JP2015189853A - Polymer compound and electronic element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound enabling an organic thin film solar cell having longer absorption edge wavelength to be manufactured, and an electronic element containing the polymer compound.SOLUTION: There is provided the polymer compound including a constitutional unit represented by the formula (I). In the formula (I), Arand Arrepresents aromatic hydrocarbon ring or heterocycle, Xand Xrepresent sulfur atom, oxygen atom or selenium atom, one of Zand Zrepresents -C(R)(R)- and the other represents an oxygen atom, a sulfur atom, -C(=O)-, -S(=O)-, -SO-, -Si(R)-, -N(R)-, -B(R)-, -P(R)- or -P(=O)(R)-, one of Zand Zrepresents -C(R)(R)- and the other represents an oxygen atom, a sulfur atom, -C(=O)-, -S(=O)-, -SO, -Si(R), -N(R), -B(R), -P(R)- or -P(=O)(R)-.

Description

  The present invention relates to a polymer compound and an electronic device using the same.

  An organic thin film solar cell using a polymer compound as an active layer has been attracting attention in recent years because it may be inexpensively manufactured only by a coating process. As a polymer compound used for an organic thin film solar cell, a polymer compound composed of a structural unit (A) and a structural unit (B) represented below has been proposed (Patent Document 1).

JP 2012-255117 A

  In the organic thin film solar cell, increasing the short-circuit current density is important for increasing the photoelectric conversion efficiency. In order to increase the short-circuit current density, it is desirable to absorb light up to a longer wavelength region, that is, it is desirable that the absorption edge wavelength is longer. However, in an organic thin film solar cell containing an organic layer containing the polymer compound, the absorption edge wavelength is not necessarily a long wavelength.

  Then, an object of this invention is to provide the high molecular compound which can manufacture the organic thin-film solar cell whose absorption edge wavelength is longer wavelength. Another object of the present invention is to provide an electronic device containing the polymer compound.

  The present invention provides the following polymer compounds, organic thin film solar cell materials and organic thin film solar cell elements containing the polymer compounds, and compounds useful as raw materials for the polymer compounds.

〔式中、Ａｒ^１およびＡｒ^２は、それぞれ独立に、芳香族炭化水素環または複素環を表し、これらの環は縮合環であってもよく、これらの環に含まれる水素原子は置換基で置換されていてもよい。
Ｘ^１およびＸ^２は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表す。
Ｚ^１およびＺ^２は、いずれか一方が−Ｃ（Ｒ^１）（Ｒ^２）−を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^５）_２−で表される基、−Ｎ（Ｒ^５）−で表される基、−Ｂ（Ｒ^５）−で表される基、−Ｐ（Ｒ^５）−で表される基または−Ｐ（＝Ｏ）（Ｒ^５）−で表される基を表す。
Ｚ^３およびＺ^４は、いずれか一方が−Ｃ（Ｒ^３）（Ｒ^４）−を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^６）_２−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｂ（Ｒ^６）−で表される基、−Ｐ（Ｒ^６）−で表される基または−Ｐ（＝Ｏ）（Ｒ^６）−で表される基を表す。
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。
Ｒ^５およびＲ^６は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基または１価の複素環基を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。Ｒ^５またはＲ^６が複数存在する場合、それらは同一でも異なっていてもよい。〕
[２] 式（Ｉ）で表される構成単位が式（ＩＩ）で表される構成単位である[１]に記載の高分子化合物。

〔式中、Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｘ^１およびＸ^２は、それぞれ前記と同じ意味を表す。Ｘ^３およびＸ^４は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表わす。Ｙ^１およびＹ^２は、それぞれ独立に、窒素原子又は＝Ｃ（Ｒ^７）−で表される基を表わす。Ｒ^７は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、これらのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。〕
[３] Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４が、いずれも硫黄原子である、[２]に記載の高分子化合物。
[４] Ｙ^１およびＹ^２が、いずれも＝Ｃ（Ｈ）−で表される基である、[２]または[３]のいずれか一項に記載の高分子化合物。
[５] Ｚ^１が−Ｃ（Ｒ^１）（Ｒ^２）−で表される基であり、Ｚ^４が−Ｃ（Ｒ^３）（Ｒ^４）−で表される基であり、Ｚ^２およびＺ^３が、いずれも酸素原子である、[１]〜[４]のいずれか一項に記載の高分子化合物。
[６] さらに、式（ＩＩＩ）で表される構成単位を含む、[１]〜[５]のいずれか一項に記載の高分子化合物。

〔式中、Ａｒは、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。ただし、Ａｒは、式（Ｉ）で表される構成単位とは異なる。〕
[７] 前記Ａｒが、式（ＩＩＩ−１）〜式（ＩＩＩ−１６）のいずれかで表される構成単位である[６]に記載の高分子化合物。

〔各式中、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、これらのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。Ｘ^ａおよびＸ^ｂは、それぞれ独立に、硫黄原子、酸素原子またはセレン原子を表す。〕
[８] 式（Ｉ）で表される構成単位と、式（ＩＩＩ）で表される構成単位とが、交互に結合した共重合体である、[６]または[７]に記載の高分子化合物。
[９] 光吸収末端波長が８５０ｎｍ以上である[１]〜[８]のいずれか一項に記載の高分子化合物。
[１０] ポリスチレン換算の重量平均分子量が３０００〜１０００００００である [１]〜[９]のいずれか一項に記載の高分子化合物。
[１１] [１]〜[１０]のいずれか一項に記載の高分子化合物を含む電子素子。
[１２] 第１の電極と、第２の電極と、前記第１の電極及び前記第２の電極の間に設けられる活性層とを有する有機光電変換素子であって、前記活性層に[１]〜[１０]のいずれか一項に記載の高分子化合物を含有する有機光電変換素子。
[１３] [１２]に記載の有機光電変換素子を含む太陽電池モジュール。
[１４] ゲート電極と、ソース電極と、ドレイン電極と、活性層とを有し、前記活性層に[１]〜[１０]のいずれか一項に記載の化合物を含有する有機薄膜トランジスタ。
[１５] 式（ＩＶ）で表される化合物。

〔式中、Ａｒ^１およびＡｒ^２は、それぞれ独立に、芳香族炭化水素環または複素環を表し、これらの環は縮合環であってもよく、これらの環に含まれる水素原子は置換基で置換されていてもよい。
Ｘ^１およびＸ^２は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表す。
Ｚ^１およびＺ^２は、いずれか一方が−Ｃ（Ｒ^１）（Ｒ^２）−を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^５）_２−で表される基、−Ｎ（Ｒ^５）−で表される基、−Ｂ（Ｒ^５）−で表される基、−Ｐ（Ｒ^５）−で表される基または−Ｐ（＝Ｏ）（Ｒ^５）−で表される基を表す。
Ｚ^３およびＺ^４は、いずれか一方が−Ｃ（Ｒ^３）（Ｒ^４）−を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^６）_２−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｂ（Ｒ^６）−で表される基、−Ｐ（Ｒ^６）−で表される基または−Ｐ（＝Ｏ）（Ｒ^６）−で表される基を表す。
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。
Ｒ^５およびＲ^６は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基または１価の複素環基を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。Ｒ^５またはＲ^６が複数存在する場合、それらは同一でも異なっていてもよい。
Ｗ^１およびＷ^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、ホウ酸残基または有機スズ残基を表す。〕 [1] A polymer compound containing a structural unit represented by the formula (I).

[In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, these rings may be condensed rings, and the hydrogen atom contained in these rings is a substituent. May be substituted.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
One of Z ¹ and Z ² represents —C (R ¹ ) (R ² ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —, and —B (R ⁵⁾ -, a group represented by, -P ^{(R 5)} - or a group represented by -P with (= O) ^{(R 5)} - represents a group represented by.
One of Z ³ and Z ⁴ represents —C (R ³ ) (R ⁴ ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —, and —B (R ⁶⁾ -, a group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different. ]
[2] The polymer compound according to [1], wherein the structural unit represented by the formula (I) is a structural unit represented by the formula (II).

[Wherein, Z ¹ , Z ² , Z ³ , Z ⁴ , X ¹ and X ² each represent the same meaning as described above. X ³ and X ⁴ each independently represents a sulfur atom, an oxygen atom or a selenium atom. Y ¹ and Y ² each independently represent a nitrogen atom or a group represented by ═C (R ⁷ ) —. R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and among these, an alkyl group, The hydrogen atom contained in each of the cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. ]
[3] The polymer compound according to [2], wherein X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms.
[4] The polymer compound according to any one of [2] or [3], wherein Y ¹ and Y ² are both groups represented by ═C (H) —.
[5] Z ¹ is a group represented by —C (R ¹ ) (R ² ) —, Z ⁴ is a group represented by —C (R ³ ) (R ⁴ ) —, and Z ² and The polymer compound according to any one of [1] to [4], wherein Z ³ is an oxygen atom.
[6] The polymer compound according to any one of [1] to [5], further comprising a structural unit represented by the formula (III).

[In the formula, Ar represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, Ar is different from the structural unit represented by the formula (I). ]
[7] The polymer compound according to [6], wherein Ar is a structural unit represented by any one of formulas (III-1) to (III-16).

[In each formula, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, 1 Represents a valent heterocyclic group or a halogen atom, and among these, it is included in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group. The hydrogen atom may be substituted with a substituent. ^Xa and ^Xb each independently represent a sulfur atom, an oxygen atom or a selenium atom. ]
[8] The polymer according to [6] or [7], which is a copolymer in which the structural unit represented by the formula (I) and the structural unit represented by the formula (III) are alternately bonded. Compound.
[9] The polymer compound according to any one of [1] to [8], which has a light absorption terminal wavelength of 850 nm or more.
[10] The polymer compound according to any one of [1] to [9], wherein the polystyrene-equivalent weight average molecular weight is 3000 to 10000000.
[11] An electronic device comprising the polymer compound according to any one of [1] to [10].
[12] An organic photoelectric conversion element having a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, wherein the active layer has [1 ] The organic photoelectric conversion element containing the high molecular compound as described in any one of [10].
[13] A solar cell module including the organic photoelectric conversion element according to [12].
[14] An organic thin film transistor having a gate electrode, a source electrode, a drain electrode, and an active layer, wherein the active layer contains the compound according to any one of [1] to [10].
[15] A compound represented by formula (IV).

[In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, these rings may be condensed rings, and the hydrogen atom contained in these rings is a substituent. May be substituted.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
One of Z ¹ and Z ² represents —C (R ¹ ) (R ² ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —, and —B (R ⁵⁾ -, a group represented by, -P ^{(R 5)} - or a group represented by -P with (= O) ^{(R 5)} - represents a group represented by.
One of Z ³ and Z ⁴ represents —C (R ³ ) (R ⁴ ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —, and —B (R ⁶⁾ -, a group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different.
W ¹ and W ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue or an organotin residue. ]

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound which can manufacture the organic thin-film solar cell whose absorption edge wavelength is a longer wavelength can be provided. The present invention can also provide an electronic device including the polymer compound.

FIG. 3 is a diagram showing an absorption spectrum of a polymer compound P1. FIG. 3 is a diagram showing an absorption spectrum of a polymer compound P2. 2 is a graph showing an absorption spectrum of polymer compound C. FIG.

  Hereinafter, the present invention will be described in detail.

〔式中、Ａｒ^１およびＡｒ^２は、それぞれ独立に、芳香族炭化水素環または複素環を表し、これらの環は縮合環であってもよく、これら環に含まれる水素原子は置換基で置換されていたもよい。
Ｘ^１およびＸ^２は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表す。
Ｚ^１およびＺ^２は、いずれか一方が−Ｃ（Ｒ^１）（Ｒ^２）−で表される基を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^５）_２−で表される基、−Ｎ（Ｒ^５）−で表される基、−Ｂ（Ｒ^５）−で表される基、−Ｐ（Ｒ^５）−で表される基または−Ｐ（＝Ｏ）（Ｒ^５）−で表される基を表す。
Ｚ^３およびＺ^４は、いずれか一方が−Ｃ（Ｒ^３）（Ｒ^４）−で表される基を表し、他方が酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^６）_２−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｂ（Ｒ^６）−で表される基、−Ｐ（Ｒ^６）−で表される基または−Ｐ（＝Ｏ）（Ｒ^６）−で表される基を表す。
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。
Ｒ^５およびＲ^６は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基または１価の複素環基を表し、こられのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。Ｒ^５またはＲ^６が複数存在する場合、それらは同一でも異なっていてもよい。〕 <Polymer compound>
The polymer compound of the present invention contains a structural unit represented by the formula (I). The polymer compound of the present invention is preferably a conjugated polymer compound.

[In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, and these rings may be condensed rings, and hydrogen atoms contained in these rings are substituted with substituents. May have been.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
Z ¹ and Z ² each represent a group represented by —C (R ¹ ) (R ² ) —, and the other represents an oxygen atom, a sulfur atom, or a group represented by —C (═O) —. , A group represented by —S (═O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —. , -B ^{(R 5)} - group represented by, -P ^{(R 5)} - or a group represented by -P with ^{(= O) (R 5)} - represents a group represented by.
Z ³ and Z ⁴ each represents a group represented by —C (R ³ ) (R ⁴ ) —, and the other represents an oxygen atom, a sulfur atom, or a group represented by —C (═O) —. , A group represented by —S (═O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —. , -B ^{(R 6)} - group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different. ]

The structural unit represented by formula (I) is specifically represented by formula (I-1), formula (I-2), or formula (I-3).

  The structural unit of the formula (I) is preferably a structural unit represented by the formula (I-1) because the synthesis of the polymer compound of the present invention is facilitated.

In Formula (I-1) to Formula (I-3), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, and these rings may be condensed rings, The hydrogen atom contained in the ring may be substituted with a substituent.

  The number of carbon atoms of the aromatic hydrocarbon ring is usually 6 to 60, and it is preferably 6 to 20 because the synthesis of the polymer compound of the present invention becomes easy. The number of carbon atoms does not include the number of carbon atoms of the substituent. The aromatic hydrocarbon ring includes a compound containing a benzene ring, a compound containing a condensed ring, and a compound containing a structure in which two or more independent benzene rings or two or more condensed rings are directly bonded.

Examples of the substituent that the aromatic hydrocarbon ring may have include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, or A halogen atom is mentioned.

Examples of the aromatic hydrocarbon ring include the following formula (100) to formula (110).

The heterocyclic ring represented by Ar ¹ and Ar ² is not only a carbon atom but also a heteroatom such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, etc., among the organic compounds having a cyclic structure. Is included in the ring.

  The number of carbon atoms of the heterocyclic ring is usually 2 to 60, and is preferably 4 to 60 and more preferably 4 to 20 in order to facilitate the synthesis of the polymer compound of the present invention. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Examples of the substituent that the heterocyclic ring may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, and a halogen atom. Can be mentioned.

  Examples of the heterocyclic ring include the following formulas (111) to (167).

In formula (I-1) to formula (I-3), X ¹ and X ² each independently represent a sulfur atom, an oxygen atom or a selenium atom.

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

In formula (I-1) to formula (I-3), Z ⁵ represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, or a group represented by —S (═O) —. , A group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —, a group represented by —B (R ⁵ ) —. , -P ^{(R 5)} - group represented by or -P with ^{(= O) (R 5)} - represents a group represented by. Z ⁶ is an oxygen atom, a sulfur atom, a group represented by —C (═O) —, a group represented by —S (═O) —, a group represented by —SO ₂ —, or —Si (R ^6). ) A group represented by _2- , a group represented by -N (R ⁶ )-, a group represented by -B (R ⁶ )-, a group represented by -P (R ⁶ )-or -P A group represented by a group represented by (═O) (R ⁶ ) — is represented. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different.

In order to facilitate the synthesis of the polymer compound of the present invention, Z ⁵ and Z ⁶ are preferably the same group, and are a group represented by an oxygen atom, a sulfur atom or —C (═O) —. It is more preferable that it is an oxygen atom.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.

The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ may be either a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group is usually 1 to 30 (usually 3 to 30 in the case of a branched alkyl group), and preferably 1 to 20 (3 to 20 in the case of a branched alkyl group). The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group and n-hexadecyl group, isopropyl And branched alkyl groups such as an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, and a 3,7-dimethyloctyl group.
The alkyl group may have a substituent, and examples of the substituent include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom. Examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The number of carbon atoms that the cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ has is usually 3 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The alkoxy group represented by R ¹ , R ² , R ³ and R ⁴ may be either a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group is usually 1 to 30 (usually 3 to 30 in the case of a branched alkoxy group), and preferably 1 to 20 (3 to 20 in the case of a branched alkoxy group). The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, and an n-hexadecyloxy group. Examples thereof include branched alkoxy groups such as linear alkoxy groups, isopropyloxy groups, isobutyloxy groups, sec-butyloxy groups, tert-butyloxy groups, 2-ethylhexyloxy groups, and 3,7-dimethyloctyloxy groups.
The alkoxy group may have a substituent, and examples of the substituent include an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The number of carbon atoms of the cycloalkoxy group represented by R ¹ , R ² , R ³ and R ⁴ is usually 3 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. The cycloalkoxy group may have a substituent, and examples of the substituent include an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The alkylthio group represented by R ¹ , R ² , R ³ and R ⁴ may be either a linear alkylthio group or a branched alkylthio group. The number of carbon atoms of the alkylthio group is usually 1 to 30 (usually 3 to 30 in the case of a branched alkylthio group), and preferably 1 to 20 (3 to 20 in the case of a branched alkylthio group). The number of carbon atoms that the cycloalkylthio group represented by R ¹ , R ² , R ³ and R ⁴ has is usually 3 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the alkylthio group include a straight chain alkylthio group such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-hexadecylthio group, isopropyl Examples thereof include branched alkylthio groups such as thio group, isobutylthio group, sec-butylthio group, tert-butylthio group, 2-ethylhexylthio group, and 3,7-dimethyloctylthio group.
The alkylthio group may have a substituent, and examples of the substituent include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The number of carbon atoms that the cycloalkylthio group represented by R ¹ , R ² , R ³ and R ⁴ has is usually 3 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Examples of the cycloalkylthio group include a cyclopentylthio group and a cyclohexylthio group. The cycloalkylthio group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The aryl group represented by R ¹ , R ² , R ³ and R ⁴ is the remainder 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 a group in which two or more selected from the group consisting of 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.
As the aryl group, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Examples include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, and 4-phenylphenyl group.
The aryl group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, a monovalent heterocyclic group, and a halogen atom. Is mentioned. Examples of the aryl group having a substituent include a 4-hexadecylphenyl group, a 3,5-dimethoxyphenyl group, and a pentafluorophenyl group. When the aryl group has a substituent, the substituent is preferably an alkyl group or a cycloalkyl group.

The monovalent heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom directly bonded to a carbon atom or a hetero atom constituting the ring from an optionally substituted heterocyclic compound. It is the remaining atomic group excluding one atom, and includes a group in which two or more selected from the group consisting of 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.
Examples of the monovalent heterocyclic group include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a 2-oxazolyl group, and a 2-thiazolyl group. 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group, 4- (2,1,3-benzothiadiazolyl) ) Group.
The monovalent heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, and a halogen atom. Is mentioned. Examples of the monovalent heterocyclic group having a substituent include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group. When the monovalent heterocyclic group has a substituent, the substituent is preferably an alkyl group or a cycloalkyl group.

Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ¹ , R ² , R ³ and R ⁴ are preferably an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group from the viewpoint of enhancing the solubility of the polymer compound. An aryl group is more preferred.
.

〔式中、Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｘ^１およびＸ^２は、それぞれ前記と同じ意味を表す。Ｘ^３およびＸ^４は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表わす。Ｙ^１およびＹ^２は、それぞれ独立に、窒素原子又は＝Ｃ（Ｒ^７）−を表わす。Ｒ^７は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、これらのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。〕 The structural unit represented by the formula (I) is preferably a structural unit represented by the following formula (II) because the synthesis of the polymer compound of the present invention is facilitated.

[Wherein, Z ¹ , Z ² , Z ³ , Z ⁴ , X ¹ and X ² each represent the same meaning as described above. X ³ and X ⁴ each independently represents a sulfur atom, an oxygen atom or a selenium atom. Y ¹ and Y ² each independently represent a nitrogen atom or ═C (R ⁷ ) —. R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and among these, an alkyl group, The hydrogen atom contained in each of the cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. ]

The definitions and specific examples of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group and halogen atom represented by R ⁷ are the above-mentioned R ¹ , R Definitions and specific examples of alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, monovalent heterocyclic groups and halogen atoms represented by ² , R ³ and R ⁴ is there.

Specifically, the structural unit represented by formula (II) is represented by formula (II-1), formula (II-2), or formula (II-3).

In formula (II-1) to formula (II-3), X ¹ , X ² , X ³ , X ⁴ , Y ¹ , Y ² , R ¹ , R ² , R ³ , R ⁴ , Z ⁵ and Z ⁶ Each represents the same meaning as described above.

  The structural unit of the formula (II) is preferably a structural unit represented by the formula (II-1) because the synthesis of the polymer compound of the present invention is facilitated.

In order to facilitate the synthesis of the polymer compound of the present invention, X ³ and X ⁴ are preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

In order to facilitate the synthesis of the polymer compound of the present invention, Y ¹ and Y ² are preferably a group represented by ═C (R ⁷ ) —, and are a group represented by ═CH—. Is more preferable.

As a structural unit represented by Formula (I), the structural unit represented by Formula (201)-Formula (248) is mentioned, for example.
Since the absorption edge wavelength of the organic thin film solar cell produced using the polymer compound of the present invention is longer, the structural unit represented by the formula (I) is represented by the formula (201) to the formula (212), It is preferably a structural unit represented by Formula (214), Formula (219), Formula (222) to Formula (233), Formula (235), or Formula (240), and Formula (201) to Formula (212) Is more preferable, and the structural unit represented by Formula (201), Formula (202), and Formula (203) is more preferable.

  The polymer compound of the present invention has a structural unit different from the structural unit represented by the formula (I) in addition to the structural unit represented by the formula (I) from the viewpoint of making the absorption edge wavelength a long wavelength. It is preferable to include. When the compound of the present invention contains a structural unit different from the structural unit represented by formula (I), the structural unit represented by formula (I) is different from the structural unit represented by formula (I). And preferably form a conjugate. Conjugation in the present invention means that an unsaturated bond is present between one single bond and exhibits an interaction. Here, the unsaturated bond refers to a double bond or a triple bond.

（式中、Ａｒは、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。ただし、Ａｒは、式（Ｉ）で表される構成単位とは異なる。） Examples of the structural unit different from the structural unit represented by formula (I) include the structural unit represented by formula (III).

(In the formula, Ar represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent. However, Ar is a structural unit represented by the formula (I). Different.)

The arylene group represented by Ar is a group obtained by removing two hydrogen atoms on a ring from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is usually 6 to 60 and may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, and a halogen atom. Definitions and specific examples of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group and halogen atom are represented by R ^{1 to} R ^4. The definition and specific examples of alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group or halogen atom are the same.
Specific examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a biphenyl-diyl group, a terphenyl-diyl group, and a condensed ring compound group. The condensed ring compound group includes a fluorene-diyl group. (Formula (301) to Formula (324))

The divalent heterocyclic group represented by Ar each may have a substituent, furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine , Pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, iso Indole, indolizine, indoline, isoindoline, chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole Benzothiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, A group obtained by removing two hydrogen atoms from a heterocyclic compound such as phenazine. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, and a halogen atom. Definitions and specific examples of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group and halogen atom are represented by R ^{1 to} R ^4. The definition and specific examples of alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group or halogen atom are the same. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable. Specific examples of the divalent heterocyclic group include formula (325) to formula (379).

  From the viewpoint of increasing the absorption edge wavelength, the structural unit represented by the formula (III) is preferably a structural unit represented by the formula (III-1) to the formula (III-16).

〔各式中、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、これらのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。Ｘ^ａおよびＸ^ｂは、それぞれ独立に、硫黄原子、酸素原子またはセレン原子を表す。〕

[In each formula, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, 1 Represents a valent heterocyclic group or a halogen atom, and among these, it is included in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group. The hydrogen atom may be substituted with a substituent. ^Xa and ^Xb each independently represent a sulfur atom, an oxygen atom or a selenium atom. ]

The R ^a to R ^d, alkyl group, preferably an alkoxy group and a halogen atom, more preferably an alkyl group and a fluorine atom.

  As the structural unit represented by the formula (III), structural units represented by the formula (III-1) to the formula (III-11) are more preferable, and the structural unit represented by the formula (III-1), the formula (III-3), and The structural unit represented by the formula (III-4) is more preferable. Specific examples of the structural unit represented by formula (III-1), formula (III-3) and formula (III-4) include formula (III-1-1) to formula (III-1-10). , Structural units represented by formula (III-3-1) to formula (III-3-7) and formula (III-4-1) to formula (III-4-10).

  When the polymer compound of the present invention includes a structural unit represented by the formula (III), from the viewpoint of making the absorption edge wavelength a long wavelength, the structural unit represented by the formula (I) and the formula (III) It is preferable that the structural unit represented is a copolymer bonded alternately. The structural unit represented by the formula (I) and the structural unit represented by the formula (III) in the copolymer may be the same or different.

  As the structural unit of the copolymer in which the structural unit represented by the formula (I) and the structural unit represented by the formula (III) are alternately bonded, the following formula (II-III-1), formula ( II-III-3) and structural units represented by the formula (II-III-4). The alternately bonded copolymer is one or more selected from the group consisting of structural units represented by formula (II-III-1), formula (II-III-3) and formula (II-III-4) It is preferable that it consists of a structural unit represented by Formula (II-III-1) or Formula (II-III-3).

〔各式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｙ^１、Ｙ^２、Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｒ^ａ、Ｒ^ｂ、Ｘ^ａおよびＸ^ｂは、それぞれ前記と同じ意味を表す。〕

[In each formula, X ¹ , X ² , X ³ , X ⁴ , Y ¹ , Y ² , Z ¹ , Z ² , Z ³ , Z ⁴ , R ^a , R ^b , X ^a and X ^b are the same as the above] Means the same. ]

Specific examples of the structural units of the copolymer bonded alternately include structural units represented by the formulas (380) to (395). Among these, structural units represented by the formulas (380) to (393) are preferable, and structural units represented by the formulas (380) and (384) are more preferable.

The polymer compound of the present invention refers to a compound having a weight average molecular weight of 1000 or more. The weight average molecular weight of the polymer compound in the present invention is preferably 3,000 to 10,000,000, more preferably 8,000 to 5,000,000, and still more preferably 10,000 to 1,000,000. If the weight average molecular weight is lower than 3000, defects may occur in film formation during device fabrication, and if it exceeds 10000000, solubility in a solvent and applicability during device fabrication may be degraded.
The weight average molecular weight in the present invention means a weight average molecular weight in terms of polystyrene calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).

  The polymer compound of the present invention may contain at least one structural unit represented by the formula (I). It is preferable that an average of 2 or more per polymer chain is included, and an average of 3 or more per polymer chain is more preferable.

  When the polymer compound of the present invention is used in a device, it is desirable that the solubility of the polymer compound in a solvent is high from the viewpoint of ease of device fabrication. Specifically, the polymer compound of the present invention preferably has a solubility capable of producing a solution containing 0.01% by weight (wt)% or more of the polymer compound, and a solution containing 0.1% by weight or more is produced. It is more preferable that it has a solubility capable of forming a solution containing 0.2 wt% or more.

<Method for producing polymer compound>
The polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like. The synthesis of the monomer can be performed, for example, with reference to the methods disclosed in JP-A Nos. 2006-182920 and 2006-335933.

  Examples of the polymerization by aryl coupling reaction include polymerization by Suzuki coupling reaction, polymerization by Stille coupling reaction, polymerization by Yamamoto coupling reaction, and polymerization by Kumada-Tamao coupling reaction.

As a method using Suzuki coupling reaction, for example, the formula (500):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (500)
Wherein, E ¹ represents a structural unit represented by the formula (II). Q ¹⁰⁰ and Q ²⁰⁰ are the same or different and represent a boric acid residue (—B (OH) ₂ ) or a boric acid ester residue. ]
One or more compounds represented by formula (600):
T ¹ -E ² -T ² (600)
[Wherein E ² represents a structural unit represented by the formula (I). T ¹ and T ² are the same or different and represent a halogen atom. ]
The manufacturing method which has a 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. E ¹ is preferably a structural unit represented by formula (C-1) to formula (C-29).

  When the compound represented by Formula (500) and the compound represented by Formula (600) are reacted, the total number of moles of one or more compounds represented by Formula (600) used for the reaction is represented by Formula (500). It is preferable that it is excessive with respect to the total number of moles of one or more compounds represented by When the total number of moles of one or more compounds represented by formula (600) used in the reaction is 1 mole, the total number of moles of one or more compounds represented by formula (500) is 0.6 to 0.00. It is preferably 99 mol, and more preferably 0.7 to 0.95 mol.

  A boric acid ester residue represents a group obtained by removing a hydroxyl group from a boric acid diester, and specific examples thereof include a group 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。）

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)

Examples of the halogen atom represented by T ¹ and T ² in Formula (600) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom or an iodine atom is preferable, and a bromine atom is more preferable.

  Specifically, the method for carrying out the Suzuki coupling reaction includes 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 a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium 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 is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (500). Yes, preferably 0.0003 mol to 0.1 mol.

  When using palladium acetate as the palladium catalyst used in the Suzuki coupling reaction, add a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine or tri (o-methoxyphenyl) phosphine as a ligand. Can do. In this case, the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst. Is a mole.

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 potassium phosphate. Examples of the organic base include triethylamine and tributylamine. An example of the inorganic salt is cesium fluoride.
The addition amount of the base is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol, relative to 1 mol of the compound represented by the formula (500). -10 mol.

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

  The temperature at which the Suzuki coupling reaction is performed depends on the solvent, but is usually about 40 to 160 ° C. From the viewpoint of increasing the molecular weight of the polymer compound, 60 to 120 ° C. is preferable. 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 0.5 to 30 hours is efficient and preferable.

  The Suzuki coupling reaction is performed in a reaction system in which the palladium catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed 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, the polymerization vessel is charged with a compound represented by the formula (500), a compound represented by the formula (600), A palladium catalyst, for example, dichlorobis (triphenylphosphine) palladium (II) is charged, and the polymerization vessel is sufficiently substituted with nitrogen gas and degassed, and then degassed by bubbling with nitrogen gas in advance, for example, After adding toluene, a base degassed by bubbling with nitrogen gas in advance, such as an aqueous sodium carbonate solution, was added dropwise to the solution, followed by heating and heating, for example, at a reflux temperature for 8 hours. Polymerize while maintaining the atmosphere.

As a method using Stille coupling reaction, for example, Formula (700):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (700)
Wherein, ^{E 3} represents a structural unit represented by the formula (II). Q ³⁰⁰ and Q ⁴⁰⁰ are the same or different and represent an organotin residue. ]
And a method of reacting one or more compounds represented by the formula (600) with one or more compounds represented by the formula (600) in the presence of a palladium catalyst. E ³ is preferably a structural unit represented by Formula (C-1) to Formula (C-29).

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.
As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, hexyl group , Isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group And chain alkyl groups such as hexadecyl group, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Preferably the organotin residues, -SnMe _3, -SnEt _3, a -SnBu ₃ and -SnPh _3, more preferably, -SnMe _3, a -SnEt ₃ and -SnBu _3. In the above preferred examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Examples of the halogen atom represented by T ¹ and T ² in Formula (600) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom and an iodine atom are preferable.

Specifically, examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst. 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, and 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 for the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (100). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.

  In the Stille coupling reaction, a ligand and 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 and tris (2-furyl) phosphine, and 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 amount of the ligand or cocatalyst added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, relative to 1 mol of the palladium catalyst. More preferably, it is 1 mol 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, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound used in the present invention, toluene and tetrahydrofuran are preferred.

The temperature at which the Stille coupling reaction is performed depends on the solvent, but is usually about 50 to 160 ° C., and 60 to 120 ° C. is preferable 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 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 hour to 30 hours is efficient and preferable.

  The Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed 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, the compound represented by the formula (700), the compound represented by the formula (600), A palladium catalyst is charged, and the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then a solvent degassed by bubbling with nitrogen gas in advance, for example, toluene, is added, and a ligand is optionally added. And a cocatalyst are added, and then heated and heated, for example, polymerization is carried out while maintaining an inert atmosphere at the reflux temperature for 8 hours.

  Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups. Polymerization.

  Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel. Examples include catalysts comprising nickel complexes other than nickel zero-valent complexes such as dichloride and ligands such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine as necessary. . Examples of the reducing agent include zinc and magnesium. Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system.

  Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.

  Polymerization by Kumada-Tamao coupling reaction is carried out by using a nickel catalyst such as [bis (diphenylphosphino) ethane] nickel dichloride and [bis (diphenylphosphino) propane] nickel dichloride, a compound having a magnesium halide group and a halogen atom. Polymerization to react with the compound having For the reaction, a dehydrated solvent may be used for the reaction, the reaction may be performed in an inert atmosphere, or a dehydrating agent may be added to the reaction system.

  In the polymerization by the aryl coupling reaction, a solvent is usually used. The solvent may be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, and N, N-dimethylformamide, organic solvents such as a mixed solvent in which two or more of these solvents are mixed, organic A solvent having two phases of a solvent phase and an aqueous phase is exemplified. The solvent used in the Stille coupling reaction is preferably an organic solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide, a mixed solvent obtained by mixing two or more of these solvents, or a solvent having two phases of an organic solvent phase and an aqueous phase. The solvent used in the Stille coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. Solvents used in the Suzuki coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed. A solvent and a solvent having two phases of an organic solvent phase and an aqueous phase are preferred. The solvent used for the Suzuki coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. Solvents used for the Yamamoto coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed. A solvent is preferred. The solvent used for the Yamamoto coupling reaction is preferably subjected to deoxygenation before the reaction in order to suppress side reactions.

  Among the polymerizations by the aryl coupling reaction, from the viewpoint of reactivity, a method of polymerizing by a Stille coupling reaction, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Yamamoto coupling reaction are preferable, and a Stille coupling reaction More preferred are a method of polymerizing by a method, a method of polymerizing by a Suzuki coupling reaction, and a method of polymerizing by a Yamamoto coupling reaction using a nickel zero-valent complex.

  The lower limit of the reaction temperature of the aryl coupling reaction is preferably −100 ° C., more preferably −20 ° C., and further preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and further preferably 120 ° C. from the viewpoint of the stability of the monomer and the compound.

  In the polymerization by the aryl coupling reaction, a known method can be used as a method for removing the polymer compound of the present invention from the reaction solution after completion of the reaction. For example, the polymer compound of the present invention can be obtained by adding a reaction solution to a lower alcohol such as methanol, filtering the deposited precipitate, and drying the filtrate. When the purity of the obtained polymer compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  When the polymer compound of the present invention is used for the production of an organic photoelectric conversion element, if a polymerization active group remains at the terminal of the polymer compound, characteristics such as durability of the organic photoelectric conversion element may be deteriorated. It is preferable to protect the terminal of the polymer compound with a stable group.

  Examples of the stable group for protecting the terminal include an alkyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Examples of the arylamino group include a phenylamino group and a diphenylamino group. Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and isoquinolyl group. Further, the polymerization active group remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group. From the viewpoint of enhancing hole transportability, it is preferable that the stable group for protecting the terminal is a group imparting electron donating properties such as an arylamino group. When the polymer compound is a conjugated polymer compound, the end of a group having a conjugated bond in which the conjugated structure of the main chain of the polymer compound and the conjugated structure of a stable group protecting the end are continuous is also protected. It can preferably be used as a stable group. Examples of the group include an aryl group and a monovalent heterocyclic group having aromaticity.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁸ . When the number average molecular weight in terms of polystyrene is 1 × 10 ³ or more, a tough thin film is easily obtained. On the other hand, when it is 10 ⁸ or less, the solubility is high and the thin film can be easily produced.

<Compound>
The compound of the present invention is a compound represented by the formula (IV).

In the formula (IV), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, and these rings may be condensed rings, and hydrogen atoms contained in these rings are substituted. It may be substituted with a group.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
One of Z ¹ and Z ² represents —C (R ¹ ) (R ² ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —, and —B (R ⁵⁾ -, a group represented by, -P ^{(R 5)} - or a group represented by -P with (= O) ^{(R 5)} - represents a group represented by.
One of Z ³ and Z ⁴ represents —C (R ³ ) (R ⁴ ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —, and —B (R ⁶⁾ -, a group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different.
W ¹ and W ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue or an organotin residue.

Definitions and specific examples of boric acid ester residues, boric acid residues and organotin residues represented by W ¹ and W ² are the boric acid ester residues, boric acid residues and organotin residues which are the above-mentioned polymerization reactive groups. The definition of the group and the specific examples are the same.

〔式中、Ａｒ^１、Ａｒ^２、Ｘ^１、Ｘ^２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｗ^１およびＷ^２は、それぞれ前記と同じ意味を表す。Ｘ^５およびＸ^６は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表わす。Ｚ^５は、酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^５）_２−で表される基、−Ｎ（Ｒ^５）−で表される基、−Ｂ（Ｒ^５）−で表される基、−Ｐ（Ｒ^５）−で表される基または−Ｐ（＝Ｏ）（Ｒ^５）−で表される基を表す。Ｚ^６は酸素原子、硫黄原子、−Ｃ（＝Ｏ）−で表される基、−Ｓ（＝Ｏ）−で表される基、−ＳＯ_２−で表される基、−Ｓｉ（Ｒ^６）_２−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｂ（Ｒ^６）−で表される基、−Ｐ（Ｒ^６）−で表される基または−Ｐ（＝Ｏ）（Ｒ^６）−で表される基で表される基を表す。Ｒ^５およびＲ^６は、それぞれ前記と同じ意味を表す。
Specifically, the compound represented by the formula (IV) is represented by the formula (IV-1), the formula (IV-2), and the formula (IV-3).

[Wherein, Ar ¹ , Ar ² , X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , W ¹ and W ² each represent the same meaning as described above. X ⁵ and X ⁶ each independently represent a sulfur atom, an oxygen atom or a selenium atom. Z ⁵ is an oxygen atom, a sulfur atom, a group represented by —C (═O) —, a group represented by —S (═O) —, a group represented by —SO ₂ —, or —Si (R). ⁵⁾ ₂ -, a group represented by, -N ^{(R 5)} -, a group represented by, -B ^{(R 5)} -, a group represented by, -P ^{(R 5)} - group, or represented by - represents a group represented by ^{- P (= O) (R} 5). Z ⁶ is an oxygen atom, a sulfur atom, a group represented by —C (═O) —, a group represented by —S (═O) —, a group represented by —SO ₂ —, or —Si (R ^6). ) A group represented by _2- , a group represented by -N (R ⁶ )-, a group represented by -B (R ⁶ )-, a group represented by -P (R ⁶ )-or -P A group represented by a group represented by (═O) (R ⁶ ) — is represented. R ⁵ and R ⁶ each have the same meaning as described above.

  The compound represented by the formula (IV) is preferably a compound represented by the formula (IV-1) because the synthesis of the polymer compound of the present invention becomes easy.

〔式中、Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｘ^１、Ｘ^２、Ｗ^１およびＷ^２は、は、それぞれ前記と同じ意味を表す。Ｘ^３およびＸ^４は、それぞれ独立に、硫黄原子、酸素原子又はセレン原子を表わす。Ｙ^１およびＹ^２は、それぞれ独立に、窒素原子又は＝Ｃ（Ｒ^７）−を表わす。Ｒ^７は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、１価の複素環基またはハロゲン原子を表し、これらのうち、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基および１価の複素環基のそれぞれに含まれる水素原子は置換基で置換されていてもよい。〕 The compound represented by the formula (IV) is preferably a compound represented by the following formula (V) in order to facilitate the synthesis of the polymer compound of the present invention.

[Wherein, Z ¹ , Z ² , Z ³ , Z ⁴ , X ¹ , X ² , W ¹ and W ² each have the same meaning as described above. X ³ and X ⁴ each independently represents a sulfur atom, an oxygen atom or a selenium atom. Y ¹ and Y ² each independently represent a nitrogen atom or ═C (R ⁷ ) —. R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and among these, an alkyl group, The hydrogen atom contained in each of the cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. ]

The definitions and specific examples of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group and halogen atom represented by R ⁷ are the above-mentioned R ¹ , R Definitions and specific examples of alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, monovalent heterocyclic groups and halogen atoms represented by ² , R ³ and R ⁴ is there.

〔式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｙ^１、Ｙ^２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ^５、Ｚ^６、Ｗ^１およびＷ^２は、それぞれ前記と同じ意味を表す。 Specifically, the compound represented by Formula (V) is represented by Formula (V-1), Formula (V-2), or Formula (V-3).

[Wherein, X ¹ , X ² , X ³ , X ⁴ , Y ¹ , Y ² , R ¹ , R ² , R ³ , R ⁴ , Z ⁵ , Z ⁶ , W ¹ and W ² are the same as the above] Represents the same meaning.

  The compound represented by the formula (V) is preferably a compound represented by the formula (V-1) because the synthesis of the polymer compound of the present invention is facilitated.

Examples of the compound represented by the formula (IV) include compounds represented by the formula (401) to the formula (433).
When the above-described polymer compound of the present invention is produced using the compound of the present invention, the absorption edge wavelength of the organic thin film solar cell produced using the polymer compound becomes a longer wavelength. ), Formula (402), Formula (405), Formula (406), Formula (407), Formula (409) to Formula (413), Formula (414), and Formula (417). More preferred are compounds represented by formula (401), formula (406), formula (407), formula (410), and formula (413).

<Method for producing compound>
Next, the manufacturing method of the compound of this invention is demonstrated.
The compound represented by the formula (IV) may be produced by any method. For example, as described below, it is produced by Suzuki coupling reaction, side chain introduction reaction, transannular reaction, functionalization reaction. can do.

When Z ² and Z ³ are oxygen atoms and Ar ¹ and Ar ² are five-membered rings, for example,
A first step of reacting a compound represented by the formula (S1), a compound represented by the formula (S2), and a compound represented by the formula (S3) by a Suzuki coupling reaction;
A second step of introducing a side chain into the compound represented by the formula (S4) obtained in the first step;
A third step of intramolecular cyclization of the compound represented by the formula (S5) obtained in the second step;
A fourth step of functionalizing the compound represented by the formula (S6) obtained in the third step;
Can be manufactured. The compound obtained in this case is a compound represented by the formula (S6).

In formulas (S1), (S2), (S3), (S4), (S5), (S6) and (S7), R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² , X ³ , X ⁴ , Y ¹ , Y ² , W ¹ and W ² each have the same meaning as described above.
M ¹ and M ² each independently represent a boric acid ester residue or a boric acid residue.
M ³ represents a lithium atom, magnesium bromide or magnesium chloride.
Hal represents an iodine atom, a bromine atom or a chlorine atom.
R ^′ represents an alkyl group, a cycloalkyl group, a silyl group or an acetyl group. Two Hal in the formula (S1) may be the same or different. Two R ^'may be the same or different, wherein R in ^(S1)' of the formula (S1) is ^'R with the formula ^(S3)' R of the formula (S2), be the same or different Good.

The polymer compound of the present invention preferably has a light absorption terminal wavelength of 850 nm or longer. The light absorption terminal wavelength can be determined by the following method.
For the measurement, a spectrophotometer (for example, JASCO-V670, made by JASCO Corporation) that operates in the wavelength region of ultraviolet, visible, and near infrared is used. When JASCO-V670 is used, since the measurable wavelength range is 200 to 1500 nm, the measurement is performed in the wavelength range. First, the absorption spectrum of the substrate used for measurement is measured. As the substrate, a quartz substrate, a glass substrate, or the like is used. Next, a thin film containing a polymer compound is formed on the substrate from a solution containing the polymer compound or a melt containing the polymer compound. In film formation from a solution, drying is performed after film formation. Thereafter, an absorption spectrum of the laminate of the thin film and the substrate is obtained. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the thin film.

  In the absorption spectrum of the thin film, the vertical axis represents the absorbance of the polymer compound, and the horizontal axis represents the wavelength. It is desirable to adjust the thickness of the thin film so that the absorbance at the largest absorption peak is about 0.5 to 2. The absorbance of the absorption peak with the longest wavelength among the absorption peaks is defined as 100%, and the intersection of the absorption peak and a straight line parallel to the horizontal axis (wavelength axis) including the absorbance of 50% of the absorption peak. The intersection point that is longer than the peak wavelength is taken as the first point. The intersection point between the absorption peak and a straight line parallel to the wavelength axis containing 25% of the absorbance, which is longer than the peak wavelength of the absorption peak, is defined as a second point. The intersection of the straight line connecting the first point and the second point and the reference line is defined as the light absorption terminal wavelength. Here, the reference line is the intersection of the absorption peak and the straight line parallel to the wavelength axis including the absorbance of 10% at the absorption peak of the longest wavelength, where the absorbance of the absorption peak is 100%. The third point on the absorption spectrum that is 100 nm longer than the reference wavelength and the absorption spectrum that is 150 nm longer than the reference wavelength with reference to the wavelength of the intersection that is longer than the peak wavelength of the absorption peak A straight line connecting the top and the fourth point.

  Since the polymer compound of the present invention can exhibit high electron and / or hole transport properties, when an organic thin film containing the polymer compound is used in an element, electrons or holes injected from an electrode, or light Charges generated by absorption can be transported. Taking advantage of these characteristics, it can be suitably used for various electronic devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.

<Photoelectric conversion element>
The photoelectric conversion element containing the polymer compound of the present invention has one or more active layers containing the polymer compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.

  A preferable form of the photoelectric conversion element containing the polymer compound of the present invention is formed from a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. Having an active layer. The polymer compound of the present invention is preferably used as a p-type organic semiconductor.

  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, indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive materials, NESA, gold, platinum, silver, Copper 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.
As the electrode material, an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.

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

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

<Active layer>
The active layer may contain the polymer compound of the present invention alone or in combination of two or more. In order to enhance the hole transport property of the active layer, compounds other than the polymer compound of the present invention can be mixed and used as the electron donating compound and / or the electron accepting compound in the active layer. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

  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.

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, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerenes and fullerene derivatives Details, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, more preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.

（式（１５）〜（１８）中、Ｒ^ｘは、アルキル基、アリール基、１価の芳香族複素環基又はエステル構造を有する基である。これらの基に含まれる水素原子は置換基で置換されていてもよい。複数個あるＲ^ｘは、同一であっても相異なってもよい。Ｒ^ｙはアルキル基又はアリール基を表し、これらの基に含まれる水素原子は置換基で置換されていてもよい。複数個あるＲ^ｙは、同一であっても相異なってもよい。） As a fullerene derivative, the compound represented by Formula (15)-Formula (18) is mentioned, for example.

(In the formulas (15) to (18), R ^x is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a group having an ester structure. The hydrogen atom contained in these groups is a substituent. A plurality of R ^x may be the same or different, and R ^y represents an alkyl group or an aryl group, and a hydrogen atom contained in these groups is substituted with a substituent. The plurality of R ^y may be the same or different.)

Specific examples of the alkyl group and aryl group represented by R ^a and R ^b are the same as the specific examples of the alkyl group and aryl group represented by R ¹ , R ² , R ³ and R ⁴ .

Examples of the aromatic heterocyclic group represented by ^Ra include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

（１９）
（式中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、アルキル基、アリール基又は１価芳香族複素環基を表し、これらの基に含まれる水素原子は置換基で置換されていてもよい。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (19).

(19)
(Wherein, u1 represents an integer of 1 to 6, u2 represents an integer of Less than six, ^{R c} represents an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, these groups The hydrogen atom contained may be substituted with a substituent.)

Specific examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ^c are the same as the specific examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ^a. It is.

Specific examples of the C60 fullerene derivative include the following compounds.

Specific examples of the C70 fullerene derivative include the following compounds.

  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-C71 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] thienyl- Examples thereof include C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

  When the active layer contains the polymer compound of the present invention and the fullerene derivative, the amount 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 weight part.

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

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

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

  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, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Application methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, capillary coating, 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 coating 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 transistor>
The polymer compound of the present invention can also be used for organic thin film transistors. The organic thin film transistor has a configuration including a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The organic semiconductor layer is constituted by the organic thin film described above. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two.
In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween. In the field effect organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing the polymer compound of the present invention.

  The static induction organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path. It is preferable to be provided in the organic semiconductor layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned. Also in the static induction organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing the polymer compound of the present invention.

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

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

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

  The above-mentioned organic thin film transistor can be used as a pixel driving element used for controlling the pixel of an electrophoretic display, a liquid crystal display, an organic electroluminescence display, etc., and controlling the uniformity of screen luminance and the screen rewriting speed. .

<Solar cell module>
The organic thin film solar cell can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The organic thin-film solar cell manufactured 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 or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
In addition, when used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, 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.

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

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

(Measurement of number average molecular weight and weight average molecular weight)
Regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

窒素で置換した200mL三つ口フラスコに、化合物1を5.01g（16.8mmol)、酸化銅（ＩＩ）（CuO）を3.07g (38.6mmol)、ヨウ化カリウム（KI）を0.170g (1.01mmol)、ナトリウムメトキサイドのメタノール溶液（5.0M）を75mL 加えた。得られた反応液を90℃に加熱し、１６時間加熱攪拌した。反応液を氷水に注ぎ反応を停止させ、クロロホルムを加えて有機層の抽出を行った。その有機層を無水硫酸ナトリウムで脱水した後ろ過し、溶媒を減圧下で留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで化合物2を3.26g（16.2mmol、収率97％）得た。

¹H NMR (300 MHz, CDCl₃): δ 6.27 (s, 2H), 3.92 (s, 6H).
(Synthesis of Compound 2)

In a 200 mL three-necked flask substituted with nitrogen, 5.01 g (16.8 mmol) of Compound 1, 3.07 g (38.6 mmol) of copper (II) oxide (CuO), 0.170 g (1.01 mmol) of potassium iodide (KI) Then, 75 mL of a methanol solution (5.0 M) of sodium methoxide was added. The resulting reaction solution was heated to 90 ° C. and stirred for 16 hours. The reaction solution was poured into ice water to stop the reaction, and chloroform was added to extract the organic layer. The organic layer was dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 3.26 g (16.2 mmol, yield 97%) of Compound 2.

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.27 (s, 2H), 3.92 (s, 6H).

窒素で置換した 200mL 四つ口フラスコに、化合物2を3.00g（15.0mmol）、ビスピナコラートジボロンを7.99g (31.5 mmol)、シクロヘキサンを100mL入れ、45分間脱気（Ar-bubbling）を行った。そこに4,4'-Di-tert-butyl-2,2'-bipyridyl(tBu-bpy)を242mg (0.900 mmol)、錯体[Ir(OMe)(cod)]2を298mg (0.45mmol) 加え、80℃で１時間半攪拌した。その溶液を一晩放置することにより、結晶を析出させ、ろ過することにより粗結晶を得た。残りの溶液も今度は-78℃に冷却し、再度粗結晶を得た。得られた粗結晶を再度ヘキサン/クロロホルム溶液に溶かし、再結晶することにより、化合物3を4.90g (10.8mmol)、収率72%で得た。

¹H NMR (300 MHz, CDCl₃): δ 4.15 (s, 6H), 1.34 (s, 24H).
(Synthesis of Compound 3)

In a 200 mL four-necked flask purged with nitrogen, add 3.00 g (15.0 mmol) of compound 2, 7.99 g (31.5 mmol) of bispinacolatodiboron, and 100 mL of cyclohexane, and degas for 45 minutes (Ar-bubbling) It was. To this, 242 mg (0.900 mmol) of 4,4′-Di-tert-butyl-2,2′-bipyridyl (tBu-bpy) and 298 mg (0.45 mmol) of complex [Ir (OMe) (cod)] 2 were added, The mixture was stirred at 80 ° C for 1.5 hours. Crystals were precipitated by allowing the solution to stand overnight, and crude crystals were obtained by filtration. The remaining solution was then cooled to -78 ° C. to obtain crude crystals again. The obtained crude crystals were dissolved again in a hexane / chloroform solution and recrystallized to obtain 4.90 g (10.8 mmol) of Compound 3 in a yield of 72%.

¹ H NMR (300 MHz, CDCl ₃ ): δ 4.15 (s, 6H), 1.34 (s, 24H).

窒素で置換した200mL四つ口フラスコに化合物3’を4.23g（18.0mmol）、[P(t-Bu)₃H]BF₄を0.550g (20mol%)、THFを60mL、3.0M K₃PO₄aq.を30mL（17.0mmol）入れ、均一溶液とした。窒素で置換した100mL滴下ロートをフラスコに取り付け、そこに化合物3 4.07g (9.00mmol) をTHF に溶かした溶液を入れた。それぞれ30分のArバブリング後、Pd₂(dba)₃を0.410g (5.0mol%)、加え、化合物3のTHF溶液を滴下しはじめた。滴下終了後70℃のオイルバスに浸し、30分間加熱下で攪拌した。その後水を加えることで反応を停止させ、ヘキサンを加えることで、有機層の抽出を行った。その有機層を無水硫酸ナトリウムで脱水した後ろ過し、溶媒を減圧下留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで化合物4を3.98ｇ（7.82 mmol、収率87％）得た。

¹H NMR (300 MHz, CDCl₃): δ 7.49 (d, 2H), 7.32 (d, 2H), 4.27 (q, 4H), 3.98 (s, 6H), 1.27 (t, 6H).
(Synthesis of Compound 4)

In a 200 mL four-necked flask substituted with nitrogen, 4.23 g (18.0 mmol) of compound 3 ′, 0.550 g (20 mol%) of [P (t-Bu) ₃ H] BF ₄ , 60 mL of THF, 3.0 MK ₃ PO ₄ 30 mL (17.0 mmol) of aq. was added to obtain a uniform solution. A 100 mL dropping funnel purged with nitrogen was attached to the flask, and a solution of 4.07 g (9.00 mmol) of Compound 3 in THF was added thereto. After each 30 minutes of Ar bubbling, 0.410 g (5.0 mol%) of Pd ₂ (dba) ₃ was added, and a THF solution of Compound 3 began to be added dropwise. After completion of dropping, the mixture was immersed in an oil bath at 70 ° C. and stirred for 30 minutes while heating. Thereafter, the reaction was stopped by adding water, and the organic layer was extracted by adding hexane. The organic layer was dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 3.98 g (7.82 mmol, yield 87%) of compound 4.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.49 (d, 2H), 7.32 (d, 2H), 4.27 (q, 4H), 3.98 (s, 6H), 1.27 (t, 6H).

窒素で置換した300mL四つ口フラスコに、ドデシルマグネシウムグリニャール試薬（1.0 M in Et₂O）を56.0mL（56.0mmol)、塩化亜鉛（ZnCl₂）を95mg (0.70mmol)加え、室温で１時間攪拌した。その溶液を0℃に冷却し、そこに化合物4 3.56 g（7.00 mmol)を加えた。0℃で１時間攪拌した後、室温まで昇温させ、さらに４時間攪拌した。その後水を加えることで反応を停止させ、ヘキサンを加えることで、有機層の抽出を行った。その有機層を無水硫酸ナトリウムで脱水した後ろ過し、溶媒を減圧下留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで化合物5を3.69ｇ（3.36 mmol、収率48％）得た。

¹H NMR (300 MHz, CDCl₃): δ 7.33 (d, 2H), 6.94 (d, 2H), 3.95 (s, 6H), 2.67 (s, 2H), 1.77 (m, 8H), 1.24 (br, 80H), 0.87 (t, 12H).
(Synthesis of Compound 5)

Add 56.0 mL (56.0 mmol) of dodecylmagnesium Grignard reagent (1.0 M in Et ₂ O) and 95 mg (0.70 mmol) of zinc chloride (ZnCl ₂ ) to a 300 mL four-necked flask purged with nitrogen, and stir at room temperature for 1 hour. did. The solution was cooled to 0 ° C., and 3.56 g (7.00 mmol) of compound 4 was added thereto. After stirring at 0 ° C. for 1 hour, the temperature was raised to room temperature and stirring was continued for 4 hours. Thereafter, the reaction was stopped by adding water, and the organic layer was extracted by adding hexane. The organic layer was dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 3.69 g (3.36 mmol, yield 48%) of compound 5.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.33 (d, 2H), 6.94 (d, 2H), 3.95 (s, 6H), 2.67 (s, 2H), 1.77 (m, 8H), 1.24 (br , 80H), 0.87 (t, 12H).

窒素で置換した100mL三つ口フラスコに、化合物5を988mg（0.900mmol）、クロロホルムを30mL入れ、均一溶液とした。その溶液を-30℃以下に冷却し、そこにN-ブロモスクシンイミド（NBS）を160mg（0.900mmol）を粉状でゆっくり加え、バスを取り除き、室温まで昇温させ、3時間半攪拌した。そこに亜硫酸ナトリウム水溶液を加えて反応を停止させ、有機層をクロロホルムで抽出したのち、水で洗浄した。抽出した有機層を無水硫酸ナトリウムで乾燥させたのち、ろ過し、減圧下で溶媒を留去することで粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで、化合物6を122mg（0.118mmol、収率13％）得た。

¹H NMR (300 MHz, CDCl3): δ 7.03 (d, 2H), 6.71 (d, 2H), 1.91 (m, 8H), 1.22 (br, 80H), 0.87 (t, 12H).
Example 1
(Synthesis of Compound 6)

In a 100 mL three-necked flask purged with nitrogen, 988 mg (0.900 mmol) of Compound 5 and 30 mL of chloroform were added to obtain a uniform solution. The solution was cooled to −30 ° C. or lower, 160 mg (0.900 mmol) of N-bromosuccinimide (NBS) was slowly added in powder form, the bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 3 and a half hours. A sodium sulfite aqueous solution was added thereto to stop the reaction, and the organic layer was extracted with chloroform and then washed with water. The extracted organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 122 mg (0.118 mmol, 13% yield) of compound 6.

¹ H NMR (300 MHz, CDCl3): δ 7.03 (d, 2H), 6.71 (d, 2H), 1.91 (m, 8H), 1.22 (br, 80H), 0.87 (t, 12H).

窒素で置換した100mL三つ口フラスコに、化合物6を122mg（0.118mmol）、テトラヒドロフランを10mL入れ、均一溶液とした。その溶液を0℃以下に冷却し、そこにN-ブロモスクシンイミド（NBS）を44mg（0.248mmol）を粉状でゆっくり加え、0℃で1時間半攪拌した。そこに亜硫酸ナトリウム水溶液を加えて反応を停止させ、有機層をヘキサンで抽出したのち、水で洗浄した。抽出した有機層を無水硫酸ナトリウムで乾燥させたのち、ろ過し、減圧下で溶媒を留去することで粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで、化合物7を152mg（0.078mmol、収率66％）得た。

¹H NMR (300 MHz, CDCl3): δ 6.67 (s, 2H), 1.85 (m, 8H), 1.23 (br, 80H), 0.87 (t, 12H).
Example 2
(Synthesis of Compound 7)

In a 100 mL three-necked flask purged with nitrogen, 122 mg (0.118 mmol) of Compound 6 and 10 mL of tetrahydrofuran were added to obtain a uniform solution. The solution was cooled to 0 ° C. or lower, and 44 mg (0.248 mmol) of N-bromosuccinimide (NBS) was slowly added in powder form and stirred at 0 ° C. for 1.5 hours. A sodium sulfite aqueous solution was added thereto to stop the reaction, and the organic layer was extracted with hexane and then washed with water. The extracted organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 152 mg (0.078 mmol, 66% yield) of Compound 7.

¹ H NMR (300 MHz, CDCl3): δ 6.67 (s, 2H), 1.85 (m, 8H), 1.23 (br, 80H), 0.87 (t, 12H).

窒素で置換した300mL四つ口フラスコに、1-Bromo-4-dodecylbenzeneを7.18g（22.0mmol)、脱水Diethyletherを100mL加え、0℃に冷却した。そこにn-Butyllithium (1.6M in hexane) 12.5mL (20mmol)を滴下し、0℃で１時間攪拌することで、リチオ化物を調整した。その溶液を-78℃に冷却した後、化合物4を2.04g (4.00mmol)を粉末で加え、１時間半攪拌した。次いで、バスを取り除いて昇温させ、さらに１時間攪拌した。その後水を加えることで反応を停止させ、酢酸水で中和した後、ヘキサンを加えることで、有機層の抽出を行った。その有機層を無水硫酸ナトリウムで脱水した後ろ過し、溶媒を減圧下留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで化合物8を3.65ｇ（2.60mmol、収率65％）得た。

¹H NMR (300 MHz, CDCl₃): δ 7.23 (d, 8H), 7.20 (d, 2H), 7.02 (d, 8H), 6.55 (d, 2H), 4.04 (s, 2H), 3.73 (s, 6H), 2.51 (t, 8H), 1.25 (br, 80H), 0.88 (t, 12H).
(Synthesis of Compound 8)

To a 300 mL four-necked flask purged with nitrogen, 7.18 g (22.0 mmol) of 1-Bromo-4-dodecylbenzene and 100 mL of dehydrated diethylether were added and cooled to 0 ° C. Thereto was added dropwise 12.5 mL (20 mmol) of n-Butyllithium (1.6M in hexane), and the mixture was stirred at 0 ° C. for 1 hour to prepare a lithiated product. The solution was cooled to −78 ° C., 2.04 g (4.00 mmol) of compound 4 was added as a powder, and the mixture was stirred for 1.5 hours. Next, the bath was removed, the temperature was raised, and the mixture was further stirred for 1 hour. Thereafter, the reaction was stopped by adding water, neutralized with aqueous acetic acid, and then the organic layer was extracted by adding hexane. The organic layer was dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 3.65 g (2.60 mmol, yield 65%) of Compound 8.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.23 (d, 8H), 7.20 (d, 2H), 7.02 (d, 8H), 6.55 (d, 2H), 4.04 (s, 2H), 3.73 (s , 6H), 2.51 (t, 8H), 1.25 (br, 80H), 0.88 (t, 12H).

窒素で置換した200mL四つ口フラスコに、化合物8を4.28g（3.05mmol)、脱水Dichloromethane (CH₂Cl₂) を60mL加え、-78℃に冷却した。そこにBoron tribromide (1.0M in CH₂Cl₂) を12.2mL (12.2mmol) を滴下し、すぐに昇温させ、５時間攪拌した。さらに40℃に加熱し、３時間半攪拌した。その後水を加えることで反応を停止させ、クロロホルムを加えることで、有機層の抽出を行った。その有機層を無水硫酸ナトリウムで脱水した後ろ過し、溶媒を減圧下留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで化合物9を1.80ｇ（1.35mmol、収率44％）得た。

¹H NMR (300 MHz, CDCl₃): δ 7.16 (d, 8H), 7.08 (d, 8H), 7.01 (d, 2H), 6.45 (d, 2H), 2.65 (t, 8H), 1.25 (br, 80H), 0.86 (t, 12H).
Example 3
(Synthesis of Compound 9)

To a 200 mL four-necked flask purged with nitrogen, 4.28 g (3.05 mmol) of Compound 8 and 60 mL of dehydrated dichloromethane (CH ₂ Cl ₂ ) were added and cooled to −78 ° C. Boron tribromide (1.0 M in CH ₂ Cl ₂ ) was dropped into 12.2 mL (12.2 mmol), and the temperature was immediately raised and stirred for 5 hours. The mixture was further heated to 40 ° C. and stirred for 3 and a half hours. Thereafter, the reaction was stopped by adding water, and the organic layer was extracted by adding chloroform. The organic layer was dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.80 g (1.35 mmol, yield 44%) of compound 9.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.16 (d, 8H), 7.08 (d, 8H), 7.01 (d, 2H), 6.45 (d, 2H), 2.65 (t, 8H), 1.25 (br , 80H), 0.86 (t, 12H).

窒素で置換した100mL三つ口フラスコに、化合物9を1.65mg（1.23 mol）、Tetrahydrofurane (THF) を30mL入れ、均一溶液とした。その溶液を0℃以下に冷却し、そこにN-ブロモスクシンイミド（NBS）を460mg（2.58mmol）を粉状でゆっくり加え、0℃で1時間半攪拌した。そこに亜硫酸ナトリウム水溶液を加えて反応を停止させ、有機層をヘキサンで抽出したのち、水で洗浄した。抽出した有機層を無水硫酸ナトリウムで乾燥させたのち、ろ過し、減圧下で溶媒を留去することで粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製することで、化合物10を1.79g（1.19mmol、収率97％）得た。

¹H NMR (300 MHz, CDCl₃): δ 7.15 (d, 8H), 7.09 (d, 8H), 6.41 (s, 2H), 2.65 (t, 8H), 1.25 (br, 80H), 0.88 (t, 12H).
Example 4
(Synthesis of Compound 10)

A 100 mL three-necked flask purged with nitrogen was charged with 1.65 mg (1.23 mol) of Compound 9 and 30 mL of Tetrahydrofurane (THF) to obtain a uniform solution. The solution was cooled to 0 ° C. or lower, and 460 mg (2.58 mmol) of N-bromosuccinimide (NBS) was slowly added in powder form and stirred at 0 ° C. for 1.5 hours. A sodium sulfite aqueous solution was added thereto to stop the reaction, and the organic layer was extracted with hexane and then washed with water. The extracted organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 1.79 g (1.19 mmol, yield 97%) of compound 10.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.15 (d, 8H), 7.09 (d, 8H), 6.41 (s, 2H), 2.65 (t, 8H), 1.25 (br, 80H), 0.88 (t , 12H).

窒素雰囲気下、還流管を取り付けた100 mL三つ口フラスコに化合物7を59.6mg（0.050mmol）、[P(t-Bu)₃H]BF₄を2.90mg (20 mol%)、THFを8.0 ml入れ均一溶液とした。30分のアルゴンガスバブリング後、3.0M K₃PO₄の水溶液を0.2 mL、Pd₂(dba)₃を2.3 mg (5.0mol%)を加えた後、化合物11を21.2mg（0.050mmol）加え、加熱を開始した。反応液を70℃で、60分間加熱攪拌した。そこにo-ジクロロベンゼンを20mL加え反応を停止させた後、ジエチルジチオカルバミン酸ナトリウム0.45gと水5.0mLを加え、90℃で30分間攪拌を行った。水層を除去後、有機層を水50 mLで２回洗浄し、次いで、3wt%の酢酸水溶液50 mLで１回洗浄し、次いで、水50 mLで１回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、再度ODCB 19 mLに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体を40mg得た。以下、この重合体を高分子化合物P1と呼称する。GPCで測定した高分子化合物P1の分子量（ポリスチレン換算）はMn.＝5,600、Mw.=20,000であった。
Example 5
(Synthesis of polymer compound P1)

In a 100 mL three-necked flask equipped with a reflux tube under a nitrogen atmosphere, 59.6 mg (0.050 mmol) of compound 7, 2.90 mg (20 mol%) of [P (t-Bu) ₃ H] BF ₄ and 8.0 of THF A homogeneous solution was added in ml. After 30 minutes of argon gas bubbling, 0.2 mL of an aqueous solution of 3.0MK ₃ PO ₄ and 2.3 mg (5.0 mol%) of Pd ₂ (dba) ₃ were added, and then 21.2 mg (0.050 mmol) of compound 11 was added and heated. Started. The reaction solution was heated and stirred at 70 ° C. for 60 minutes. 20 mL of o-dichlorobenzene was added thereto to stop the reaction, 0.45 g of sodium diethyldithiocarbamate and 5.0 mL of water were added, and the mixture was stirred at 90 ° C. for 30 minutes. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then once with 50 mL of a 3 wt% aqueous acetic acid solution and then once with 50 mL of water, and the resulting solution was methanolic. To precipitate the polymer. After filtration, the polymer was dissolved again in 19 mL of ODCB and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 40 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound P1. The molecular weight (polystyrene conversion) of the polymer compound P1 measured by GPC was Mn. = 5,600 and Mw. = 20,000.

窒素雰囲気下、還流管を取り付けた100mL三つ口フラスコに化合物7を59.6mg（0.050mmol）、[P(t-Bu)₃H]BF₄を2.90mg (20mol%)、THFを8.0ml入れ均一溶液とした。30分のアルゴンガスバブリング後、3.0M K₃PO₄aq.を0.2mL、Pd₂(dba)₃を2.3mg (5.0 mol%)を加えた後、化合物12を24.8mg（0.050mmol）加え、加熱を開始した。反応液を70℃で、60分間加熱攪拌した。そこにo-ジクロロベンゼンを20mL加え反応を停止させた後、ジエチルジチオカルバミン酸ナトリウム0.45 gと水5.0 mLを加え、90 ℃で30分間攪拌を行った。水層を除去後、有機層を水50 mLで２回洗浄し、次いで、3wt%の酢酸水溶液50 mLで１回洗浄し、次いで、水50mLで１回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、再度ODCB 19 mLに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体を45mg得た。以下、この重合体を高分子化合物P2と呼称する。GPCで測定した高分子化合物P2の分子量（ポリスチレン換算）はMn.＝17,000、Mw.=110,000であった。
Example 6
(Synthesis of polymer compound P2)

In a 100 mL three-necked flask equipped with a reflux tube under nitrogen atmosphere, 59.6 mg (0.050 mmol) of Compound 7, 2.90 mg (20 mol%) of [P (t-Bu) ₃ H] BF ₄ and 8.0 ml of THF A homogeneous solution was obtained. After 30 minutes of argon gas bubbling, 0.2 mL of 3.0MK ₃ PO ₄ aq. And 2.3 mg (5.0 mol%) of Pd ₂ (dba) ₃ were added, and then 24.8 mg (0.050 mmol) of Compound 12 was added and heated. Started. The reaction solution was heated and stirred at 70 ° C. for 60 minutes. 20 mL of o-dichlorobenzene was added thereto to stop the reaction, 0.45 g of sodium diethyldithiocarbamate and 5.0 mL of water were added, and the mixture was stirred at 90 ° C. for 30 minutes. After removing the aqueous layer, the organic layer is washed twice with 50 mL of water, then once with 50 mL of 3 wt% aqueous acetic acid, and then once with 50 mL of water, and the resulting solution is taken up in methanol. The polymer was precipitated by pouring. After filtration, the polymer was dissolved again in 19 mL of ODCB and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 45 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound P2. The molecular weight (polystyrene conversion) of the polymer compound P2 measured by GPC was Mn. = 17,000 and Mw. = 110,000.

窒素雰囲気下、還流管を取り付けた100mL三つ口フラスコに化合物13を45.4mg（0.035mmol）、[P(t-Bu)₃H]BF₄を0.81mg (0.28mmol)、THFを5.0ml入れ均一溶液とした。30分のアルゴンガスバブリング後、3.0M K₃PO₄ aq.を0.2mL、Pd₂(dba)₃を0.64mg(0.7mmol)を加えた後、化合物11を13.6mg（0.035mmol）加え、加熱を開始した。反応液を70℃で、60分間加熱攪拌した。そこにo-ジクロロベンゼンを20mL加え反応を停止させた後、ジエチルジチオカルバミン酸ナトリウム0.45gと水5.0mLを加え、90℃で30分間攪拌を行った。水層を除去後、有機層を水50mLで２回洗浄し、次いで、3wt%の酢酸水溶液50mLで１回洗浄し、次いで、水50mLで１回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、再度ODCB 19 mLに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体を25mg得た。以下、この重合体を高分子化合物Cと呼称する。GPCで測定した高分子化合物Cの分子量（ポリスチレン換算）はMn.＝3,200、Mw.=96,000であった。
なお、化合物11は、特開2012−255117号公報に記載された方法に従って合成した。 Comparative Example 1
(Synthesis of polymer compound C)

In a 100 mL three-necked flask equipped with a reflux tube under a nitrogen atmosphere, 45.4 mg (0.035 mmol) of compound 13, 0.81 mg (0.28 mmol) of [P (t-Bu) ₃ H] BF ₄ and 5.0 ml of THF were added. A homogeneous solution was obtained. After 30 minutes of argon gas bubbling, 0.2 mL of 3.0MK ₃ PO ₄ aq. And 0.64 mg (0.7 mmol) of Pd ₂ (dba) ₃ were added, and then 13.6 mg (0.035 mmol) of compound 11 was added and heated. Started. The reaction solution was heated and stirred at 70 ° C. for 60 minutes. 20 mL of o-dichlorobenzene was added thereto to stop the reaction, 0.45 g of sodium diethyldithiocarbamate and 5.0 mL of water were added, and the mixture was stirred at 90 ° C. for 30 minutes. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then once with 50 mL of a 3 wt% aqueous acetic acid solution and then once with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. After filtration, the polymer was dissolved again in 19 mL of ODCB and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer. The polymer was filtered and dried to obtain 25 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound C. The molecular weight (polystyrene conversion) of the polymer compound C measured by GPC was Mn. = 3,200 and Mw. = 96,000.
Compound 11 was synthesized according to the method described in JP 2012-255117 A.

Example 7
(Measurement of absorption edge wavelength of organic thin film)
The polymer compound P1 was dissolved in o-dichlorobenzene at a concentration of 0.75% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on 120 degreeC conditions in air | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. The absorption spectrum of the organic thin film was measured with a spectrophotometer (manufactured by JASCO Corporation, trade name: V-670). The measured spectrum is shown in FIG. The absorption edge wavelength at this time was 900 nm.

Example 8
(Measurement of absorbance of organic thin film)
An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound P2 was used instead of the polymer compound P1, and the absorption spectrum thereof was measured. The measured spectrum is shown in FIG. The absorption edge wavelength at this time was 940 nm.

Comparative Example 2
(Measurement of absorbance of organic thin film)
An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound C was used in place of the polymer compound P1, and the absorption spectrum thereof was measured. The measured spectrum is shown in FIG. The absorption edge wavelength at this time was 750 nm.

Table 1 Measurement result of absorption edge wavelength

Example 9
(Production and evaluation of ink and organic thin film solar cell)
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering was subjected to surface treatment by ozone UV treatment. Next, the film was applied onto the ITO film by PEDOT: PSS, and heated in air at 120 ° C. for 10 minutes to form a 50 nm-thick hole injection layer. Next, when the polymer compound P1 and fullerene C70PCBM (phenyl 71-butyric acid methyl ester, manufactured by Frontier Carbon Co.) are used, the weight ratio of C70PCBM to the weight of the polymer compound P1 is 2. In this way, it was dissolved in orthodichlorobenzene to prepare an ink. The total weight of the polymer compound P1 and the weight of C70PCBM was 2.0% by weight with respect to the weight of the ink. The ink was applied onto a glass substrate by spin coating to produce an organic film containing the polymer compound P1. The film thickness was about 100 nm. Thereafter, calcium was deposited on the organic film with a thickness of 4 nm by a vacuum deposition machine, and then aluminum was deposited with a thickness of 100 nm to produce an organic thin film solar cell. The shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm. The obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. The photoelectric conversion efficiency and the short circuit current density were determined. Jsc (short circuit current density) was 1.88 mA / cm2, Voc (open short voltage) was 0.66 V, FF (fill factor, fill factor) was 0.43, and photoelectric conversion efficiency (η) was 0.54%.

Example 10
(Production and evaluation of ink and organic thin film solar cell)
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering was subjected to surface treatment by ozone UV treatment. Next, the film was applied onto the ITO film by PEDOT: PSS, and heated in air at 120 ° C. for 10 minutes to form a 50 nm-thick hole injection layer. Next, when the polymer compound P2 and fullerene C70PCBM (phenyl 71-butyric acid methyl ester, manufactured by Frontier Carbon Co.) are used, the weight ratio of C70PCBM to the weight of the polymer compound P2 is 2. In this way, it was dissolved in orthodichlorobenzene to prepare an ink. The total weight of the polymer compound P2 and the C70PCBM was 2.0% by weight with respect to the weight of the ink. The ink was applied on a glass substrate by spin coating to produce an organic film containing the polymer compound P2. The film thickness was about 100 nm. Thereafter, calcium was deposited on the organic film with a thickness of 4 nm by a vacuum deposition machine, and then aluminum was deposited with a thickness of 100 nm to produce an organic thin film solar cell. The shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm. The obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. The photoelectric conversion efficiency and the short circuit current density were determined. Jsc (short-circuit current density) was 5.25 mA / cm2, Voc (open short-circuit voltage) was 0.63 V, FF (fill factor, fill factor) was 0.57, and photoelectric conversion efficiency (η) was 1.9%.

Claims (15)

The high molecular compound containing the structural unit represented by a formula (I).

[In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, these rings may be condensed rings, and the hydrogen atom contained in these rings is a substituent. May be substituted.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
Z ¹ and Z ² each represent a group represented by —C (R ¹ ) (R ² ) —, and the other represents an oxygen atom, a sulfur atom, or a group represented by —C (═O) —. , A group represented by —S (═O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —. , -B ^{(R 5)} - group represented by, -P ^{(R 5)} - or a group represented by -P with ^{(= O) (R 5)} - represents a group represented by.
Z ³ and Z ⁴ each represents a group represented by —C (R ³ ) (R ⁴ ) —, and the other represents an oxygen atom, a sulfur atom, or a group represented by —C (═O) —. , A group represented by —S (═O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —. , -B ^{(R 6)} - group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, , A hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different. ] The polymer compound according to claim 1, wherein the structural unit represented by the formula (I) is a structural unit represented by the formula (II).

[Wherein, Z ¹ , Z ² , Z ³ , Z ⁴ , X ¹ and X ² each represent the same meaning as described above. X ³ and X ⁴ each independently represents a sulfur atom, an oxygen atom or a selenium atom. Y ¹ and Y ² each independently represent a nitrogen atom or ═C (R ⁷ ) —. R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and among these, an alkyl group, The hydrogen atom contained in each of the cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. ] The polymer compound according to claim ² , wherein X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms. The high molecular compound as described in any one of Claim 2 or 3 whose Y < ¹ > and Y < ² > are groups respectively represented by = C (H)-. Z ¹ is a group represented by —C (R ¹ ) (R ² ) —, Z ⁴ is a group represented by —C (R ³ ) (R ⁴ ) —, and Z ² and Z ³ are The polymer compound according to any one of claims 1 to 4, wherein all are oxygen atoms. Furthermore, the high molecular compound as described in any one of Claims 1-5 containing the structural unit represented by Formula (III).

[In the formula, Ar represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, Ar is different from the structural unit represented by the formula (I). ] The polymer compound according to claim 6, wherein Ar is a structural unit represented by any one of formulas (III-1) to (III-16).

[In each formula, R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, 1 Represents a valent heterocyclic group or a halogen atom, and among these, it is included in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group. The hydrogen atom may be substituted with a substituent. ^Xa and ^Xb each independently represent a sulfur atom, an oxygen atom or a selenium atom. ]   The high molecular compound of Claim 6 or 7 which is a copolymer which the structural unit represented by Formula (I) and the structural unit represented by Formula (III) couple | bonded alternately.   The polymer compound according to any one of claims 1 to 8, which has a light absorption terminal wavelength of 850 nm or more.   The polymer compound according to any one of claims 1 to 9, which has a polystyrene-reduced weight average molecular weight of 3000 to 10000000.   The electronic device containing the high molecular compound as described in any one of Claims 1-10.   It is an organic photoelectric conversion element which has a 1st electrode, a 2nd electrode, and an active layer provided between the 1st electrode and the 2nd electrode, Comprising: In the said active layer, Claims 1-10 Organic photoelectric conversion element containing the high molecular compound as described in any one of these.   The solar cell module containing the organic photoelectric conversion element of Claim 12.   The organic thin-film transistor which has a gate electrode, a source electrode, a drain electrode, and an active layer, and contains the compound as described in any one of Claims 1-10 in the said active layer. A compound represented by formula (IV).

[In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, these rings may be condensed rings, and the hydrogen atom contained in these rings is a substituent. May be substituted.
X ¹ and X ² each independently represents a sulfur atom, an oxygen atom or a selenium atom.
One of Z ¹ and Z ² represents —C (R ¹ ) (R ² ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁵ ) ₂ —, a group represented by —N (R ⁵ ) —, and —B (R ⁵⁾ -, a group represented by, -P ^{(R 5)} - or a group represented by -P with (= O) ^{(R 5)} - represents a group represented by.
One of Z ³ and Z ⁴ represents —C (R ³ ) (R ⁴ ) —, the other represents an oxygen atom, a sulfur atom, a group represented by —C (═O) —, —S (= A group represented by O) —, a group represented by —SO ₂ —, a group represented by —Si (R ⁶ ) ₂ —, a group represented by —N (R ⁶ ) —, and —B (R ⁶⁾ -, a group represented by, -P ^{(R 6)} -, a group represented by or ^{-P (= O) (R 6} ) - represents a group represented by.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, monovalent heterocyclic group Or a halogen atom, of which a hydrogen atom contained in each of an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group is substituted It may be substituted with a group.
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, Among them, the hydrogen atom contained in each of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group and monovalent heterocyclic group may be substituted with a substituent. When a plurality of R ⁵ or R ⁶ are present, they may be the same or different.
W ¹ and W ² each independently represent a hydrogen atom, a halogen atom, a boric acid ester residue, a boric acid residue or an organotin residue. ]

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