JP2013095813A - Polymer compound and photoelectric conversion element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound which enables production of an organic photoelectric conversion element with high open end voltage.SOLUTION: The polymer compound has a structural unit represented by formula (1), wherein Xand Xeach independently represent a nitrogen atom or =CH-; Yrepresents a sulfur atom, an oxygen atom, a selenium atom, -N(R)- or -CR=CR-; R, Rand Reach independently represent a hydrogen atom or a substituent; Wrepresents a cyano group, a nitro group, a monovalent organic group having a fluorine atom or a fluorine atom; and Wrepresents a group different from W.

Description

  The present invention relates to a polymer compound and a photoelectric conversion element 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, switching to a solar system using a pn junction type silicon solar cell or the like on the roof of a house has been proposed, and the single crystal, polycrystal and amorphous silicon used in the silicon solar cell are manufactured in the process However, there is a problem that high temperature and high vacuum conditions are required.

  On the other hand, the organic thin film solar cell which is one aspect of the 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 at low cost only by the coating process. Has been. 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) is described (Patent Document 1).

繰り返し単位（Ａ） 繰り返し単位（Ｂ）

Repeating unit (A) Repeating unit (B)

Special table 2009-506519

  However, a photoelectric conversion element having an organic layer containing the polymer compound does not necessarily have sufficient photoelectric conversion efficiency.

  An object of this invention is to provide the high molecular compound from which the photoelectric conversion efficiency of a photoelectric conversion element becomes high when it uses for the organic layer contained in a photoelectric conversion element.

（１）
〔式中、Ｘ^１及びＸ^２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^１は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^１）−又は−ＣＲ^２＝ＣＲ^３−を表す。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は置換基を表す。Ｗ^１は、シアノ基、ニトロ基、フッ素原子を有する１価の有機基又はフッ素原子を表す。Ｗ^２は、Ｗ^１とは異なる基を表す。〕 That is, the present invention first provides a polymer compound having a structural unit represented by the formula (1).

(1)
[Wherein, X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Y ¹ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 1)} - or ^-CR 2 = CR ³ - represents a. R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ¹ represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ² represents a group different from W ¹ . ]

（３）
〔式中、Ｘ^３ａ１及びＸ^３ａ２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^３ａ１は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^１）−又は−ＣＲ^２＝ＣＲ^３−を表す。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は置換基を表す。Ｗ^３ａ１は、シアノ基、ニトロ基、フッ素原子を有する１価の有機基又はフッ素原子を表す。Ｗ^３ａ２は、Ｗ^３ａ１とは異なる基を表す。Ｑ^３ａ１及びＱ^３ａ２は、それぞれ独立に、塩素原子、臭素原子、ヨウ素原子、ジヒドロキシボリル基又は１価の有機基を表す。〕 The present invention secondly provides a compound represented by the formula (3).

(3)
[ ^Wherein , X ^3a1 and X ^3a2 each independently represent a nitrogen atom or ═CH—. Y ^3a1 represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ¹ )-or -CR ² = CR ^3- . R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ^3a1 represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ^3a2 represents a group different from W ^3a1 . Q ^3a1 and Q ^3a2 each independently represent a chlorine atom, a bromine atom, an iodine atom, a dihydroxyboryl group, or a monovalent organic group. ]

  Thirdly, the present invention has a first electrode and a second electrode, an active layer between the first electrode and the second electrode, and the polymer compound in the active layer Or the photoelectric conversion element containing the said compound is provided.

  Fourthly, the present invention provides an organic thin film transistor having a gate electrode, a source electrode, a drain electrode, and an active layer, and containing the polymer compound or the compound in the active layer.

  Fifthly, the present invention includes a first electrode and a second electrode, a light emitting layer between the first electrode and the second electrode, and the polymer compound in the light emitting layer. Or the organic electroluminescent element containing the said compound is provided.

  Since the photoelectric conversion element which has the organic layer containing the high molecular compound of this invention has large photoelectric conversion efficiency, this invention is very useful.

  Hereinafter, the present invention will be described in detail.

（１）
〔式中、Ｘ^１及びＸ^２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^１は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^１）−又は−ＣＲ^２＝ＣＲ^３−を表す。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は置換基を表す。Ｗ^１は、シアノ基、ニトロ基、フッ素原子を有する１価の有機基又はフッ素原子を表す。Ｗ^２は、Ｗ^１とは異なる基を表す。〕 The polymer compound of the present invention has a structural unit represented by the formula (1).

(1)
[Wherein, X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Y ¹ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 1)} - or ^-CR 2 = CR ³ - represents a. R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ¹ represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ² represents a group different from W ¹ . ]

Examples of the substituent represented by R ¹ , R ² and R ³ include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and a substituted group. Aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, substituted Arylalkylthio group, acyl group, acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group , Heterocyclic thio group, optionally substituted arylalkenyl group, optionally substituted arylalkynyl group , A carboxy group, and a cyano group.

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

  Here, the alkyl group may be linear, branched, or cyclic. Carbon number of an alkyl group is 1-30 normally. The alkyl group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkyl group which may be substituted include 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, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7- Examples include chain alkyl groups such as dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group. .

  The alkyl part of the alkoxy group may be linear, branched or cyclic. The alkoxy group may have a substituent. Carbon number of an alkoxy group is 1-20 normally, and a halogen atom and an alkoxy group (for example, C1-C20) are mentioned as a substituent. Specific examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyl group. Oxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group Perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group and 2-methoxyethyloxy group.

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

  An aryl group means the group remove | excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the carbon number is 6-60 normally. The aryl group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryl group which may have a substituent include a phenyl group and a C1-C12 alkoxyphenyl group (C1-C12 alkoxy is alkoxy having 1 to 12 carbon atoms. C1-C12 alkoxy) Is preferably C1 to C8 alkoxy, more preferably C1 to C6 alkoxy, C1 to C8 alkoxy represents alkoxy having 1 to 8 carbons, and C1 to C6 alkoxy represents 1 to C6 alkoxy. It is an alkoxy of 6. Specific examples of C1-C12 alkoxy, C1-C8 alkoxy and C1-C6 alkoxy include those described and exemplified for the alkoxy group, and the same applies to the following. C1-C12 alkylphenyl group (C1-C12 alkyl indicates alkyl having 1 to 12 carbon atoms. C1 C12 alkyl is preferably C1 to C8 alkyl, more preferably C1 to C6 alkyl, C1 to C8 alkyl represents alkyl having 1 to 8 carbon atoms, and C1 to C6 alkyl represents carbon atoms. It shows that it is alkyl of 1 to 6. Specific examples of C1 to C12 alkyl, C1 to C8 alkyl and C1 to C6 alkyl include those described and exemplified for the above alkyl group, and the same applies to the following. ), 1-naphthyl group, 2-naphthyl group and pentafluorophenyl group. Among the C1-C12 alkoxyphenyl groups, a preferred embodiment is a C1-C8 alkoxyphenyl group, and a more preferred embodiment is a C1-C6 alkoxyphenyl group. Specific examples of C1 to C8 alkoxy and C1 to C6 alkoxy include C1 to C8 and C1 to C6 among the alkoxy exemplified for the above alkoxy group.

  The aryloxy group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryloxy group which may have a substituent include phenoxy group, C1-C12 alkoxyphenoxy group, C1-C12 alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and pentafluorophenoxy. Groups.

The arylthio group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Specific examples of the arylthio group which may have a substituent include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenylthio. Groups.

  The arylalkyl group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkyl group which may have a substituent include a phenyl-C1-C12 alkyl group, a C1-C12 alkoxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, Examples include 1-naphthyl-C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group.

  The arylalkoxy group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkoxy group which may have a substituent include a phenyl-C1-C12 alkoxy group, a C1-C12 alkoxyphenyl-C1-C12 alkoxy group, a C1-C12 alkylphenyl-C1-C12 alkoxy group, Examples include 1-naphthyl-C1 to C12 alkoxy groups and 2-naphthyl-C1 to C12 alkoxy groups.

  The arylalkylthio group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkylthio group which may have a substituent include a phenyl-C1-C12 alkylthio group, a C1-C12 alkoxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, Examples include 1-naphthyl-C1-C12 alkylthio group and 2-naphthyl-C1-C12 alkylthio group.

  An acyl group means the group except the hydroxyl group in carboxylic acid, The carbon number is 2-20 normally. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, an alkylcarbonyl group that may be substituted with a halogen having 2 to 20 carbon atoms, a benzoyl group, Examples thereof include a phenylcarbonyl group which may be substituted with a halogen such as a pentafluorobenzoyl group.

  The acyloxy group means a group excluding a hydrogen atom in the carboxylic acid, and the carbon number is usually 2-20. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

  An amide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and the carbon number is usually 2 to 20. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

  The imide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from imide (—CO—NH—CO—), and specific examples include a succinimide group and a phthalimide group.

A substituted amino group is one in which one or two hydrogen atoms of the amino group are substituted, and the substituent is, for example, an alkyl group and an optionally substituted aryl group. Specific examples of the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R ¹ and the optionally substituted aryl group. Carbon number of a substituted amino group is 1-40 normally. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alcohol Siphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyrida Dinylamino 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-naphthyl-C1- C12 alkylamino Group, and the like.

A substituted silyl group is one in which one, two, or three of the hydrogen atoms of the silyl group are substituted, generally one in which all three hydrogen atoms of the silyl group are substituted. And an aryl group which may be substituted. Specific examples of the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R ¹ and the optionally substituted aryl group. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

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

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

  The substituted silylamino group is one in which one or two hydrogen atoms of the amino group are substituted with a substituted silyl group, and the substituted silyl group is as described above. Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl. Silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, 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-xylylsilyl) amino group, bis (tribe Jirushiriru) amino group, bis (diphenylmethylsilyl) amino group, bis (tert- butyldiphenylsilyl) amino group and bis (dimethylphenylsilyl) and amino group.

  As the heterocyclic group, optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, Triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline , Chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, in Sol, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinazoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine, etc. And a group obtained by removing one hydrogen atom from a heterocyclic compound. Aromatic heterocyclic groups are preferred.

（１１） （１２）
〔式（１１）及び式（１２）中、Ａｒ^７は複素環基を表す。〕 Examples of the heterocyclic oxy group 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.

(11) (12)
[In Formula (11) and Formula (12), Ar ⁷ represents a heterocyclic group. ]

The heterocyclic oxy group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
The heterocyclic thio group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

  The arylalkenyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkenyl group include a styryl group.

  The arylalkynyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the arylalkynyl group include a phenylacetylenyl group.

Y ¹ is preferably a sulfur atom, an oxygen atom or a selenium atom, more preferably a sulfur atom or an oxygen atom, and particularly preferably a sulfur atom.

W ¹ represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom.

  Examples of the monovalent organic group having a fluorine atom include a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkylthio group, a fluoroaryl group, a fluoroaryloxy group, and a fluoroarylthio group.

The fluoroalkyl group is usually one in which one or more hydrogen atoms of an alkyl group having 1 to 30 carbon atoms are substituted with a fluorine atom, and specific examples of the alkyl group are represented by R ¹ , R ² and R ^3. The same as the specific examples of the alkyl group. Specific examples of the fluoroalkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a difluoroethyl group, a pentafluoromethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a tridecafluorohexyl group.

The fluoroalkoxy group is usually one in which one or more hydrogen atoms of an alkoxyl group having 1 to 20 carbon atoms are substituted with a fluorine atom, and specific examples of the alkoxy group are represented by R ¹ , R ² and R ^3. This is the same as the specific example of the alkoxy group. Specific examples of the fluoroalkoxy group include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a difluoroethoxy group, a pentafluoromethoxy group, a heptafluoropropoxy group, a nonafluorobutoxy group, and a tridecafluorohexyloxy group. It is done.

The fluoroalkylthio group is usually one in which one or more hydrogen atoms of an alkylthio group having 1 to 20 carbon atoms are substituted with a fluorine atom, and specific examples of the alkylthio group are represented by R ¹ , R ² and R ^3. The same as the specific examples of the alkylthio group. Specific examples of the fluoroalkylthio group include a fluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a difluoroethylthio group, a pentafluoromethylthio group, a heptafluoropropylthio group, a nonafluorobutylthio group, and a tridecafluorohexylthio group. Is mentioned.

  The fluoroaryl group is usually one in which one or more hydrogen atoms of a phenyl group or a naphthyl group are substituted with a fluorine atom. Specific examples of the fluoroaryl group include a fluorophenyl group, a difluorophenyl group, and a trifluorophenyl group. , Pentafluorophenyl group, fluorobiphenyl group, nonafluorobiphenyl group, fluoronaphthyl group and heptafluoronaphthyl group.

  The fluoroaryloxy group is a group in which an oxygen atom is bonded to the above fluoroaryl group. Specific examples of the fluoroaryloxy group include a fluorophenoxy group, a difluorophenoxy group, a trifluorophenoxy group, a pentafluorophenoxy group, a fluorobiphenyloxy group, a nonafluorobiphenyloxy group, a fluoronaphthyloxy group, and a heptafluoronaphthyloxy group. Can be mentioned.

  The fluoroarylthio group is a group in which a sulfur atom is bonded to the above fluoroaryl group. Specific examples of the fluoroarylthio group include a fluorophenylthio group, a difluorophenylthio group, a trifluorophenylthio group, a pentafluorophenylthio group, a fluorobiphenylthio group, a nonafluorobiphenylthio group, a fluoronaphthylthio group, and a heptafluoro group. A naphthylthio group is mentioned.

W ¹ is preferably a fluorine atom.

W ² represents a group different from W ¹ . W ² includes a monovalent organic group composed of an atom different from a fluorine atom. Examples of the monovalent organic group composed of an atom different from a fluorine atom include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and an optionally substituted aryl. Group, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, arylalkylthio group which may be substituted Acyl group, acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, Optionally substituted arylalkenyl groups, optionally substituted arylalkynyl groups and carboxy It is preferred.
The optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the optionally substituted aryl group, the optionally substituted aryloxy group, the substituted Arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, arylalkylthio group which may be substituted, acyl group, acyloxy group, amide group, imide group, substituted amino group Group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, optionally substituted arylalkenyl group and optionally substituted arylalkynyl specific examples of the groups, said R ¹ to R optionally substituted alkyl group represented by ^3, location An optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, and an optionally substituted Good arylalkyl group, optionally substituted arylalkoxy group, optionally substituted arylalkylthio group, acyl group, acyloxy group, amide group, imide group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted Of the groups described as specific examples of the silylthio group, the substituted silylamino group, the heterocyclic group, the heterocyclic oxy group, the heterocyclic thio group, the optionally substituted arylalkenyl group and the optionally substituted arylalkynyl group, fluorine Examples include groups that do not contain atoms.

W ² is preferably an alkyl group, an alkoxy group, an aryl group or an aryloxy group, more preferably an alkyl group or an alkoxy group, and particularly preferably an alkoxy group.

X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Preferably, at least one of X ¹ and X ² is a nitrogen atom, and more preferably X ¹ and X ² are both nitrogen atoms.

  As a structural unit represented by Formula (1), the structural unit represented by Formula (1001)-Formula (1225) is mentioned, for example.

In formula (1001) to formula (1225), R ¹ , R ² and R ³ represent the same meaning as described above. Among the structural units represented by formula (1001) to formula (1225), from the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element containing the polymer compound of the present invention, the formula (1001) to formula (1075) are used. The structural unit represented by Formula (1001) to Formula (1030) is more preferable, the structural unit represented by Formula (1001) and the structural unit represented by Formula (1016) are particularly preferable. .

（２）
〔式中、Ａｒ^１は、アリーレン基又は２価の複素環基を表す。〕 The polymer compound of the present invention may further have a structural unit represented by the formula (2).

(2)
[Wherein Ar ¹ represents an arylene group or a divalent heterocyclic group. ]

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon, and the number of carbon atoms constituting the aromatic ring contained in the arylene group is usually 6 to 60. Yes, preferably 6-20. Aromatic hydrocarbons include those having a benzene ring, those having a condensed ring, those having two or more independent benzene rings or two or more condensed rings directly bonded, or those bonded via a group such as vinylene. Examples of the substituent that the aromatic hydrocarbon may have include the same groups as the substituents represented by R ¹ , R ^2, and R ³ described above.

The divalent heterocyclic group is an atomic group obtained by removing two hydrogen atoms from an optionally substituted heterocyclic compound, and the number of carbon atoms constituting the aromatic ring contained in the divalent heterocyclic group is usually It is 2-60, Preferably it is 3-20. A heterocyclic compound is an organic compound having a ring structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, and silicon in the ring. Say things. Examples of the substituent that the heterocyclic compound may have include the same groups as the substituents represented by R ¹ , R ^2, and R ³ described above. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable.

  Two or more structural units represented by the formula (2) may be present in succession in the polymer compound of the present invention, or the formulas may be present on both sides of the structural unit represented by the formula (2). The structural unit represented by (1) may exist. When two or more structural units represented by the formula (2) are present in succession, the structural units represented by the formula (2) present in succession may be the same or different from each other. Good.

〔式（Ｄ−１）及び式（Ｄ−２）中、ｄ環は、置換基を有していてもよい芳香環を表す。ｍは、１以上の整数を表す。Ｚは、式（ｚ−１）〜式（ｚ−８）で表される基を表さす。ｄ環が複数個ある場合、それらは同一でもあっても相異なってもよい。Ｚが複数個ある場合、それらは同一であっても相異なってもよい。

（式（ｚ−１）〜式（ｚ−８）中、Ｒは、水素原子又は置換基を表す。Ｒが複数個ある場合、それらは同一でも相異なってもよい。Ｒが互いに結合し、環状構造を形成していてもよい。）〕

〔式中、Ｒは、水素原子又は置換基を表す。２個あるＲは同一でも相異なってもよい。〕 Examples of the structural unit represented by the formula (2) include a structural unit represented by the formula (D-1), a structural unit represented by the formula (D-2), and a structural unit represented by the formula 234. Can be mentioned.

[In formula (D-1) and formula (D-2), ring d represents an aromatic ring which may have a substituent. m represents an integer of 1 or more. Z represents a group represented by formula (z-1) to formula (z-8). When there are a plurality of d rings, they may be the same or different. When there are a plurality of Z, they may be the same or different.

(In formula (z-1) to formula (z-8), R represents a hydrogen atom or a substituent. When there are a plurality of R, they may be the same or different. An annular structure may be formed.)]

[Wherein, R represents a hydrogen atom or a substituent. Two R may be the same or different. ]

Aromatic rings include aromatic carbocycles and aromatic heterocycles.
Examples of the aromatic carbocycle include a benzene ring, a naphthalene ring, and an anthracene ring.
Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a pyrrole ring, a silole ring, a borol ring, a phosphole ring, an imidazole ring, a triazole ring, a thiazole ring, an oxazole ring, an isoxazole ring, a pyrazole ring, an isothiazole ring, Examples include pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinoline ring, indole ring, benzofuran ring, isobenzofuran ring, benzoimidazole ring, benzothiophene ring, benzothiazole ring, and benzoxazole ring.

  m represents an integer of 1 or more. m is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

  Examples of the substituent represented by R include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, and a substituted group. An optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, a substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, heterocyclic group, carboxy group, An alkoxycarbonyl group, a nitro group, and a cyano group are mentioned.

An optionally substituted alkyl group represented by R, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group , An optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, an optionally substituted arylalkenyl group, Definitions and specific examples of the optionally substituted arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group and heterocyclic group are as described above for R ¹ , R ² and R ^3. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkyl group Ruthio group, aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted , Optionally substituted arylalkylthio group, optionally substituted arylalkenyl group, optionally substituted arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group And the definitions and specific examples of the heterocyclic group.

  An alkoxycarbonyl group is a group in which a hydrogen atom in a carboxy group is substituted with an alkyl group. The carbon number of the alkoxycarbonyl group is usually 2-20. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

  R is preferably an alkyl group, an alkoxy group, an aryl group or an aryloxy group, an alkyl group having 9 to 18 carbon atoms, an alkoxy group having 9 to 18 carbon atoms, an aryl group having 9 to 18 carbon atoms and a carbon number. Is more preferably an aryloxy group having 9 to 18 carbon atoms, particularly preferably an alkyl group having 9 to 18 carbon atoms.

The aromatic carbocycle and the aromatic heterocycle may have a substituent. When the aromatic carbocycle and the aromatic heterocycle have two or more substituents, the substituents may be bonded to each other to form a cyclic structure. Examples of the substituent that the aromatic carbocycle and aromatic heterocycle may have include the same groups as the substituents represented by R ¹ , R ^2, and R ³ described above.

〔式（Ｄ−３）〜（Ｄ−５）中、ｅ環は、置換基を有していてもよい単環の芳香環を表す。ｎは、１以上の整数を表す。ｐは、０〜５の整数を表す。ｅ環が複数個ある場合、それらは、同一であっても相異なってもよい。〕 Examples of the structural unit represented by the formula (D-2) include a structural unit represented by the formula (D-3), a structural unit represented by the formula (D-4), and the formula (D-5). The structural unit represented is mentioned.

[In formulas (D-3) to (D-5), ring e represents a monocyclic aromatic ring optionally having a substituent. n represents an integer of 1 or more. p represents an integer of 0 to 5. When there are a plurality of e-rings, they may be the same or different. ]

  Examples of the monocyclic aromatic ring include a benzene ring and a monocyclic aromatic heterocycle. Examples of the substituent that the monocyclic aromatic ring may have include the same groups as the substituent that the aromatic carbocycle or aromatic heterocycle included in the d ring may have.

n is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2.
p is preferably 0 to 4, more preferably 0 to 3, and particularly preferably 0 to 2.

  When using the polymer compound of the present invention for a photoelectric conversion element, from the viewpoint of increasing the photoelectric conversion efficiency, among the structural units represented by the formula (2), the structural unit and the formula represented by the formula (D-1). The structural unit represented by (D-5) is preferable, and the structural unit represented by Formula (D-1) is more preferable.

  When using the polymer compound of the present invention for an organic thin film transistor, from the viewpoint of increasing hole mobility, among the structural units represented by the formula (2), the structural unit represented by the formula (D-1) and the formula ( The structural unit represented by D-4) is preferable, and the structural unit represented by Formula (D-1) is more preferable.

  As a structural unit represented by Formula (D-1), the structural unit represented by Formula 1-Formula 152 is mentioned, for example.

  In Formula 1 to Formula 152, R represents the same meaning as described above.

  Examples of the structural unit represented by Formula (D-3) include structural units represented by Formula 201 to Formula 233.

  In formula 201 to formula 233, R represents the same meaning as described above.

As a structural unit represented by Formula (D-4), for example, a structural unit represented by Formula 235 to Formula 238 can be given.

  In formula 235 to formula 238, R represents the same meaning as described above.

Examples of the structural unit represented by Formula (D-5) include structural units represented by Formula 301 to Formula 323.

  In Formula 301 to Formula 323, R represents the same meaning as described above.

  When the polymer compound of the present invention is used for a photoelectric conversion element, from the viewpoint of increasing the photoelectric conversion efficiency, the structural unit represented by the formula (2) is represented by the formula 1, formula 5, formula 7, formula 8, formula 12, Formula 14, Formula 15, Formula 25, Formula 35, Formula 39, Formula 41, Formula 49, Formula 50, Formula 54, Formula 60, Formula 62, Formula 63, Formula 67, Formula 73, Formula 75, Formula 76, Formula 80 , Formula 86, Formula 101, Formula 106, Formula 112, Formula 114, Formula 119, Formula 125, Formula 127, Formula 132, Formula 138, Formula 140, Formula 145, Formula 151, Formula 215, Formula 218, Formula 229, Formula 230, Formula 234, Formula 309, Formula 310, Formula 311, Formula 311, Formula 312, Formula 313, Formula 318, Formula 318, Formula 321, Formula 322, and Formula 323 are preferred, and Formula 1, Formula 8, Formula 15, Formula 25, Formula 35, Formula 49, Formula 62, Formula 75, Formula 101, Formula 114, 127, formula 215, formula 234, formula 309, formula 310, formula 3101, formula 311, formula 314, formula 321, formula 322 and formula 323 are more preferred, and structural units represented by formula 75, formula 309, formula 314, The structural unit represented by Formula 322 and Formula 323 is more preferable, and the structural unit represented by Formula 75 is particularly preferable.

  When the polymer compound of the present invention is used in an organic thin film transistor, from the viewpoint of increasing hole mobility, the structural unit represented by formula (2) is represented by formula 1, formula 8, formula 25, formula 35, formula 49, formula 54, Formula 62, Formula 67, Formula 75, Formula 80, Formula 101, Formula 114, Formula 201, Formula 202, Formula 203, Formula 204, Formula 205, Formula 206, Formula 207, Formula 208, Formula 209, Formula 210, Formula 215, Formula 216, Formula 217, Formula 218, Formula 219, Formula 220, Formula 221, Formula 222, Formula 229, Formula 230, Formula 231, Formula 232, Formula 233, Formula 235, Formula 236, Formula 237, Formula 238 , Formula 309, Formula 310, Formula 311, Formula 312, Formula 313, Formula 314, Formula 318, Formula 319, Formula 322, and Formula 323 are preferred units, Formula 25, Formula 75, Formula 80, Formula 114 , Formula 203, Formula 204 Formula 207, Formula 208, Formula 215, Formula 216, Formula 217, Formula 218, Formula 219, Formula 220, Formula 232, Formula 233, Formula 235, Formula 236, Formula 309, Formula 314, and Formula 322 More preferred are structural units represented by Formula 75, Formula 114, Formula 204, Formula 208, Formula 215, Formula 216, Formula 217, Formula 232, Formula 236, Formula 309, and Formula 314. The structural unit is particularly preferred.

  The polymer compound of the present invention may have a group in which structural units represented by two or more formulas (D-1) to (D-5) are bonded. Examples of the group include groups represented by formula 401 to formula 414.

  In formula 401 to formula 414, R represents the same meaning as described above. a and b represent the integer of 1-5 each independently. a and b are 1 to 3, and 1 is particularly preferable.

  When using the polymer compound of the present invention for a photoelectric conversion element, from the viewpoint of increasing the photoelectric conversion efficiency, among the groups represented by Formula 401 to Formula 414, Formula 401, Formula 402, Formula 409, Formula 410, Formula 411 Groups represented by formula 412, formula 413 and formula 414 are preferred, groups represented by formula 401, formula 409, formula 413 and formula 414 are more preferred, and groups represented by formula 401 and formula 409 are particularly preferred. .

Ar ¹ is preferably a divalent heterocyclic group, more preferably a divalent heterocyclic group containing a thiophene ring, from the viewpoint of lengthening the light absorption terminal wavelength.

When the polymer compound of the present invention has a structural unit represented by the formula (2), it is represented by the number of structural units represented by the formula (1) in the polymer compound of the present invention and the formula (2). From the viewpoint of increasing the solubility of the polymer compound of the present invention in the solvent, the ratio of the number of structural units is preferably such that the numerical value of S represented by the following formula is 0.10 to 0.80. 0.15 to 0.60 is more preferable, and 0.20 to 0.50 is particularly preferable.

S = (number of structural units represented by formula (1)) / {(number of structural units represented by formula (1))) + (number of structural units represented by formula (2))}

  The polymer compound in the present invention refers to a compound having a polystyrene-equivalent number average molecular weight of 2,000 or more measured by gel permeation chromatography (hereinafter sometimes referred to as GPC). The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably from 2,000 to 1,000,000, more preferably from 2,500 to 1,000,000, particularly preferably from 3,000 to 100,000.

  The content of the structural unit represented by the formula (1) in the polymer compound of the present invention may be at least one in the compound. Preferably, the polymer compound contains an average of 2 or more per polymer chain, more preferably an average of 3 or more per polymer chain.

  In addition, when the polymer compound of the present invention is used in an element, it is desirable that the solubility in a solvent is high in terms of ease of device production. Specifically, the polymer compound of the present invention preferably has a solubility capable of producing a solution containing 0.01% by weight or more of the polymer compound, and can produce a solution containing 0.1% by weight or more. It is more preferable to have solubility, and it is more preferable to have solubility capable of producing a solution containing 0.4% by weight or more.

  The polymer compound of the present invention is preferably a π-conjugated polymer compound. The π-conjugated polymer compound refers to a polymer compound in which multiple bonds are present in the main chain with one single bond in between.

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

As a method using the Suzuki coupling reaction, for example, the formula (100):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
Wherein, E ¹ represents a structural unit represented by the formula (2). Q ¹⁰⁰ and Q ²⁰⁰ each independently represent a dihydroxyboryl group [—B (OH) ₂ ] or a borate ester residue. ]
One or more compounds represented by formula (200):
T ¹ -E ² -T ² (200)
Wherein, E ² represents a structural unit represented by the formula (1). T ¹ and T ² each independently represent a halogen atom or a sulfonic acid residue. ]
The manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. E ¹ is preferably a structural unit represented by Formula 1 to Formula 152, Formula 201 to Formula 233, Formula 235 to Formula 238, and Formula 301 to Formula 323.
In this case, the total number of moles of one or more compounds represented by formula (200) used in the reaction is excessive with respect to the total number of moles of one or more compounds represented by formula (100). Is preferred. When the total number of moles of one or more compounds represented by formula (200) used in the reaction is 1 mole, the total number of moles of one or more compounds represented by formula (100) 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。）
で表される基が例示される。 The boric acid ester residue means a group obtained by removing a hydroxyl group from a boric acid diester, and examples thereof include a dialkyl ester residue, a diaryl ester residue, and a di (arylalkyl) ester residue. Specific examples of the boric acid ester residue include the following formula:

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

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

In the formula (200), the sulfonic acid residue represented by T ¹ and T ² means an atomic group obtained by removing acidic hydrogen from sulfonic acid (—SO ₃ H), and specific examples include an alkyl sulfonate group. (For example, methanesulfonate group, ethanesulfonate group), arylsulfonate group (for example, benzenesulfonate group, p-toluenesulfonate group), arylalkylsulfonate group (for example, benzylsulfonate group) and trifluoromethanesulfonate group.

  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. 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 (100). Yes, preferably 0.0003 mol to 0.1 mol.

  When palladium acetate is used as a palladium catalyst used in the Suzuki coupling reaction, for example, a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine is added 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 there.

Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, inorganic salts and the like. Examples of the inorganic base include potassium carbonate, sodium carbonate, and barium hydroxide. 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 to 10 mol, relative to 1 mol of the compound represented by the formula (100). is there.

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

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

  The Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is 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 (100), the compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) was charged, the polymerization vessel was sufficiently replaced with nitrogen gas, degassed, and then degassed by adding a degassed solvent such as toluene by bubbling with nitrogen gas in advance. Thereafter, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution, is dropped into this solution, and then heated and heated, for example, while maintaining an inert atmosphere at the reflux temperature for 8 hours. Polymerize.

As a method using the Stille coupling reaction, for example, the formula (300):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (300)
Wherein, E ³ represents a structural unit represented by the formula (2). Q ³⁰⁰ and Q ⁴⁰⁰ each independently represent a substituted stannyl group. ]
And a method of reacting one or more compounds represented by the formula (200) with one or more compounds represented by the formula (200) in the presence of a palladium catalyst. E ³ is preferably a group represented by Formula 1 to Formula 152, Formula 201 to Formula 233, Formula 235 to Formula 238, and Formula 301 to Formula 323.

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.
The alkyl group usually has 1 to 30 carbon atoms, and specific examples thereof include 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 And chain alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, 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. Substituted stannyl preferably -SnMe ₃ as a base, -SnEt _3, -SnBu _3, an -SnPh _3, more preferably -SnMe _3, -SnEt _3, is -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.

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.

Moreover, in a Stille coupling reaction, a ligand and a co-catalyst can also be used as needed. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, triphenylarsine, and triphenoxyarsine. Examples include arsenic compounds. Examples of the cocatalyst include copper iodide, copper bromide, copper chloride, and copper (I) 2-thenoylate.
When using a ligand or a cocatalyst, the 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, tetrahydrofuran and the like. 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 preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The 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 polymerization vessel is charged with a compound represented by the formula (300), a compound represented by the formula (200), A palladium catalyst is charged, and the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene, and then coordinate as necessary. After adding the catalyst and the cocatalyst, the mixture is heated and heated, for example, and polymerized while maintaining an inert atmosphere at the reflux temperature for 8 hours.

The terminal group of the polymer compound of the present invention has characteristics of a device obtained when used for manufacturing a device when a polymerization active group represented by Q ^{100 to} Q ⁴⁰⁰ , T ¹ and T ² remains. In addition, since the lifetime may be shortened, it may be protected with a stable group. The stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the main chain. The stable group may have a structure bonded to an aryl group or a heterocyclic group via a vinylene group. Examples of the stable group include a phenyl group having no substituent, a naphthyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, and a pentafluoroethyl group.

A smaller amount of the metal element contained in the polymer compound of the present invention is preferable because photoelectric conversion efficiency and hole mobility are increased. Among these, it is preferable that the amount of the transition metal element contained in the polymer compound of the present invention is small. Examples of the transition metal element include palladium, iron, tin, nickel, and copper. Especially, it is preferable that there are few amounts of palladium, iron, and tin. Although the amount of impurities contained in the polymer compound of the present invention is measured by elemental analysis, the total amount of palladium, iron and tin is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less, particularly preferably 30 ppm or less.
Elemental analysis methods include atomic absorption analysis, emission spectroscopy analysis, plasma emission analysis, fluorescent X-ray analysis, plasma mass analysis, glow discharge mass analysis, ion chromatograph analysis and the like.

（３）
〔式中、Ｘ^３ａ１及びＸ^３ａ２は、それぞれ独立に、窒素原子又は＝ＣＨ−を表す。Ｙ^３ａ１は、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^１）−又は−ＣＲ^２＝ＣＲ^３−を表す。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は置換基を表す。Ｗ^３ａ１は、シアノ基、ニトロ基、フッ素原子を有する１価の有機基又はフッ素原子を表す。Ｗ^３ａ２は、Ｗ^３ａ１とは異なる基を表す。Ｑ^３ａ１及びＱ^３ａ２は、それぞれ独立に、塩素原子、臭素原子、ヨウ素原子、ジヒドロキシボリル基又は１価の有機基を表す。〕 The polymer compound of the present invention is characterized by having a structural unit represented by the formula (1). For example, the polymer compound includes a compound represented by the formula (3) as one of the raw materials. It can be synthesized by using.

(3)
[ ^Wherein , X ^3a1 and X ^3a2 each independently represent a nitrogen atom or ═CH—. Y ^3a1 represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ¹ )-or -CR ² = CR ^3- . R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ^3a1 represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ^3a2 represents a group different from W ^3a1 . Q ^3a1 and Q ^3a2 each independently represent a chlorine atom, a bromine atom, an iodine atom, a dihydroxyboryl group, or a monovalent organic group. ]

In the formula ^(3), it is preferable that at least one of ^{X 3a1} and ^{X 3a2} is a nitrogen ^atom, it is more preferred that both of ^{X 3a1} and ^{X 3a2} is a nitrogen atom.

In formula (3), Y ^3a1 is preferably a sulfur atom, an oxygen atom, —N (R ¹ ) — and —CR ² ═CR ³ —, more preferably a sulfur atom, an oxygen atom and —CR ² ═CR ³ —. More preferred are a sulfur atom and an oxygen atom.

Examples of the monovalent organic group represented by Q ^3a1 and Q ^3a2 include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and a substituted An optionally substituted aryloxy group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted Arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, complex A ring thio group, an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, Include acid ester residue and a substituted stannyl group.

The optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the optionally substituted aryl group, the optionally substituted aryloxy group, the substituted Arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, arylalkylthio group which may be substituted, acyl group, acyloxy group, amide group, acid imide group, amino group Group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, optionally substituted arylalkenyl group and substituted The definition and specific examples of the arylalkynyl group which may be substituted are those represented by the aforementioned R ¹ , R ² and R ^3. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, and an optionally substituted A good arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, an acyl group, an acyloxy group, an amide group, an acid imide group, an 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, optionally substituted arylalkenyl group and optionally substituted The definition and specific examples of the arylalkynyl group are the same. The definition and specific examples of the boric acid ester residue are the same as the definitions and specific examples of the boric acid ester residue represented by Q ¹⁰⁰ and Q ²⁰⁰ described above. The definition and specific examples of the substituted stannyl group are the same as the definition and specific examples of the substituted stannyl group represented by Q ³⁰⁰ and Q ⁴⁰⁰ described above.

Q ^3a1 and Q ^3a2 are preferably a bromine atom, a dihydroxyboryl group, a boric acid ester residue, a substituted stannyl group and a substituted silyl group, more preferably a bromine atom, a dihydroxyboryl group, a boric acid ester residue and a substituted stannyl group, A dihydroxyboryl group, a borate residue and a substituted stannyl group are particularly preferred.

Specific examples of the monovalent organic group having a fluorine atom represented by W ^3a1 are the same as the specific examples of the monovalent organic group having a fluorine atom represented by W ¹ .
W ^3a2 represents a group different from W ^3a1 . Examples of the group different from W ^3a1 include a monovalent organic group consisting of only an atom different from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the monovalent organic group consisting only of atoms different from the fluorine atom are the same as the specific examples of the monovalent organic group consisting only of atoms different from the fluorine atom represented by W ² .

  As a compound represented by Formula (3), the compound represented by Formula 501-Formula 680 is mentioned, for example.

In Formula 501 to Formula 680, R ¹ , R ² and R ³ represent the same meaning as described above. Me represents a methyl group, and Bu represents a butyl group.

Among the compounds represented by Formula 501 to Formula 680, from the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element containing a polymerized polymer compound, the compounds represented by Formula 501 to Formula 580 are preferable. The compound represented by Formula 515, Formula 531 to Formula 545, Formula 550, Formula 552, and Formula 553 is more preferable, and the compound represented by Formula 505 and the compound represented by Formula 550 are particularly preferable.

（３−１）
（式中、Ｙ^３ａ１は前述と同じ意味を表す。Ｒ^３ａは、置換されていてもよいアルキル基を表す。）
で表される化合物は、式（３−２）

（３−２）
（式中、Ｙ^３ａ１は前述と同じ意味を表す。）
で表される化合物をアルコキシ化することで製造することが可能である。 Formula (3-1) which is one aspect | mode of the compound represented by Formula (3)

(3-1)
(In the formula, Y ^3a1 represents the same meaning as described above. R ^3a represents an optionally substituted alkyl group.)
The compound represented by the formula (3-2)

(3-2)
( ^Wherein Y ^3a1 represents the same meaning as described above.)
It can be produced by alkoxylating the compound represented by

Specific examples of the optionally substituted alkyl group represented by R ^3a are the same as the above-described specific examples of the optionally substituted alkyl group represented by R ¹ , R ² and R ³ .

Although a well-known method can be used for alkoxylation, For example, the method of making an alkoxide and the compound represented by Formula (3-2) react in a solvent-free or solvent is mentioned.
When a solvent is used, examples of the solvent include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane, and bromopentane. Halogenated hydrocarbon solvents such as chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dioxolane, dimethoxymethane, and tetrahydropyran, dimethyl sulfoxide, Examples include polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
A well-known thing can be used as an alkoxide, it is also possible to use a commercial item, and it is also possible to use what was synthesize | combined from corresponding alcohol.

  Examples of the method for synthesizing alkoxide from alcohol include a method in which alcohol is reacted with an alkali metal or an alkali metal hydride. Examples of the alkali metal include sodium, potassium, lithium, and cesium. Examples of the alkali metal hydride include sodium hydride, potassium hydride, cesium hydride, and lithium hydride. In the reaction between the alcohol and the alkali metal or alkali metal hydride, a solvent may be used. Examples of the solvent include ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dioxolane, dimethoxymethane, and tetrahydropyran, and hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, and xylene. it can.

  The compound represented by formula (3-2) can be synthesized, for example, according to the method described in International Publication No. 2011/052709.

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 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 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 of the present invention has one or more active layers containing the polymer compound of the present invention between the first electrode and the second electrode.
The photoelectric conversion element of the present invention is a photoelectric conversion element having a pair of electrodes, at least one of which is transparent or translucent, and an active layer formed from an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. preferable. The polymer compound of the present invention is preferably used as a p-type organic semiconductor.

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

  The photoelectric conversion element of the present invention has an active layer containing a compound represented by formula (3) instead of an active layer containing a polymer compound having a structural unit represented by formula (1). May be.

  It is preferable that the photoelectric conversion element of this invention has an active layer containing the high molecular compound which has a structural unit represented by Formula (1).

  The photoelectric conversion element 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. When the substrate is opaque, the electrode on the opposite side of the substrate (that is, the electrode far from the substrate) is preferably transparent or translucent.

Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Examples thereof include gold, platinum, silver, and copper, 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, and a plating method.
As the electrode, a transparent conductive film formed from an organic compound such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.

  One electrode may not be transparent, and examples of the material of the electrode include metals and conductive polymers. Specific examples of electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. Selected from the group consisting of metals, alloys of two or more of those metals, one or more of those metals, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin And alloys with one or more metals, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  As a means for improving the photoelectric conversion efficiency, an additional intermediate layer other than the active layer may be used. Examples of the material used for the intermediate layer include alkali metal or alkaline earth metal halides such as lithium fluoride, 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. Moreover, in order to improve the hole transport property of the said active layer, compounds other than the polymer compound of this invention can also be mixed and used as an electron-donating compound and / or an electron-accepting compound in the said active layer. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

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

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, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinolines and derivatives thereof, polyquinoxalines and Derivatives thereof, polyfluorene and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine), fullerenes and fullerene derivatives. Preferably, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）

（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいヘテロアリール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置換されていてもよいアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).

(I) (II) (III) (IV)

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

Definitions and specific examples of the optionally substituted alkyl group and the optionally substituted aryl group represented by R ^a and R ^b are the substituted and the substituted groups represented by R ¹ , R ² and R ^3. The definition and specific examples of the good alkyl group and the optionally substituted aryl group are the same.

Examples of the heteroaryl group represented by ^Ra include a thiophenediyl group, a pyridinediyl group, a furandiyl group, and a pyrrolediyl group.

（Ｖ）
（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、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

(V)
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R ^c represents an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted group. Represents an optionally substituted heteroaryl group.)

Definition and specific examples of R optionally substituted alkyl group represented by ^c, optionally substituted aryl and optionally substituted heteroaryl group, substituted represented by R ^a The definition and specific examples of the alkyl group which may be substituted, the aryl group which may be substituted and the heteroaryl group which may be substituted are the same.

Specific examples of the C ₆₀ derivative include the following compounds.

Specific examples of the C ₇₀ 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] 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, and 20 to 500 parts by weight. Is more preferable.

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

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

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, 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 inkjet coating method and a spin coating method are preferred.
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.

<Application of photoelectric conversion element>
The photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by irradiating light such as sunlight to generate a photovoltaic force between the electrodes. 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 irradiating light with a voltage applied between the electrodes or without applying a voltage, 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.

<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. Depending on the purpose, 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 filled resin 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.

<Organic thin film 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 active layer (organic semiconductor layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path And the polymer compound of the present invention is contained in the active layer. Examples of the organic thin film transistor include a field effect organic thin film transistor and an electrostatic induction organic thin film transistor.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an active layer (organic semiconductor 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 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 active layer is constituted by an organic thin film containing the polymer compound of the present invention.

  The electrostatic induction organic thin film transistor has a source electrode and a drain electrode, an active layer (organic semiconductor layer) serving as a current path between them, and a gate electrode for controlling the amount of current passing through the current path. It is preferable to be provided in the active layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the active layer are preferably provided in contact with the active 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 electrostatic induction organic thin film transistor, the active layer is constituted by an organic thin film containing the polymer compound of the present invention.

  The organic thin film transistor of the present invention has an active layer containing a compound represented by formula (3) instead of an active layer containing a polymer compound having a structural unit represented by formula (1). Also good.

  The organic thin film transistor of the present invention preferably has an active layer containing a polymer compound having a structural unit represented by the formula (1).

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

<Organic electroluminescence device>
The polymer compound of the present invention can also be used for an organic electroluminescence device (organic EL device). The organic EL element has a light emitting layer between the first electrode and the second electrode. The organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer. The light emitting layer contains the polymer compound of the present invention. 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. At least one of the first electrode and the second electrode is preferably transparent or translucent.

  The organic EL device of the present invention may contain a compound represented by the formula (3) in the light emitting layer instead of the polymer compound having the structural unit represented by the formula (1).

  The organic EL device of the present invention preferably contains a polymer compound having a structural unit represented by the formula (1) in the light emitting layer.

  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.

化合物１

５００ｍｌフラスコに、４，５−ジフルオロ−１，２−ジアミノベンゼン（東京化成工業製）を１０．２ｇ（７０．８ｍｍｏｌ）、ピリジンを１５０ｍＬ入れて均一な溶液とした。フラスコを０℃に保ったまま、フラスコ内に塩化チオニルを１６．０ｇ（１３４ｍｍｏｌ）滴下した。滴下後、フラスコを２５℃に温めて、６時間反応を行った。その後、反応液に水２５０ｍｌを加え、さらにクロロホルムを加えて反応生成物を含む有機層を抽出した。有機層を硫酸ナトリウムで乾燥させ、濾過した。濾液をエバポレーターで濃縮し、析出した固体を再結晶で精製した。再結晶の溶媒には、メタノールを用いた。精製後、化合物１を１０．５ｇ（６１．０ｍｍｏｌ）得た。 Reference example 1
(Synthesis of Compound 1)

Compound 1

In a 500 ml flask, 10.5 g (70.8 mmol) of 4,5-difluoro-1,2-diaminobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of pyridine were added to obtain a uniform solution. While maintaining the flask at 0 ° C., 16.0 g (134 mmol) of thionyl chloride was dropped into the flask. After dropping, the flask was warmed to 25 ° C. and reacted for 6 hours. Thereafter, 250 ml of water was added to the reaction solution, and chloroform was further added to extract an organic layer containing the reaction product. The organic layer was dried over sodium sulfate and filtered. The filtrate was concentrated with an evaporator, and the precipitated solid was purified by recrystallization. Methanol was used as the solvent for recrystallization. After purification, 10.5 g (61.0 mmol) of Compound 1 was obtained.

¹ H NMR (CDCl ₃ , ppm): 7.75 (t, 2H)
¹⁹ F NMR (CDCl ₃ , ppm): -128.3 (s, 2F)

化合物１ 化合物２

１００ｍＬフラスコに、化合物１を２．００ｇ（１１．６ｍｍｏｌ）、鉄粉を０．２０ｇ（３．５８ｍｍｏｌ）入れ、フラスコを９０℃に加熱した。該フラスコに、臭素３１ｇ（１９４ｍｍｏｌ）を１時間かけて滴下した。滴下後、反応液を９０℃で３８時間攪拌した。その後、フラスコを室温（２５℃）まで冷却し、クロロホルム１００ｍＬを入れて希釈した。得られた溶液を、５重量％の亜硫酸ナトリウム水溶液３００ｍＬに注ぎ込み、１時間攪拌した。得られた混合液の有機層を分液ロートで分離し、水層をクロロホルムで３回抽出した。得られた抽出液を有機層に混合し、混合した溶液を硫酸ナトリウムで乾燥させた。乾燥後の溶液を濾過し、濾液をエバポレーターで濃縮し、溶媒を留去した。得られた黄色の固体を、５５℃に熱したメタノール９０ｍＬに溶解させ、その後、２５℃まで冷却した。析出した結晶を濾過して集め、室温（２５℃）で減圧乾燥して化合物２を１．５０ｇ得た。 Reference example 2
(Synthesis of Compound 2)

Compound 1 Compound 2

In a 100 mL flask, 2.00 g (11.6 mmol) of Compound 1 and 0.20 g (3.58 mmol) of iron powder were placed, and the flask was heated to 90 ° C. To the flask, 31 g (194 mmol) of bromine was added dropwise over 1 hour. After the dropping, the reaction solution was stirred at 90 ° C. for 38 hours. Thereafter, the flask was cooled to room temperature (25 ° C.) and diluted with 100 mL of chloroform. The resulting solution was poured into 300 mL of a 5 wt% aqueous sodium sulfite solution and stirred for 1 hour. The organic layer of the obtained mixture was separated with a separatory funnel, and the aqueous layer was extracted with chloroform three times. The obtained extract was mixed with the organic layer, and the mixed solution was dried over sodium sulfate. The dried solution was filtered, the filtrate was concentrated with an evaporator, and the solvent was distilled off. The obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C., and then cooled to 25 ° C. The precipitated crystals were collected by filtration and dried under reduced pressure at room temperature (25 ° C.) to obtain 1.50 g of compound 2.

¹⁹ F NMR (CDCl ₃ , ppm): -118.9 (s, 2F)

化合物２ 化合物３

１００ｍＬフラスコに、ヘキサノールを３１０ｍｇ（３．０ｍｍｏｌ）、テロラヒドロフランを３０ｍＬ入れ、均一な溶液とした。フラスコを２５℃に保ったまま、６０重量％の水素化ナトリウムを鉱物油中に分散させた分散液を１２０ｍｇ（３．０ｍｍｏｌ）添加した。添加後、３０分攪拌し、攪拌後、化合物２を１．００ｇ（３．０ｍｍｏｌ）加えた。２５℃で２０分間攪拌後、フラスコを４０℃に加熱し、２時間１５分間攪拌した。攪拌後、塩化アンモニウム水溶液を１００ｍＬ加えて反応を停止させ、酢酸エチル５０ｍＬで２回抽出した。有機層を飽和塩化ナトリウム水溶液で洗浄し、硫酸ナトリウムを用いて乾燥させた。有機層を濾過後、濾液をロータリーエバポレーターで濃縮し、溶媒を留去して粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィで精製し、化合物３を３０１ｍｇ得た。シリカゲルカラムクロマトグラフィの溶出溶媒には、ヘキサンと酢酸エチルとを、酢酸エチルに対するヘキサンの体積比が４０となるように混合した混合液を用いた。 Example 1
(Synthesis of Compound 3)

Compound 2 Compound 3

A 100 mL flask was charged with 310 mg (3.0 mmol) of hexanol and 30 mL of terahydrofuran to obtain a uniform solution. While maintaining the flask at 25 ° C., 120 mg (3.0 mmol) of a dispersion obtained by dispersing 60% by weight of sodium hydride in mineral oil was added. After the addition, the mixture was stirred for 30 minutes. After stirring, 1.00 g (3.0 mmol) of Compound 2 was added. After stirring at 25 ° C. for 20 minutes, the flask was heated to 40 ° C. and stirred for 2 hours and 15 minutes. After stirring, 100 mL of an aqueous ammonium chloride solution was added to stop the reaction, and the mixture was extracted twice with 50 mL of ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution and dried using sodium sulfate. After filtering the organic layer, the filtrate was concentrated on a rotary evaporator, and the solvent was distilled off to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 301 mg of compound 3. As an elution solvent for silica gel column chromatography, a mixed solution in which hexane and ethyl acetate were mixed so that the volume ratio of hexane to ethyl acetate was 40 was used.

¹ H NMR (CDCl ₃ , ppm): 4.24 (t, 2H), 1.90 (m, 2H), 1.39 (m, 4H), 1.26 (t, 2H), 0.93 ( m, 3H)
¹⁹ F NMR (CDCl ₃ , ppm): −116.0 (s, 1F)

化合物４ 化合物３

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、国際公開第２０１１／０５２７０９号に記載された方法で合成した化合物４を２５５ｍｇ（０．２４３ｍｍｏｌ）、化合物３を１００ｍｇ（０．２４３ｍｍｏｌ）、トルエンを１９ｍｌ入れて均一な溶液とした。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３．３３ｍｇ（０．００３６ｍｍｏｌ）、トリス(２−トルイル)ホスフィンを６．６ｍｇ（０．０２２ｍｍｏｌ）加え、１００℃で６時間攪拌した。その後、反応液にフェニルトリメチルスズ１０ｍｇを加えて３時間反応させ、その後フェニルブロミドを５０ｍｇ加え、さらに５時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール３００ｍＬに注いだ。析出したポリマーを濾過して集め、得られたポリマーを、円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒濾紙内に残ったポリマーを、トルエン１００ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２ｇと水４ｍＬを加え、８時間還流下で攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３重量%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９ｍＬに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーを濾過後、乾燥させ、精製された重合体を１２９ｍｇ得た。以下、この重合体を高分子化合物Ａと呼称する。ＧＰＣで測定した高分子化合物Ａのポリスチレン換算の分子量は、重量平均分子量が４７３００であり、数平均分子量が１４３００であった。 Example 2
(Synthesis of polymer compound A)

Compound 4 Compound 3

In a 200 mL flask in which the gas in the flask was replaced with argon, 255 mg (0.243 mmol) of Compound 4 synthesized by the method described in International Publication No. 2011/052709, 100 mg (0.243 mmol) of Compound 3, and toluene were added. 19ml was put into a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.33 mg (0.0036 mmol) of tris (dibenzylideneacetone) dipalladium and 6.6 mg (0.022 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, 10 mg of phenyltrimethyltin was added to the reaction solution and reacted for 3 hours, and then 50 mg of phenylbromide was added, followed by further stirring for 5 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 0.2 g of sodium diethyldithiocarbamate and 4 mL of water were added, and the mixture was stirred under reflux for 8 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% by weight aqueous acetic acid solution and then twice with 50 mL of water, and the resulting solution was poured into methanol. To precipitate the polymer. The polymer was filtered and dried, and the resulting polymer was dissolved in 9 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 129 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A. The molecular weight in terms of polystyrene of the polymer compound A measured by GPC was a weight average molecular weight of 47300 and a number average molecular weight of 14300.

Example 3
(Production and evaluation of ink and organic thin film solar cell)
A glass substrate on which an ITO film having a thickness of 150 nm was applied by a sputtering method was subjected to surface treatment using an ozone UV apparatus. Next, polymer compound A and phenyl C61-butyric acid methyl ester (fullerene C60PCBM) (manufactured by Frontier Carbon) were dissolved in orthodichlorobenzene so that the weight ratio of fullerene C60PCBM to polymer compound A was 3, and the ink 1 was produced. In ink 1, the total weight of polymer compound A and fullerene C60PCBM was 2.0% by weight with respect to the weight of ink 1. The ink 1 was applied on the ITO film of the glass substrate by spin coating to produce an organic film containing the polymer compound A. The thickness of the organic film was about 100 nm. The light absorption terminal wavelength of the organic film was measured and found to be 880 nm. Then, on the organic film, lithium fluoride was vapor-deposited with a thickness of 2 nm 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 7.24 mA / cm ² , Voc (open end voltage) is 0.673 V, ff (fill factor) is 0.595, and photoelectric conversion efficiency (η ) Was 2.90%.

Example 4
(Production and evaluation of organic thin-film solar cells)
In Example 3, an organic thin film solar cell was produced in the same manner except that [6,6] phenyl-C71 butyric acid methyl ester (fullerene C70PCBM) (manufactured by Frontier Carbon Co.) was used instead of fullerene C60PCBM, and the photoelectric conversion efficiency The short-circuit current density, the open-circuit voltage and the fill factor were determined. The light absorption terminal wavelength of the organic film was 880 nm. Jsc (short circuit current density) is 11.67 mA / cm ² , Voc (open circuit voltage) is 0.638 V, ff (fill factor) is 0.534, and photoelectric conversion efficiency (η ) Was 3.97%.

化合物５ 化合物３

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、国際公開第２０１１／０５２７０９号に記載された方法で合成した化合物５を２７０ｍｇ（０．２４３ｍｍｏｌ）、化合物３を１００ｍｇ（０．２４３ｍｍｏｌ）、トルエンを２０ｍｌ入れて均一な溶液とした。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３．３３ｍｇ（０．００３６ｍｍｏｌ）、トリス(２−トルイル)ホスフィンを６．６ｍｇ（０．０２２ｍｍｏｌ）加え、１００℃で６時間攪拌した。その後、反応液にフェニルトリメチルスズを１０ｍｇ加え、３時間反応させた。その後、フェニルブロミドを５０ｍｇ加え、さらに５時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール３００ｍＬに注いだ。析出したポリマーを濾過して集め、得られたポリマーを、円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒濾紙内に残ったポリマーを、トルエン１００ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２ｇと水４ｍＬを加え、８時間還流下で攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３重量%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９ｍＬに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーを濾過後、乾燥させ、精製された重合体を１２９ｍｇ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のポリスチレン換算の分子量は、重量平均分子量が５１７００であり、数平均分子量が１６４００であった。 Example 5
(Synthesis of polymer compound B)

Compound 5 Compound 3

In a 200 mL flask in which the gas in the flask was replaced with argon, 270 mg (0.243 mmol) of Compound 5 synthesized by the method described in International Publication No. 2011/052709, 100 mg (0.243 mmol) of Compound 3, and toluene were added. 20 ml was put into a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.33 mg (0.0036 mmol) of tris (dibenzylideneacetone) dipalladium and 6.6 mg (0.022 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, 10 mg of phenyltrimethyltin was added to the reaction solution and reacted for 3 hours. Thereafter, 50 mg of phenyl bromide was added, and the mixture was further stirred for 5 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 0.2 g of sodium diethyldithiocarbamate and 4 mL of water were added, and the mixture was stirred under reflux for 8 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% by weight aqueous acetic acid solution and then twice with 50 mL of water, and the resulting solution was poured into methanol. To precipitate the polymer. The polymer was filtered and dried, and the resulting polymer was dissolved in 9 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 129 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound B. The molecular weight in terms of polystyrene of the polymer compound B measured by GPC was a weight average molecular weight of 51700 and a number average molecular weight of 16,400.

Example 6
(Production and evaluation of organic thin-film solar cells)
In Example 3, an organic thin film solar cell was prepared in the same manner except that the polymer compound B was used instead of the polymer compound A, and the photoelectric conversion efficiency, the short-circuit current density, the open-circuit voltage, and the fill factor were determined. The light absorption terminal wavelength of the organic film was 880 nm. Jsc (short circuit current density) is 6.56 mA / cm ² , Voc (open circuit voltage) is 0.667 V, ff (fill factor) is 0.565, and photoelectric conversion efficiency (η ) Was 2.47%.

Example 7
(Production and evaluation of organic thin-film solar cells)
In Example 6, an organic thin-film solar cell was produced in the same manner except that fullerene C70PCBM was used instead of fullerene C60PCBM, and photoelectric conversion efficiency, short-circuit current density, open-end voltage, and fill factor were determined. The light absorption terminal wavelength of the organic film was 880 nm. Jsc (short circuit current density) is 10.2 mA / cm ² , Voc (open circuit voltage) is 0.655 V, ff (fill factor) is 0.531, and photoelectric conversion efficiency (η ) Was 3.55%.

化合物６ 化合物７

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６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、室温（２５℃）で２４時間攪拌した。反応後、反応液に水１００ｍＬを加え、ヘキサンで生成物を抽出し、展開溶媒がヘキサンであるシリカゲルカラムで精製を行い、化合物７を２．６１ｇ得た。 Reference example 3
(Synthesis of Compound 7)

Compound 6 Compound 7

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.78 g (10.0 mmol) of compound 6, 5.83 g (25.0 mmol) of 2-ethylhexyl bromide, and 41.5 mg (0.25 mmol) of potassium iodide. ) And 1.68 g (30.0 mmol) of potassium hydroxide were 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 to the reaction solution, the product was extracted with hexane, and purified with a silica gel column where the developing solvent was hexane to obtain 2.61 g of Compound 7.

化合物７ 化合物８

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７を１．３１ｇ（３．２５ｍｍｏｌ)、Ｎ，Ｎ−ジメチルホルムアミドを２５ｍＬ加え、フラスコを０℃に冷却して、Ｎ−ブロモスクシンイミドを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。展開溶媒がヘキサンであるシリカゲルカラムで精製を行い、化合物８を１．７０ｇ得た。 Reference example 4
(Synthesis of Compound 8)

Compound 7 Compound 8

To a 200 mL flask in which the gas in the flask was replaced with argon, 1.31 g (3.25 mmol) of Compound 7 and 25 mL of N, N-dimethylformamide were added, the flask was cooled to 0 ° C., and 1 N-bromosuccinimide was added. .21 g was added and 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. Purification was performed with a silica gel column in which the developing solvent was hexane, and 1.70 g of Compound 8 was obtained.

化合物９ 化合物８
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８を５６１ｍｇ（１．００ｍｍｏｌ）、化合物９（シグマアルドリッチ社製）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）、シグマアルドリッチ社製）を２０２ｍｇ加え、トルエン２０ｍｌに溶解させ、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、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)ホスフィンを１２．３ｍｇ、１６．７重量％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５０ｍｇを加え、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。水層を除去後、有機層を水２０ｍｌで２回洗浄し、次いで、３重量%の酢酸水溶液２０ｍＬで２回洗浄し、さらに水２０ｍＬ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、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、精製された重合体を２８０ｍｇ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のポリスチレン換算の分子量は、重量平均分子量が３００００であり、数平均分子量が１４０００であった。 Reference Example 5
(Synthesis of polymer compound C)

Compound 9 Compound 8
In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of Compound 8, 388.1 mg (1.00 mmol) of Compound 9 (manufactured by Sigma-Aldrich), methyltrialkylammonium chloride (trade name Aliquat 336) (Registered Trademark, manufactured by Sigma-Aldrich) (202 mg) was added and dissolved in 20 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine, and 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, followed by stirring at 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, the organic layer was washed twice with 20 ml of water, then twice with 20 mL of a 3% by weight acetic acid aqueous solution and further twice with 20 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 in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer. The polymer was filtered and dried to obtain 280 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound C. The molecular weight in terms of polystyrene of the polymer compound C measured by GPC was a weight average molecular weight of 30,000 and a number average molecular weight of 14,000.

Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
In Example 3, an organic thin film solar cell was produced in the same manner except that the polymer compound C was used instead of the polymer compound A, and the photoelectric conversion efficiency, the short-circuit current density, the open-circuit voltage and the fill factor were determined. The light absorption terminal wavelength of the organic film was 870 nm. The results are shown in Table 1.

化合物１０ 化合物１１

２００ｍＬフラスコ内に、化合物１０（ＣＨＥＭＳＴＥＰ社製）を２．００ｇ、ヨウ素を５．００ｇ、三酸化硫黄を３０重量％含む発煙硫酸を２０ｍＬ入れて均一な溶液とした。フラスコを６０℃のオイルバスに浸し、１２時間加熱下で得られた溶液を攪拌した。その後、反応液を２５℃まで冷却し、１ｋｇの砕いた氷中に徐々に注いだ。得られた懸濁液にクロロホルムを１００ｍＬ加え、分液ロートでクロロホルム層を分離した。得られたクロロホルム層を硫酸ナトリウムで乾燥させ、濾過した。得られた濾液をエバポレーターで濃縮して溶媒を留去し、粗生成物を得た。得られた粗生成物を、シリカゲルカラムを備えたクロマトグラフィで精製し、化合物１１を１．２３ｇ得た。クロマトグラフィの展開溶媒には、ヘキサンと酢酸エチルとを、ヘキサンの容積に対する酢酸エチルの容積比が４となるよう混合した混合溶媒を用いた。 Reference Example 6
(Synthesis of Compound 11)

Compound 10 Compound 11

In a 200 mL flask, 2.00 g of Compound 10 (manufactured by CHEMSTEP), 5.00 g of iodine, and 20 mL of fuming sulfuric acid containing 30% by weight of sulfur trioxide were added to obtain a uniform solution. The flask was immersed in an oil bath at 60 ° C., and the resulting solution was stirred under heating for 12 hours. Thereafter, the reaction solution was cooled to 25 ° C. and gradually poured into 1 kg of crushed ice. 100 mL of chloroform was added to the obtained suspension, and the chloroform layer was separated with a separatory funnel. The resulting chloroform layer was dried over sodium sulfate and filtered. The obtained filtrate was concentrated with an evaporator and the solvent was distilled off to obtain a crude product. The obtained crude product was purified by chromatography equipped with a silica gel column to obtain 1.23 g of compound 11. As a developing solvent for the chromatography, a mixed solvent in which hexane and ethyl acetate were mixed so that the volume ratio of ethyl acetate to hexane volume was 4 was used.

¹⁹ F NMR in CDCl ₃ (ppm): −112.0

化合物１１ 化合物１２

１００ｍＬフラスコに、ヘキサノールを１０２ｍｇ（１．０ｍｍｏｌ）、テトラヒドロフランを１０ｍＬ入れた。フラスコを２５℃に保ったまま、６０重量％の水素化ナトリウムの鉱物油中に分散させた分散液を４０ｍｇ（１．０ｍｍｏｌ）添加した。添加後、３０分攪拌し、その後、化合物１１を４０７．９ｍｇ（１．０ｍｍｏｌ）加えた。その後、２５℃で６時間攪拌した。攪拌後、塩化アンモニウム水溶液を１００ｍＬ加えて反応を停止し、酢酸エチル５０ｍＬで２回抽出した。有機層を飽和塩化ナトリウム水溶液で洗浄し、硫酸ナトリウムを用いて乾燥させた。有機層を濾過後、濾液をロータリーエバポレーターで濃縮し、溶媒を留去して粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィで精製し、化合物１２を２００ｍｇ得た。シリカゲルカラムクロマトグラフィーの溶出溶媒には、ヘキサンと酢酸エチルとを酢酸エチルの体積に対するヘキサンの体積比が５０となるように混合した液を用いた。 Example 8
(Synthesis of Compound 12)

Compound 11 Compound 12

In a 100 mL flask, 102 mg (1.0 mmol) of hexanol and 10 mL of tetrahydrofuran were added. While the flask was kept at 25 ° C., 40 mg (1.0 mmol) of a dispersion dispersed in 60 wt% sodium hydride mineral oil was added. After the addition, the mixture was stirred for 30 minutes, and then 407.9 mg (1.0 mmol) of Compound 11 was added. Then, it stirred at 25 degreeC for 6 hours. After stirring, 100 mL of an aqueous ammonium chloride solution was added to stop the reaction, and the mixture was extracted twice with 50 mL of ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution and dried using sodium sulfate. After filtering the organic layer, the filtrate was concentrated on a rotary evaporator, and the solvent was distilled off to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 200 mg of compound 12. As an elution solvent for silica gel column chromatography, a solution in which hexane and ethyl acetate were mixed so that the volume ratio of hexane to the volume of ethyl acetate was 50 was used.

¹ H NMR (CDCl ₃ , ppm): 4.29 (t, 2H), 1.92 (m, 2H), 1.41 (m, 4H), 1.25 (t, 2H), 0.92 ( m, 3H)
¹⁹ F NMR (CDCl ₃ , ppm): −115.5 (s, 1F)

化合物４ 化合物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４を２５８ｍｇ（０．２４５ｍｍｏｌ）、化合物１２を１２０ｍｇ（０．２４５ｍｍｏｌ）、トルエンを２０ｍｌ入れて均一な溶液とした。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３．３６ｍｇ（０．００３７ｍｍｏｌ）、トリス(２−トルイル)ホスフィンを６．７ｍｇ（０．０２２ｍｍｏｌ）加え、１００℃で６時間攪拌した。その後、反応液にフェニルトリメチルスズ１０ｍｇを加えて３時間反応させ、その後フェニルブロミドを５０ｍｇ加え、さらに５時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール３００ｍＬに注いだ。析出したポリマーを濾過して集め、得られたポリマーを、円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒濾紙内に残ったポリマーを、トルエン１００ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２ｇと水４ｍＬを加え、８時間還流下で攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３重量%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９ｍＬに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーを濾過後、乾燥させ、精製された重合体５６ｍｇを得た。以下、この重合体を高分子化合物Ｄと呼称する。ＧＰＣで測定した高分子化合物Ｄのポリスチレン換算の分子量は、重量平均分子量が１２９００であり、数平均分子量が９３００であった。 Example 9
(Synthesis of polymer compound D)

Compound 4 Compound 12

In a 200 mL flask in which the gas in the flask was replaced with argon, 258 mg (0.245 mmol) of compound 4, 120 mg (0.245 mmol) of compound 12, and 20 ml of toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.36 mg (0.0037 mmol) of tris (dibenzylideneacetone) dipalladium and 6.7 mg (0.022 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, 10 mg of phenyltrimethyltin was added to the reaction solution and reacted for 3 hours, and then 50 mg of phenylbromide was added, followed by further stirring for 5 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 0.2 g of sodium diethyldithiocarbamate and 4 mL of water were added, and the mixture was stirred under reflux for 8 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% by weight aqueous acetic acid solution and then twice with 50 mL of water, and the resulting solution was poured into methanol. To precipitate the polymer. The polymer was filtered and dried, and the resulting polymer was dissolved in 9 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 56 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound D. The molecular weight in terms of polystyrene of the polymer compound D measured by GPC was a weight average molecular weight of 12,900 and a number average molecular weight of 9,300.

Claims (15)

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

(1)
[Wherein, X ¹ and X ² each independently represent a nitrogen atom or ═CH—. Y ¹ is a sulfur atom, an oxygen atom, a selenium atom, -N ^{(R 1)} - or ^-CR 2 = CR ³ - represents a. R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ¹ represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ² represents a group different from W ¹ . ]   The polymer compound according to claim 1, which is a π-conjugated polymer compound. The polymer compound according to claim 1, wherein W ¹ is a fluorine atom. W < ² > is an alkoxy group, The high molecular compound as described in any one of Claims 1-3. The polymer compound according to claim 1, wherein at least one of X ¹ and X ² is a nitrogen atom. The polymer compound according to claim 5, wherein X ¹ and X ² are nitrogen atoms. Y < ¹ > is a sulfur atom or an oxygen atom, The high molecular compound as described in any one of Claims 1-6. Furthermore, the high molecular compound as described in any one of Claims 1-7 containing the structural unit represented by Formula (2).

(2)
[Wherein Ar ¹ represents an arylene group or a divalent heterocyclic group. ] The polymer compound according to claim 8, wherein Ar ¹ is a divalent heterocyclic group.   The polymer compound according to claim 9, wherein the divalent heterocyclic group is a group containing a thiophene ring. The compound represented by Formula (3).

(3)
[ ^Wherein , X ^3a1 and X ^3a2 each independently represent a nitrogen atom or ═CH—. Y ^3a1 represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ¹ )-or -CR ² = CR ^3- . R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. W ^3a1 represents a cyano group, a nitro group, a monovalent organic group having a fluorine atom, or a fluorine atom. W ^3a2 represents a group different from W ^3a1 . Q ^3a1 and Q ^3a2 each independently represent a chlorine atom, a bromine atom, an iodine atom, a dihydroxyboryl group, or a monovalent organic group. ] The compound according to claim 11, wherein Q ^3a1 and Q ^3a2 are a dihydroxyboryl group, a boric acid ester residue, or a substituted stannyl group.   It has a 1st electrode and a 2nd electrode, it has an active layer between this 1st electrode and this 2nd electrode, and this active layer is any one of Claims 1-10. The photoelectric conversion element containing the high molecular compound of Claim 13, or the compound of Claim 11 or 12.   It has a gate electrode, a source electrode, a drain electrode, and an active layer, The polymer compound as described in any one of Claims 1-10 or the compound as described in Claim 11 or 12 is provided in this active layer. Contains organic thin film transistor.   It has a 1st electrode and a 2nd electrode, has a light emitting layer between this 1st electrode and this 2nd electrode, and it is in any 1 paragraph of Claims 1-10 in this light emitting layer. An organic electroluminescence device comprising the polymer compound according to claim 11 or the compound according to claim 11 or 12.