JP2014189721A - Polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound capable of manufacturing a thin organic film solar cell having a sufficiently high open end voltage.SOLUTION: The provided polymer compound includes a structural unit expressed by the formula (1): [in the formula (1), Arand Arare mutually identical or different and each express a trivalent aromatic hydrocarbon group or trivalent heterocyclic group; n expresses a natural number; X expresses -C(R)(R)-, -Si(R)(R)-, -Ge(R)(R)-, -Sn(R)(R)-, -N(R)-, -P(R)-, -P(=O)(R)-, or -B(R)-; in a case where n is 2 or greater, the multiple members of X may be mutually identical or different].

Description

  The present invention relates to a polymer compound, and an organic photoelectric conversion element and an organic thin film transistor using the same.

In recent years, in order to prevent global warming, reduction of CO ₂ released into the atmosphere has been demanded. For example, it has been proposed to install a solar system using a pn junction type silicon solar cell or the like on the roof of a house. Monocrystalline, polycrystalline and amorphous silicon used in the silicon solar cell are manufactured by the following methods. There is a problem that high temperature conditions and high vacuum conditions are necessary in the process.

  On the other hand, the organic thin film solar cell which is one aspect of the organic photoelectric conversion element can omit the high temperature and high vacuum process used in the manufacturing process of the silicon-based solar cell, and can be manufactured inexpensively only by the coating process. Attention has been paid. As a polymer compound used for an organic thin film solar cell, 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, an organic thin film solar cell containing an organic layer containing the polymer compound has a problem that the open-circuit voltage is not necessarily high.

  Then, an object of this invention is to provide the high molecular compound which can manufacture an organic thin-film solar cell with a sufficiently high open end voltage.

〔式（１）中、Ａｒ^１及びＡｒ^２は、同一又は相異なり、３価の芳香族炭素環基または３価の複素環基を表す。ｎは自然数を表す。Ｘは、−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Ｘは、同一又は相異なる。Ｒ^１〜Ｒ^１２は、同一又は相異なり、芳香族炭素環基、複素環基、ハロゲン原子、又は１つ以上のハロゲン原子で置換されている置換基を表す。前記１つ以上のハロゲン原子で置換されている置換基は、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、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、およびアリールアルキニル基のうちのいずれか１つの基が１つ以上のハロゲン原子で置換された置換基である。〕 That is, the present invention first provides a polymer compound having a structural unit represented by the formula (1).

[In Formula (1), Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic carbocyclic group or a trivalent heterocyclic group. n represents a natural number. X represents —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, a plurality of Xs are the same or different. R ^{1 to} R ¹² are the same or different and represent an aromatic carbocyclic group, a heterocyclic group, a halogen atom, or a substituent substituted with one or more halogen atoms. Substituents substituted with one or more halogen atoms are alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, acyl groups, Acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, And any one of arylalkynyl groups is a substituent group substituted with one or more halogen atoms. ]

In the present invention, secondly,-(X) n- in the formula (1) is such that n is 2 or more,
One selected from the group consisting of —O—, —S—, —Se—, —C (═O) —, —C (═S) —, —S (═O) —, and —SO ₂ —. And more
^{-C (R 1) (R 2} ) -, - Si (R 3) (R 4) -, - Ge (R 5) (R 6) -, - Sn (R 7) (R 8) -, - N Including one or more selected from the group consisting of (R ⁹ )-, -P (R ¹⁰ )-, -P (= O) (R ¹¹ )-, and -B (R ¹² )-. However, R < ¹ > -R < ¹² > provides the said high molecular compound which represents the same meaning as the above-mentioned thing.

Thirdly, the present invention provides the polymer compound, wherein at least one of Ar ¹ and Ar ² includes a 5-membered ring or a 5-membered ring structure, and n is 2 or more.

Fourthly, the present invention provides the polymer compound, wherein n is 2 and at least one of the two Xs is —C (R ¹ ) (R ² ) —.

Fifth, the present invention provides the polymer compound, wherein one of the two Xs is —C (R ¹ ) (R ² ) — and the other is —O—.

Sixth, the present invention provides the polymer compound, wherein at least one of Ar ¹ and Ar ² is a group obtained by removing three hydrogen atoms from a thiophene ring.

  Seventhly, the present invention provides the polymer compound containing three or more halogen atoms in the-(X) n-.

  Eighthly, in the present invention, the polymer atom according to any one of claims 1 to 7, wherein the halogen atom is a fluorine atom. The polymer compound is provided.

Ninthly, the present invention provides the polymer compound, wherein R ^{1 to} R ¹² are aromatic carbocyclic groups or heterocyclic groups.

Tenthly, the present invention provides the polymer compound, wherein R ¹ and R ² are aromatic carbocyclic groups.

〔式（２）中、Ａｒ^４は、アリーレン基又は２価の複素環基を表す。ただし、Ａｒ^４は、式（１）で表される構成単位とは異なる。〕 Eleventhly, the present invention provides the polymer compound having a structural unit represented by the formula (2) in addition to the structural unit represented by the formula (1).

[In the formula (2), Ar ⁴ represents an arylene group or a divalent heterocyclic group. However, Ar ⁴ is different from the structural unit represented by the formula (1). ]

  Thirteenth, the present invention includes a first electrode and a second electrode, an active layer between the first electrode and the second electrode, and the polymer in the active layer. An organic photoelectric conversion device containing a compound is provided.

  14thly this invention provides the organic thin-film transistor which has a gate electrode, a source electrode, a drain electrode, and an active layer, and contains the said high molecular compound in this active layer.

  Since the organic thin-film solar cell which has an organic layer containing the high molecular compound of this invention has a large open end voltage, this invention is very useful.

  Hereinafter, the present invention will be described in detail.

〔式（１）中、Ａｒ^１及びＡｒ^２は、同一又は相異なり、３価の芳香族炭素環基または３価の複素環基を表す。ｎは自然数を表す。Ｘは、−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Ｘは、同一又は相異なる。Ｒ^１〜Ｒ^１２は、同一又は相異なり、芳香族炭素環基、複素環基、ハロゲン原子、又は１つ以上のハロゲン原子で置換されている置換基を表す。前記１つ以上のハロゲン原子で置換されている置換基は、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、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、およびアリールアルキニル基のうちのいずれか１つの基が１つ以上のハロゲン原子で置換された置換基である。〕 <Polymer compound>
The high molecular compound of this invention contains the structural unit represented by Formula (1).

[In Formula (1), Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic carbocyclic group or a trivalent heterocyclic group. n represents a natural number. X represents —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, a plurality of Xs are the same or different. R ^{1 to} R ¹² are the same or different and represent an aromatic carbocyclic group, a heterocyclic group, a halogen atom, or a substituent substituted with one or more halogen atoms. Substituents substituted with one or more halogen atoms are alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, acyl groups, Acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, And any one of arylalkynyl groups is a substituent group substituted with one or more halogen atoms. ]

  The polymer compound of the present invention is a π-conjugated polymer compound having a side chain substituted with a halogen atom. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a fluorine atom.

The aromatic carbocyclic 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 aromatic carbocyclic group may have a substituent. Examples of the substituent include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and an optionally substituted group. A good alkylthio group is mentioned. Specific examples of the aromatic carbocyclic group which may have a substituent include a phenyl group and a C1-C12 alkoxyphenyl group (C1-C12 alkoxy represents alkoxy having 1 to 12 carbon atoms. C1. -C12 alkoxy is preferably C1-C8 alkoxy, more preferably C1-C6 alkoxy, C1-C8 alkoxy is C1-C8 alkoxy, C1-C6 alkoxy is carbon It represents an alkoxy having a number of 1 to 6. Specific examples of C1 to C12 alkoxy, C1 to C8 alkoxy and C1 to C6 alkoxy include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group. Tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, hept Ruoxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group), C1-C12 alkylphenyl group (C1-C12 alkyl is C1 to C12 alkyl is preferably C1 to C8 alkyl, more preferably C1 to C6 alkyl, and C1 to C8 alkyl is C1 to C8 alkyl. C1-C6 alkyl represents alkyl having 1 to 6 carbon atoms, and specific examples of C1-C12 alkyl, C1-C8 alkyl and C1-C6 alkyl include methyl group, ethyl Group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group Group, 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 Group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group and dodecyl group.), 1-naphthyl group, 2-naphthyl group and pentafluorophenyl group.

The heterocyclic group represented by R ^{1 to} R ¹² is an 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, benzene Thiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine and phenazine And a group obtained by removing one hydrogen atom from a heterocyclic compound. The heterocyclic group is preferably an aromatic heterocyclic group.

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, and a fluorine atom is preferable.

The alkyl group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. Carbon number of an alkyl part is 1-30 normally. The alkyl group may have a substituent other than a halogen atom. Specific examples of the alkyl group which is substituted with one or more halogen atoms and may be substituted with other substituents include a methyl group, an ethyl group, a propyl group, an isopropyl group substituted with a halogen atom, 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, 2-methylpentyl group, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl Chain alkyl group such as a group, cyclopentyl group, cyclohexyl group and adamantyl A cycloalkyl group such as.

The alkyl part of the alkoxy group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. The alkoxy group may have a substituent other than a halogen atom. Carbon number of an alkoxy group is 1-20 normally, and an alkoxy group (for example, C1-C20) is mentioned as a substituent, for example. Specific examples of the alkoxy group substituted with one or more halogen atoms and optionally substituted with other substituents include methoxy group, ethoxy group, propoxy group, isopropoxy group substituted with halogen atom , 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-dimethyloctyl An oxy group and a lauryloxy group are mentioned.

The alkyl portion of the alkylthio group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² may be linear, branched, or cyclic. The alkylthio group may have a substituent other than a halogen atom. Carbon number of an alkylthio group is 1-20 normally. Specific examples of the alkylthio group substituted with one or more halogen atoms and optionally substituted with other substituents include a methylthio group, an ethylthio group, a propylthio group, and an isopropylthio group substituted with a halogen atom. , 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 and A laurylthio group is mentioned.

The aryl group substituted with a halogen atom 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 carbon number is usually 6 to 60. It is. The aryl group may have a substituent other than a halogen atom, and examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryl group which is substituted with one or more halogen atoms and may be substituted with other substituents include a phenyl group substituted with a halogen atom, a C1 to C12 alkoxyphenyl group (C1 C12 alkoxy indicates alkoxy having 1 to 12 carbon atoms, C1 to C12 alkoxy is preferably C1 to C8 alkoxy, more preferably C1 to C6 alkoxy, and C1 to C8 alkoxy is carbon number. C1-C6 alkoxy is C1-C6 alkoxy, and specific examples of C1-C12 alkoxy, C1-C8 alkoxy and C1-C6 alkoxy are as follows: And those exemplified and exemplified above for the alkoxy group, and the same shall apply hereinafter.), C1-C12 alkylpheny The group (C1-C12 alkyl indicates alkyl having 1 to 12 carbon atoms. C1-C12 alkyl is preferably C1-C8 alkyl, more preferably C1-C6 alkyl. C1-C8 alkyl. Represents an alkyl having 1 to 8 carbon atoms, and C1 to C6 alkyl represents an alkyl having 1 to 6 carbon atoms.Specific examples of C1 to C12 alkyl, C1 to C8 alkyl, and C1 to C6 alkyl Examples include those described and exemplified above for the alkyl group, and so on.), 1-naphthyl group and 2-naphthyl group.

The aryloxy group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 6 to 60 carbon atoms, and the aryl moiety has a substituent other than a halogen atom. Also good. Examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryloxy group which is substituted with one or more halogen atoms and may be substituted with other substituents include a phenoxy group substituted with a halogen atom, a C1-C12 alkoxyphenoxy group, C1 -C12 alkylphenoxy group, 1-naphthyloxy group, and 2-naphthyloxy group are mentioned.

The arylthio group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent other than a halogen atom. Good. Specific examples of the arylthio group substituted with one or more halogen atoms and optionally substituted with other substituents include a phenylthio group substituted with a halogen atom, a C1-C12 alkoxyphenylthio group, C1 -C12 alkylphenylthio group, 1-naphthylthio group, and 2-naphthylthio group are mentioned.

The arylalkyl group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms, and the aryl moiety has a substituent other than a halogen atom. Also good. Examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkyl group which is substituted with one or more halogen atoms and may be substituted with other substituents include a phenyl-C1 to C12 alkyl group substituted with a halogen atom, and C1 to C12. Examples include alkoxyphenyl-C1-C12 alkyl group, C1-C12 alkylphenyl-C1-C12 alkyl group, 1-naphthyl-C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group.

The arylalkoxy group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms, and the aryl moiety has a substituent other than a halogen atom. Also good. Examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkoxy group substituted with one or more halogen atoms and optionally substituted with other substituents include phenyl-C1 to C12 alkoxy groups substituted with halogen atoms, and C1 to C12. Examples include alkoxyphenyl-C1-C12 alkoxy group, C1-C12 alkylphenyl-C1-C12 alkoxy group, 1-naphthyl-C1-C12 alkoxy group and 2-naphthyl-C1-C12 alkoxy group.

The arylalkylthio group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent other than the halogen atom include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkylthio group which is substituted with one or more halogen atoms and may be substituted with other substituents include phenyl-C1 to C12 alkylthio groups substituted with halogen atoms, C1 to C12 Examples include an alkoxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, a 1-naphthyl-C1-C12 alkylthio group, and a 2-naphthyl-C1-C12 alkylthio group.

The acyl group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² means a group excluding a hydroxyl group in carboxylic acid, and the number of carbon atoms is usually 2-20. Specific examples of the acyl group substituted with one or more halogen atoms include alkyl carbonyl having 2 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group substituted with a halogen atom. Groups, benzoyl groups and phenylcarbonyl groups.

The acyloxy group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² means a group excluding a hydrogen atom in carboxylic acid, and the carbon number thereof is usually 2-20. Specific examples of the acyloxy group substituted with one or more halogen atoms include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group substituted with a halogen atom. It is done.

The amide group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide, and the number of carbon atoms is usually 2 ~ 20. Specific examples of the amide group substituted with one or more halogen atoms include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a diformamide group, a diacetamide group, and a dipropioamide substituted with a halogen atom. Groups, dibutyroamide groups and dibenzamide groups.

The imide group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² is a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an imide (—CO—NH—CO—). Meaning and specific examples include succinimide groups and phthalimide groups substituted with halogen atoms.

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 substituted with a halogen atom and An aryl group. Definitions and specific examples of alkyl groups and aryl groups substituted with halogen atoms include definitions of alkyl groups substituted with halogen atoms represented by R ^{1 to} R ¹² and aryl groups substituted with halogen atoms, and It is the same as a specific example. Carbon number of a substituted amino group is 1-40 normally. Specific examples of the substituted amino group include a methylamino group substituted with a halogen atom, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, an isopropylamino group, a diisopropylamino group, and a butylamino group. 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-dimethyloctyl Amino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenyl Mino group, C1-C12 alkoxyphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group , Pyridylamino group, pyridazinylamino 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, 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-Naphth -C1~C12 include alkylamino groups.

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 substituted with a halogen atom. The definitions and specific examples of the alkyl group and aryl group substituted with a halogen atom are the same as the definitions and specific examples of the alkyl group and aryl group substituted with a halogen atom represented by R ^{1 to} R ¹² . Specific examples of the substituted silyl group include a trimethylsilyl group substituted with a halogen atom, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a tri-p-xylylsilyl group. Group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group and 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 substituted with a halogen atom. , Tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, tert-butyldiphenylsilyloxy group and 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 substituted with a halogen atom. , Tri-p-xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, tert-butyldiphenylsilylthio group and 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 substituted with a halogen atom. , Tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, bis (trimethylsilyl) amino group, bis (triethylsilyl) amino Group, bis (tripropylsilyl) amino group, bis (triisopropylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, bis (triphenylsilyl) amino group, bis (tri-p-xylylsilane) ) Amino group, bis (tribenzylsilyl) amino group, bis (diphenylmethylsilyl) amino group, bis (tert- butyldiphenylsilyl) amino group and bis (dimethylphenylsilyl) and amino group.

Examples of the heterocyclic group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, substituted with a halogen atom. 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, i Quinoline, quinolidine, benzimidazole, benzothiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxati And groups obtained by removing one hydrogen atom from a heterocyclic compound such as in, phenoxazine, phenothiazine, and phenazine. The heterocyclic group is preferably an aromatic heterocyclic group.

〔式（１１）及び式（１２）中、Ａｒ^３は複素環基を表す。〕 Examples of the heterocyclic oxy group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² include a group represented by the formula (11) in which an oxygen atom is bonded to the above heterocyclic group. . Examples of the heterocyclic thio group include a group represented by the formula (12) in which a sulfur atom is bonded to the above heterocyclic group.

[In Formula (11) and Formula (12), Ar ³ represents a heterocyclic group. ]

  The heterocyclic oxy group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic oxy group substituted with one or more halogen atoms include thienyloxy groups substituted with halogen atoms, C1-C12 alkylthienyloxy groups, pyrrolyloxy groups, furyloxy groups, pyridyloxy groups, C1. -C12 alkyl pyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyloxy group, oxazolyloxy group, thiazoleoxy group and thiadiazoleoxy group are mentioned.

  The heterocyclic thio group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic thio group substituted with one or more halogen atoms include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group substituted with halogen atom. C1-C12 alkylpyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group, triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

The arylalkenyl group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 8 to 20 carbon atoms, and the aryl moiety has a substituent other than a halogen atom. May be. Examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples include a styryl group substituted with a halogen atom.

The arylalkynyl group substituted with one or more halogen atoms represented by R ^{1 to} R ¹² usually has 8 to 20 carbon atoms, and the aryl moiety has a substituent other than a halogen atom. May be. Examples of the substituent include an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples include a phenylacetylenyl group substituted with a halogen atom.

-(X) n- in formula (1), when n is 1, X is preferably -C (R ¹ ) (R ² )-or -Si (R ³ ) (R ⁴ )- More preferably, it is —C (R ¹ ) (R ² ) —. In terms of-(X) n- in formula (1), n is preferably 2 or more, and n is 2 from the viewpoint of increasing the open-circuit voltage of the organic thin-film solar cell containing the polymer compound of the present invention. It is more preferable.

When n is 2 or more,-(X) n- in formula (1) is -O-, -S-, -Se-, -C (= O)-, -C (= S)-, One or more selected from the group consisting of —S (═O) — and —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 It is more preferable to include at least one selected from the group consisting of-)-and -B (R ¹² )-(wherein R ^{1 to} R ¹² represent the same meaning as described above).

When n is 2, it is preferable that at least one of the two Xs is —C (R ¹ ) (R ² ) —. When n is 2 and one of two Xs is —C (R ¹ ) (R ² ) —, the other is preferably —O— or —C (═O) —, and is —O—. Is more preferable. At this time, R ^{1 to} R ¹² are preferably aromatic carbocyclic groups or heterocyclic groups, and R ¹ and R ² are more preferably aromatic carbocyclic rings.

  -(X) n- preferably contains three or more halogen atoms from the viewpoint of increasing the open-circuit voltage of the organic thin-film solar cell containing the polymer compound of the present invention.

  The halogen atom contained in-(X) n- includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a fluorine atom.

  Examples of-(X) n- include groups represented by the following formulas (21) to (40).

  Among these, as-(X) n-, Formula (29) and Formula (30) are preferable.

The trivalent heterocyclic group represented by Ar ¹ and Ar ² refers to the remaining atomic group obtained by removing three hydrogen atoms from 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. .

  Among the trivalent heterocyclic groups, a trivalent aromatic heterocyclic group is preferable from the viewpoint of increasing the open-circuit voltage of the organic thin film solar cell containing the polymer compound of the present invention. The trivalent aromatic heterocyclic group means an atomic group remaining after removing three hydrogen atoms on an aromatic ring from a heterocyclic compound having aromaticity. Carbon number which a trivalent aromatic heterocyclic group has is 2-60 normally, Preferably it is 4-60, More preferably, it is 4-20.

Examples of the substituent represented by R that the heterocyclic compound having aromaticity may have include a halogen atom and a monovalent group. Examples of monovalent groups include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, imide groups, Amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, arylalkynyl group, carboxyl group and cyano group Is given. As these monovalent groups, the same monovalent groups as exemplified in the alkyl group described in the description of R ^{1 to} R ¹² can be used, and further, the alkyl described in the description of R ^{1 to} R ¹² can be used. A substituent obtained by substituting a halogen atom of a monovalent group exemplified as a group with a hydrogen atom may be used.

  Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

  Examples of the trivalent aromatic heterocyclic group include groups represented by formula (101) to formula (201).

The trivalent aromatic carbocyclic group represented by Ar ¹ and Ar ² is the remaining atomic group obtained by removing three hydrogen atoms on the aromatic ring from the aromatic hydrocarbon which may have a substituent. Say. The carbon number of the trivalent aromatic carbocyclic group is usually 6 to 60, preferably 6 to 20. Aromatic hydrocarbons include compounds containing a benzene ring, compounds containing a condensed ring, compounds containing a structure in which two or more independent benzene rings or two or more condensed rings are directly bonded, and two or more independent benzene rings or condensed rings are vinylene. Also included are compounds bonded through groups such as

  The substituent represented by R that the aromatic hydrocarbon may have represents, for example, a halogen atom or a monovalent group. Specific examples of the halogen atom and monovalent group are the same as the specific examples of the halogen atom and monovalent group represented by R.

  Examples of the trivalent aromatic carbocyclic group include groups represented by the following formulas (202) to (211).

  As the trivalent heterocyclic group and the trivalent aromatic carbocyclic group, among the formulas (101) to (211), from the viewpoint of ease of synthesis of the monomer that is a raw material of the polymer compound of the present invention. , Formula (102), formula (105), formula (106), formula (107), formula (110), formula (112), formula (120), formula (135), formula (138), formula (170) , Formula (171), Formula (172), Formula (173), Formula (174), Formula (175), Formula (186), Formula (187), Formula (188), Formula (191), Formula (192) , Formula (193), formula (196), groups represented by formula (201) and formula (202) are preferable, and formula (135), formula (171), formula (172), formula (173), formula ( 174), formula (186), formula (191), formula (196), formula (201) and group represented by formula (202) More preferably, the formula (171), formula (172), formula (173), group is more preferably represented by the formula (174) and (211), a group represented by the formula (173) is particularly preferred.

Examples of combinations of Ar ¹ and Ar ² include, for example, Formula (173) and Formula (101), Formula (173) and Formula (107), Formula (173) and Formula (109), Formula (173) and Formula (165). ), Formula (173) and Formula (166), Formula (173) and Formula (167), Formula (173) and Formula (168), Formula (173) and Formula (169), Formula (173) and Formula (170) ), Formula (173) and Formula (171), Formula (173) and Formula (172), Formula (173) and Formula (173), Formula (173) and Formula (174), Formula (173) and Formula (175) ), Formula (173) and Formula (186), Formula (173) and Formula (187), Formula (173) and Formula (188), Formula (173) and Formula (201), Formula (173) and Formula (202) ), And among these, Formula (173), Formula (170), Formula (173) and (171), Formula (173) and Formula (172), Formula (173) and Formula (173), Formula (173) and Formula (174), Formula (173) and Formula (175), Formula (173) and Formula (186), Formula (173) and Formula (187), Formula (173) and Formula (188), Formula (173) and Formula (201), Formula (173) and Formula (202) are preferable.

From the viewpoint of increasing the open-circuit voltage of the organic thin-film solar cell including the polymer compound of the present invention, it is preferable that at least one of Ar ¹ and Ar ^{2 includes} a 5-membered ring or a 5-membered ring structure. Examples of such a group include Formula (165), Formula (166), Formula (167), Formula (168), Formula (169), Formula (170), Formula (171), Formula (172), Formula (173). ), Formula (174), formula (175), formula (176), formula (177), formula (178), 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), formula (192), formula (193) ), Formula (194), Formula (195), Formula (196), Formula (197), Formula (198), Formula (199), Formula (200), and Formula (201) are preferable.

From the viewpoint of increasing the open-circuit voltage of the organic thin-film solar cell containing the polymer compound of the present invention, at least one of Ar ¹ and Ar ² is more preferably a group obtained by removing three hydrogen atoms from the thiophene ring, Formula (168), formula (173), and formula (201) are preferable.

  Examples of the structural unit represented by the formula (1) include structural units represented by the following formulas (301) to (404).

Among the structural units represented by the above formulas (301) to (404), from the viewpoint of ease of synthesis of a monomer that is a raw material of the polymer compound of the present invention, formulas (301) to (305) The structural units represented by formula (313) to formula (319), formula (333) to formula (356), and formula (365) to formula (388) are preferred, and formula (333) to formula (356) and formula (365) to the structural unit represented by formula (388) are more preferred, and structural units represented by formula (333) to formula (356) and formula (365) to formula (376) are more preferred. ), Structural units represented by formula (370) and formula (374) are particularly preferred.

  The polymer 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 polymer compound of the present invention includes a structural unit different from the structural unit represented by the formula (1), the structural unit represented by the formula (1) is different from the structural unit represented by the formula (1). It is preferable that the structural unit forms 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^４は、アリーレン基又は２価の複素環基を表す。ただし、Ａｒ^４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 the structural unit represented by the formula (2).

(In the formula, Ar ⁴ represents an arylene group or a divalent heterocyclic group. However, Ar ⁴ is different from the structural unit represented by the formula (1).)

The arylene group represented by Ar ⁴ is an atomic group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The carbon number of the arylene group is usually about 6 to 60, preferably 6 to 20.

  The substituent that the aromatic hydrocarbon may have represents, for example, a halogen atom or a monovalent group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the monovalent group are the same as the specific examples of the monovalent group represented by R.

  The structural unit represented by the formula (2) is represented by the formula (Cy-1) to the formula (Cy-5) from the viewpoint of increasing the photoelectric conversion efficiency of the organic thin film solar cell containing the polymer compound of the present invention. The structural unit is preferred.

（式（Ｃｙ−１）〜（Ｃｙ−５）中、Ｒはそれぞれ独立に、水素原子、ハロゲン原子又は１価の基を表す。１ユニット中のＲは同一でも相異なっていてもよい。Ｒは、連結して環状構造を形成してもよい。環Ｃｙは、同一又は相異なり、置換基を有していてもよい芳香環を表す。Ｒ^'は、２価の基を表す。）

(In the formulas (Cy-1) to (Cy-5), each R independently represents a hydrogen atom, a halogen atom or a monovalent group. The R in one unit may be the same or different. May be linked to form a cyclic structure. Rings Cy are the same or different and each represents an optionally substituted aromatic ring. R ^′ represents a divalent group.)

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

  Specific examples of the monovalent group represented by R are the same as the specific examples of the monovalent group represented by R described above.

（式（Ｄ−１）〜式（Ｄ−５）中、Ｒは、前述と同じ意味を表す。） R may be linked to form a cyclic structure. Specific examples of the cyclic structure include structures represented by formula (D-1) to formula (D-5).

(In formula (D-1) to formula (D-5), R represents the same meaning as described above.)

  The aromatic ring represented by the ring Cy may be a single ring or a condensed ring. Examples of the aromatic ring that is a single ring include a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, an oxazole ring, a thiazole ring, a thiadiazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, an imidazole ring, a triazole ring, and an isoxazole ring. , Isothiazole ring, pyrimidine ring, pyridazine ring and triazine ring.

  As an aromatic ring which is a condensed ring, an aromatic ring obtained by condensing an arbitrary ring to the above-mentioned single ring can be mentioned. Examples of the ring condensed with a single ring include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiadiazole ring, imidazole ring, imidazoline ring, and imidazole. Lysine ring, pyrazole ring, pyrazoline ring, prazolidine ring, furazane ring, triazole ring, thiadiazole ring, oxadiazole ring, tetrazole ring, pyran ring, pyridine ring, piperidine ring, thiopyran ring, lidazine ring, pyrimidine ring, pyrazine ring, Piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chromane, isochroman, Zopyran ring, quinoline ring, isoquinoline ring, quinolidine ring, benzimidazole ring, benzothiazole ring, indazole ring, naphthyridine ring, quinoxaline ring, quinazoline ring, quinazolidine ring, cinnoline ring, phthalazine ring, purine ring, pteridine ring, carbazole ring, Examples include xanthene ring, phenanthridine ring, acridine ring, β-carboline ring, perimidine ring, phenanthroline ring, thianthrene ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring and phenazine ring.

  In the ring Cy, examples of the substituent that the aromatic ring may have include a halogen atom and a monovalent group. Specific examples of the halogen atom and monovalent group are the same as the specific examples of the halogen atom and monovalent group represented by R.

（式（ｂ−１）〜式（ｂ−５）中、Ｒは、前述と同じ意味を表す。） Specific examples of the divalent group represented by R ^′ include groups represented by formula (b-1) to formula (b-5).

(In formula (b-1) to formula (b-5), R represents the same meaning as described above.)

  As a structural unit represented by Formula (Cy-1)-Formula (Cy-5), the structural unit represented by the following formula (C-1)-Formula (C-29) is mentioned, for example.

（式（Ｃ−１）〜式（Ｃ−２９）中、Ｒは前述と同じ意味を表す。）

(In formula (C-1) to formula (C-29), R represents the same meaning as described above.)

As the structural unit represented by Formula (C-15), a structural unit represented by Formula (C-30) or a structural unit represented by Formula (C-31) is preferable.

  The polymer compound in the present invention refers to a compound having a weight average molecular weight of 1,000 or more. The weight average molecular weight of the polymer compound of the present invention is preferably 3,000 to 10,000,000. If the weight average molecular weight is lower than 3,000, defects may occur in the film formed during device fabrication, and if it exceeds 10,000,000, the solubility in a solvent and the coating property during device fabrication may be degraded. is there. The weight average molecular weight of the polymer compound is more preferably 4,000 to 5,000,000, and particularly preferably 5,000 to 1,000,000. The weight average molecular weight in the present invention refers to a weight average molecular weight in terms of polystyrene calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).

  The structural unit represented by Formula (1) should just be contained at least 1 in the high molecular compound of this invention. It is preferable that an average of 2 or more per polymer chain is included, and an average of 3 or more per polymer chain is more preferable.

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

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

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

As a method using Suzuki coupling reaction, for example, the formula (500):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (500)
Wherein, E ¹ represents a structural unit represented by the formula (II). Q ¹⁰⁰ and Q ²⁰⁰ are the same or different and 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 the process of making the 1 or more types of compound represented by these react with 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 polymer compound, a bromine atom or an iodine atom is preferable, and a bromine atom is more preferable.

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

  Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium are mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, dichlorobis (Triphenylphosphine) palladium, palladium acetate and tris (dibenzylideneacetone) dipalladium are preferred. The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (500). Yes, preferably 0.0003 mol to 0.1 mol.

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

Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide, and potassium phosphate. Examples of the organic base include triethylamine and tributylamine. An example of the inorganic salt is cesium fluoride.
The addition amount of the base is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol, relative to 1 mol of the compound represented by the formula (500). -10 mol.

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

  The temperature at which the Suzuki coupling reaction is performed depends on the solvent, but is usually about 40 to 160 ° C. From the viewpoint of increasing the molecular weight of the polymer compound, 60 to 120 ° C. is preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 0.5 to 30 hours is efficient and preferable.

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

As a method using Stille coupling reaction, for example, Formula (700):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (700)
Wherein, ^{E 3} represents a structural unit represented by the formula (II). Q ³⁰⁰ and Q ⁴⁰⁰ are the same or different and 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 polymer compound, a bromine atom and an iodine atom are preferable.

Specifically, examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst. Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specific examples include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium. Palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable from the viewpoints of easy reaction (polymerization) operation and reaction (polymerization) rate.
The addition amount of the palladium catalyst used for the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (100). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.

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

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

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

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

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

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

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

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

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

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

  The lower limit of the reaction temperature of the aryl coupling reaction is preferably −100 ° C., more preferably −20 ° C., and 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 the stability of the monomer and the polymer compound.

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

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

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

The number average molecular weight in terms of polystyrene of the polymer compound 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.

  The polymer compound of the present invention has a structural unit represented by the formula (1), and the polymer compound is, for example, a compound represented by the following formula (13) as one of the raw materials. It can be synthesized by using as

In formula (13), R ¹ and R ² represent 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 the formula (13) in which W is a hydrogen atom is used, a polymer compound having a structural unit represented by the 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.). Further, by using a copper / amine catalyst system (J. Org. Chem. 1999, 64, 2264., J. Polym. Sci. Part A, Polym. Chem. 1999, 37, 3702.) Can be increased.

  As the solvent in the oxidative polymerization, any solvent that does not cause poisoning of the catalyst can be used without particular limitation. Examples of 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 polymer compound of the present invention is a copolymer, as a method for producing the copolymer, a method in which two or more monomers are mixed and polymerized, one monomer is polymerized, and then the second monomer is added. The method of doing is mentioned. 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 (13) 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 the formula (13) is a hydrogen atom, a known method can be used as a method for converting W in the compound represented by the formula (13) into a bromine atom. Is, for example, a method in which bromine or N-bromosuccinimide (NBS) is contacted with a compound represented by the formula (13) in which W is a hydrogen atom and brominated. 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 (13) in which W is a hydrogen atom. After the reaction, for example, after adding water to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as distilling off the solvent, and represented by the formula (13) in which W is a bromine atom. Can be obtained. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

  As a compound represented by Formula (13), the following compounds are mentioned, for example.

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

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

  Since the polymer compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, an organic photoelectric conversion element manufactured using the polymer compound of the present invention has a short-circuit current. Density increases. Moreover, the high molecular compound of this invention can obtain a big open end voltage.

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

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

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

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

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

Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive materials, NESA, gold, platinum, silver, Copper is used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
As the electrode material, an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.

  One electrode may not be transparent, and a metal, a conductive polymer, etc. can be used as an electrode material of the electrode. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, 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 polymer compound of the present invention alone or in combination of two or more. In order to enhance the hole transport property of the active layer, compounds other than the polymer compound of the present invention can be mixed and used as the electron donating compound and / or the electron accepting compound in the active layer. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

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

As the electron-accepting compound, in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof Derivatives, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof Derivatives, polyfluorenes and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerenes and fullerene derivatives Details, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, 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 active layer contains the polymer compound of the present invention and the fullerene derivative, the amount of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is -500 weight part.

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

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

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

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

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Application methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, capillary coating, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet coating method, and a spin coating method are preferable.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

<Organic transistor>
The polymer compound of the present invention can also be used for organic thin film transistors. The organic thin film transistor has a configuration including a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The organic semiconductor layer is constituted by the organic thin film described above. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

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

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

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

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

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

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

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

In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
In addition, when used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface. In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. A module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 can also be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

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

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

(Measurement of number average molecular weight and weight average molecular weight)
Regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer 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１００ｍＬ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２．３５ｇ（１１．３ｍｍｏｌ）と脱水テトラヒドロフランを８０ｍＬ入れて均一な溶液とした。フラスコを−２０℃に保ちながら、反応液に事前に調整した１．０Ｍの４，４，４−トリフルオロブチルマグネシウムブロマイドのテトラヒドロフラン溶液を２６．０ｍＬ（２６．０ｍｍｏｌ）加えた。その後、３０分かけて温度を−５℃まで上げ、そのままの温度で反応液を３０分攪拌した。その後、１０分かけて温度を０℃に上げ、そのままの温度で反応液を１．５時間攪拌した。その後、反応液に水を加えて反応を停止し、酢酸を加えて溶液を弱酸性にした後に、酢酸エチルを加え、反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液の溶媒を留去し、化合物２の粗体を得た。 Synthesis example 1
(Synthesis of Compound 2)

In a 100 mL three-necked flask in which the gas in the flask was replaced with nitrogen, 2.35 g (11.3 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 80 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. While maintaining the flask at −20 ° C., 26.0 mL (26.0 mmol) of 1.0 M 4,4,4-trifluorobutylmagnesium bromide tetrahydrofuran solution prepared in advance was added to the reaction solution. Thereafter, the temperature was raised to −5 ° C. over 30 minutes, and the reaction solution was stirred at the same temperature for 30 minutes. Thereafter, the temperature was raised to 0 ° C. over 10 minutes, and the reaction solution was stirred at the same temperature for 1.5 hours. Thereafter, water was added to the reaction solution to stop the reaction, and acetic acid was added to make the solution weakly acidic. Then, ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer which is an ethyl acetate solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent of the filtrate was distilled off to obtain a crude compound 2.

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物２の粗体、トルエンを１００ｍＬ入れて均一な溶液とした。該溶液にｐ−トルエンスルホン酸ナトリウム１水和物を０．３６５ｇ（１．９２ｍｍｏｌ）入れて１２０℃で２時間攪拌を行った。反応液を室温（２５℃）まで冷却後、水５０ｍＬを加え、さらにトルエンを加えて反応生成物を含む有機層を抽出した。トルエン溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、溶媒を留去した。得られた粗生成物を、展開溶媒がヘキサンであるシリカゲルカラムで生成し、化合物３を４．０８ｇ（９．８４ｍｍｏｌ）得た。 Synthesis example 2
(Synthesis of Compound 3)

In a 300 mL flask in which the gas in the flask was replaced with nitrogen, 100 mL of the crude compound 2 and toluene were added to obtain a uniform solution. 0.365 g (1.92 mmol) of sodium p-toluenesulfonate monohydrate was added to the solution and stirred at 120 ° C. for 2 hours. After cooling the reaction solution to room temperature (25 ° C.), 50 mL of water was added, and toluene was further added to extract the organic layer containing the reaction product. The organic layer which is a toluene solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent was distilled off. The obtained crude product was produced on a silica gel column whose developing solvent was hexane, and 4.08 g (9.84 mmol) of Compound 3 was obtained.

¹ H NMR (CDCl ₃ ): δ1.58-1.76 (m, 4H), 1.92-2.13 (m, 8H), 6.67 (d, 1H), 6.69 (d, 1H), 7.01 (d, 1H), 7.09 (d, 1H).

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物３を３．５５ｇ(８．５６ ｍｍｏｌ)、脱水テトラヒドロフランを１８０ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液を１２．３ｍＬ（１９．７ｍｍｏｌ）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（２５℃）で２．５時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを６．９６ｇ（２１．４ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水１００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ５ｗｔ％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４を７．１８ｇ（７．２３ｍｍｏｌ）得た。 Synthesis example 3
(Synthesis of Compound 4)

A 300 mL flask in which the gas in the flask was replaced with nitrogen was charged with 3.55 g (8.56 mmol) of Compound 3 and 180 mL of dehydrated tetrahydrofuran to obtain a uniform solution. The solution was maintained at −78 ° C., and 1.6 M n-butyllithium hexane solution (12.3 mL, 19.7 mmol) was added dropwise to the solution over 10 minutes. After the dropping, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2.5 hours. Thereafter, the flask was cooled to −78 ° C., and 6.96 g (21.4 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 100 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, the organic layer was filtered, the filtrate was concentrated with an evaporator, and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 7.18 g (7.23 mmol) of compound 4 was obtained.

¹ H NMR (CDCl ₃ ): δ 0.90 (m, 18H), 1.07-2.10 (m, 48H), 6.66 (s, 1H), 6.70 (s, 1H).

フラスコ内の気体を窒素で置換した３００ｍＬ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４．１７ｇ（２０．０ｍｍｏｌ）と脱水テトラヒドロフランを２００ｍＬ入れて均一な溶液とした。フラスコを−２０℃に保ちながら、反応液に事前に調整した１．０Ｍの４−プロピルフェニルマグネシウムブロマイドのテトラヒドロフラン溶液を５０．０ｍＬ（５０．０ｍｍｏｌ）加えた。その後、３０分かけて温度を−５℃まで上げ、そのままの温度で反応液を３０分攪拌した。その後、１０分かけて温度を０℃に上げ、そのままの温度で反応液を１．５時間攪拌した。その後、反応液に水を加えて反応を停止し、酢酸を加えて溶液を弱酸性にした後に、酢酸エチルを加え、反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液の溶媒を留去し、化合物５の粗体を得た。 Synthesis example 4
(Synthesis of Compound 5)

To a 300 mL three-necked flask in which the gas in the flask was replaced with nitrogen, 4.17 g (20.0 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 200 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. While maintaining the flask at −20 ° C., 50.0 mL (50.0 mmol) of a 1.0 M 4-propylphenylmagnesium bromide tetrahydrofuran solution prepared in advance was added to the reaction solution. Thereafter, the temperature was raised to −5 ° C. over 30 minutes, and the reaction solution was stirred at the same temperature for 30 minutes. Thereafter, the temperature was raised to 0 ° C. over 10 minutes, and the reaction solution was stirred at the same temperature for 1.5 hours. Thereafter, water was added to the reaction solution to stop the reaction, and acetic acid was added to make the solution weakly acidic. Then, ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer which is an ethyl acetate solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent of the filtrate was distilled off to obtain a crude product of compound 5.

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物５の粗体、トルエンを１００ｍＬ入れて均一な溶液とした。該溶液にｐ−トルエンスルホン酸ナトリウム１水和物を０．６５ｇ（３．４０ｍｍｏｌ）入れて１２０℃で２時間攪拌を行った。反応液を室温（２５℃）まで冷却後、水５０ｍＬを加え、さらにトルエンを加えて反応生成物を含む有機層を抽出した。トルエン溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、溶媒を留去した。得られた粗生成物を、展開溶媒がヘキサンであるシリカゲルカラムで生成し、化合物６を３．４０ｇ（１５．８ｍｍｏｌ）得た。 Synthesis example 5
(Synthesis of Compound 6)

In a 300 mL flask in which the gas in the flask was replaced with nitrogen, 100 mL of the crude compound 5 and toluene were added to obtain a uniform solution. To this solution, 0.65 g (3.40 mmol) of sodium p-toluenesulfonate monohydrate was added and stirred at 120 ° C. for 2 hours. After cooling the reaction solution to room temperature (25 ° C.), 50 mL of water was added, and toluene was further added to extract the organic layer containing the reaction product. The organic layer which is a toluene solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent was distilled off. The obtained crude product was produced on a silica gel column whose developing solvent was hexane, and 3.40 g (15.8 mmol) of Compound 6 was obtained.

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物６を３．２３ｇ(７．５０ ｍｍｏｌ)、脱水テトラヒドロフランを１２０ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液を１０．８ｍＬ（１７．３ｍｍｏｌ）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（２５℃）で２．５時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを６．１０ｇ（１８．７ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水１００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ５ｗｔ％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７を６．０４ｇ（５．９８ｍｍｏｌ）得た。 Synthesis Example 6
(Synthesis of Compound 7)

A 300 mL flask in which the gas in the flask was replaced with nitrogen was charged with 3.23 g (7.50 mmol) of Compound 6 and 120 mL of dehydrated tetrahydrofuran to obtain a uniform solution. The solution was kept at −78 ° C., and 10.8 mL (17.3 mmol) of 1.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After the dropping, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2.5 hours. Thereafter, the flask was cooled to −78 ° C., and 6.10 g (18.7 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 100 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, the organic layer was filtered, the filtrate was concentrated with an evaporator, and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 6.04 g (5.98 mmol) of Compound 7 was obtained.

フラスコ内の気体を窒素で置換した３００ｍＬ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３．１２ｇ（１５．０ｍｍｏｌ）と脱水テトラヒドロフランを１５０ｍＬ入れて均一な溶液とした。フラスコを−２０℃に保ちながら、反応液に事前に調整した１．０Ｍの４−トリフルオロメチルフェニルマグネシウムブロマイドのテトラヒドロフラン溶液を４５．０ｍＬ（４５．０ｍｍｏｌ）加えた。その後、３０分かけて温度を−５℃まで上げ、そのままの温度で反応液を３０分攪拌した。その後、１０分かけて温度を０℃に上げ、そのままの温度で反応液を１．５時間攪拌した。その後、反応液に水を加えて反応を停止し、酢酸を加えて溶液を弱酸性にした後に、酢酸エチルを加え、反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液の溶媒を留去し、化合物８の粗体を得た。 Synthesis example 7
(Synthesis of Compound 8)

A 300 mL three-necked flask in which the gas in the flask was replaced with nitrogen was charged with 3.12 g (15.0 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 150 mL of dehydrated tetrahydrofuran to obtain a uniform solution. While maintaining the flask at −20 ° C., 45.0 mL (45.0 mmol) of 1.0 M 4-trifluoromethylphenylmagnesium bromide tetrahydrofuran solution prepared in advance was added to the reaction solution. Thereafter, the temperature was raised to −5 ° C. over 30 minutes, and the reaction solution was stirred at the same temperature for 30 minutes. Thereafter, the temperature was raised to 0 ° C. over 10 minutes, and the reaction solution was stirred at the same temperature for 1.5 hours. Thereafter, water was added to the reaction solution to stop the reaction, and acetic acid was added to make the solution weakly acidic. Then, ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, the organic layer was filtered, and then the solvent of the filtrate was distilled off to obtain a crude product of compound 8.

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物８の粗体、トルエンを１００ｍＬ入れて均一な溶液とした。該溶液にｐ−トルエンスルホン酸ナトリウム１水和物を０．４９０ｇ（２．６０ｍｍｏｌ）入れて１２０℃で２時間攪拌を行った。反応液を室温（２５℃）まで冷却後、水５０ｍＬを加え、さらにトルエンを加えて反応生成物を含む有機層を抽出した。トルエン溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、溶媒を留去した。得られた粗生成物を、展開溶媒がヘキサンであるシリカゲルカラムで生成し、化合物９を５．６０ｇ（１１．６ｍｍｏｌ）得た。 Synthesis example 8
(Synthesis of Compound 9)

In a 300 mL flask in which the gas in the flask was replaced with nitrogen, 100 mL of the crude compound 8 and toluene were added to obtain a uniform solution. 0.490 g (2.60 mmol) of sodium p-toluenesulfonate monohydrate was added to the solution, and the mixture was stirred at 120 ° C. for 2 hours. After cooling the reaction solution to room temperature (25 ° C.), 50 mL of water was added, and toluene was further added to extract the organic layer containing the reaction product. The organic layer which is a toluene solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent was distilled off. The obtained crude product was produced on a silica gel column whose developing solvent was hexane, and 5.60 g (11.6 mmol) of Compound 9 was obtained.

¹ H NMR (CDCl ₃ ): δ6.45 (d, 1H), 6.78 (d, 1H), 7.03 (d, 1H), 7.10 (d, 1H), 7.40 (d, 4H), 7.58 (d, 4H ).

フラスコ内の気体を窒素で置換した３００ｍＬフラスコに、化合物９を２．４１ｇ(５．００ ｍｍｏｌ)、脱水テトラヒドロフランを９０ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液を７．１９ｍＬ（７．１９ｍｍｏｌ）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（２５℃）で２．５時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを４．０７ｇ（１２．５ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水１００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ５ｗｔ％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１０を１．６３ｇ（１．５３ｍｍｏｌ）得た。 Synthesis Example 9
(Synthesis of Compound 10)

In a 300 mL flask in which the gas in the flask was replaced with nitrogen, 2.41 g (5.00 mmol) of Compound 9 and 90 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. The solution was kept at −78 ° C., and 7.19 mL (7.19 mmol) of a 1.6 M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After the dropping, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2.5 hours. Thereafter, the flask was cooled to −78 ° C., and 4.07 g (12.5 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 100 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, the organic layer was filtered, the filtrate was concentrated with an evaporator, and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 1.63 g (1.53 mmol) of Compound 10 was obtained.

¹ H NMR (CDCl ₃ ): δ0.85 (m, 18H), 1.03-1.56 (m, 36H), 6.40 (d, 1H), 6.80 (d, 1H), 7.39 (d, 4H), 7.56 (d , 4H).

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、化合物１１を１．７８ｇ（１０．０ｍｍｏｌ)、２−エチルヘキシルブロミドを５．８３ｇ（２５．０ｍｍｏｌ)、ヨウ化カリウムを４１．５ｍｇ（０．２５ｍｍｏｌ)、水酸化カリウムを１．６８ｇ（３０．０ｍｍｏｌ)入れ、ジメチルスルホキシド３５ｍＬに溶解させて、室温（２５℃）で２４時間攪拌した。反応後、水１００ｍＬを加え、ヘキサンで生成物を抽出し、ヘキサンを展開溶媒に用いたシリカゲルカラムで精製を行い、化合物１２を２．６１ｇ得た。 Synthesis Example 10
(Synthesis of Compound 12)

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.78 g (10.0 mmol) of Compound 11, 5.83 g (25.0 mmol) of 2-ethylhexyl bromide, and 41.5 mg (0.25 mmol) of potassium iodide. ), 1.68 g (30.0 mmol) of potassium hydroxide was dissolved in 35 mL of dimethyl sulfoxide and stirred at room temperature (25 ° C.) for 24 hours. After the reaction, 100 mL of water was added, the product was extracted with hexane, and purified with a silica gel column using hexane as a developing solvent, to obtain 2.61 g of Compound 12.

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、化合物１２を１．３１ｇ（３．２５ｍｍｏｌ)、及び、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を２５ｍＬ加えた。その後、フラスコを０℃に冷却して、Ｎ−ブロモスクシンイミド（ＮＢＳ）を１．２１ｇ加え、１２時間攪拌した。反応液中に水１００ｍＬを入れて反応を停止し、エーテルで生成物を抽出した。展開溶媒にヘキサンを用いたシリカゲルカラムで生成物の精製を行い、化合物１３を１．７０ｇ得た。 Synthesis Example 11
(Synthesis of Compound 13)

To a 200 mL flask in which the gas in the flask was replaced with argon, 1.31 g (3.25 mmol) of Compound 12 and 25 mL of N, N-dimethylformamide (DMF) were added. Thereafter, the flask was cooled to 0 ° C., 1.21 g of N-bromosuccinimide (NBS) was added, and the mixture was stirred for 12 hours. The reaction was stopped by adding 100 mL of water to the reaction solution, and the product was extracted with ether. The product was purified by a silica gel column using hexane as a developing solvent, and 1.70 g of Compound 13 was obtained.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物４を１９８ｍｇ（０．２００ｍｍｏｌ）、Organic Electronics 2010, 11, 1740.に記載の合成法で合成した化合物１４を１０８ｍｇ（０．２００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを５．５ｍｇ（０．０１８ｍｍｏｌ）、脱水トルエン１６ｍＬ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２．７ｍｇ（０．００３０ｍｍｏｌ）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３７０ｍｇ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２００ｍＬと濃塩酸２０ｍＬ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８ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１７ｇと水２．０ｍＬ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５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬ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８ｍＬ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８３ｍｇ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, 198 mg (0.200 mmol) of compound 4 and 108 mg (0.200 mmol) of compound 14 synthesized by the synthesis method described in Organic Electronics 2010, 11, 1740. 5.5 mg (0.018 mmol) of (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 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 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 8 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 then 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１００ｍＬフラスコに、化合物７を１３４ｍｇ（０．１３３ｍｍｏｌ）、化合物１４を７１．６ｍｇ（０．１３３ｍｍｏｌ）、トリス(２−トリル)ホスフィンを３．６ｍｇ（０．０１２ｍｍｏｌ）、脱水トルエン１１ｍＬ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１．８ｍｇ（０．００２０ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で１．５時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５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２００ｍＬと濃塩酸２０ｍＬ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、アセトンおよ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、トルエン６ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１１ｇと水１．０ｍＬを加え、９０℃で２．５時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬ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トルエン５ｍＬ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７１ｍｇを得た。以下、この重合体を高分子化合物Ｂと呼称する。ＧＰＣで測定した高分子化合物Ｂの分子量（ポリスチレン換算）はＭｎ＝３５１００、Ｍｗ＝３１１７００であった。 Example 2
(Synthesis of polymer compound B)

In a 100 mL flask in which the gas in the flask was replaced with argon, 134 mg (0.133 mmol) of compound 7, 71.6 mg (0.133 mmol) of compound 14, and 3.6 mg (0.012 mmol) of tris (2-tolyl) phosphine ), 11 mL of dehydrated toluene was added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 1.8 mg (0.0020 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 1.5 hours. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 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 6 mL of toluene, 0.11 g of sodium diethyldithiocarbamate and 1.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2.5 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 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene 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 71 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound B. The molecular weight (polystyrene conversion) of the high molecular compound B measured by GPC was Mn = 35100 and Mw = 311700.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１０を２１２ｍｇ（０．２００ｍｍｏｌ）、化合物１４を１０８ｍｇ（０．２００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを５．５ｍｇ（０．０１８ｍｍｏｌ）、脱水トルエン１７ｍＬ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２．７ｍｇ（０．００３０ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で１．５時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５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２００ｍＬと濃塩酸２０ｍＬ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、アセトンおよ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９ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１７ｇと水２．０ｍＬを加え、９０℃で２．５時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬ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トルエン５ｍＬ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９３ｍｇを得た。以下、この重合体を高分子化合物Ｃと呼称する。ＧＰＣで測定した高分子化合物Ｃの分子量（ポリスチレン換算）はＭｎ＝２８６００、Ｍｗ＝１１２２００であった。 Example 3
(Synthesis of polymer compound C)

In a 100 mL flask in which the gas in the flask was replaced with argon, 212 mg (0.200 mmol) of compound 10, 108 mg (0.200 mmol) of compound 14, 5.5 mg (0.018 mmol) of tris (2-tolyl) phosphine, 17 mL of dehydrated toluene was added to make 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 1.5 hours. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 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 9 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 2.5 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 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 93 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound C. The molecular weight (polystyrene conversion) of the high molecular compound C measured by GPC was Mn = 28600 and Mw = 112200.

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、化合物１３を５６１ｍｇ（１．００ｍｍｏｌ）、化合物１５（４,７−ｂｉｓ(４,４,５,５−ｔｅｔｒａｍｅｔｈｙｌ−１,３,２−ｄｉｏｘａｂｏｒｏｌａｎ−２−ｙｌ)−２,１,３−ｂｅｎｚｏｔｈｉａｄｉａｚｏｌｅ）（アルドリッチ社製）を３８８．１ｍｇ（１．００ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、アルドリッチ社製）を２０２ｍｇ加え、トルエン２０ｍｌに溶解させた。得られたトルエン溶液にアルゴンガスを導入し、３０分バブリングした。その後、反応液に酢酸パラジウムを２．２５ｍｇ、トリス(２−メトキシフェニル)ホスフィン（Ｔｒｉｓ（２−ｍｅｔｈｏｘｙｐｈｅｎｙｌ）ｐｈｏｓｐｈｉｎｅ）を１２．３ｍｇ、１６．７ｗｔ％の炭酸ナトリウム水溶液を６．５ｍＬ加え、１００℃で５時間攪拌を行った。その後、反応液にフェニルホウ酸を５０ｍｇ加え、さらに７０℃で２時間反応させた。その後、反応液にジエチルジチオカルバミン酸ナトリウム２ｇと水２０ｍＬを加え、２時間還流下で攪拌を行った。反応液中の水層を除去後、有機層を水２０ｍｌで２回、３ｗｔ％の酢酸水溶液２０ｍＬで２回、さらに水２０ｍＬで２回洗浄し、メタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、得られたポリマーをｏ−ジクロロベンゼン３０ｍＬに溶解させた。ｏ−ジクロロベンゼン溶液をアルミナ／シリカゲルカラムに通し、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。ポリマーを濾過後、乾燥させ、重合体を２８０ｍｇ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＝１４０００、Ｍｗ＝３００００であった。 Comparative Example 1
(Synthesis of polymer compound Z)

In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of Compound 13 and Compound 15 (4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxabolanan- 2-yl) -2,1,3-benzothiadiazole) (manufactured by Aldrich) 388.1 mg (1.00 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Aldrich) 202 mg, Dissolved in 20 ml of toluene. Argon gas was introduced into the obtained toluene solution and bubbled for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine), 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, and 100 ° C. For 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours. After removing the aqueous layer in the reaction solution, the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3 wt% acetic acid aqueous solution and further twice with 20 mL of water, and poured into methanol to precipitate a polymer. The polymer was filtered and dried, and the resulting polymer was dissolved in 30 mL of o-dichlorobenzene. The o-dichlorobenzene solution was passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate a polymer. The polymer was filtered and dried to obtain 280 mg of a polymer. Hereinafter, this polymer is referred to as polymer compound Z. The molecular weight (polystyrene conversion) of the high molecular compound Z measured by GPC was Mn = 14000 and Mw = 30000.

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, 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, short-circuit current density, open-circuit voltage, and fill factor were determined. Jsc (short circuit current density) is 12.7 mA / cm ² , Voc (open end voltage) is 0.86 V, FF (fill factor) is 0.54, and photoelectric conversion efficiency (η ) Was 5.9%. 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 Example Measurement Example 1 except that the polymer compound B was used instead of the polymer A. Jsc (short circuit current density) is 13.2 mA / cm ² , Voc (open circuit voltage) is 0.88 V, FF (fill factor) is 0.54, and photoelectric conversion efficiency (η ) Was 6.2%. The results are shown in Table 1.

Measurement example 3
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 C was used instead of the polymer A. Jsc (short circuit current density) is 2.58 mA / cm ² , Voc (open end voltage) is 1.05 V, FF (fill factor) is 0.41, and photoelectric conversion efficiency (η ) Was 1.1%. The results are shown in Table 1.

Measurement example 4
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 A. Jsc (short circuit current density) is 4.61 mA / cm ² , Voc (open end voltage) is 0.60 V, FF (fill factor) is 0.33, and photoelectric conversion efficiency (η ) Was 0.9%. The results are shown in Table 1.

Table 1 Evaluation results of photoelectric conversion elements

Claims (13)

The high molecular compound which has a structural unit represented by Formula (1).

[In Formula (1), Ar ¹ and Ar ² are the same or different and each represents a trivalent aromatic carbocyclic group or a trivalent heterocyclic group. n represents a natural number. X represents —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, a plurality of Xs are the same or different. R ^{1 to} R ¹² are the same or different and represent an aromatic carbocyclic group, a heterocyclic group, a halogen atom, or a substituent substituted with one or more halogen atoms. Substituents substituted with one or more halogen atoms are alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, acyl groups, Acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, And any one of arylalkynyl groups is a substituent group substituted with one or more halogen atoms. ] In-(X) n- in the formula (1), n is 2 or more,
One selected from the group consisting of —O—, —S—, —Se—, —C (═O) —, —C (═S) —, —S (═O) —, and —SO ₂ —. And more
^{-C (R 1) (R 2} ) -, - Si (R 3) (R 4) -, - Ge (R 5) (R 6) -, - Sn (R 7) (R 8) -, - N Including one or more selected from the group consisting of (R ⁹ )-, -P (R ¹⁰ )-, -P (= O) (R ¹¹ )-, and -B (R ¹² )-. However, R < ¹ > -R < ¹² > is a high molecular compound of Claim ¹ showing the same meaning as the above-mentioned thing. The polymer compound according to claim 1, wherein at least one of Ar ¹ and Ar ² includes a 5-membered ring or a 5-membered ring structure, and n is 2 or more. 4. The polymer compound according to claim 1, wherein n is 2, and at least one of the two Xs is —C (R ¹ ) (R ² ) —. The polymer compound according to claim 4, wherein one of the two Xs is —C (R ¹ ) (R ² ) — and the other is —O—. The polymer compound according to any one of claims 1 to 5, wherein at least one of Ar ¹ and Ar ² is a group obtained by removing three hydrogen atoms from a thiophene ring.   The high molecular compound according to any one of claims 1 to 6, wherein the-(X) n- contains three or more halogen atoms.   The polymer compound according to any one of claims 1 to 7, wherein the halogen atom is a fluorine atom. The polymer compound according to claim 4 or 5, wherein R ^{1 to} R ¹² are an aromatic carbocyclic group or a heterocyclic group. The polymer compound according to claim 9, wherein R ¹ and R ² are aromatic carbocyclic groups. The polymer compound according to claim 1, further comprising a structural unit represented by the following formula (2).

[In the formula (2), Ar ⁴ represents an arylene group or a divalent heterocyclic group. However, Ar ⁴ is different from the structural unit represented by the formula (1). ]   It has a 1st electrode and a 2nd electrode, has an active layer between this 1st electrode and this 2nd electrode, and it is in any 1 paragraph of Claims 1-11 in this active layer. The organic photoelectric conversion element containing the high molecular compound of description.   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 1-11 in this active layer.