JP2013079302A - Polymer compound and electronic element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound having high ionization potential.SOLUTION: The polymer compound includes a constitutional unit represented by formula (I). In the formula: X is a sulfur atom, an oxygen atom, a selenium atom, -NH- or -N(R)-; Z is an oxygen atom, a sulfur atom, -C(=O)-, -S(=O)-, -SO-, -Si(R)-, -N(R)-, -B(R)-, -P(R)- or -P(=O)(R)-; and two X may be the same or different from each other.

Description

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

In recent years, in order to prevent global warming, reduction of CO ₂ released into the atmosphere has been demanded. Therefore, the adoption of a solar system using a pn junction type silicon-based solar cell which is one embodiment of an electronic element has been proposed. However, single crystal silicon, polycrystalline silicon, and amorphous silicon, which are materials for silicon-based solar cells, require high temperature and high vacuum processes in their production.

  On the other hand, organic thin-film solar cells containing an organic layer containing a polymer compound can omit the high-temperature and high-vacuum processes used in the production process of silicon-based solar cells, and can be manufactured inexpensively only by the coating process. Yes, it has been attracting attention in recent years. As a polymer compound used for an organic thin film solar cell, a polymer compound composed of a repeating unit (A) and a repeating unit (B) has been proposed (Patent Document 1).

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, the polymer compound has an ionization potential of 5.0 eV, and the ionization potential is not necessarily sufficiently large. When a compound having a small ionization potential is used for the electron donating compound or the electron accepting compound contained in the photoelectric conversion element, the open-circuit voltage of the photoelectric conversion element is reduced.

  An object of the present invention is to provide a polymer compound having a sufficiently high ionization potential.

（Ｉ）
（式中、Ｘは、硫黄原子、酸素原子、セレン原子、−ＮＨ−、又は、−Ｎ（Ｒ）−を表わす。２個あるＸは、同一でも相異なってもよい。Ｚは、酸素原子、硫黄原子、−Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）−、−ＳＯ_２−、−Ｓｉ（Ｒ）_２−、−Ｎ（Ｒ）−、−Ｂ（Ｒ）−、−Ｐ（Ｒ）−又は−Ｐ（＝Ｏ）（Ｒ）−を表す。Ｒは、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。複数個あるＲは、同一でも相異なってもよい。） That is, the present invention first provides a polymer compound containing the structural unit represented by the formula (I).

(I)
(In the formula, X represents a sulfur atom, an oxygen atom, a selenium atom, —NH—, or —N (R) —. The two Xs may be the same or different. Z represents an oxygen atom. , Sulfur atom, —C (═O) —, —S (═O) —, —SO ₂ —, —Si (R) ₂ —, —N (R) —, —B (R) —, —P ( R)-or -P (= O) (R)-, where R represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted. An 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 , Optionally substituted arylalkylthio group, acyl group, acyl Oxy group, amide group, imide group, imino 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, substituted And represents an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or a cyano group, and a plurality of R may be the same or different.

（ＩＩ）
（式中、Ｚ及びＲは、前述と同じ意味を表わす。） The present invention secondly provides the polymer compound, wherein the structural unit represented by the formula (I) is the structural unit represented by the formula (II).

(II)
(In the formula, Z and R have the same meaning as described above.)

（ＩＩＩ）
（式中、Ｒは、前述と同じ意味を表わす。） Thirdly, the present invention provides the polymer compound, wherein the structural unit represented by the formula (II) is a structural unit represented by the formula (III).

(III)
(In the formula, R represents the same meaning as described above.)

  Fourthly, the present invention provides the polymer compound having a polystyrene equivalent weight average molecular weight of 3000 or more.

  Fifthly, the present invention provides a thin film containing the polymer compound.

  Sixthly, this invention provides the composition containing the said high molecular compound and an electron-accepting compound.

  Seventh, the present invention provides the composition, wherein the electron-accepting compound is a fullerene derivative.

  Eighth, the present invention provides a thin film containing the composition.

  Ninthly, the present invention provides an electronic device using the thin film.

（ＩＶ）
（式中、Ｒは、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルキルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。２個あるＲは、同一でも相異なってもよい。Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。） Tenth aspect of the present invention provides a compound represented by formula (IV).

(IV)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted group. An optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkyloxy group, an optionally substituted arylalkylthio group, Acyl group, acyloxy group, amide group, imido group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio Group, arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, carboxyl group Represents a cyano group, and two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. The two Ws may be the same or different.)

（Ｖ）
（式中、Ｒは、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。２個あるＲは、同一でも相異なってもよい。Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。Ｖは、水素原子、アルカリ金属、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アリールアルキルを表す。２個あるＶは、同一でも相異なってもよい。） Eleventhly, the present invention provides a compound represented by formula (V).

(V)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted 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, imino 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, An optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or Each of the two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. Two W's may be the same or different, and V represents a hydrogen atom, an alkali metal, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted arylalkyl. The two Vs may be the same or different.)

（ＶＩ）
（式中、Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。） Twelfthly, the present invention provides a compound represented by formula (VI).

(VI)
(In the formula, W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group. The two Ws may be the same or different.)

  Since the polymer compound of the present invention has a large ionization potential, the present invention is extremely useful.

  Hereinafter, the present invention will be described in detail.

（Ｉ） The polymer compound of the present invention has a structural unit represented by the formula (I).

(I)

  In the formula (I), R represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, or 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, Acyl group, acyloxy group, amide group, imido group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio Group, arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, carboxyl group It represents a cyano group. A plurality of R may be the same or different.

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

  The alkyl group represented by R 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 have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl grave, a pentyl group, and an isopentyl group. 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3 , 7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups, cyclopentyl group, cyclohexyl group and adamantyl group and other cycloalkyl groups Is mentioned.

  The alkyl part of the alkoxy group represented by R 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 represented by R 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.

  The aryl group represented by R means a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is usually 6 to 60. The aryl group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the aryl group 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.

  The aryloxy group represented by R 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 pentafluorophenyl. An oxy group is mentioned.

  The arylthio group represented by R 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 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 represented by R 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 represented by R 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 represented by R 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.

  The acyl group represented by R means a group excluding the hydroxyl group in the carboxylic acid, and usually has 2 to 20 carbon atoms. 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 represented by R means a group in which a hydrogen atom in carboxylic acid is removed, and the number of carbon atoms 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.

  The amide group represented by R means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide, and the number of carbon atoms is usually 1-20. 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 represented by R means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an imide (—CO—NH—CO—), and specific examples include a succinimide group and a phthalimide group. It is done.

  The substituted amino group represented by R is a group in which one or two hydrogen atoms of the amino group are substituted. Examples of the substituent include an optionally substituted alkyl group and a substituted group. A good aryl group. Specific examples of the optionally substituted alkyl group and the optionally substituted aryl group are the same as the specific examples of the optionally substituted alkyl group and the optionally substituted aryl group represented by R. is there. Carbon number of a substituted amino group is 1-40 normally. Specific examples of the substituent 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 al Kiroxyphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkoxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkylamino group Groups, di (C1-C12 alkoxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl-C1 ~ C12 Al Arylamino group, and the like.

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

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

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

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

  The heterocyclic group represented by R is an optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, Prazolidine, furazane, triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, Indoline, isoindoline, chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole Indazole, naphthyridine, quinoxaline, quinazoline, quinazoline, cinnoline, 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. As the heterocyclic group, an aromatic heterocyclic group is preferable.

（Ａ−１） （Ａ−２）
（式（Ａ−１）及び式（Ａ−２）中、Ａｒ^１は複素環基を表す。） Examples of the heterocyclic oxy group represented by R include a group represented by the formula (A-1) in which an oxygen atom is bonded to the above heterocyclic group.
Examples of the heterocyclic thio group represented by R include a group represented by the formula (A-2) in which a sulfur atom is bonded to the above heterocyclic group.

(A-1) (A-2)
(In Formula (A-1) and Formula (A-2), Ar ¹ represents a heterocyclic group.)

The heterocyclic oxy group usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
The heterocyclic thio group usually has 2 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

  The arylalkenyl group represented by R 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 represented by R 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.

  In formula (I), X represents a sulfur atom, an oxygen atom, a selenium atom, -NH-, or -N (R)-. Two Xs may be the same or different. From the viewpoint of increasing the photoelectric conversion efficiency of the organic thin film solar cell containing the organic layer containing the polymer compound of the present invention, X is preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom.

In formula (I), Z is an oxygen atom, a sulfur atom, -C (= O) -, - S (= O) -, - SO 2 -, - Si (R) 2 -, - N (R) - , -B (R)-, -P (R)-or -P (= O) (R)-. From the viewpoint of ease of production of the monomer that is a raw material for the polymer compound of the present invention, Z is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

  From the viewpoint of increasing the solubility of the polymer compound of the present invention in a solvent, R is an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an alkylthio group having 6 or more carbon atoms, an aryl group, or an aryloxy group. An arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group having 6 or more carbon atoms and an acyloxy group having 6 or more carbon atoms, an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, An aryl group and an aryloxy group are more preferable, and an alkyl group having 6 or more carbon atoms is more preferable.

  Examples of the alkyl group having 6 or more carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl Group, icosyl group, triacontyl group, tetracontyl group, pentacontyl group and other linear alkyl groups, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 2-ethylhexyl group, 3,7 -Dimethyloctyl group, 1-propylpentyl group, 2-hexyldecyl group, 2-heptylundecyl group, 2-octyldodecyl group, 3,7,11-trimethyldodecyl group, 3,7,11,15-tetramethyl Branched alkyl groups such as hexadecyl group and 3,5,5-trimethylhexyl group It is below.

  The alkyl group having 6 or more carbon atoms is hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethylhexyl, 3, 7 -Dimethyloctyl, 1-propylpentyl and 2-hexyldecyl are preferred, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl, 2-ethylhexyl, 3,7-dimethyloctyl and 2-hexyldecyl group is more preferable, and hexyl group, octyl group, hexadecyl group, 2-ethylhexyl group and 3,7-dimethyloctyl group are more preferable.

  As the aryl group, a phenyl group substituted with an alkyl group is preferable. The position where the alkyl group is substituted with the phenyl group is preferably the para position. Examples of the phenyl group substituted with an alkyl group at the para position include p-hexylphenyl group, p-heptylphenyl group, p-octylphenyl group, p-nonylphenyl group, p-decylphenyl group, p-undecylphenyl group, p-dodecylphenyl group, p-tridecylphenyl group, p-tetradecylphenyl group, p-pentadecylphenyl group, p-hexadecylphenyl group, p-2-ethylhexylphenyl group, p-3,7-dimethyloctyl A phenyl group, p-1-propylpentylphenyl group and p-2-hexyldecylphenyl group are preferred, and p-hexylphenyl group, p-heptylphenyl group, p-octylphenyl group, p-dodecylphenyl group, p-penta Decylphenyl group, p-hexadecylphenyl group, p-2-ethylhexylphenyl group, -3,7-dimethyloctylphenyl group and p-2-hexyldecylphenyl group are more preferred, p-dodecylphenyl group, p-pentadecylphenyl group, p-2-ethylhexylphenyl group and p-3,7-dimethyl An octylphenyl group is more preferred.

（ＩＩ）
（式中、Ｚ及びＲは、前述と同じ意味を表わす。） From the viewpoint of increasing the open-circuit voltage of the organic solar cell including the polymer compound of the present invention, the structural unit represented by the formula (I) is preferably a structural unit represented by the formula (II).

(II)
(In the formula, Z and R have the same meaning as described above.)

  From the viewpoint of ease of synthesis of the polymer compound, the structural unit represented by the formula (I) is represented by the structural unit represented by the formula (III) and the formulas (B-2) to (B-16). The structural unit represented is preferred.

（式（ＩＩＩ）及び式（Ｂ−２）〜式（Ｂ−１６）中、Ｒは、前述と同じ意味を表わす。）

(In formula (III) and formula (B-2) to formula (B-16), R represents the same meaning as described above.)

  Among the structural units represented by the formula (III) and the structural units represented by the formulas (B-2) to (B-16), the photoelectric conversion efficiency of the organic thin-film solar cell using the polymer compound of the present invention From the viewpoint of enhancing the ratio, preferably, the structural unit represented by the formula (III) and the structural unit represented by the formula (B-2) to the formula (B-4) are preferable, and are represented by the formula (III). The structural unit represented by the structural unit and the formula (B-4) is more preferred, and the structural unit represented by the formula (III) is more preferred.

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

（ＶＩＩＩ）
（式中、Ａｒ^２は、置換基を有していてもよいアリーレン基又は２価の複素環基を表す。ただし、Ａｒ^２は、式（Ｉ）で表される構成単位とは異なる。） Examples of the structural unit different from the structural unit represented by formula (I) include the structural unit represented by formula (VIII).

(VIII)
(In the formula, Ar ² represents an arylene group or a divalent heterocyclic group which may have a substituent. However, Ar ² is different from the structural unit represented by the formula (I).)

  An arylene group means the group remove | excluding two hydrogen atoms on an aromatic ring from aromatic hydrocarbon, The carbon number is 6-60 normally, Preferably it is 6-20. The arylene group includes a group containing a benzene ring, a group containing a condensed ring, a group containing a structure in which two or more rings selected from the group consisting of a benzene ring and a condensed ring are directly bonded, a group consisting of a benzene ring and a condensed ring. And a group containing a structure in which two or more rings selected from are bonded via a group such as vinylene. The arylene 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).

  Examples of the arylene group which may have a substituent include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalenediyl group (formulas 4 to 13 in the following figure), and an anthracenediyl group (formulas 14 to 19 in the following figure). , Biphenyl-diyl groups (formulas 20 to 25 in the lower figure), terphenyl-diyl groups (formulas 26 to 28 in the lower figure), and condensed ring compound groups (formulas 29 to 38 in the lower figure). The condensed ring compound group includes a fluorene-diyl group (formulas 36 to 38 in the following figure).

  The divalent heterocyclic group is an optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine , Furazane, triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline , Isoindoline, chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, Such as dazole, naphthyridine, quinoxaline, quinazoline, quinazoline, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine And a group obtained by removing two hydrogen atoms from a heterocyclic compound. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable.

As a divalent heterocyclic group,
Divalent heterocyclic group containing nitrogen as a hetero atom: pyridine-diyl group (formulas 39 to 44 in the following figure), diazaphenylene group (formulas 45 to 48 in the following figure), quinoline diyl group (formulas 49 to 63 in the following figure) A quinoxaline diyl group (formulas 64-68 in the figure below), an acridine diyl group (formulas 69-72 in the figure below), a bipyridyldiyl group (formulas 73-75 in the figure below), a phenanthroline diyl group (formulas 76-78 in the figure below)
Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (the following formulas 79 to 84 and formulas 88 to 93);
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulae 94 to 98 in the following figure);
5-membered ring condensed hetero groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 99 to 110 in the following figure);
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, bonded at the α-position of the heteroatom to form a dimer or oligomer (formulas 111 to 112 in the following figure);
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom, which is bonded to the phenyl group at the α-position of the heteroatom (formulas 113 to 119 in the figure below);
Groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom (formulas 120 to 127 in the following figure);
Examples include groups in which 5-membered heterocycles containing nitrogen, sulfur, selenium, etc. as heteroatoms are condensed (see FIGS. 128 to 139 below); groups in which benzene rings and thiophene rings are condensed (see FIGS. 140 to 143 below). .

  In Formula 1 to Formula 143, R represents the same meaning as described above. a and b represent the integer of 1-5 each independently. a and b are preferably 1 to 3, and more preferably 1.

（式中、Ｒは、前述と同じ意味を表す。Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。Ｒ^１とＲ^２は、連結して環状構造を形成してもよい。環Ｃｙは、置換基を有していてもよい芳香環を表す。環Ｃｙ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^３は、２価の基を表す。） As the structural unit different from the structural unit represented by the formula (I), from the viewpoint of increasing the photoelectric conversion efficiency of the organic thin film solar cell containing the polymer compound of the present invention, the formula (Cy-1) to the formula ( The structural unit represented by Cy-5) is preferred.

(Wherein R represents the same meaning as described above. R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted group. Alkylthio group which may be substituted, aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, Arylalkylthio group which may be substituted, acylalkylthio group which may be substituted, acyl group, acyloxy group, amide group, imido group, imino 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, substituted Which do may be arylalkynyl group, .R ¹ and R ² representing a carboxyl group or a cyano group, linked to may form a cyclic structure. Ring Cy is optionally aromatic may have a substituent Represents a ring, and when there are a plurality of rings Cy, they may be the same or different. R ³ represents a divalent group.)

Halogen atom represented by R ¹ and R ² , optionally substituted alkyl group, optionally substituted alkoxy group, optionally substituted alkylthio group, optionally substituted aryl group, substituted 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 acyl group, Acyloxy group, amide group, imide 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 aryl Definitions and specific examples of the alkenyl group and the optionally substituted arylalkynyl group include a halogen represented by R. Atoms, optionally substituted alkyl groups, optionally substituted alkoxy groups, optionally substituted alkylthio groups, optionally substituted aryl groups, optionally substituted aryloxy groups, 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, 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 aryl The definition and specific examples of the alkynyl group are the same.

（式（Ｄ−１）〜式（Ｄ−５）中、Ｒは、前述と同じ意味を表す。） R ¹ and R ² may be linked to form a cyclic structure. Specific examples of the cyclic structure include structures represented by formula (D-1) to formula (D-5).

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

  The aromatic ring represented by the ring Cy may be a single ring or a condensed ring. As the monocyclic aromatic ring, for example, benzene ring, pyrrole ring, furan ring, thiophene ring, oxazole ring, thiazole ring, thiadiazole ring, pyrazole ring, pyridine ring, pyrazine ring, imidazole ring, triazole ring, isoxazole ring, Examples include isothiazole ring, pyrimidine ring, pyridazine ring and triazine ring.

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

  Ring Cy may have a substituent. Examples of the substituent include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, and a substituted 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, imino 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, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, carboxyl group and A cyano group. The halogen atom, 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, 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, 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 Definitions and specific examples of a good arylalkynyl group include a halogen atom represented by R, A good alkyl group, 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 acyl group, an acyloxy group, an amide group, an imide group, a substituted amino group, a substituted silyl group, Definitions of substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, optionally substituted arylalkenyl group and optionally substituted arylalkynyl group And the same as the specific example.

（式（ｂ−１）〜式（ｂ−５）中、Ｒは、前述と同じ意味を表す。） Specific examples of the divalent group represented by R ³ include groups represented by formula (b-1) to formula (b-5).

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

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

（式（Ｃ−１）〜式（Ｃ−２９）中、Ｒは前記と同じ意味を表す。）

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

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

The polymer compound of the present invention may have a structure in which a structural unit represented by formula (I) and a structural unit different from the structural unit represented by formula (I) are bonded. Examples of the structure include structures represented by formulas (601) to (648).

（式（６０１）〜（６４８）中、Ｒは、前述と同じ意味を表す。）

(In formulas (601) to (648), R represents the same meaning as described above.)

（ＩＸ） （Ｘ）
(式（ＩＸ）及び式(Ｘ）中、Ａｒ^３は、式（６０１）〜式（６４８）で表される構造を表す。Ａｒ^３が２個ある場合、それらは同一でも相異なってもよい。Ａｒ^４は、置換基を有していてもよいアリーレン基又は２価の複素環基を表す。本発明の高分子化合物は、式（ＩＸ）で表される繰り返し単位２個繋がった連鎖、又は、式（Ｘ）で表される繰り返し単位が２個繋がった連鎖を有していてもよい。 The polymer compound of the present invention may have a repeating unit represented by the formula (IX) or a repeating unit represented by the formula (X).

(IX) (X)
(In Formula (IX) and Formula (X), Ar ³ represents a structure represented by Formula (601) to Formula (648). When two Ar ³ exist, they may be the same or different. Ar ⁴ represents an arylene group or divalent heterocyclic group which may have a substituent, and the polymer compound of the present invention has a chain in which two repeating units represented by the formula (IX) are linked, Alternatively, it may have a chain in which two repeating units represented by the formula (X) are connected.

The definitions and specific examples of the arylene group and the divalent heterocyclic group are the same as the definitions and specific examples of the arylene group and the divalent heterocyclic group represented by Ar ² described above.

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

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

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

As a method using the Suzuki coupling reaction, for example, the formula (100):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
Wherein, E ¹ represents a structural unit represented by the formula (VIII). 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 (I). T ¹ and T ² each independently represent a halogen atom. ]
The manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. E ¹ is preferably a structural unit represented by formula (C-1) to formula (C-29).

  When the compound represented by the formula (100) and the compound represented by the formula (200) are reacted, the total number of moles of one or more compounds represented by the formula (200) used in the reaction is the formula (100). It is preferable that it is excessive with respect to the total number of moles of one or more compounds represented by When the total number of moles of one or more compounds represented by formula (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。） The boric acid ester residue means a group obtained by removing a hydroxyl group from a boric acid diester, and specific examples thereof include a group represented by the following formula.

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

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

  As a specific method for carrying out the Suzuki coupling reaction, there may be mentioned a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is carried out in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium are mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, palladium The catalyst is preferably dichlorobis (triphenylphosphine) palladium, palladium acetate and tris (dibenzylideneacetone) dipalladium.
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 acetates are used in the Suzuki coupling reaction, it is preferable to add a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine as a ligand. When adding a phosphorus compound as a ligand, the addition amount of the ligand 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.

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

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

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

  The Suzuki coupling reaction is performed in a reaction system in which the palladium catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the gas in the polymerization vessel (reaction system) is sufficiently replaced with nitrogen gas and degassed, the polymerization vessel is represented by the compound represented by the formula (100) and the formula (200). A solvent deaerated by charging a compound, a palladium catalyst and dichlorobis (triphenylphosphine) palladium (II), and sufficiently degassing the gas in the polymerization vessel with nitrogen gas, followed by bubbling with nitrogen gas in advance. After adding (for example, toluene), a base degassed by bubbling with nitrogen gas in advance (for example, sodium carbonate aqueous solution) was added dropwise to the solution, and then heated, heated, and refluxed for 8 hours. And polymerizing while maintaining an inert atmosphere.

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 (VIII). 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 structural unit represented by Formula (C-1) to Formula (C-29).

Examples of the substituted stannyl group include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an optionally substituted alkyl group and an optionally substituted aryl group.
Definitions and specific examples of the optionally substituted alkyl group represented by R ¹⁰⁰ and the optionally substituted aryl group include the optionally substituted alkyl group represented by R and the optionally substituted group. The definition and specific examples of the aryl group are the same.
The substituted stannyl group, a group represented by -SnMe _3, a group represented by -SnEt _3, a group represented by -SnBu ₃ and -SnPh ₃ Preferably, the group represented by -SnMe _3, -SnEt A group represented by ₃ and a group represented by —SnBu ₃ are more preferred. 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.

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

A specific method of the Stille coupling reaction includes a method of reacting in an arbitrary solvent in the presence of a catalyst.
Examples of the catalyst used in the Stille coupling reaction include a palladium catalyst. Examples of the palladium catalyst 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 preferred from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate.
The addition amount of the palladium catalyst used in the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (300). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.

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

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

The temperature at which the Stille coupling reaction is performed depends on the solvent, but is usually about 50 to 160 ° C. From the viewpoint of increasing the molecular weight of the polymer compound, 60 to 120 ° C. is preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The 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 gas in the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the compound represented by the formula (300), represented by the formula (200), is represented in the polymerization vessel. Necessary after adding a compound and a palladium catalyst, and after degassing by sufficiently replacing the gas in the polymerization vessel with nitrogen gas, adding a solvent (for example, toluene) deaerated by bubbling with nitrogen gas in advance Depending on the conditions, a ligand and a co-catalyst are added, and then heated, the temperature is raised, for example, polymerization is carried out while maintaining an inert atmosphere at the reflux temperature for 8 hours.

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

  The terminal group of the polymer compound of the present invention is protected with a stable group because if the polymerization active group remains as it is, there is a possibility that the characteristics and life of the element obtained when used for the preparation of the element may be reduced. May be. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group may be used.

（ＩＶ）
（式中、Ｒは、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。２個あるＲは、同一でも相異なってもよい。Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。） The polymer compound of the present invention can be synthesized, for example, by using a compound represented by the formula (IV) as one of the raw materials.

(IV)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted 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, imino 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, An optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or Each of the two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. The two Ws may be the same or different.)

When W is a hydrogen atom, a polymer compound having a structural unit represented by formula (I) can be produced by oxidative polymerization of the compound represented by formula (IV). In oxidative polymerization, a catalyst is usually used. As such a catalyst, a known catalyst can be used. For example, a metal halide or a mixture of a metal halide and an amine complex (metal halide / amine complex) is used. As the metal halide, a monovalent, divalent, or trivalent halide of a metal such as copper, iron, vanadium, or chromium can be used.
Examples of the amine used for producing the amine complex include pyridine, lutidine, 2-methylimidazole, and N, N, N ′, N′-tetramethylethylenediamine. The metal halide / amine complex can be produced by mixing a metal halide and an amine in a solvent in the presence of oxygen. The molar ratio of mixing the metal halide and the amine is, for example, a metal Halide / amine = 1/0. 1 to 1/200, preferably 1 / 0.3 to 1/100.

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

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

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

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

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

（Ｖ）
（式中、Ｒは、水素原子、ハロゲン原子、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ルコキシ基、置換されていてもよいアルキルチオ基、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アリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、イミド基、イミノ基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、複素環基、複素環オキシ基、複素環チオ基、置換されていてもよいアリールアルケニル基、置換されていてもよいアリールアルキニル基、カルボキシル基又はシアノ基を表す。２個あるＲは、同一でも相異なってもよい。Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。Ｖは、水素原子、アルカリ金属、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アリールアルキルを表す。２個あるＶは、同一でも相異なってもよい。） The compound represented by the formula (IV) can be produced by reacting the compound represented by the formula (V) in the presence of an acid.

(V)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted 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, imino 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, An optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or Each of the two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. Two W's may be the same or different, and V represents a hydrogen atom, an alkali metal, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted arylalkyl. The two Vs may be the same or different.)

  The definition and specific examples of the optionally substituted alkyl group represented by V, the optionally substituted aryl group, and the optionally substituted arylalkyl group are the above-described substituted R represented by R. The definitions and specific examples of the alkyl group which may be substituted, the aryl group which may be substituted and the arylalkyl group which may be substituted are the same.

  In formula (V), R is an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an alkylthio group having 6 or more carbon atoms, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group. , An arylalkylthio group, an acyl group having 6 or more carbon atoms, and an acyloxy group having 6 or more carbon atoms are preferable.

The acid used for the synthesis of the compound represented by formula (IV) may be any of Lewis acid or Bronsted acid, hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, sulphuric acid. Examples include acids, benzoic acid, boron fluoride, aluminum chloride, tin (IV) chloride, iron (II) chloride, titanium tetrachloride, benzenesulfonic acid and p-toluenesulfonic acid. Two or more acids may be mixed and used. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.
Solvents used in the reaction include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, chloro Halogenated hydrocarbon solvents such as hexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, tert-butyl alcohol, formic acid, acetic acid, propion Carboxylic acid solvent such as acid, dimethyl ether, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, teto Hydropyran, an ether solvent such as dioxane, hydrochloric, hydrobromic, hydrofluoric, sulfuric acid, and inorganic acids solvents such as nitric acid. These solvents may be used alone or in combination.

  After the reaction, for example, after adding the water to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent to obtain the compound represented by the formula (IV). Can do. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

  In the compound represented by the formula (V), W is preferably a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group or a substituted stannyl group from the viewpoint of ease of functional group conversion.

（ＶＩ）
（式中、Ｗは、水素原子、ハロゲン原子、ホウ酸エステル残基、ジヒドロキシボリル基、ホルミル基、ビニル基又は置換スタンニル基を表す。２個あるＷは、同一でも相異なってもよい。） The compound represented by the formula (V) can be synthesized by reacting the compound represented by the formula (VI) with a Grignard reagent or an organolithium compound.

(VI)
(In the formula, W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group. The two Ws may be the same or different.)

  Examples of the Grignard reagent used in the above reaction include methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, hexyl magnesium bromide, octyl magnesium. Examples include bromide, decylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, benzylmagnesium chloride, phenylmagnesium bromide, naphthylmagnesium bromide, and tolylmagnesium bromide.

  Examples of the organic lithium compound include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, phenyl lithium, naphthyl lithium, benzyl lithium, and tolyl lithium.

  The reaction can be carried out in the presence of a solvent under an inert gas atmosphere such as nitrogen or argon. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

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

  After the reaction, for example, water is added to stop the reaction, and then the product is extracted with an organic solvent, followed by usual post-treatment such as distilling off the solvent to obtain the compound represented by the formula (V). it can. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

（ＶＩＩ）
（式（ＶＩＩ）中、Ｗは、前記と同じ意味を表す。） The compound represented by the formula (VI) can be produced by reacting the compound represented by the formula (VII) with a peroxide.

(VII)
(In formula (VII), W represents the same meaning as described above.)

  Examples of the peroxide include sodium perborate, m-chloroperbenzoic acid, hydrogen peroxide, and benzoyl peroxide. The peroxide is preferably sodium perborate and m-chloroperbenzoic acid, more preferably sodium perborate.

  The reaction can be carried out in the presence of a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid, butyric acid. In order to increase the solubility of the compound represented by the formula (VI), it is preferably carried out in a solvent system in which carbon tetrachloride, chloroform, dichloromethane, benzene, toluene and the like are mixed. The reaction temperature is preferably 0 ° C. to the boiling point of the solvent.

  After the reaction, for example, after adding water to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent to obtain the compound represented by the formula (VI). be able to. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

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 electronic devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.

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

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

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

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

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

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

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

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

As the electron-accepting compound, in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof Derivatives, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof Derivatives, polyfluorenes and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerenes and fullerene derivatives Details, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.

（ＸＩ） （ＸＩＩ） （ＸＩＩＩ） （ＸＩＶ）

（式（ＸＩ）〜（ＸＩＶ）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、芳香族複素環基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂは置換されていてもよいアルキル基又は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 (XI), a compound represented by the formula (XII), a compound represented by the formula (XIII), and a compound represented by the formula (XIV).

(XI) (XII) (XIII) (XIV)

(In the formulas (XI) to (XIV), R ^a is an optionally substituted alkyl group, an optionally substituted aryl group, an aromatic heterocyclic group, or a group having an ester structure. 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 may be the same It may be different.)

The definition and specific examples of the optionally substituted alkyl group represented by R ^a and R ^b and the optionally substituted aryl group are as follows. The definition and specific examples of the aryl group that may be used are the same.

The aromatic heterocyclic group represented by R ^a, of the heterocyclic group represented by the aforementioned R, include groups having aromatic character. The aromatic heterocyclic group usually has 3 to 60 carbon atoms, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

（ＸＶ）
（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芳香族複素環基を表す。） Examples of the group having an ester structure represented by R ^a include a group represented by the formula (XV).

(XV)
(Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an optionally substituted alkyl group, an optionally substituted aryl group or aromatic. Represents a heterocyclic group.)

Optionally substituted good alkyl group represented by R ^c, definitions and specific examples of good substituted aryl group and aromatic heterocyclic group, yo alkyl group optionally substituted as represented by R ^a The definition and specific examples of the aryl group and aromatic heterocyclic group, which may be substituted, are the same.

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

Specific examples of the C ₇₀ fullerene derivative include the following.

  Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C71 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] thienyl- Examples thereof include C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

  When the active layer contains the polymer compound of the present invention and the fullerene derivative, the amount of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is -500 weight part.

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

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

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

  The solvent used for film formation from a solution may be any one that dissolves the polymer compound of the present invention. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Examples thereof include halogenated hydrocarbon solvents such as chlorobutane, 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 ink jet coating method, and a spin coating method are preferable.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

  The polymer compound of the present invention has a large ionization potential and can be suitably used for an active layer of a photoelectric conversion element. When the ionization potential of the electron donating compound or the electron accepting compound contained in the active layer is large, it becomes possible to produce a photoelectric conversion element having a high open circuit voltage, and to produce a photoelectric conversion element having a high photoelectric conversion efficiency. it can.

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

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

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

（式（Ｔ−１）〜式（Ｔ−３）中、Ｘ、Ｚ及びＲは、前述と同じ意味を表す。Ａｒ^５は、置換基を有していてもよいアリーレン基又は２価の複素環基を表す。〕 When the polymer compound of the present invention is used in the active layer of an electrostatic induction organic thin film transistor, from the viewpoint of transistor characteristics, the polymer compound of the present invention is represented by the structural unit represented by the formula (T-1), the formula (T -2) and at least one structural unit selected from the group consisting of the structural unit represented by formula (T-3). From the viewpoint of ease of synthesis, the polymer compound of the present invention is at least one selected from the group consisting of a structural unit represented by formula (T-1) and a structural unit represented by formula (T-2). It is preferable to have the structural unit.

(In formula (T-1) to formula (T-3), X, Z and R represent the same meaning as described above. Ar ⁵ represents an arylene group which may have a substituent or a divalent complex. Represents a cyclic group.]

The definitions and specific examples of the arylene group and divalent heterocyclic group represented by Ar ⁵ are the same as the definitions and specific examples of the arylene group and divalent heterocyclic group represented by Ar ² described above.

  The polymer compound of the present invention is selected from the group consisting of a structural unit represented by the formula (T-1), a structural unit represented by the formula (T-2), and a structural unit represented by the formula (T-3). In the case where at least one kind of structural unit is included, it is preferable that R is a linear alkyl group from the viewpoint of transistor characteristics. Among the linear alkyl groups, a linear alkyl group having 3 to 20 carbon atoms is preferable, and a linear alkyl group having 6 to 18 carbon atoms is more preferable.

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

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

Further, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, a photocurrent flows and the organic light sensor can be operated. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
The above-mentioned organic thin film transistor can be used as a pixel driving element used for controlling the pixel of an electrophoretic display, a liquid crystal display, an organic electroluminescence display, etc., and controlling the uniformity of screen luminance and the screen rewriting speed. .

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

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

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

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

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

５００ｍＬ四ツ口フラスコに、国際公開２００９／６９６８７号のｐ．７７−７８に記載された方法で合成した化合物１を１０．１４ｇ（２０．００ｍｍｏｌ）、クロロホルムを１２０ｍＬ、トリフルオロ酢酸を８０ｍＬ加え、均一な溶液とした。得られた反応液に、過ホウ酸ナトリウム一水和物を４．０ｇ（４０ｍｍｏｌ）加え、６０℃で４８時間攪拌した。その後、反応液に水を２００ｍＬ加え、６０℃で３０分攪拌を行った。反応液中に析出物が析出したことを確認後、反応液をろ過し、黄褐色粉末を得た。得られた褐色粉末を、ヘキサンで洗浄し、化合物２を２．５３ｇ得た。 Example 1
(Synthesis of Compound 2)

In a 500 mL four-necked flask, p. 10.14 g (20.00 mmol) of Compound 1 synthesized by the method described in 77-78, 120 mL of chloroform, and 80 mL of trifluoroacetic acid were added to obtain a uniform solution. To the obtained reaction liquid, 4.0 g (40 mmol) of sodium perborate monohydrate was added and stirred at 60 ° C. for 48 hours. Thereafter, 200 mL of water was added to the reaction solution, and the mixture was stirred at 60 ° C. for 30 minutes. After confirming that a precipitate was deposited in the reaction solution, the reaction solution was filtered to obtain a tan powder. The obtained brown powder was washed with hexane to obtain 2.53 g of Compound 2.

¹ H-NMR (DMSO-d ₆ , δ (ppm)): 9.34 (s, 1H), 9.40 (s, 1H)

グリニャール試薬の調整を行った。２００ｍＬ四ツ口フラスコに、マグネシウム（２５２ｍｇ）、テトラヒドロフラン（２ｍＬ）、ジブロモエタン（１ｍｇ）を加えた後、１−ブロモ−４−ドデシルベンゼン（３．０６ｇ）を加え、６０℃で1時間攪拌した。その後、テトラヒドロフラン（８ｍＬ）を加え、グリニャール溶液を調製した。
３００ｍＬ四ツ口フラスコをアルゴン雰囲気下にし、化合物２（６６１ｍｇ，３．１４ｍｍｏｌ）、テトラヒドロフラン（６６ｍＬ）を入れ、均一な溶液とした。その後、系中の溶存気体をアルゴンにより置換した。系中を−２０℃まで冷却し、調整したグリニャール試薬を５分かけて滴下した。３０分後、反応溶液を室温まで昇温し、4時間攪拌を行った。系中に水（５０ｍＬ）を加え、クロロホルムを用いて有機層を抽出し、化合物３を含む混合物を得た。 Example 2
(Synthesis of Compound 3)

The Grignard reagent was adjusted. After adding magnesium (252 mg), tetrahydrofuran (2 mL), and dibromoethane (1 mg) to a 200 mL four-necked flask, 1-bromo-4-dodecylbenzene (3.06 g) was added, and the mixture was stirred at 60 ° C. for 1 hour. . Thereafter, tetrahydrofuran (8 mL) was added to prepare a Grignard solution.
A 300 mL four-necked flask was placed under an argon atmosphere, and Compound 2 (661 mg, 3.14 mmol) and tetrahydrofuran (66 mL) were added to obtain a uniform solution. Thereafter, the dissolved gas in the system was replaced with argon. The system was cooled to −20 ° C., and the adjusted Grignard reagent was added dropwise over 5 minutes. After 30 minutes, the reaction solution was warmed to room temperature and stirred for 4 hours. Water (50 mL) was added to the system, and the organic layer was extracted with chloroform to obtain a mixture containing Compound 3.

¹ H-NMR (CDCl ₃ , δ (ppm)): 0.88 (t, 6H), 1.26 (m, 32H), 1.54 (m, 8H), 2.51 (t, 4H),
7.01 (d, 4H), 7.19 (d, 4H), 8.25 (s, 1H), 8.82 (s, 1H)

２００ｍＬナス型フラスコに、化合物３を含む混合物、トルエン（５０ｍＬ）、パラトルエンスルホン酸（５ｍｇ）を加え、６０℃で4時間攪拌を行った。反応溶液に水（１００ｍＬ）を加え、クロロホルムを用いて化合物３を含む有機層を抽出した。有機層から、溶媒を留去した後、得られた粗生成物をシリカゲルカラム（ヘキサン：クロロホルム＝１：１）で精製を行い、黒褐色オイルを得た。黒褐色オイルに対し、５０℃に加熱したエタノールを用いた抽出を行った。化合物４はエタノールにより黒褐色オイル中から抽出され、エタノールを留去した後、化合物４を７７３ｍｇ得た。 Example 3
(Synthesis of Compound 4)

A mixture containing Compound 3, toluene (50 mL), and paratoluenesulfonic acid (5 mg) were added to a 200 mL eggplant-shaped flask, and the mixture was stirred at 60 ° C. for 4 hours. Water (100 mL) was added to the reaction solution, and the organic layer containing compound 3 was extracted using chloroform. After the solvent was distilled off from the organic layer, the obtained crude product was purified with a silica gel column (hexane: chloroform = 1: 1) to obtain a black brown oil. The black brown oil was extracted with ethanol heated to 50 ° C. Compound 4 was extracted from black-brown oil with ethanol, and after ethanol was distilled off, 773 mg of compound 4 was obtained.

¹ H-NMR (CDCl ₃ , δ (ppm)): 0.88 (t, 6H), 1.25 (m, 32H), 1.58 (m, 8H), 2.57 (t, 4H),
7.12 (d, 4H), 7.27 (d, 4H), 8.46 (s, 1H), 8.63 (s, 1H)

四つ口フラスコに、化合物４を６８５、１ｍｇ（１．０００ｍｍｏｌ)、ジメチルホルムアミドを４０ｍＬ加え、得られた反応液に室温（２５℃）で３０分間アルゴンガスを導入し、バブリングを行った。その後、Ｎ−ブロモスクシンイミドを７１１．９ｍｇ（４．０００ｍｍｏｌ)加え、室温で攪拌した。３時間後に、液体クロマトグラフィーにより原料の消失を確認した。その後、反応液にチオ硫酸ナトリウム水溶液を加え、さらにヘキサンを加え、有機層の抽出を行った。その後、展開溶媒にヘキサンを用い、トリエチルアミン処理をした中性シリカゲルを用いたカラムクロマトグラフィーにより有機層の分離を行い、分離して得られた成分を乾燥させて溶媒を除去し、化合物５を２５６．０ｍｇ得た。 Example 4
(Synthesis of Compound 5)

Into a four-necked flask, 685, 1 mg (1.000 mmol) of Compound 4 and 40 mL of dimethylformamide were added, and argon gas was introduced into the resulting reaction solution at room temperature (25 ° C.) for 30 minutes for bubbling. Thereafter, 711.9 mg (4.0000 mmol) of N-bromosuccinimide was added and stirred at room temperature. After 3 hours, disappearance of the raw material was confirmed by liquid chromatography. Then, the sodium thiosulfate aqueous solution was added to the reaction liquid, and also hexane was added, and the organic layer was extracted. Thereafter, the organic layer is separated by column chromatography using neutral silica gel treated with triethylamine using hexane as a developing solvent, the components obtained by separation are dried, the solvent is removed, and Compound 5 is converted to 256. 0.0 mg was obtained.

¹ H-NMR (CDCl ₃ , δ (ppm)): 0.88 (t, 6H), 1.25 (m, 32H), 1.58 (m, 8H), 2.57 (t, 4H),
7.12 (d, 4H), 7.28 (d, 4H), 8.47 (s, 1H)

四つ口フラスコに、化合物５を８２．５ｍｇ（０．１０８ｍｍｏｌ）及び、テトラヒドロフランを７ｍＬ加え、室温（２５℃）で３０分間アルゴンバブリングを行った。その後、反応溶液にトリス（ジベンジリデンアセトン）パラジウムを１．９８ｍｇ（０．００２１６ｍｍｏｌ）、［トリ（ターシャリーブチル）ホスホニウム］テトラフルオロボレートを２．５１ｍｇ（０．００８６４ｍｍｏｌ）及び、２ｍｏｌ／Ｌのリン酸カリウム水溶液を０．５ｇ（１．１ｍｍｏｌ）加えた。反応溶液を４５℃で攪拌しながら、２１．０ｍｇの化合物６（０．０５４ｍｍｏｌ）を３ｍＬのテトラヒドロフランに溶かし、その溶液を、５分かけて滴下した。２時間後、液体クロマトグラフィーにより原料の消失を確認した。反応溶液に水及びヘキサンを加え、有機層の抽出を行い、展開溶媒にヘキサン及びクロロホルムを５：５の体積比率調製した溶媒を用い、カラムクロマトグラフィーで有機層の精製を行った。その後、精製した有機層を乾燥させて溶媒を除去し、化合物７を３１ｍｇ得た。 Example 5
(Synthesis of Compound 7)

In a four-necked flask, 82.5 mg (0.108 mmol) of Compound 5 and 7 mL of tetrahydrofuran were added, and argon bubbling was performed at room temperature (25 ° C.) for 30 minutes. Thereafter, 1.98 mg (0.00216 mmol) of tris (dibenzylideneacetone) palladium, 2.51 mg (0.00864 mmol) of [tri (tertiarybutyl) phosphonium] tetrafluoroborate, and 2 mol / L phosphorus were added to the reaction solution. 0.5 g (1.1 mmol) of potassium acid aqueous solution was added. While stirring the reaction solution at 45 ° C., 21.0 mg of compound 6 (0.054 mmol) was dissolved in 3 mL of tetrahydrofuran, and the solution was added dropwise over 5 minutes. After 2 hours, disappearance of the raw material was confirmed by liquid chromatography. Water and hexane were added to the reaction solution, the organic layer was extracted, and the organic layer was purified by column chromatography using a solvent prepared by volume ratio of hexane and chloroform of 5: 5 as a developing solvent. Thereafter, the purified organic layer was dried to remove the solvent, and 31 mg of Compound 7 was obtained.

¹ H-NMR (CDCl ₃ , δ (ppm)): 0.86 (t, 12H), 1.24 (m, 64H), 1.56 (m, 16H), 2.58 (t, 8H),
7.13 (d, 8H), 7.39 (d, 4H), 8.48 (s, 1H), 8.50 (s, 1H)

四つ口フラスコに、化合物７を３１ｍｇ（０．０２１ｍｍｏｌ)、クロロホルムを１０ｍＬ加え、得られた反応液に室温（２５℃）で３０分間アルゴンガスを導入し、バブリングを行った。その後、Ｎ−ブロモスクシンイミドを９．２ｍｇ（０．０５２５ｍｍｏｌ)加え、室温で攪拌した。３時間後に、液体クロマトグラフィーにより原料の消失を確認した。その後、反応液にチオ硫酸ナトリウム水溶液を加え、さらにヘキサンを加え、有機層の抽出を行った。その後、展開溶媒にヘキサンを用い、トリエチルアミン処理をした中性シリカゲルを用いたカラムクロマトグラフィーにより有機層の分離を行い、分離して得られた成分を乾燥させて溶媒を除去し、化合物８を２２．５ｍｇ得た。 Example 6
(Synthesis of Compound 8)

To a four-necked flask, 31 mg (0.021 mmol) of Compound 7 and 10 mL of chloroform were added, and argon gas was introduced into the resulting reaction solution for 30 minutes at room temperature (25 ° C.) to perform bubbling. Thereafter, 9.2 mg (0.0525 mmol) of N-bromosuccinimide was added and stirred at room temperature. After 3 hours, disappearance of the raw material was confirmed by liquid chromatography. Then, the sodium thiosulfate aqueous solution was added to the reaction liquid, and also hexane was added, and the organic layer was extracted. Then, the organic layer is separated by column chromatography using neutral silica gel treated with triethylamine using hexane as a developing solvent, the components obtained by separation are dried, the solvent is removed, and the compound 8 is converted into 22 .5 mg was obtained.

¹ H-NMR (CDCl ₃ , δ (ppm)): 0.86 (t, 12H), 1.24 (m, 64H), 1.56 (m, 16H), 2.58 (t, 8H),
7.13 (d, 8H), 7.38 (d, 4H)

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物９を６．９ｍｇ（０．０１３ｍｍｏｌ）、化合物８を２１．６ｍｇ（０．０１３ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、アルドリッチ社製）を３０ｍｇ加え、トルエン５ｍｌ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、酢酸パラジウムを０．０９ｍｇ、トリス(２−メトキシフェニル)ホスフィン（Ｔｒｉｓ（２−ｍｅｔｈｏｘｙｐｈｅｎｙｌ）ｐｈｏｓｐｈｉｎｅ）を０．４８ｍｇ、１６．７ｗｔ％の炭酸ナトリウム水溶液を０．１ｇ加え、１００℃で５時間攪拌を行った。その後、フェニルホウ酸を５０ｍｇ加え、さらに７０℃で２時間反応させた。その後、ジエチルジチオカルバミン酸ナトリウム２ｇと水２０ｍＬを加え、２時間還流下で攪拌を行った。反応液中の水層を除去後、有機層を水２０ｍｌで２回、３ｗｔ％の酢酸水溶液２０ｍＬで２回、さらに水２０ｍＬで２回洗浄し、メタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをｏ−ジクロロベンゼン３０ｍＬに再度溶解した。ｏ−ジクロロベンゼン溶液をアルミナ／シリカゲルカラムに通し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、精製した重合体Ａを２８０ｍｇ得た。ＧＰＣで測定した重合体Ａの分子量（ポリスチレン換算）はＭｗが５，０００、Ｍｎが３，５００であった。 Example 7
(Synthesis of polymer A)

In a 100 mL flask in which the gas in the flask was replaced with argon, 6.9 mg (0.013 mmol) of compound 9 and 21.6 mg (0.013 mmol) of compound 8, methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark)) (Manufactured by Aldrich) was dissolved in 5 ml of toluene, and the obtained toluene solution was bubbled with argon for 30 minutes. Thereafter, 0.09 mg of palladium acetate, 0.48 mg of tris (2-methoxyphenyl) phosphine (0.18 g) and 0.1 g of a 16.7 wt% aqueous sodium carbonate solution were added, and the mixture was added at 100 ° C. for 5 hours. Stirring was performed. Thereafter, 50 mg of phenylboric acid was added, and the mixture was further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added, and the mixture was stirred under reflux for 2 hours. After removing the aqueous layer in the reaction solution, the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3 wt% acetic acid aqueous solution and further twice with 20 mL of water, and poured into methanol to precipitate a polymer. The polymer was filtered and dried, and the obtained polymer was dissolved again in 30 mL of o-dichlorobenzene. The o-dichlorobenzene solution was passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate a polymer. The polymer was filtered and then dried to obtain 280 mg of purified polymer A. The molecular weight (in terms of polystyrene) of the polymer A measured by GPC was 5,000 for Mw and 3,500 for Mn.

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１０１を１．７８ｇ（１０．０ｍｍｏｌ)、２−エチルヘキシルブロミドを５．８３ｇ（２５．０ｍｍｏｌ)、ヨウ化カリウムを４１．５ｍｇ（０．２５ｍｍｏｌ)、水酸化カリウムを１．６８ｇ（３０．０ｍｍｏｌ)入れ、ジメチルスルホキシド３５ｍＬに溶解させて、室温（２５℃）で２４時間攪拌した。反応後、水１００ｍＬを加え、ヘキサンで生成物を抽出し、ヘキサンを展開溶媒に用いたシリカゲルカラムで精製を行い、化合物１０２を２．６１ｇ得た。 Synthesis example 1
(Synthesis of Compound 102)

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.78 g (10.0 mmol) of compound 101, 5.83 g (25.0 mmol) of 2-ethylhexyl bromide, and 41.5 mg (0.25 mmol) of potassium iodide. ), 1.68 g (30.0 mmol) of potassium hydroxide was dissolved in 35 mL of dimethyl sulfoxide and stirred at room temperature (25 ° C.) for 24 hours. After the reaction, 100 mL of water was added, the product was extracted with hexane, and purified with a silica gel column using hexane as a developing solvent, to obtain 2.61 g of Compound 102.

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１０２を１．３１ｇ（３．２５ｍｍｏｌ)、及び、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を２５ｍＬ加えた。その後、フラスコを０℃に冷却して、Ｎ−ブロモスクシンイミド (１．２１ｇ)を加え、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。シリカゲルカラム(展開溶媒はヘキサン)で精製を行い、化合物１０３を１．７０ｇ得た。 Synthesis example 2
(Synthesis of Compound 103)

To a 200 mL flask in which the gas in the flask was replaced with argon, 1.31 g (3.25 mmol) of Compound 102 and 25 mL of N, N-dimethylformamide (DMF) were added. Thereafter, the flask was cooled to 0 ° C., N-bromosuccinimide (1.21 g) was added, and the mixture was stirred for 12 hours. The reaction was stopped by adding 100 mL of water to the reaction solution, and the product was extracted with ether. Purification was performed with a silica gel column (developing solvent was hexane) to obtain 1.70 g of Compound 103.

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２８を５６１ｍｇ（１．００ｍｍｏｌ）、化合物２５（４,７−ｂｉｓ(４,４,５,５−ｔｅｔｒａｍｅｔｈｙｌ−１,３,２−ｄｉｏｘａｂｏｒｏｌａｎ−２−ｙｌ)−２,１,３−ｂｅｎｚｏｔｈｉａｄｉａｚｏｌｅ）（アルドリッチ社製）を３８８．１ｍｇ（１．００ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、アルドリッチ社製）を２０２ｍｇ加え、トルエン２０ｍｌに溶解させた。得られたトルエン溶液にアルゴンガスを導入し、３０分バブリングした。その後、反応液に酢酸パラジウムを２．２５ｍｇ、トリス(２−メトキシフェニル)ホスフィン（Ｔｒｉｓ（２−ｍｅｔｈｏｘｙｐｈｅｎｙｌ）ｐｈｏｓｐｈｉｎｅ）を１２．３ｍｇ、１６．７ｗｔ％の炭酸ナトリウム水溶液を６．５ｍＬ加え、１００℃で５時間攪拌を行った。その後、反応液にフェニルホウ酸を５０ｍｇ加え、さらに７０℃で２時間反応させた。その後、反応液にジエチルジチオカルバミン酸ナトリウム２ｇと水２０ｍＬを加え、２時間還流下で攪拌を行った。反応液中の水層を除去後、有機層を水２０ｍｌで２回、３ｗｔ％の酢酸水溶液２０ｍＬで２回、さらに水２０ｍＬで２回洗浄し、メタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをｏ−ジクロロベンゼン３０ｍＬに溶解させた。ｏ−ジクロロベンゼン溶液をアルミナ／シリカゲルカラムに通し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、重合体Ｂを２８０ｍｇ得た。ＧＰＣで測定した重合体Ｂの分子量（ポリスチレン換算）はＭｗが３０，０００、Ｍｎが１４，０００であった。 Synthesis example 3
(Synthesis of polymer B)

In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of compound 28 and compound 25 (4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxabolanan- 2-yl) -2,1,3-benzothiadiazole) (manufactured by Aldrich) 388.1 mg (1.00 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Aldrich) 202 mg, Dissolved in 20 ml of toluene. Argon gas was introduced into the obtained toluene solution and bubbled for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine), 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, and 100 ° C. For 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours. After removing the aqueous layer in the reaction solution, the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3 wt% acetic acid aqueous solution and further twice with 20 mL of water, and poured into methanol to precipitate a polymer. The polymer was filtered and dried, and the obtained polymer was dissolved in 30 mL of o-dichlorobenzene. The o-dichlorobenzene solution was passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate a polymer. The polymer was filtered and dried to obtain 280 mg of polymer B. The molecular weight (polystyrene conversion) of the polymer B measured by GPC was 30,000 for Mw and 14,000 for Mn.

Example 8
(Ink and organic thin film production, ionization potential measurement)
Polymer A was dissolved in orthodichlorobenzene so as to be 0.5% by weight to prepare an ink. The ink was applied onto a quartz glass substrate by spin coating to produce an organic film containing the polymer A. The film thickness was about 30 nm. The ionization potential of the obtained organic film was measured using AC2 (manufactured by Riken Keiki Co., Ltd., photoelectron spectrometer, model: AC-2). The result was 5.69 eV. The results are shown in Table 1.

Comparative Example 1
The ionization potential was measured in the same manner as in Example 8 except that the polymer B was used instead of the polymer A. The result was 5.00 eV. The results are shown in Table 1.

Table 1 Measurement results of ionization potential

Claims (12)

A polymer compound containing a structural unit represented by the formula (I).

(I)
(In the formula, X represents a sulfur atom, an oxygen atom, a selenium atom, —NH—, or —N (R) —. The two Xs may be the same or different. Z represents an oxygen atom. , Sulfur atom, —C (═O) —, —S (═O) —, —SO ₂ —, —Si (R) ₂ —, —N (R) —, —B (R) —, —P ( R)-or -P (= O) (R)-, where R represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted. An 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 , Optionally substituted arylalkylthio group, acyl group, acyl Oxy group, amide group, imide group, imino 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, substituted And represents an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or a cyano group, and a plurality of R may be the same or different. The polymer compound according to claim 1, wherein the structural unit represented by the formula (I) is a structural unit represented by the formula (II).

(II)
(In the formula, Z and R have the same meaning as described above.) The polymer compound according to claim 2, wherein the structural unit represented by the formula (II) is a structural unit represented by the formula (III).

(III)
(In the formula, R represents the same meaning as described above.)   The polymer compound according to any one of claims 1 to 3, which has a polystyrene-equivalent weight average molecular weight of 3000 or more.   The thin film containing the high molecular compound as described in any one of Claims 1-4.   The composition containing the high molecular compound and electron-accepting compound as described in any one of Claims 1-4.   The composition according to claim 6, wherein the electron-accepting compound is a fullerene derivative.   A thin film comprising the composition according to claim 6 or 7.   An electronic device using the thin film according to claim 5. A compound represented by formula (IV).

(IV)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted 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, imino 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, An optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or Each of the two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. The two Ws may be the same or different.) A compound represented by formula (V).

(V)
(In the formula, R is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, or a substituted 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, imino 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, An optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, a carboxyl group or Each of the two Rs may be the same or different, and W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group, or a substituted stannyl group. Two W's may be the same or different, and V represents a hydrogen atom, an alkali metal, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted arylalkyl. The two Vs may be the same or different.) A compound represented by formula (VI).

(VI)
(In the formula, W represents a hydrogen atom, a halogen atom, a boric acid ester residue, a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group. The two Ws may be the same or different.)