応溶液に対して、３０分間アルゴンガスバブリングによって脱気したフェニルボロン酸（２０ｍｇ，０．１６４ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を加え、８０℃で２時間攪拌した後、ジエチルジチオカルバミン酸ナトリウム二水和物（２．１５ｇ）およびイオン交換水（１０ｍＬ）を加え、９０℃で２時間加熱した。得られた反応液中の水層を除去後、得られた有機層をイオン交換水（２０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（２０ｍＬ）で２回、イオン交換水（２０ｍＬ）で２回洗浄した後、メタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン（１１ｍＬ）に再溶解させ、次いで、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をろ過し、乾燥することにより、高分子化合物Ｅを６６ｍｇ得た。高分子化合物Ｅのポリスチレン換算の数平均分子量は２．３×１０^４であり、ポリスチレン換算の重量平均分子量は４．７×１０^４であった。なお、高分子化合物Ｅを含む有機薄膜のイオン化ポテンシャルは５．３４ｅＶであった。 Example 15
(Synthesis of polymer compound E)

After the gas in the 100 mL four-necked flask was placed under a nitrogen gas atmosphere, Compound 4 (150 mg, 0.191 mmol) and dry chlorobenzene (4 mL) were added, and degassed by argon gas bubbling for 30 minutes. Then, tris (dibenzylideneacetone) dipalladium (8.75 mg, 0.00956 mmol), tri-tert-butylphosphonium tetrafluoroborate (11.1 mg, 0.0382 mmol) and 3M aqueous potassium phosphate solution (2 mL) were added. And heated to 80 ° C. To this reaction solution, a dry THF (4 mL) solution of Compound 14 (148 mg, 0.191 mmol) degassed by argon gas bubbling for 30 minutes was added dropwise over 5 minutes and stirred at 80 ° C. for 2 hours. To this reaction solution, a solution of phenylboronic acid (20 mg, 0.164 mmol) deaerated by argon gas bubbling for 30 minutes in dry THF (5 mL) was added, stirred at 80 ° C. for 2 hours, and then sodium diethyldithiocarbamate. Hydrate (2.15 g) and ion-exchanged water (10 mL) were added and heated at 90 ° C. for 2 hours. After removing the aqueous layer in the obtained reaction solution, the obtained organic layer was washed twice with ion-exchanged water (20 mL), twice with 10 wt% acetic acid aqueous solution (20 mL), and twice with ion-exchanged water (20 mL). Then, it was poured into methanol (50 mL) to precipitate a solid. The obtained solid was redissolved in o-dichlorobenzene (11 mL), then passed through column chromatography (SiO ₂ and alumina), and the resulting solution was poured into methanol (50 mL) to precipitate a solid. The obtained solid was filtered and dried to obtain 66 mg of polymer compound E. The number average molecular weight of polystyrene conversion of the high molecular compound E was 2.3 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 4.7 * 10 < ⁴ >. The ionization potential of the organic thin film containing the polymer compound E was 5.34 eV.

１００ｍＬの四つ口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物１５（１．２ｇ，３．０ｍｍｏｌ）、ビス（ピナコラト）ジボラン（２．２９ｇ，９．０ｍｍｏｌ)、酢酸カリウム（１．７７ｇ，１８ｍｍｏｌ）および［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）ジクロリドジクロロメタン付加物(２９４ｍｇ，０．３６ｍｍｏｌ）を加えた後、さらに、１，４−ジオキサン（４５ｍＬ）を加えた。得られた反応混合物を１０分間窒素ガスバブリングし、十分に脱気した。これを１００℃で６時間加熱還流しながら撹拌した。得られた反応混合物を室温に冷却後、ろ過することで酢酸カリウムを除去し、得られたろ液を減圧下で濃縮した。ヘキサン／酢酸エチル混合溶媒（ヘキサン：酢酸エチル＝１：１（ｖｏｌ／ｖｏｌ））を溶出溶媒として用いたシリカゲルカラムクロマトグラフィで精製し、メタノールで再結晶することにより化合物１６を得た。化合物１６の得量は６１３ｍg、収率は５６％であった。 Synthesis example 2
(Synthesis of Compound 16)

After the gas in the 100 mL four-necked flask was placed in a nitrogen gas atmosphere, compound 15 (1.2 g, 3.0 mmol), bis (pinacolato) diborane (2.29 g, 9.0 mmol), potassium acetate (1. 77 g, 18 mmol) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (294 mg, 0.36 mmol), followed by further 1,4-dioxane (45 mL). added. The resulting reaction mixture was bubbled with nitrogen gas for 10 minutes and thoroughly degassed. This was stirred while heating to reflux at 100 ° C. for 6 hours. The obtained reaction mixture was cooled to room temperature and then filtered to remove potassium acetate, and the obtained filtrate was concentrated under reduced pressure. Compound 16 was obtained by purification by silica gel column chromatography using a hexane / ethyl acetate mixed solvent (hexane: ethyl acetate = 1: 1 (vol / vol)) as an elution solvent and recrystallization from methanol. The yield of Compound 16 was 613 mg, and the yield was 56%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 8.26 (s, 2H), 3.86 (s, 6H), 3.08-3.03 (m, 4H), 1.90 (quint) 4H), 1.49 (quint, 4H), 1.03 (t, 6H).

１００ｍＬの四つ口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（２１９．３ｍｇ，０．２７９ｍｍｏｌ）および乾燥ＴＨＦ（１０ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（７．６８ｍｇ，０．００２７９ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボラート（１１．１ｍｇ，０．０３８２ｍｍｏｌ）および３Ｍリン酸カリウム水溶液（１ｍＬ）を加え、８０℃に加熱した。得られた反応溶液に対して、３０分間アルゴンガスバブリングにより脱気した化合物１６（１００ｍｇ，０．２７９ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、その後、８０℃で６時間攪拌した。得られた反応溶液を室温まで冷却し、メタノールに注ぐことで固体を析出させた後、得られた固体をろ過して回収した。得られた固体を、アセトンを用いて３時間ソックスレー洗浄し、続いて、ヘキサンを用いて３時間ソックスレー抽出を行い、得られたヘキサン溶液をメタノールに注ぐことで固体を析出させた。得られた固体をろ取した後、展開溶媒にｏ−ジクロロベンゼンを展開溶媒としてアルミナ/シリカゲルカラムクロマトグラフィーで精製を行い、得られたオルトジクロロベンゼン溶液をメタノールに注ぐことで固体を析出させた。得られた固体をろ過し、乾燥することにより、高分子化合物Ｆを１０５ｍｇ得た。高分子化合物Ｆのポリスチレン換算の数平均分子量は１．７×１０^４であり、ポリスチレン換算の重量平均分子量は３．２×１０^４であった。なお、高分子化合物Ｅを含む有機薄膜のイオン化ポテンシャルは５．４４ｅＶであった。 Example 16
(Synthesis of polymer compound F)

After the gas in the 100 mL four-necked flask was placed in a nitrogen gas atmosphere, Compound 4 (219.3 mg, 0.279 mmol) and dry THF (10 mL) were added, and degassed by argon gas bubbling for 30 minutes. Then, tris (dibenzylideneacetone) dipalladium (7.68 mg, 0.00279 mmol), tri-tert-butylphosphonium tetrafluoroborate (11.1 mg, 0.0382 mmol) and 3M aqueous potassium phosphate solution (1 mL) were added. And heated to 80 ° C. To the obtained reaction solution, a dry THF (5 mL) solution of Compound 16 (100 mg, 0.279 mmol) degassed by argon gas bubbling for 30 minutes was added dropwise over 5 minutes, and then stirred at 80 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature and poured into methanol to precipitate a solid, and then the obtained solid was collected by filtration. The obtained solid was subjected to Soxhlet washing with acetone for 3 hours, followed by Soxhlet extraction with hexane for 3 hours, and the obtained hexane solution was poured into methanol to precipitate a solid. After the obtained solid was collected by filtration, purification was performed by alumina / silica gel column chromatography using o-dichlorobenzene as a developing solvent, and the resulting orthodichlorobenzene solution was poured into methanol to precipitate a solid. . The obtained solid was filtered and dried to obtain 105 mg of polymer compound F. The number average molecular weight in terms of polystyrene of the polymer compound F was 1.7 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 3.2 × 10 ⁴ . The ionization potential of the organic thin film containing the polymer compound E was 5.44 eV.

Example 17
(Production and Evaluation of Organic Solar Cell 2)
Polymer compound D and electron-accepting compound fullerene C70PCBM (Phenyl C71-butyric acid methyl ester, manufactured by American Dye Source, trade name: ADS71BFA) were combined with polymer compound D and C70PCBM ( The polymer compound D / C70PCBM = 2/1) was dissolved in orthodichlorobenzene at a weight ratio, and the resulting solution was filtered with a Teflon (registered trademark) filter having a pore diameter of 0.5 μm to obtain ink 2 (weight). %, The sum of polymer compound D and C70PCBM was 2.25 wt%).

A glass substrate on which ITO with a thickness of about 150 nm formed by sputtering was patterned was washed with an organic solvent, an alkaline detergent and ultrapure water, and dried. Thereafter, the glass substrate was subjected to ultraviolet ozone (UV-O ₃ ) treatment using an ultraviolet ozone (UV-O ₃ ) apparatus.
Next, the PEDOT: PSS solution (CleviosP VP AI4083 manufactured by Heraeus) was filtered through a filter having a pore diameter of 0.45 μm. The PEDOT: PSS solution after filtration was spin-coated on the ITO side of the substrate to form a film with a thickness of 50 nm. Subsequently, the organic layer was formed in the air | atmosphere by heating on a hotplate at 120 degreeC for 10 minute (s).
Next, the ink 2 was spin-coated on the organic layer of the substrate to form an active layer with a thickness of 100 nm. The active layer thus fabricated had a light absorption edge wavelength end of 680 nm.
Next, the organic solar cell 2 which is a photoelectric conversion element was produced by vapor-depositing calcium with a film thickness of 4 nm with a vacuum evaporation machine, and then vapor-depositing aluminum with a film thickness of 100 nm. The vacuum degree during the metal deposition was ^{1.0 × 10 -3 ~9 × 10 -3} Pa. The shape of the obtained organic solar cell 2 was a 2 mm × 2 mm square.
The obtained organic solar cell 2 is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined by measurement. Jsc (short-circuit current density) is 7.90 mA / cm ² , Voc (open-circuit voltage) is 0.96 V, ff (fill factor) is 0.41, and photoelectric conversion efficiency (η ) Was 3.08%.

Example 18
(Production and Evaluation of Organic Solar Cell 3)
An organic solar cell 3 was produced in the same manner as in Example 17 except that the polymer compound F was used in place of the polymer compound D. The light absorption edge wavelength end of the active layer was 680 nm.

The obtained organic solar cell 3 was irradiated with constant light using a solar simulator, and the generated current and voltage were measured to obtain photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor. Jsc (short circuit current density) is 5.36 mA / cm ² , Voc (open circuit voltage) is 0.97 V, ff (fill factor) is 0.51, and photoelectric conversion efficiency (η ) Was 2.62%.

１００ｍＬフラスコ内の気体を窒素ガスで置換した後、化合物３（３．０ｇ，４．８７ｍｍｏｌ）、およびＴＨＦ（５０ｍＬ）を加えた。その後、Ｎ−ブロモ琥珀酸イミド（０．８５ｇ，４．７８ｍｍｏｌ）を加え、室温で７時間攪拌した。その後、飽和チオ硫酸ナトリウム水溶液（３ｍＬ）を加えて反応を停止させ、反応溶液を飽和食塩水で洗浄した。その後、分液した有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。得られた残渣を、シリカゲルカラムクロマトグラフィによって精製することで化合物１７を１．８４ｇ得た。収率は５４％であった。 Example 19
(Synthesis of Compound 17)

After the gas in the 100 mL flask was replaced with nitrogen gas, Compound 3 (3.0 g, 4.87 mmol) and THF (50 mL) were added. Thereafter, N-bromosuccinimide (0.85 g, 4.78 mmol) was added, and the mixture was stirred at room temperature for 7 hours. Then, saturated sodium thiosulfate aqueous solution (3 mL) was added to stop the reaction, and the reaction solution was washed with saturated brine. Thereafter, the separated organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue obtained was purified by silica gel column chromatography to obtain 1.84 g of compound 17. The yield was 54%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.84 (t, 6H), 1.24 (m, 52H), 1.66 (m, 2H), 2.16 (m, 2H) ), 6.95 (s, 1H), 7.06 (d, 1H), 7.43 (d, 1H).

１００ｍＬフラスコ内の気体を窒素ガスで置換した後、化合物１８（０．７７ｇ，１．０４ｍｍｏｌ）、およびＴＨＦ（５０ｍＬ）を加え、３０分間アルゴンガスバブリングすることによって脱気した。その後、化合物１７（１．５０ｇ，２．１５ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０）（１９．５ｍｇ，０．０２ｍｍｏｌ）およびトリス（ｏ−トルイル）ホスフィン（２６ｍｇ，０．０８ｍｍｏｌ）を加え、８０℃で４時間攪拌した。その後、反応溶液を飽和食塩水で洗浄した。その後、分液した有機層を無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。得られた残渣を、シリカゲルカラムクロマトグラフィによって精製することで、化合物１９を１．１８ｇ得た。収率は７９％であった。 Example 20
(Synthesis of Compound 19)

After replacing the gas in the 100 mL flask with nitrogen gas, Compound 18 (0.77 g, 1.04 mmol) and THF (50 mL) were added, and degassed by bubbling with argon gas for 30 minutes. Compound 17 (1.50 g, 2.15 mmol), tris (dibenzylideneacetone) dipalladium (0) (19.5 mg, 0.02 mmol) and tris (o-toluyl) phosphine (26 mg, 0.08 mmol) were then added. In addition, the mixture was stirred at 80 ° C. for 4 hours. Thereafter, the reaction solution was washed with saturated brine. Thereafter, the separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.18 g of compound 19. The yield was 79%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.86 (t, 12H), 1.24 (m, 52H), 1.74 (m, 104H), 2.19 (m, 4H) ), 7.05 (s, 2H), 7.08 (d, 22H).

１００ｍＬフラスコ内の気体を窒素ガスで置換した後、化合物１９（１．１８ｇ，０．８３ｍｍｏｌ）、およびＤＭＦ（８３ｍＬ）を加え、８０℃で攪拌した。その後、Ｎ−ブロモ琥珀酸イミド（０．８５ｇ，４．７８ｍｍｏｌ）を８０℃で加え、８０℃で２時間攪拌した。その後、室温まで冷却した後、飽和チオ硫酸ナトリウム水溶液（３ｍＬ）と水（４０ｍＬ）を加えた。反応溶液をトルエンで２回抽出したのち、得られた有機層を、飽和食塩水で洗浄した。その後、分液した有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。得られた残渣を、シリカゲルカラムクロマトグラフィによって精製することで化合物２０を６１５ｍｇ得た。収率は４７％であった。 Example 21
(Synthesis of Compound 20)

After replacing the gas in the 100 mL flask with nitrogen gas, Compound 19 (1.18 g, 0.83 mmol) and DMF (83 mL) were added, and the mixture was stirred at 80 ° C. Thereafter, N-bromosuccinimide (0.85 g, 4.78 mmol) was added at 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours. Then, after cooling to room temperature, saturated sodium thiosulfate aqueous solution (3 mL) and water (40 mL) were added. The reaction solution was extracted twice with toluene, and the obtained organic layer was washed with saturated brine. Thereafter, the separated organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 615 mg of compound 20. The yield was 47%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.84 (t, 12H), 1.24 (m, 40H), 1.75 (m, 4H), 2.20 (m, 4H) ), 7.03 (s, 2H), 7.14 (d, 2H), 7.18 (d, 2H), 7.42 (s, 2H).

還流管を取り付けた１００ｍＬ四口フラスコ内の気体を窒素ガスで置換した後、化合物２０（７５．６ｍｇ、０．０４８ｍｍｏｌ）、化合物３（２９．５ｍｇ、０．０６ｍｍｏｌ）及び乾燥トルエン（１２ｍＬ）を加え、アルゴンガスで３０分間バブリングすることによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（１．１０ｍｇ、１．２μｍｏｌ）及びトリス（ｏ−トルイル）ホスフィン（１．４８ｍｇ、４．８μｍｏｌ）を加え、１００℃で３時間攪拌した。その後、得られた混合溶液に、アルゴンガスで３０分間バブリングすることによって脱気したフェニルブロマイド（７０．７ｍｇ、０．４５ｍｍｏｌ）のｏ−ジクロロベンゼン溶液（６．２ｍＬ）を加え、１００℃で１時間攪拌した。その後、Ｎ、Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物（０．３ｇ）と水（２．７ｇ）とを加え、１００℃で３時間攪拌した。得られた反応溶液を静置し、分液した有機層を水および１０重量％酢酸水溶液で洗浄した。その後、分液した有機層をアセトン（４０ｍＬ）に滴下し、析出物を得た。得られた析出物を、ｏ−ジクロロベンゼンを展開溶媒として用いたシリカゲルカラムで精製し、その後、得られたｏ−ジクロロベンゼン溶液をメタノール（４０ｍＬ）に注ぎ、固体を析出させ、得られた固体を濾過した。ソックスレー抽出器を用いて、得られた固体を、アセトンで３時間洗浄し、乾燥させることで、高分子化合物Ｇを７０ｍｇ得た。収率は５５％であった。得られた高分子化合物Ｇのポリスチレン換算の数平均分子量は１．３×１０^４、重量平均分子量は５．５×１０^４であった。 Example 22
(Synthesis of polymer compound G)

After replacing the gas in the 100 mL four-necked flask equipped with a reflux tube with nitrogen gas, Compound 20 (75.6 mg, 0.048 mmol), Compound 3 (29.5 mg, 0.06 mmol) and dry toluene (12 mL) were added. In addition, degassing was performed by bubbling with argon gas for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (0) (1.10 mg, 1.2 μmol) and tris (o-toluyl) phosphine (1.48 mg, 4.8 μmol) were added, and the mixture was stirred at 100 ° C. for 3 hours. Thereafter, an o-dichlorobenzene solution (6.2 mL) of phenyl bromide (70.7 mg, 0.45 mmol) deaerated by bubbling with argon gas for 30 minutes was added to the obtained mixed solution, and 1 at 100 ° C. Stir for hours. Thereafter, sodium N, N-diethyldithiocarbamate trihydrate (0.3 g) and water (2.7 g) were added, and the mixture was stirred at 100 ° C. for 3 hours. The obtained reaction solution was allowed to stand, and the separated organic layer was washed with water and a 10% by weight aqueous acetic acid solution. Thereafter, the separated organic layer was added dropwise to acetone (40 mL) to obtain a precipitate. The obtained precipitate was purified by a silica gel column using o-dichlorobenzene as a developing solvent, and then the obtained o-dichlorobenzene solution was poured into methanol (40 mL) to precipitate a solid, and the obtained solid Was filtered. The obtained solid was washed with acetone for 3 hours using a Soxhlet extractor and dried to obtain 70 mg of polymer compound G. The yield was 55%. The obtained polymer compound G had a polystyrene-equivalent number average molecular weight of 1.3 × 10 ⁴ and a weight average molecular weight of 5.5 × 10 ⁴ .

１００ｍＬフラスコ内の気体を窒素ガス雰囲気下とした後、化合物４（５００ｍｇ，０．６３７ｍｍｏｌ）および乾燥ＴＨＦ（１５ｍＬ）を加え、均一溶液とした。その後、反応溶液を−７８℃に冷却し、ｎ−ブチルリチウムのヘキサン溶液（２．０ｍＬ，３．２ｍｍｏｌ）を同温で加えた。その後、反応溶液を１時間かけて室温まで昇温し、同温にて３時間攪拌した。その後、反応溶液を−７８℃に冷却し、トリブチルスズクロリド（１．０４ｇ，３．２ｍｍｏｌ）を加え、反応溶液を１時間かけて室温まで昇温し、同温にて１時間攪拌した。その後、水（５０ｍＬ）を加えることで反応を終了させ、酢酸エチル（３０ｍＬ）で２回抽出した。得られた有機層を水（３０ｍＬ）で１回、飽和食塩水（３０ｍＬ）で１回洗浄し、無水硫酸ナトリウムで乾燥した。得られた溶液を濾過後、得られた濾液をシリカゲルカラムに通過させ、得られた溶液をエバポレーターで濃縮した。得られた粗精製物を、クロロホルムを溶出溶媒として用いたリサイクルＧＰＣ（日本分析工業社製、ＬＣ−２５０ＨＳ）で精製することで、化合物２１を得た。化合物２１の得量は５１２ｍｇ、収率は６６％であった。 Example 23
(Synthesis of Compound 21)

After the gas in the 100 mL flask was placed in a nitrogen gas atmosphere, Compound 4 (500 mg, 0.637 mmol) and dry THF (15 mL) were added to obtain a homogeneous solution. Thereafter, the reaction solution was cooled to −78 ° C., and a hexane solution of n-butyllithium (2.0 mL, 3.2 mmol) was added at the same temperature. Thereafter, the reaction solution was warmed to room temperature over 1 hour and stirred at the same temperature for 3 hours. Thereafter, the reaction solution was cooled to −78 ° C., tributyltin chloride (1.04 g, 3.2 mmol) was added, the reaction solution was warmed to room temperature over 1 hour, and stirred at the same temperature for 1 hour. The reaction was then terminated by adding water (50 mL) and extracted twice with ethyl acetate (30 mL). The obtained organic layer was washed once with water (30 mL) and once with saturated brine (30 mL), and dried over anhydrous sodium sulfate. After filtering the obtained solution, the obtained filtrate was passed through a silica gel column, and the obtained solution was concentrated with an evaporator. The obtained crude purified product was purified by recycled GPC (manufactured by Nippon Analytical Industries, Ltd., LC-250HS) using chloroform as an elution solvent to obtain Compound 21. The yield of compound 21 was 512 mg, and the yield was 66%.

¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.47 (s, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.53 (m, 90H), 0.87 (t, 24H).

１００ｍＬフラスコ内の気体をアルゴンガス雰囲気下とした後、化合物２１（１７６ｍｇ，０．１４６ｍｍｏｌ）、国際公開第２０１１／０５２７１２号に記載の方法に従って合成した化合物２３（１００ｍｇ，０．１４６ｍｍｏｌ）、トリス（２−トリル）ホスフィン（４．０ｍｇ，０．０１３ｍｍｏｌ）および脱水トルエン（５ｍＬ）を加え均一溶液とした後、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（２．０１ｍｇ，０．００２２ｍｍｏｌ）を加え、１０５℃で４．５時間攪拌し、さらに、１２０℃で２時間攪拌した。その後、得られた反応溶液にフェニルブロミド（１００ｍｇ）を加え、２時間攪拌した。その後、得られた反応溶液を室温まで冷却し、該反応溶液を、メタノール（２００ｍＬ）および３７ｗｔ％の濃塩酸（２０ｍＬ）の混合溶液に注いだ。析出した固体を濾過して集め、得られた固体を円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。その後、円筒濾紙内に残った残渣をトルエン（１５ｍＬ）に溶解させ、ジエチルジチオカルバミン酸ナトリウム（０．１８ｇ）および水（２．０ｍＬ）を加え、９０℃で３時間攪拌を行った。水層を分液して除去後、得られた有機層を水（５０ｍＬ）で２回、３ｗｔ%酢酸水溶液（５０ｍＬ）で２回、水（５０ｍＬ）で２回洗浄した後、得られた溶液をメタノールに注ぐことで固体を析出させた。得られた固体を濾過後、乾燥させ、得られた固体をｏ−ジクロロベンゼン（８ｍＬ）に再度溶解させた後、アルミナ／シリカゲルカラムを通過させた。得られた溶液をメタノールに注ぐことで固体を析出させ、得られた固体を濾過後、乾燥させることで、高分子化合物Ｈを５７ｍｇ得た。高分子化合物Ｈのポリスチレン換算の数平均分子量は２．３×１０^４であり、ポリスチレン換算の重量平均分子量は４．７×１０^４であった。 Example 24
(Synthesis of polymer compound H)

After the gas in the 100 mL flask was placed under an argon gas atmosphere, Compound 21 (176 mg, 0.146 mmol), Compound 23 (100 mg, 0.146 mmol) synthesized according to the method described in WO 2011/052712, Tris ( 2-Tolyl) phosphine (4.0 mg, 0.013 mmol) and dehydrated toluene (5 mL) were added to obtain a homogeneous solution, and then degassed by argon gas bubbling for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (2.01 mg, 0.0022 mmol) was added, and the mixture was stirred at 105 ° C. for 4.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, phenyl bromide (100 mg) was added to the obtained reaction solution, and the mixture was stirred for 2 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of methanol (200 mL) and 37 wt% concentrated hydrochloric acid (20 mL). The precipitated solid was collected by filtration, and the obtained solid was placed in a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. Thereafter, the residue remaining in the cylindrical filter paper was dissolved in toluene (15 mL), sodium diethyldithiocarbamate (0.18 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. The aqueous layer was separated and removed, and the obtained organic layer was washed twice with water (50 mL), twice with 3 wt% aqueous acetic acid (50 mL) and twice with water (50 mL), and then the obtained solution Was poured into methanol to precipitate a solid. The obtained solid was filtered and dried, and the obtained solid was dissolved again in o-dichlorobenzene (8 mL), and then passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a solid, and the obtained solid was filtered and dried to obtain 57 mg of polymer compound H. The number average molecular weight in terms of polystyrene of the polymer compound H was 2.3 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 4.7 × 10 ⁴ .

１００ｍＬフラスコ内の気体をアルゴンガス雰囲気下とした後、化合物１１（２６３ｍｇ，０．２３５ｍｍｏｌ）、化合物２４（８０．０ｍｇ，０．２３５ｍｍｏｌ）、トリス（２−トリル）ホスフィン（６．４０ｍｇ，０．０２１ｍｍｏｌ）および脱水トルエン（１２ｍＬ）を加え均一溶液とした後、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（３．２２ｍｇ，０．００３５ｍｍｏｌ）を加え、１０５℃で４．５時間攪拌し、さらに、１２０℃で２時間攪拌した。その後、得られた反応溶液にフェニルブロミド（１００ｍｇ）を加え、２時間攪拌した。その後、得られた反応溶液を室温まで冷却し、該反応溶液を、メタノール（２００ｍＬ）および３７ｗｔ％の濃塩酸（２０ｍＬ）の混合溶液に注いだ。析出した固体を濾過して集め、得られた固体を円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。その後、円筒濾紙内に残った残渣をｏ−ジクロロベンゼン（６ｍＬ）に溶解させ、ジエチルジチオカルバミン酸ナトリウム（０．２０ｇ）および水（２．０ｍＬ）を加え、９０℃で３時間攪拌を行った。水層を分液にて除去後、得られた有機層を水（５０ｍＬ）で２回、３ｗｔ%酢酸水溶液（５０ｍＬ）で２回、水（５０ｍＬ）で２回洗浄した後、得られた溶液をメタノールに注ぐことで固体を析出させた。得られた固体を濾過後、乾燥させ、得られた固体をｏ−ジクロロベンゼン（８ｍＬ）に再度溶解させた後、アルミナ／シリカゲルカラムを通過させた。得られた溶液をメタノールに注ぐことで固体を析出させ、得られた固体を濾過後、乾燥させることで、高分子化合物Ｉを８２ｍｇ得た。高分子化合物Ｉのポリスチレン換算の数平均分子量は１．３×１０^４であり、ポリスチレン換算の重量平均分子量は３．７×１０^４であった。 Example 25
(Synthesis of polymer compound I)

After the gas in the 100 mL flask was placed under an argon gas atmosphere, Compound 11 (263 mg, 0.235 mmol), Compound 24 (80.0 mg, 0.235 mmol), Tris (2-tolyl) phosphine (6.40 mg, 0.45 mmol). 021 mmol) and dehydrated toluene (12 mL) were added to make a homogeneous solution, and then degassed by argon gas bubbling for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (3.22 mg, 0.0035 mmol) was added, and the mixture was stirred at 105 ° C. for 4.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, phenyl bromide (100 mg) was added to the obtained reaction solution, and the mixture was stirred for 2 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of methanol (200 mL) and 37 wt% concentrated hydrochloric acid (20 mL). The precipitated solid was collected by filtration, and the obtained solid was placed in a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. Thereafter, the residue remaining in the cylindrical filter paper was dissolved in o-dichlorobenzene (6 mL), sodium diethyldithiocarbamate (0.20 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer by liquid separation, the obtained organic layer was washed twice with water (50 mL), twice with 3 wt% aqueous acetic acid (50 mL), and twice with water (50 mL), and then the obtained solution Was poured into methanol to precipitate a solid. The obtained solid was filtered and dried, and the obtained solid was dissolved again in o-dichlorobenzene (8 mL), and then passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a solid, and the obtained solid was filtered and dried to obtain 82 mg of polymer compound I. The number average molecular weight of polystyrene conversion of the high molecular compound I was 1.3 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 3.7 * 10 < ⁴ >.

１００ｍＬフラスコ内の気体をアルゴンガス雰囲気下とした後、化合物２１（１９０ｍｇ，０．１５８ｍｍｏｌ）、化合物２５（７２．０ｍｇ，０．１５７ｍｍｏｌ）、トリス（２−トリル）ホスフィン（４．３ｍｇ，０．０１４ｍｍｏｌ）および脱水トルエン（９ｍＬ）を加え均一溶液とした後、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（２．１６ｍｇ，０．００２３６ｍｍｏｌ）を加え、１０５℃で４．５時間攪拌し、さらに、１２０℃で２時間攪拌した。その後、得られた反応溶液にフェニルブロミド（５０ｍｇ）を加え、２時間攪拌した。その後、得られた反応溶液を室温まで冷却し、該反応溶液を、メタノール（２００ｍＬ）および３７ｗｔ％の濃塩酸（２０ｍＬ）の混合溶液に注いだ。析出した固体を濾過して集め、得られた固体を円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。その後、円筒濾紙内に残った残渣をトルエン（１５ｍＬ）に溶解させ、ジエチルジチオカルバミン酸ナトリウム（０．１３ｇ）および水（１．０ｍＬ）を加え、９０℃で３時間攪拌を行った。水層を分液して除去後、得られた有機層を水（５０ｍＬ）で２回、３ｗｔ%酢酸水溶液（５０ｍＬ）で２回、水（５０ｍＬ）で２回洗浄した後、得られた溶液をメタノールに注ぐことで固体を析出させた。得られた固体を濾過後、乾燥し、得られた固体をｏ−ジクロロベンゼン（８ｍＬ）に再度溶解させた後、アルミナ／シリカゲルカラムを通過させた。得られた溶液をメタノールに注ぐことで固体を析出させ、得られた固体を濾過後、乾燥させることで、高分子化合物Ｊを１０５ｍｇ得た。高分子化合物Ｊのポリスチレン換算の数平均分子量は２．１×１０^４であり、ポリスチレン換算の重量平均分子量は４．３×１０^４であった。なお、高分子化合物Ｊを含む有機薄膜のイオン化ポテンシャルは５．４２ｅＶであった。 Example 26
(Synthesis of polymer compound J)

After the gas in the 100 mL flask was placed under an argon gas atmosphere, Compound 21 (190 mg, 0.158 mmol), Compound 25 (72.0 mg, 0.157 mmol), Tris (2-tolyl) phosphine (4.3 mg, 0.35 mmol). 014 mmol) and dehydrated toluene (9 mL) to make a homogeneous solution, and then degassed by argon gas bubbling for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (2.16 mg, 0.00236 mmol) was added, and the mixture was stirred at 105 ° C. for 4.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, phenyl bromide (50 mg) was added to the obtained reaction solution, and the mixture was stirred for 2 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of methanol (200 mL) and 37 wt% concentrated hydrochloric acid (20 mL). The precipitated solid was collected by filtration, and the obtained solid was placed in a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. Thereafter, the residue remaining in the cylindrical filter paper was dissolved in toluene (15 mL), sodium diethyldithiocarbamate (0.13 g) and water (1.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. The aqueous layer was separated and removed, and the obtained organic layer was washed twice with water (50 mL), twice with 3 wt% aqueous acetic acid (50 mL) and twice with water (50 mL), and then the obtained solution Was poured into methanol to precipitate a solid. The obtained solid was filtered and dried, and the obtained solid was dissolved again in o-dichlorobenzene (8 mL), and then passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a solid, and the obtained solid was filtered and dried to obtain 105 mg of polymer compound J. The polymer compound J had a polystyrene-equivalent number average molecular weight of 2.1 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 4.3 × 10 ⁴ . The ionization potential of the organic thin film containing the polymer compound J was 5.42 eV.

１００ｍＬフラスコ内の気体をアルゴンガス雰囲気下とした後、化合物２１（２００ｍｇ，０．１６６ｍｍｏｌ）、European Journal of Organic Chemistry、2011、25、4841-4852に記載の方法に従って合成した化合物２６（１０４．０ｍｇ，０．１６６ｍｍｏｌ）およびトリス（２−トリル）ホスフィン（４．５ｍｇ，０．０１５ｍｍｏｌ）、脱水トルエン（１１ｍＬ）を加え均一溶液とした後、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（２．２８ｍｇ，０．００２５ｍｍｏｌ）を加え、１０５℃で４．５時間攪拌し、さらに、１２０℃で２時間攪拌した。その後、得られた反応溶液にフェニルブロミド（５０ｍｇ）を加え、２時間攪拌した。その後、得られた反応溶液を室温まで冷却し、該反応溶液を、メタノール（２００ｍＬ）および３７ｗｔ％の濃塩酸（２０ｍＬ）の混合溶液に注いだ。析出した固体を濾過して集め、得られた固体を円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。その後、円筒濾紙内に残った残渣をトルエン（１５ｍＬ）に溶解させ、ジエチルジチオカルバミン酸ナトリウム（０．１８ｇ）および水（２．０ｍＬ）を加え、９０℃で３時間攪拌を行った。水層を分液して除去後、得られた有機層を水（５０ｍＬ）で２回、３ｗｔ%酢酸水溶液（５０ｍＬ）で２回、水（５０ｍＬ）で２回洗浄した後、得られた溶液をメタノールに注ぐことで固体を析出させた。得られた固体を濾過後、乾燥させ、得られた固体をｏ−ジクロロベンゼン（８ｍＬ）に再度溶解させた後、アルミナ／シリカゲルカラムを通過させた。得られた溶液をメタノールに注ぐことで固体を析出させ、得られた固体を濾過後、乾燥させることで、高分子化合物Ｋを１２４ｍｇ得た。高分子化合物Ｋのポリスチレン換算の数平均分子量は２．３×１０^４であり、ポリスチレン換算の重量平均分子量は４．７×１０^４であった。なお、高分子化合物Ｋを含む有機薄膜のイオン化ポテンシャルは５．１９ｅＶであった。 Example 27
(Synthesis of polymer compound K)

After the gas in the 100 mL flask was put under an argon gas atmosphere, Compound 21 (200 mg, 0.166 mmol), Compound 26 (104.0 mg) synthesized according to the method described in European Journal of Organic Chemistry, 2011, 25, 4841-4852 , 0.166 mmol), tris (2-tolyl) phosphine (4.5 mg, 0.015 mmol) and dehydrated toluene (11 mL) to obtain a homogeneous solution, and then degassed by argon gas bubbling for 30 minutes. Thereafter, tris (dibenzylideneacetone) dipalladium (2.28 mg, 0.0025 mmol) was added, and the mixture was stirred at 105 ° C. for 4.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, phenyl bromide (50 mg) was added to the obtained reaction solution, and the mixture was stirred for 2 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of methanol (200 mL) and 37 wt% concentrated hydrochloric acid (20 mL). The precipitated solid was collected by filtration, and the obtained solid was placed in a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. Thereafter, the residue remaining in the cylindrical filter paper was dissolved in toluene (15 mL), sodium diethyldithiocarbamate (0.18 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. The aqueous layer was separated and removed, and the obtained organic layer was washed twice with water (50 mL), twice with 3 wt% aqueous acetic acid (50 mL) and twice with water (50 mL), and then the obtained solution Was poured into methanol to precipitate a solid. The obtained solid was filtered and dried, and the obtained solid was dissolved again in o-dichlorobenzene (8 mL), and then passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a solid, and the obtained solid was filtered and dried to obtain 124 mg of polymer compound K. The number average molecular weight in terms of polystyrene of the polymer compound K was 2.3 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 4.7 × 10 ⁴ . The ionization potential of the organic thin film containing the polymer compound K was 5.19 eV.

１００ｍＬの四つ口フラスコ内の気体を窒素ガス雰囲気下とした後、化合物１０（１８０．０ｍｇ，０．２５７ｍｍｏｌ）および乾燥クロロベンゼン（５ｍＬ）を加え、３０分間アルゴンガスバブリングによって脱気した。その後、トリス（ジベンジリデンアセトン）ジパラジウム（１１．７６ｍｇ，０．０１２８ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（１４．９１ｍｇ，０．０５１ｍｍｏｌ）および３Ｍリン酸カリウム水溶液（２ｍＬ）を加え、８０℃に加熱した。その後、得られた反応溶液に、３０分間アルゴンガスバブリングにより脱気した化合物７（５０．５ｍｇ，０．１２９ｍｍｏｌ）および化合物１４（１００．０ｍｇ，０．１２９ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で２時間攪拌した。その後、得られた反応溶液に、３０分間アルゴンガスバブリングによって脱気したフェニルブロマイド（１００ｍｇ，０．６８ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を加え、８０℃で２時間攪拌した後、ジエチルジチオカルバミン酸ナトリウム二水和物（２．８９ｇ）およびイオン交換水（２９ｍＬ）を加え、９０℃で２時間加熱した。得られた反応液中の水層を除去後、得られた有機層をイオン交換水（２０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（２０ｍＬ）で２回、イオン交換水（２０ｍＬ）で２回洗浄した後、メタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン（１１ｍＬ）に再溶解させ、次いで、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体を濾過し、乾燥させることにより、高分子化合物Ｌを５９ｍｇ得た。高分子化合物Ｌのポリスチレン換算の数平均分子量は２．７×１０^４であり、ポリスチレン換算の重量平均分子量は５．２×１０^４であった。なお、高分子化合物Ｌを含む有機薄膜のイオン化ポテンシャルは５．３１ｅＶであった。 Example 28
(Synthesis of polymer compound L)

After the gas in the 100 mL four-necked flask was placed under a nitrogen gas atmosphere, Compound 10 (180.0 mg, 0.257 mmol) and dry chlorobenzene (5 mL) were added, and degassed by argon gas bubbling for 30 minutes. Then, tris (dibenzylideneacetone) dipalladium (11.76 mg, 0.0128 mmol), tri-tert-butylphosphonium tetrafluoroborate (14.91 mg, 0.051 mmol) and 3M aqueous potassium phosphate solution (2 mL) were added. And heated to 80 ° C. Thereafter, a dry THF (5 mL) solution of Compound 7 (50.5 mg, 0.129 mmol) and Compound 14 (100.0 mg, 0.129 mmol) degassed by argon gas bubbling for 30 minutes was added to the obtained reaction solution. The solution was added dropwise over a period of time and stirred at 80 ° C for 2 hours. Then, a dry THF (5 mL) solution of phenyl bromide (100 mg, 0.68 mmol) deaerated by argon gas bubbling for 30 minutes was added to the obtained reaction solution, and the mixture was stirred at 80 ° C. for 2 hours, and then sodium diethyldithiocarbamate. Dihydrate (2.89 g) and ion-exchanged water (29 mL) were added, and the mixture was heated at 90 ° C. for 2 hours. After removing the aqueous layer in the obtained reaction solution, the obtained organic layer was washed twice with ion-exchanged water (20 mL), twice with 10 wt% acetic acid aqueous solution (20 mL), and twice with ion-exchanged water (20 mL). Then, it was poured into methanol (50 mL) to precipitate a solid. The obtained solid was redissolved in o-dichlorobenzene (11 mL), then passed through column chromatography (SiO ₂ and alumina), and the resulting solution was poured into methanol (50 mL) to precipitate a solid. The obtained solid was filtered and dried to obtain 59 mg of polymer compound L. The number average molecular weight of polystyrene conversion of the high molecular compound L was 2.7 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 5.2 * 10 < ⁴ >. The ionization potential of the organic thin film containing the polymer compound L was 5.31 eV.

Example 29
(Production and Evaluation of Organic Solar Cell 4)
An organic solar cell 4 was produced in the same manner as in Example 17 except that the polymer compound J was used in place of the polymer compound D. The light absorption edge wavelength end of the active layer was 800 nm.

The obtained organic solar cell 4 was irradiated with constant light using a solar simulator, and the generated current and voltage were measured to obtain photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor. Jsc (short circuit current density) is 6.60 mA / cm ² , Voc (open circuit voltage) is 0.83 V, ff (fill factor) is 0.61, and photoelectric conversion efficiency (η ) Was 3.34%.

Example 30
(Production and Evaluation of Organic Solar Cell 5)
An organic solar cell 5 was produced in the same manner as in Example 17 except that the polymer compound K was used in place of the polymer compound D. The light absorption edge wavelength end of the active layer was 760 nm.

The obtained organic solar cell 5 was irradiated with constant light using a solar simulator, and the generated current and voltage were measured to obtain photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor. Jsc (short circuit current density) is 4.99 mA / cm ² , Voc (open end voltage) is 0.87 V, ff (fill factor) is 0.60, and photoelectric conversion efficiency (η ) Was 2.60%.

Example 23
(Production and Evaluation of Organic Transistor 4)
An organic transistor 4 was produced in the same manner as in Example 6 except that the polymer compound G was used in place of the polymer compound A.

The gate voltage Vg and source-drain voltage Vsd of the obtained organic transistor 4 were changed, and transistor characteristics were measured. The field effect mobility was 4.5 × 10 ⁻² cm ² / Vs.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode,
6 ... drain electrode, 7a ... first electrode, 7b ... second electrode, 100, 110, 120, 130, 140, 150, 160, 170, 180 ... organic transistor, 300 ... photoelectric conversion element.

Claims (18)

The compound represented by Formula (1).

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups May have a substituent.
Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or an organic tin residue. Represent.
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )   The compound according to claim 1, wherein the ring A and ring B are the same. The compound of Claim 1 or 2 whose compound represented by said Formula (1) is a compound represented by Formula (2).

(Where
R ¹ , R ² , Z ¹ and Z ² represent the same meaning as described above.
X represents an oxygen atom, a sulfur atom or a selenium atom. Two X's may be the same or different.
Y represents a nitrogen atom or —CR ³ ═. Two Y's may be the same or different. R ³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms. These groups may have a substituent. When two R ³ are present, they may be the same or different. )   4. A compound according to claim 3, wherein Y is -CH =.   The compound according to claim 3 or 4, wherein X is a sulfur atom. The compound according to claim ¹ , wherein R ¹ and R ² are the same. The compound according to claim 6, wherein R ¹ and R ² are alkyl groups having 1 to 30 carbon atoms. The compound according to any one of claims 1 to 7, wherein Z ¹ and Z ² are the same. The compound according to claim 8, wherein Z ¹ and Z ² are hydrogen atoms. A first step of reacting a compound represented by formula (3) with at least one compound selected from the group consisting of a compound represented by formula (4) and a compound represented by formula (5); ,

(Where
Ring A and ring B each independently represent a heterocycle, and the heterocycle may have a substituent. )

R ¹ -Mtl (4)
(Where
R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. It may be.
Mtl represents a lithium atom or a magnesium halide. )

R ² -Mtl (5)
(Where
R ² represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups have a substituent. It may be.
Mtl represents the same meaning as described above. )
A second step of reacting the compound obtained in the first step in the presence of an acid;
The manufacturing method of the compound of Claim 9 containing this. A compound represented by formula (A).

^{Z 3 -W 1 -Ar 1 -W 2} -Z 4 (A)
(In the formula, Z ³ and Z ⁴ each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue (meaning a group represented by —B (OH) ₂ ) or organic. Represents a tin residue, Ar ¹ represents an arylene group or a divalent heterocyclic group, and W ¹ represents a group represented by the formula (A-1) or a group represented by the formula (A-2). W ² represents a group represented by the formula (A-3) or a group represented by the formula (A-4).

(In Formula (A-1) to Formula (A-4), R ′, R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 30 carbon atoms, or having 6 to 30 carbon atoms. Represents an aryl group or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups may have a substituent, and ring C, ring D, ring E, and ring F are each independently Represents a heterocyclic ring, which may have a substituent. The compound according to claim 11, which is a compound represented by formula (7), a compound represented by formula (8), or a compound represented by formula (9).

(In Formula (7) to Formula (9), R ′, R ⁴ , R ⁵ , R ⁶ , Z ³ , Z ⁴ , Ar ¹ , Ring C, Ring D, Ring E, and Ring F are the same as above. Represents meaning.) The compound according to claim 12, which is a compound represented by formula (10), a compound represented by formula (11), or a compound represented by formula (12).

(In the formula (10) to Formula ^{(12), R ', R} 4, R 5, R 6, Z 3, and ^{Z 4 are, .R} 7, R ⁸ represent the same meanings as defined above, R ^{9, R 10} , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or a monovalent group having 2 to 30 carbon atoms. And these groups may have a substituent.)   The high molecular compound obtained by homopolymerizing or copolymerizing the compound as described in any one of Claims 1-9 and 11-13.   An organic thin film comprising the polymer compound according to claim 14. A first electrode and a second electrode;
The organic-semiconductor element which has an active layer between this 1st electrode and this 2nd electrode, and contains the high molecular compound of Claim 14 in this active layer.   The organic-semiconductor element of Claim 16 which is a photoelectric conversion element.   The organic-semiconductor element of Claim 16 which is an organic transistor.

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