JP6373567B2 - Compound and electronic device using the same - Google Patents

Description

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

As a compound used for an organic thin film solar cell which is one embodiment of an organic photoelectric conversion element, a polymer compound composed of a repeating unit (A) and a repeating unit (B) has been proposed (Patent Document 1).

Special table 2009-506519

  However, the organic thin film solar cell containing the organic layer containing the compound has a problem that the short-circuit current density is not necessarily high.

  Then, an object of this invention is to provide the compound which can manufacture an organic thin-film solar cell with a high short circuit current density. Another object of the present invention is to provide an electronic device containing the compound.

〔式（１）中、環Ａ及び環Ｂは、それぞれ独立に、置換基を有していてもよい複素環を表す。環Ｃは置換基を有していてもよい単環の脂環式炭化水素環を表す。ｎは０又は自然数を表す。Ｚは、−Ｏ−、−Ｓ−、−Ｓｅ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｓ）−、−Ｓ（＝Ｏ）−、−ＳＯ_２−、−Ｃ（Ｒ^１）（Ｒ^２）−、−Ｓｉ（Ｒ^３）（Ｒ^４）−、−Ｇｅ（Ｒ^５）（Ｒ^６）−、−Ｓｎ（Ｒ^７）（Ｒ^８）−、−Ｎ（Ｒ^９）−、−Ｐ（Ｒ^１０）−、−Ｐ（＝Ｏ）（Ｒ^１１）−、又は−Ｂ（Ｒ^１２）−を表す。ｎが２以上の場合、複数あるＺは、互いに同一であっても異なってもよい。Ｒ^１〜Ｒ^１２は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、複素環オキシ基、複素環チオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基又はシアノ基を表す。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。〕 That is, this invention is [1] The compound which has a structural unit represented by Formula (1).

[In Formula (1), Ring A and Ring B each independently represent a heterocyclic ring optionally having a substituent. Ring C represents a monocyclic alicyclic hydrocarbon ring which may have a substituent. n represents 0 or a natural number. Z represents —O—, —S—, —Se—, —C (═O) —, —C (═S) —, —S (═O) —, —SO ₂ —, —C (R ¹ ). (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —Ge (R ⁵ ) (R ⁶ ) —, —Sn (R ⁷ ) (R ⁸ ) —, —N (R ⁹ ) —, ^{-P (R 10) -, -} P (= O) (R 11) -, or -B ^{(R 12)} - represents a. When n is 2 or more, the plurality of Z may be the same or different from each other. R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, or an acyl group. , Acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, An arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented. The hydrogen atom contained in these groups may be substituted with a substituent. ]

〔環Ｃ、ｎ及びＺは前記と同じ意味を表す。Ｘは、酸素原子、硫黄原子又はセレン原子を表す。Ｙは、窒素原子又は＝Ｃ（Ｒ^１３）−を表す。Ｒ^１３は水素原子、フッ素原子、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の複素環基又は炭素原子数１〜３０のアルコキシ基を表す。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。〕
〔３〕前記環Ｃが置換基を有しない７員環以上の単環の脂環式炭化水素環である〔１〕または〔２〕に記載の化合物。
〔４〕前記ｎが１又は２である〔１〕〜〔３〕のいずれか一項に記載の化合物。
〔５〕前記Ｙが＝Ｃ（Ｈ）−である〔２〕〜〔４〕のいずれか一項に記載の化合物。
〔６〕前記Ｘが硫黄原子である〔２〕〜〔５〕のいずれか一項に記載の化合物。
〔７〕前記ｎが１であり、Ｚが−Ｏ−である〔１〕〜〔６〕のいずれか一項に記載の化合物。
〔８〕前記化合物が、式（３）で表される構成単位をさらに有する〔１〕〜〔７〕のいずれか一項に記載の化合物。

〔Ａｒは、アリーレン基又は２価の複素環基を表す。ただし、Ａｒは、式（１）又は式（２）で表される構成単位とは異なる。〕
〔９〕前記Ａｒが、式（３−１）〜式（３−９）のいずれかで表される構成単位である〔８〕に記載の化合物。

〔式（３−１）〜式（３−９）中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１及びＲ^４２は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、複素環オキシ基、複素環チオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基又はシアノ基を表す。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。Ｘ^２１、Ｘ^２２、Ｘ^２３、Ｘ^２４、Ｘ^２５、Ｘ^２６、Ｘ^２７、Ｘ^２８、Ｘ^２９及びＸ^３０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。〕
〔１０〕光吸収末端波長が７００ｎｍ以上である〔１〕〜〔９〕のいずれか一項に記載の化合物。
〔１１〕ポリスチレン換算の重量平均分子量が３０００〜１０００００００である〔１〕〜〔１０〕のいずれか一項に記載の化合物。 The present invention further provides the following compounds [2] to [11].
[2] The compound according to [1], wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2).

[Ring C, n and Z have the same meaning as described above. X represents an oxygen atom, a sulfur atom or a selenium atom. Y represents a nitrogen atom or ═C (R ¹³ ) —. R ¹³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. Represent. The hydrogen atom contained in these groups may be substituted with a substituent. ]
[3] The compound according to [1] or [2], wherein the ring C is a 7-membered or higher monocyclic alicyclic hydrocarbon ring having no substituent.
[4] The compound according to any one of [1] to [3], wherein n is 1 or 2.
[5] The compound according to any one of [2] to [4], wherein Y is = C (H)-.
[6] The compound according to any one of [2] to [5], wherein X is a sulfur atom.
[7] The compound according to any one of [1] to [6], wherein n is 1 and Z is —O—.
[8] The compound according to any one of [1] to [7], wherein the compound further has a structural unit represented by the formula (3).

[Ar represents an arylene group or a divalent heterocyclic group. However, Ar is different from the structural unit represented by Formula (1) or Formula (2). ]
[9] The compound according to [8], wherein Ar is a structural unit represented by any one of formulas (3-1) to (3-9).

[In the formulas (3-1) to (3-9), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio Group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, arylalkynyl group, Carboxyl represents a group or a cyano group. The hydrogen atom contained in these groups may be substituted with a substituent. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ²⁹ and X ³⁰ each independently represent a sulfur atom, an oxygen atom or a selenium atom. ]
[10] The compound according to any one of [1] to [9], wherein the light absorption terminal wavelength is 700 nm or more.
[11] The compound according to any one of [1] to [10], wherein the weight average molecular weight in terms of polystyrene is 3000 to 10000000.

The present invention further provides the following [12] thin film, the following [13] electronic device, the following [14] organic photoelectric conversion device, the following [14] solar cell module, and the following [15] organic thin film transistor. It is.
[12] An electronic device comprising the compound according to any one of [1] to [11].
[13] An organic photoelectric conversion device 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 compound as described in any one of [11].
[14] A solar cell module including the organic photoelectric conversion element according to [13].
[15] An organic thin film transistor comprising 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 [11].

  ADVANTAGE OF THE INVENTION According to this invention, the compound which can manufacture an organic thin film solar cell with a high short circuit current density can be provided. The present invention can also provide an electronic device containing the compound.

  Hereinafter, the present invention will be described in detail.

〔式（１）中、環Ａ、環Ｂ、環Ｃ、ｎは前記と同じ意味を表す。Ｚは、−Ｏ−、−Ｓ−、−Ｓｅ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｓ）−、−Ｓ（＝Ｏ）−、−ＳＯ_２−、−Ｃ（Ｒ^１）（Ｒ^２）−、−Ｓｉ（Ｒ^３）（Ｒ^４）−、−Ｇｅ（Ｒ^５）（Ｒ^６）−、−Ｓｎ（Ｒ^７）（Ｒ^８）−、−Ｎ（Ｒ^９）−、−Ｐ（Ｒ^１０）−、−Ｐ（＝Ｏ）（Ｒ^１１）−、又は−Ｂ（Ｒ^１２）−を表す。ｎが２以上の場合、複数あるＺは、互いに同一であっても異なってもよい。Ｒ^１〜Ｒ^１２は、前記と同じ意味を表す。〕 <Compound>
The compound of this invention contains the structural unit represented by Formula (1).

[In Formula (1), Ring A, Ring B, Ring C, and n represent the same meaning as described above. Z represents —O—, —S—, —Se—, —C (═O) —, —C (═S) —, —S (═O) —, —SO ₂ —, —C (R ¹ ). (R ² ) —, —Si (R ³ ) (R ⁴ ) —, —Ge (R ⁵ ) (R ⁶ ) —, —Sn (R ⁷ ) (R ⁸ ) —, —N (R ⁹ ) —, ^{-P (R 10) -, -} P (= O) (R 11) -, or -B ^{(R 12)} - represents a. When n is 2 or more, the plurality of Z may be the same or different from each other. R ^{1 to} R ¹² represent the same meaning as described above. ]

Examples of the halogen atom represented by R ^{1 to} R ¹² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. Carbon number of an alkyl group is 1-30 normally. The alkyl group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl. Group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group And chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.

The alkyl part of the alkoxy group represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. The alkoxy group may have a substituent. Carbon number of an alkoxy group is 1-20 normally, and a halogen atom is mentioned as a substituent. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy Group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyloxy group, perfluoro Examples include octyloxy group, methoxymethyloxy group and 2-methoxyethyloxy group.

The alkyl part of the alkylthio group represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. The alkylthio group may have a substituent. Carbon number of an alkylthio group is 1-20 normally, and a halogen atom is mentioned as a substituent. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2 -Ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and trifluoromethylthio group are mentioned.

The aryl group represented by R ^{1 to} R ¹² means a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is usually 6 to 60. The aryl group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryl group include a phenyl group and a C1 to C12 alkoxyphenyl group (C1 to C12 alkoxy is an alkoxy having 1 to 12 carbon atoms. The C1 to C12 alkoxy is preferably a C1 to C8 alkoxy. Yes, more preferably C1 to C6 alkoxy, C1 to C8 alkoxy represents alkoxy having 1 to 8 carbon atoms, and C1 to C6 alkoxy represents alkoxy having 1 to 6 carbon atoms. Specific examples of C1 to C12 alkoxy, C1 to C8 alkoxy and C1 to C6 alkoxy include those described and exemplified for the above alkoxy group, and the same applies to the following, and C1 to C12 alkylphenyl groups (C1 to C1). C12 alkyl indicates alkyl having 1 to 12 carbon atoms, and C1 to C12 alkyl is preferred. Or C1 to C8 alkyl, more preferably C1 to C6 alkyl, C1 to C8 alkyl is an alkyl having 1 to 8 carbon atoms, and C1 to C6 alkyl is an alkyl having 1 to 6 carbon atoms. Specific examples of C1 to C12 alkyl, C1 to C8 alkyl, and C1 to C6 alkyl include those described and exemplified above for the alkyl group, and the same applies to the following. A naphthyl group, 2-naphthyl group, and a pentafluorophenyl group are mentioned.

The aryloxy group represented by R ^{1 to} R ¹² usually has 6 to 60 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryloxy group include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.

The arylthio group represented by R ^{1 to} R ¹² usually has 6 to 60 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The arylalkyl group represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkyl group include a phenyl-C1-C12 alkyl group, a C1-C12 alkoxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, and a 1-naphthyl-C1-C12 alkyl group. And 2-naphthyl-C1-C12 alkyl group.

The arylalkoxy group represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkoxy group include a phenyl-C1-C12 alkoxy group, a C1-C12 alkoxyphenyl-C1-C12 alkoxy group, a C1-C12 alkylphenyl-C1-C12 alkoxy group, and a 1-naphthyl-C1-C12 alkoxy group. And 2-naphthyl-C1-C12 alkoxy group.

The arylalkylthio group represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkylthio group include a phenyl-C1-C12 alkylthio group, a C1-C12 alkoxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, and a 1-naphthyl-C1-C12 alkylthio group. And 2-naphthyl-C1-C12 alkylthio group.

The acyl group represented by R ^{1 to} R ¹² means a group excluding the hydroxyl group in the carboxylic acid, and the carbon number is usually 2 to 20. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, and the like, an alkylcarbonyl group that may be substituted with a halogen atom, benzoyl group, and the like. Group, a phenylcarbonyl group which may be substituted with a halogen atom such as a pentafluorobenzoyl group.

Acyloxy group represented by R ¹ to R ¹² means a group obtained by removing a hydrogen atom in the carboxylic acid, the number of carbon atoms thereof is generally from 2 to 20. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The amide group represented by R ^{1 to} R ¹² means a group in which one hydrogen atom bonded to a nitrogen atom is removed from the amide, and the carbon number is usually 1 to 20. Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

The imide group represented by R ^{1 to} R ¹² means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an imide (—CO—NH—CO—), and specific examples include a succinimide group, A phthalimide group is mentioned.

The substituted amino group represented by R ^{1 to} R ¹² is one in which one or two hydrogen atoms of the amino group are substituted, and the substituent is, for example, an alkyl group or an aryl group. Specific examples of the alkyl group and aryl group are the same as the specific examples of the alkyl group and aryl group represented by R ^{1 to} R ¹² . Carbon number of a substituted amino group is 1-40 normally. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alcohol Ruoxyphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkoxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkylamino group Groups, di (C1-C12 alkoxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl-C1 ~ C12 Archi And amino group.

The substituted silyl group represented by R ^{1 to} R ¹² is one in which one, two, or three of the silyl group's hydrogen atoms are substituted, and in general, all three hydrogen atoms in the silyl group are substituted. And the substituent is, for example, an alkyl group or an aryl group. Specific examples of the alkyl group and aryl group are the same as the specific examples of the alkyl group and aryl group represented by R ^{1 to} R ¹² . Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

The substituted silyloxy group represented by R ^{1 to} R ¹² is a group in which an oxygen atom is bonded to the above substituted silyl group. Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group. Examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

The substituted silylthio group represented by R ^{1 to} R ¹² is a group in which a sulfur atom is bonded to the above substituted silyl group. Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, and tri-p-xylyl. Examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

The substituted silylamino group represented by R ^{1 to} R ¹² is one in which one or two hydrogen atoms of the amino group are substituted with a substituted silyl group, and the substituted silyl group is as described above. Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl. Silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tripropylsilyl) ) Amino group, di (triisopropylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) amino group, di (tribenzylsilyl) A Amino group, di (diphenylmethyl silyl) amino, di (tert- butyldiphenylsilyl) amino group and di (dimethylphenylsilyl) and amino group.

The monovalent heterocyclic group represented by R ^{1 to} R ¹² is optionally substituted 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 , Isoindole, 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 one hydrogen atom from a heterocyclic compound such as phenazine. As the heterocyclic group, an aromatic heterocyclic group is preferable.

〔式（４）及び式（５）中、Ａｒ^１は１価の複素環基を表す。〕 Examples of the heterocyclic oxy group represented by R ^{1 to} R ¹² include a group represented by the formula (4) in which an oxygen atom is bonded to the above heterocyclic group.
Examples of the heterocyclic thio group represented by R ^{1 to} R ¹² include a group represented by the formula (5) in which a sulfur atom is bonded to the above heterocyclic group.

[In Formula (4) and Formula (5), Ar ¹ represents a monovalent heterocyclic group. ]

The heterocyclic oxy group represented by R ^{1 to} R ¹² usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.

The heterocyclic thio group represented by R ^{1 to} R ¹² usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

The arylalkenyl group represented by R ^{1 to} R ¹² usually has 8 to 20 carbon atoms or may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkenyl group include a styryl group.

The arylalkynyl group represented by R ^{1 to} R ¹² usually has 8 to 20 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkynyl group include a phenylacetylenyl group.

In the carboxy group represented by R ^{1 to} R ¹² , a hydrogen atom in the carboxy group may be substituted with a substituent. As this substituent, a C1-C20 alkyl group is mentioned, for example. Examples of the substituted carboxy group include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

  In formula (1), the heterocyclic ring which may have a substituent represented by ring A and ring B represents a heterocyclic compound which may have a substituent.

  The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring. .

When there are two or more substituents represented by R which the heterocyclic ring may have, they may be the same as or different from each other. The definition and specific examples of R are the same as the definitions and specific examples of R ^{1 to} R ¹² .

  The heterocyclic ring which may have a substituent represented by ring A and ring B usually has 2 to 60 carbon atoms, preferably 4 to 60 carbon atoms, more preferably 4 to 20 carbon atoms. . Examples of the heterocyclic ring include pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, acridine ring, phenanthroline ring, thiophene ring, thienothiophene ring, benzothiophene ring, benzodiphene Examples include a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyrrole ring, a phosphole ring, a phosol oxide ring, a silole ring, and a borol ring. The sulfur atom in the thiophene ring, benzothiophene ring and dibenzothiophene ring may be substituted with an oxo group to form a cyclic sulfoxide or a cyclic sulfone.

  Specific examples of the heterocyclic ring include trivalent groups represented by formula (101) to formula (217).

  Among formulas (101) to (217), from the viewpoint of ease of synthesis, formula (102), formula (179), formula (180), formula (181), formula (182), formula (183) , Formula (184), Formula (185), Formula (186), Formula (187), Formula (188), Formula (189), Formula (190), Formula (191) and Formula (192) Group represented by formula (179), formula (181), formula (183), formula (191) and formula (192) is more preferred, and groups represented by formula (179) and formula (183) Are more preferable, and a group represented by the formula (179) is particularly preferable.

  From the viewpoint of increasing the short-circuit current density, the heterocyclic ring optionally having a substituent represented by ring A and ring B preferably has a 5-membered ring structure or a 5-membered condensed ring structure. Therefore, ring A and ring B are a thiophene ring, a thienothiophene ring, a benzothiophene ring, a benzodithiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyrrole ring, a phosphole ring, a phosol oxide ring, a silole ring and a borol ring. It is preferably a thiophene ring, a thienothiophene ring, a benzodithiophene ring, a thiazole ring, or an oxazole ring, and particularly preferably a thiophene ring.

  Moreover, it is preferable that the heterocyclic ring which may have the substituent represented by the ring A and the ring B is the same from a viewpoint of the ease of a synthesis | combination.

〔環Ｃ、ｎ及びＺは前記と同じ意味を表す。Ｘは、酸素原子、硫黄原子又はセレン原子を表す。Ｙは、窒素原子又は＝Ｃ（Ｒ^１３）−を表す。Ｒ^１３は水素原子、ハロゲン原子、炭素原子数１〜３０のアルキル基、炭素原子数１〜３０のアルコキシ基、炭素原子数６〜３０のアリール基又は炭素原子数２〜３０の１価の複素環基を表す。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。〕 The structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (2) from the viewpoint of increasing the short-circuit current density and the ease of synthesis.

[Ring C, n and Z have the same meaning as described above. X represents an oxygen atom, a sulfur atom or a selenium atom. Y represents a nitrogen atom or ═C (R ¹³ ) —. R ¹³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent complex having 2 to 30 carbon atoms. Represents a cyclic group. The hydrogen atom contained in these groups may be substituted with a substituent. ]

Examples of the halogen atom represented by R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of increasing the short-circuit current density, the halogen atom is preferably fluorine.

The alkyl group having 1 to 30 carbon atoms represented by R ¹³ may be linear, branched, or cyclic. Carbon number of an alkyl group is 1-30. The alkyl group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkyl group include the specific examples represented by the alkyl groups represented by R ^{1 to} R ¹² .

The alkyl part of the alkoxy group having 1 to 30 carbon atoms represented by R ¹³ may be linear, branched, or cyclic. Carbon number of an alkoxy group is 1-20, and the alkoxy group may have a substituent. A halogen atom is mentioned as a substituent. Specific examples of the alkoxy group having 1 to 30 carbon atoms include specific examples represented by the alkoxy group represented by R ^{1 to} R ¹² .

In the aryl group having 6 to 30 carbon atoms represented by R ¹³ , the aryl group means a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The aryl group has 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryl group having 6 to 30 carbon atoms include specific examples represented by the aryl group represented by R ^{1 to} R ¹² .

In the monovalent heterocyclic group having 2 to 30 carbon atoms represented by R ¹³ , the definition of the monovalent heterocyclic group is the same as the definition of the monovalent heterocyclic group represented by R ^{1 to} R ^12. It is. Specific examples of the monovalent heterocyclic group having 2 to 30 carbon atoms include specific examples represented by monovalent heterocyclic rings represented by R ^{1 to} R ¹² .

From the viewpoint of increasing the short-circuit current density, R ¹³ is preferably a hydrogen atom. In formula (2), Y is preferably ═C (H) —, and X is preferably a sulfur atom.

  In terms of-(Z) n- in formula (1) and formula (2), from the viewpoint of increasing the short-circuit current density, n is preferably 1 or more, n is more preferably 1 or 2, and n Is more preferably 1.

When n is 1 or more, Z is —O—, —S—, —C (═O) —, —C (═S) —, —S (═O) —, and —SO ₂ —. Are preferred, —O—, —C (═O) — are more preferred, and —O— is even more preferred.

  In Formula (1), specific examples of-(Z) n- include structural units represented by Formula (11) to Formula (30) below.

  Among these, as-(Z) n-, Formula (12) and Formula (15) are preferable, and Formula (12) is more preferable.

  In formula (1) and formula (2), ring C represents a monocyclic alicyclic hydrocarbon ring which may have a substituent R. R represents the same meaning as described above. From the viewpoint of increasing the short-circuit current density, the ring C is preferably a 7-membered or higher monocyclic alicyclic hydrocarbon ring having no substituent.

  In formula (1), specific examples of ring C include, for example, formula (301) to formula (322).

  As ring C, among the formulas (301) to (322), from the viewpoint of increasing the short-circuit current density, the formula (309), the formula (310), the formula (311), the formula (312), and the formula (313). Formula (314), Formula (315), Formula (316), Formula (317), Formula (318), Formula (319), Formula (320), Formula (321), and Formula (322) are preferable.

  In formula (1), ring A, ring B, ring C, n and Z are preferably combined in their preferred embodiments from the viewpoint of increasing the short-circuit current density. Moreover, in Formula (2), it is preferable to combine ring C, n, X, Y, and Z in each preferable aspect from a viewpoint of raising a short circuit current density.

  As a structural unit represented by Formula (1), the structural unit represented by the following formula (401)-Formula (454) is mentioned, for example.

  Among the structural units represented by the above formulas (401) to (454), the structural units represented by the formulas (409) to (444) are preferable from the viewpoint of increasing the short-circuit current density. The structural units represented by formula (426) and the structural units represented by formula (431) to formula (444) are more preferred.

  From the viewpoint of increasing the short circuit current density, the compound of the present invention preferably contains a structural unit different from the structural unit represented by the formula (1) in addition to the structural unit represented by the formula (1). When the compound of the present invention contains a structural unit different from the structural unit represented by formula (1), the structural unit represented by formula (1) and the structural unit represented by formula (1) are different. 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、アリーレン基又は２価の複素環基を表す。ただし、Ａｒは、式（１）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 the formula (1) include a structural unit represented by the formula (3).

(In the formula, Ar represents an arylene group or a divalent heterocyclic group. However, Ar is different from the structural unit represented by Formula (1).)

The arylene group represented by Ar is a group obtained by removing two hydrogen atoms on an aromatic 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 a halogen atom and an alkoxy group (for example, 1 to 20 carbon atoms).
Specific examples of the arylene group include a phenylene group (formulas 1 to 3 in the figure below), a naphthalenediyl group (formulas 4 to 13 in the figure below), an anthracenediyl group (formulas 14 to 19 in the figure below), and a biphenyl-diyl group (in the figure below). Formula 20-25), a terphenyl-diyl group (formula 26-28 of the following figure), and a condensed ring compound group (formula 29-38 of the following figure) are mentioned. The condensed ring compound group includes a fluorene-diyl group (formulas 36 to 38 in the following figure).

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 a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, and an aryl group. Definitions and specific examples of the halogen atom, alkyl group, alkoxy group, alkylthio group and aryl group include definitions and specific examples of the halogen atom, alkyl group, alkoxy group, alkylthio group and aryl group represented by R ^{1 to} R ^12. Is the same. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable.
Specific examples of the divalent heterocyclic group include the following groups.
Divalent heterocyclic groups containing nitrogen as a heteroatom:
A pyridine-diyl group which may have a substituent (formulas 39 to 44 in the following figure).
Diazaphenylene group which may have a substituent (Formula 45-48 of the following figure).
A quinolinediyl group which may have a substituent (formulas 49 to 63 in the following figure).
A quinoxalinediyl group which may have a substituent (formulas 64-68 in the following figure).
An acridinediyl group which may have a substituent (formulas 69 to 72 in the following figure).
Bipyridyldiyl group which may have a substituent (formula 73-75 of the following figure).
A phenanthrolinediyl group which may have a substituent (formulas 76 to 78 in the following figure).
Groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulae 94 to 98 in the following figure).
5-membered ring condensed hetero groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 99 to 110 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms:
A group bonded at the α-position of a heteroatom to form a dimer or oligomer (formulas 111 to 112 in the figure below).
A group bonded to a phenyl group at the α-position of the heteroatom (formulas 113 to 119 in the figure below).
A group in which a benzene ring and a thiophene ring are condensed (formulas 120 to 122 in the following figure).

  In Formula 1 to Formula 122, R represents the same meaning as described above.

From the viewpoint of improving the short-circuit current density of the organic photoelectric conversion element of the present invention, as the structural unit represented by the formula (3), structural units represented by the formula (3-1) to the formula (3-9) are included. preferable.

In formulas (3-1) to (3-9), the definitions and specific examples of R ^{21 to} R ⁴² are the same as the definitions and specific examples of R ^{1 to} R ¹² .

R ²¹ and R ²² are preferably an alkyl group, an alkoxy group, and an alkylthio group, more preferably an alkyl group and an alkoxy group, and particularly preferably an alkyl group. From the viewpoint of increasing the solubility of the compound in an organic solvent, the alkyl group is preferably a branched alkyl group.

R ²³ and R ²⁴ are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, and more preferably a hydrogen atom, a fluorine atom, or an alkoxy group.

R ³² and R ³³ are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and an aryl group, and more preferably an alkyl group and an aryl group.

R ³⁹ is preferably a hydrogen atom or a halogen atom, more preferably a fluorine atom.

R ⁴⁰ is preferably a hydrogen atom, a halogen atom, an acyl group or an acyloxy group, more preferably an acyl group or an acyloxy group.

R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ⁴¹ and R ⁴² include a hydrogen atom, a halogen atom, Alkyl groups, alkoxy groups, alkylthio groups and aryl groups are preferred.

In formula (3-1) to formula (3-9), X ^{21 to} X ³⁰ each independently represents a sulfur atom, an oxygen atom or a selenium atom. X ^{21 to} X ³⁰ are preferably a sulfur atom and an oxygen atom, and more preferably a sulfur atom.

  As the structural unit represented by Formula (3), structural units represented by Formula (3-1) to Formula (3-7) are more preferable. In Formula (3-2) and Formula (3-5), The structural unit represented is particularly preferred. Specific examples of the structural unit represented by Formula (3-2) include Formula (3-2-1) to Formula (3-2-9) and Formula (3-5-1) to Formula (3-5). And the structural unit represented by -6).

In formula (3-2-1) to formula (3-2-9) and formula (3-5-1) to formula (3-5-6), the definition and specific examples of R ′ are R ^{1 to} R ¹² definitions and specific examples are the same.

The compound of the present invention is preferably a polymer compound.
In the present invention, the polymer compound 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 particularly 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 (1). 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 compound of the present invention is used in a device, it is desirable that the compound has a high solubility in a solvent from the viewpoint of ease of device fabrication. Specifically, it is preferable that the compound of the present invention has a solubility capable of producing a solution containing 0.01% by weight or more of the compound, and a solubility capable of producing a solution containing 0.1% by weight or more. It is more preferable to have a solubility capable of producing a solution containing 0.2 wt% or more.

<Method for producing compound>
The 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 as necessary, and an alkali, catalyst And can be synthesized by polymerization using a known aryl coupling reaction using a ligand or 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 each represents a dihydroxyboryl group (—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.

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。） 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.

(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 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 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 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 each represents a substituted stannyl group. ]
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 substituted stannyl group 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. The substituent is preferably an stannyl group, -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 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 compound used in the present invention, toluene and tetrahydrofuran are preferred.

Although the temperature at which the Stille coupling reaction is performed depends on the solvent, it is usually about 50 to 160 ° C., and 60 to 120 ° C. is preferable from the viewpoint of increasing the molecular weight of the 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 particularly preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of monomer and compound stability.

  In the polymerization by the aryl coupling reaction, a known method may be used as a method for removing the compound of the present invention from the reaction solution after completion of the reaction. For example, the 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 compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  When the compound of the present invention is used for the production of an organic photoelectric conversion element, if a polymerization active group remains at the end of the compound, characteristics such as durability of the organic photoelectric conversion element may be deteriorated. It is preferred to protect 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. In addition, the polymerization active group remaining at the end of the 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 compound is a conjugated polymer compound, 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 terminal are continuous also protects the terminal. It can be preferably used as a small 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 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 production of the thin film is easy.

  Although the compound of this invention has a structural unit represented by Formula (1), this compound uses the compound represented by following formula (1-1) as one of the raw materials, for example. Can be synthesized.

In formula (1-1), ring C represents the same meaning as described above.
W is a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group, and two Ws may be the same or different.

  When the compound represented by formula (1-1) in which W is a hydrogen atom is used, a compound having a structural unit represented by formula (1) can be produced by oxidative polymerization. In oxidative polymerization, a catalyst is usually used. As such a catalyst, a known catalyst can be used. For example, a metal halide or a mixture of a metal halide and an amine complex (metal halide / amine complex) is used. As the metal halide, monovalent, divalent or trivalent halides of metals such as copper, iron, vanadium and chromium can be used.

  Examples of the amine used for producing the amine complex include pyridine, lutidine, 2-methylimidazole, and N, N, N ′, N′-tetramethylethylenediamine. The metal halide / amine complex can be produced by mixing a metal halide and an amine in a solvent in the presence of oxygen. The molar ratio of mixing the metal halide and the amine is, for example, a metal Halide / amine = 1/0. 1 to 1/200, preferably 1 / 0.3 to 1/100.

  As the catalyst, iron chloride can also be used (Polym. Prep. Japan 1999, 48, 309.). Furthermore, the molecular weight of the compound is increased by using a copper / amine catalyst system (J. Org. Chem. 1999, 64, 2264., J. Polym. Sci. Part A, Polym. Chem. 1999, 37, 3702.). be able to.

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

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

  When the compound of the present invention is a copolymer, a method for producing the copolymer is a method of polymerizing by mixing two or more types of monomers, a method of polymerizing one type of monomer and then adding a second type of monomer. Etc. By using or combining these methods, it is possible to produce block copolymers, random copolymers, alternating copolymers, multiblock copolymers, graft copolymers, and the like.

  From the viewpoint of ease of functional group conversion, W in formula (1-1) is the same or different and is preferably a halogen atom, a boric acid ester residue, a dihydroxyboryl group or a substituted stannyl group.

  When W in the compound represented by formula (1-1) is a hydrogen atom, a known method is used as a method for converting W in the compound represented by formula (1-1) to a bromine atom. Examples of the method include bromination by bringing a compound represented by the formula (1-1) in which W is a hydrogen atom into contact with bromine or N-bromosuccinimide (NBS). The conditions for bromination can be arbitrarily set. For example, a method of reacting with NBS in a solvent is desirable because the bromination rate is high and the selectivity of the introduction position of bromine atoms is high. Examples of the solvent used at this time include N, N-dimethylformamide, chloroform, methylene chloride, and carbon tetrachloride. The reaction time is usually about 1 minute to 10 hours, and the reaction temperature is usually about −50 ° C. to 50 ° C. The amount of bromine used is preferably about 1 mol to 5 mol with respect to 1 mol of the compound represented by the formula (1-1) in which W is a hydrogen atom. After the reaction, for example, after stopping the reaction by adding water, the product is extracted with an organic solvent and subjected to a usual post-treatment such as distilling off the solvent, wherein W is a bromine atom (1-1) Can be obtained. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

  Examples of the compound represented by the formula (1-1) include the following compounds.

（式（１−２）中、環Ｃは、前述と同じ意味を表す。） The compound represented by the formula (1-1) is prepared by, for example, reacting the compound represented by the formula (1-2) with an organolithium compound to produce an intermediate, and then the intermediate and the trialkyltin halide. Can be made to react.

(In formula (1-2), ring C represents the same meaning as described above.)

  Examples of the organic lithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide. Of the organic lithium compounds, n-butyllithium is preferable. Examples of the trialkyltin halide include trimethyltin chloride, triethyl chloride, and tributyl chloride.

  The reaction for producing an intermediate from the compound represented by formula (1-2) and the organolithium compound and the reaction for producing the compound represented by formula (1-1) from the intermediate and trialkyltin halide are usually performed. Carried out in a solvent. As the solvent, sufficiently dehydrated tetrahydrofuran, fully dehydrated 1,4-dioxane, and fully dehydrated diethyl ether are preferably used.

  The temperature at the time of reacting the organolithium compound and the compound represented by the formula (1-2) is usually −100 to 50 ° C., preferably −80 to 0 ° C. The time for reacting the organolithium compound with the compound represented by formula (1-2) is usually 1 minute to 10 hours, preferably 30 minutes to 5 hours. The amount of the organolithium compound to be reacted is usually 2 to 5 molar equivalents (hereinafter, the molar equivalent is simply referred to as equivalent), preferably 2 with respect to the compound represented by the formula (1-2). ~ 3 equivalents.

  The temperature at the time of reacting the intermediate and the trialkyltin halide is usually −100 to 100 ° C., preferably −80 ° C. to 50 ° C. The reaction time of the intermediate and the trialkyltin halide is usually 1 minute to 30 hours, preferably 1 to 10 hours. The amount of the trialkyl tin halide to be reacted is usually 2 to 6 equivalents, preferably 2 to 3 equivalents, relative to the compound represented by the formula (1-2).

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (1-1). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

（式（１−３）中、環Ｃは、前述と同じ意味を表す。） The compound represented by the formula (1-2) can be produced, for example, by reacting the compound represented by the formula (1-3) in the presence of an acid.

(In formula (1-3), ring C represents the same meaning as described above.)

  The acid used in the reaction for producing the compound represented by the formula (1-2) from the compound represented by the formula (1-3) may be a Lewis acid or a Bronsted acid. Hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, boron fluoride, aluminum chloride, tin (IV) chloride, iron (II) chloride, Examples include titanium tetrachloride, benzenesulfonic acid, p-toluenesulfonic acid and mixtures of these compounds.

  The reaction for producing the compound represented by formula (1-2) from the compound represented by formula (1-3) is preferably carried out in the presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

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

  After the reaction, normal post-treatment can be performed to obtain a compound represented by the formula (1-2). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (1-3) can be produced, for example, by reacting the compound represented by the formula (1-4) with a Grignard reagent or an organolithium (Li) compound. .

  Grignard reagents used in the above reaction include ethyl dimagnesium chloride, ethyl dimagnesium bromide, propyl dimagnesium chloride, propyl dimagnesium bromide, butyl dimagnesium chloride, butyl dimagnesium bromide, hexyl dimagnesium bromide, octyl dimagnesium bromide, Examples include decyl dimagnesium bromide.

  Examples of the organic Li compound include ethyl dilithium, propyl dilithium, and butyl dilithium.

  The reaction for producing the compound represented by the formula (1-3) 6 from the compound represented by the formula (1-4) 7 and the Grignard reagent or the organolithium (Li) compound is carried out by using a reaction such as nitrogen or argon. It is preferable to carry out in an active gas atmosphere. Moreover, it is preferable to implement this reaction in presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

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

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (1-3) 6. For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound of the present invention preferably has a light absorption terminal wavelength of 700 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 compound is formed on the substrate from a solution containing the compound or a melt containing the 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 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 compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, the organic photoelectric conversion element manufactured using the compound of the present invention has a high short-circuit current density. .

  Since the compound of the present invention can exhibit high electron and / or hole transport properties, when an organic thin film containing the compound is used in a device, it is generated by electrons or holes injected from an electrode or light absorption. Charge 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 compound of the present invention has one or more active layers containing the 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 compound of the present invention is formed from an organic composition of a pair of electrodes, at least one of which is transparent or translucent, and a p-type organic semiconductor and an n-type organic semiconductor. Has an active layer. The compound of the present invention is preferably used as a p-type organic semiconductor.

  The photoelectric conversion element manufactured using the 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 compound of the present invention, a first active layer containing the compound of the present invention is interposed between a pair of electrodes, at least one of which is transparent or translucent, and the first active layer. Adjacent to the photoelectric conversion element is a second active layer containing an electron-accepting compound such as a fullerene derivative.

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, etc. 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 compound of this invention individually by 1 type, or may contain 2 or more types in combination. In order to improve the hole transport property of the active layer, compounds other than the compound of the present invention can be used as an electron-donating compound and / or an 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 compound of the present invention, for example, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, oligothiophene and its derivative, polyvinylcarbazole and its derivative, polysilane and its derivative, side chain Alternatively, polysiloxane derivatives having an aromatic amine residue in the main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof can be mentioned.

As the electron-accepting compound, in addition to the 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, Anthraquinone 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, Preferred examples include polyfluorene and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerenes and fullerene derivatives. , Titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.

（１５） （１６） （１７） （１８）

（式（１５）〜（１８）中、Ｒ^ａは、置換されていてもよいアルキル基、アリール基、芳香族複素環基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂは置換されていてもよいアルキル基又はアリール基を表す。複数個あるＲ^ｂ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.

(15) (16) (17) (18)

(In the formulas (15) to (18), R ^a is an optionally substituted alkyl group, aryl group, aromatic heterocyclic group or group having an ester structure. A plurality of R ^a are the same. R ^b represents an optionally substituted alkyl group or aryl group, and a plurality of R ^b may be the same or different.)

Specific examples of the optionally substituted alkyl group and aryl group represented by R ^a and R ^b are the same as the specific examples of the optionally substituted alkyl group and aryl group represented by R.

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、置換されていてもよいアルキル基、アリール基又は芳香族複素環基を表す。） 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 1-6, is u2, represents an integer of Less than six, R ^c is an optionally substituted alkyl group, an aryl group or an aromatic heterocyclic group. )

Optionally substituted alkyl group represented by R ^c, specific examples of the aryl group and aromatic heterocyclic group, optionally substituted alkyl group represented by R ^a, an aryl group and an aromatic heterocyclic ring The same as the specific example of the group.

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 compound of the present invention and the fullerene derivative are contained in the active layer, the amount of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the compound of the present invention. It is more preferable that

  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 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, An element having a step of forming an active layer by applying a solution (ink) containing the 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 It is a manufacturing method.

  The solvent used for film formation from a solution may be any that dissolves the 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 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 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 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 compound of the present invention.

<Organic electroluminescence device>
The compound of this invention can also be used for an organic electroluminescent element (organic EL element). 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 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 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 compound of the present invention can be 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. . 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 produced using the compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

In a typical super straight type or substrate type module, cells are 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.

フラスコ内の気体を窒素で置換した100 mL三つ口フラスコに、WO2011/052709A1に記載の方法で合成した化合物１を1.45 g（7.00 mmol）と脱水テトラヒドロフランを700 mL入れて均一な溶液とした。その反応液を80℃まで加熱し、事前に調整したグリニャール試薬（化合物２）のテトラヒドロフラン溶液（0.50 M）20 mL（10 mmol）を滴下し、３時間攪拌した。その後、反応液に水および酢酸を加えて反応を停止し、酢酸エチルを用いて有機層を抽出した。得られた有機層を無水硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液の溶媒を減圧下で留去し、化合物３の粗体を得た。 Synthesis example 1
(Synthesis of Compound 2)

Into a 100 mL three-necked flask in which the gas in the flask was replaced with nitrogen, 1.45 g (7.00 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 700 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. The reaction solution was heated to 80 ° C., and 20 mL (10 mmol) of a previously prepared Grignard reagent (Compound 2) in tetrahydrofuran (0.50 M) was added dropwise and stirred for 3 hours. Thereafter, water and acetic acid were added to the reaction solution to stop the reaction, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and after filtering the organic layer, the solvent of the filtrate was distilled off under reduced pressure to obtain a crude compound 3.

フラスコ内の気体を窒素で置換した300 mLフラスコに、化合物３の粗体、トルエンを70mL、ｐ−トルエンスルホン酸ナトリウム１水和物を323 mg（1.7 mmol）を入れて均一な溶液とし、120 ℃で２時間攪拌した。反応液を室温まで冷却後、水50 mLを加え、トルエンで有機層を抽出した。得られたトルエン溶液を無水硫酸ナトリウムで乾燥し、有機層をろ過後、減圧下で溶媒を留去した。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し（展開溶媒：ヘキサン）、化合物４を645 mg（1.79 mmol、収率17.9%）得た。 Synthesis example 2
(Synthesis of Compound 4)

A 300 mL flask in which the gas in the flask was replaced with nitrogen was charged with a crude solution of Compound 3, 70 mL of toluene, and 323 mg (1.7 mmol) of sodium p-toluenesulfonate monohydrate to obtain a uniform solution. Stir for 2 hours at ° C. After cooling the reaction solution to room temperature, 50 mL of water was added, and the organic layer was extracted with toluene. The obtained toluene solution was dried over anhydrous sodium sulfate, the organic layer was filtered, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane) to obtain 645 mg (1.79 mmol, yield 17.9%) of compound 4.

¹ H NMR (CDCl ₃ ): δ 7.03 (d, 1H), 6.98 (d, 1H), 6.81 (d, 1H), 6.69 (d, 1H), 2.06-1.89 (m, 4H), 1.40 (br, 20H).

フラスコ内の気体を窒素で置換した300 mLフラスコに、化合物４を645 mg（1.79 mmol)、脱水テトラヒドロフランを20 mL入れて均一な溶液とした。該溶液を−７８℃に冷却し、1.6 Mのn-ブチルリチウムのn-ヘキサン溶液を2.58 mL（4.12 mmol）を１０分かけて滴下した。滴下後、反応液を−７８℃で３０分攪拌し、次いで、室温で２．５時間攪拌した。その後、フラスコを−７８℃に再冷却し、反応液にトリブチルスズクロリドを1.46 g（4.48 mmol）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温で２時間攪拌した。その後、反応液に水100 mLを加えて反応を停止させ、酢酸エチルを加えて有機層を抽出した。得られた有機層を硫酸ナトリウムで乾燥し、ろ過後、減圧下で溶媒を留去した。得られの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（展開溶媒：ヘキサン）した。シリカゲルには、あらかじめ5 wt%のトリエチルアミンを含むヘキサンに５分間浸し、その後、ヘキサンで濯いだシリカゲルを用いた。精製後、化合物５を1.33 g（1.41 mmol, 収率79%）得た。 Synthesis example 3
(Synthesis of Compound 5)

Into a 300 mL flask in which the gas in the flask was replaced with nitrogen, 645 mg (1.79 mmol) of Compound 4 and 20 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. The solution was cooled to −78 ° C., and 2.58 mL (4.12 mmol) of 1.6 M n-butyllithium in n-hexane was added dropwise over 10 minutes. After the dropwise addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature for 2.5 hours. Thereafter, the flask was re-cooled to −78 ° C., and 1.46 g (4.48 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction was stirred at −78 ° C. for 30 minutes and then at room temperature for 2 hours. Thereafter, 100 mL of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract the organic layer. The obtained organic layer was dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane). As silica gel, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 1.33 g (1.41 mmol, yield 79%) of compound 5 was obtained.

フラスコ内の気体をアルゴンで置換した100 mLフラスコに、化合物５を188 mg（0.200 mmol）、Organic Electronics 2010, 11, 1740.に記載の合成法で合成した化合物６を108 mg（0.200 mmol）、トリス(２−トリル)ホスフィンを5.5 mg（0.018 mmol）、脱水トルエン16 mLを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを2.7 mg（0.0030 mmol）加え、105℃で３時間攪拌した後にさらに120℃で３時間攪拌した。その後、反応液にフェニルブロミドを370 mg加え、さらに２時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール200 mLと濃塩酸20 mLの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、o-ジクロロベンゼン8.0 mLに溶解させ、ジエチルジチオカルバミン酸ナトリウム0.17 gと水2.0 mLを加え、90℃で３時間攪拌を行った。水層を除去後、有機層を水50 mLで２回洗浄し、次いで、3.0 wt%の酢酸水溶液50 mLで２回洗浄し、次いで、水50 mLで２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、乾燥し、得られたポリマーをo-ジクロロベンゼン8.0 mLに再度溶解し、アルミナ／シリカゲルカラムを通した。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83 mg得た。以下、この重合体を高分子化合物Ａと呼称する。 Example 1
(Synthesis of polymer compound A)

In a 100 mL flask in which the gas in the flask was replaced with argon, Compound 5 (188 mg, 0.200 mmol), Compound 6 synthesized by the synthesis method described in Organic Electronics 2010, 11, 1740., 108 mg (0.200 mmol), 5.5 mg (0.018 mmol) of tris (2-tolyl) phosphine and 16 mL of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.7 mg (0.0030 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 3 hours, and further stirred at 120 ° C. for 3 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 8.0 mL of o-dichlorobenzene, 0.17 g of sodium diethyldithiocarbamate and 2.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3.0 wt% aqueous acetic acid solution and then twice with 50 mL of water. The polymer was precipitated by pouring into methanol. The polymer was filtered and dried, and the resulting polymer was dissolved again in 8.0 mL of o-dichlorobenzene 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 83 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A.

フラスコ内の気体をアルゴンで置換した100 mLフラスコに、WO2011/052709A1に記載の方法で合成した化合物化合物７を316 mg（0.300 mmol）、化合物６を162 mg（0.300 mmol）、トリス(２−トリル)ホスフィンを8.2 mg（0.027 mmol）、脱水トルエン24 mLを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを4.1 mg（0.0045 mmol）加え、105℃で３時間攪拌した後にさらに120℃でで３時間攪拌した。その後、反応液にフェニルブロミドを370 mg加え、さらに２時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール200 mLと濃塩酸20 mLの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、o-ジクロロベンゼン8.0 mLに溶解させ、ジエチルジチオカルバミン酸ナトリウム0.25 gと水3.0 mLを加え、90℃で３時間攪拌を行った。水層を除去後、有機層を水50 mLで２回洗浄し、次いで、3.0 wt%の酢酸水溶液50 mLで２回洗浄し、次いで、水50 mLで２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、乾燥し、得られたポリマーをo-ジクロロベンゼン12 mLに再度溶解し、アルミナ／シリカゲルカラムを通した。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221 mg得た。以下、この重合体を高分子化合物Ｙと呼称する。ＧＰＣで測定した高分子化合物Ｙの分子量（ポリスチレン換算）はMn＝17,600、Mw=45,100であった。 Comparative Example 1
(Synthesis of polymer compound Y)

Compound 100 synthesized by the method described in WO2011 / 052709A1, 316 mg (0.300 mmol), compound 6 162 mg (0.300 mmol), tris (2-tolyl) was synthesized in a 100 mL flask in which the gas in the flask was replaced with argon. ) Phosphine (8.2 mg, 0.027 mmol) and dehydrated toluene (24 mL) were added to obtain a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, followed by stirring at 105 ° C. for 3 hours and further stirring at 120 ° C. for 3 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 8.0 mL of o-dichlorobenzene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3.0 wt% aqueous acetic acid solution and then twice with 50 mL of water. The polymer was precipitated by pouring into methanol. The polymer was filtered and dried, and the resulting polymer was dissolved again in 12 mL of o-dichlorobenzene 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 221 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound Y. The molecular weight (polystyrene conversion) of the high molecular compound Y measured by GPC was Mn = 17,600 and Mw = 45,100.

フラスコ内の気体をアルゴンで置換した100 mLフラスコに、化合物７と同様の方法で合成した化合物８を299 mg（0.300 mmol）、化合物６を162 mg（0.300 mmol）、トリス(２−トリル)ホスフィンを8.2 mg（0.027 mmol）、脱水トルエン24 mLを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを4.1 mg（0.0045 mmol）加え、105℃で３時間攪拌した後にさらに120℃でで３時間攪拌した。その後、反応液にフェニルブロミドを370 mg加え、さらに２時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール200 mLと濃塩酸20 mLの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、o-ジクロロベンゼン8.0 mLに溶解させ、ジエチルジチオカルバミン酸ナトリウム0.25 gと水3.0 mLを加え、90℃で３時間攪拌を行った。水層を除去後、有機層を水50 mLで２回洗浄し、次いで、3.0 wt%の酢酸水溶液50 mLで２回洗浄し、次いで、水50 mLで２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、乾燥し、得られたポリマーをo-ジクロロベンゼン12 mLに再度溶解し、アルミナ／シリカゲルカラムを通した。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176 mg得た。以下、この重合体を高分子化合物Ｚと呼称する。ＧＰＣで測定した高分子化合物Ｚの分子量（ポリスチレン換算）はMn＝18,600、Mw=49,200であった。 Comparative Example 2
(Synthesis of polymer compound Z)

Compound 8 synthesized in the same manner as compound 7 was 299 mg (0.300 mmol), compound 6 was 162 mg (0.300 mmol), tris (2-tolyl) phosphine in a 100 mL flask in which the gas in the flask was replaced with argon. 8.2 mg (0.027 mmol) and 24 mL of dehydrated toluene were added to make a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, followed by stirring at 105 ° C. for 3 hours and further stirring at 120 ° C. for 3 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 8.0 mL of o-dichlorobenzene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3.0 wt% aqueous acetic acid solution and then twice with 50 mL of water. The polymer was precipitated by pouring into methanol. The polymer was filtered and dried, and the resulting polymer was dissolved again in 12 mL of o-dichlorobenzene 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 176 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound Z. The molecular weight (polystyrene conversion) of the polymer compound Z measured by GPC was Mn = 18,600 and Mw = 49,200.

Measurement example 1
(Production and evaluation of ink and organic thin film solar cell)
A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by HC Starck Co., Ltd.) is applied onto the ITO film by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to thereby form a hole injection layer having a thickness of 50 nm. It was created. Next, when the polymer compound A and fullerene C70PCBM (phenyl 71-butyric acid methyl ester, manufactured by Frontier Carbon Co.) are used, the ratio of the weight of C70PCBM to the weight of the polymer compound A is 2. In this way, it was dissolved in orthodichlorobenzene to prepare an ink. The total weight of the polymer compound A and 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 A. The film thickness was about 100 nm. The light absorption edge wavelength of the organic film thus produced was 820 nm. Then, calcium was vapor-deposited with a thickness of 4 nm on the organic film by a vacuum vapor deposition machine, and then aluminum was vapor-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 11.8 mA / cm ² , and the photoelectric conversion efficiency (η) was 3.6%. The results are shown in Table 1.

Measurement example 2
An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Measurement Example 1 except that the polymer compound Y was used instead of the polymer compound A. Jsc (short circuit current density) was 4.64 mA / cm ² , and the photoelectric conversion efficiency (η) was 2.2%. The results are shown in Table 1.

Measurement example 2
An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Measurement Example 1 except that the polymer compound Z was used instead of the polymer compound A. Jsc (short circuit current density) was 8.71 mA / cm ² , and the photoelectric conversion efficiency (η) was 3.5%. The results are shown in Table 1.

Table 1 Evaluation results of photoelectric conversion elements

Claims (9)

The high molecular compound which has a structural unit represented by Formula (1) and whose weight average molecular weight of polystyrene conversion is 3000-10 million.

[Ring A and Ring B each independently represents a thiophene ring which may have a substituent. Ring C represents an alicyclic hydrocarbon ring monocyclic or 7-membered ring having no substituent. n represents 1. Z represents -O-. ] The polymer compound according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2).

[Ring C, n and Z have the same meaning as described above. X represents a sulfur atom. Y represents = C (R < ¹³ >)-. R ¹³ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. Represent. The hydrogen atom contained in the alkyl group, the aryl group, the heterocyclic group or the alkoxy group may be substituted with a substituent. ]   The polymer compound according to claim 2, wherein Y is = C (H)-. The polymer compound according to any one of claims 1 to 3 , wherein the polymer compound further has a structural unit represented by the formula (3).

[Ar represents an arylene group or a divalent heterocyclic group. However, Ar is different from the structural unit represented by Formula (1) or Formula (2). ] The polymer compound according to claim 4 , wherein Ar is a structural unit represented by any one of formulas (3-1) to (3-9).

[In the formulas (3-1) to (3-9), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio Group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group which is a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, Imido group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, which is a group obtained by removing one hydrogen atom bonded to a nitrogen atom from imide Substituted silylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, arylalkenyl group, arylalkynyl group, a carboxyl group or a cyano group. The hydrogen atom contained in these groups may be substituted with a substituent. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ²⁹ and X ³⁰ each independently represent a sulfur atom, an oxygen atom or a selenium atom. ] The electronic device containing the high molecular compound as described in any one of Claims 1-5 . A first electrode, a second electrode, an organic photoelectric conversion element having an active layer provided between the first electrode and the second electrode, according to claim 1 in the active layer 5 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 7 . The organic thin-film transistor which has a gate electrode, a source electrode, a drain electrode, and an active layer, and contains the high molecular compound as described in any one of Claims 1-5 in the said active layer.