JP2009073808A - Polymer compound and organic photo-electric conversion element produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound having excellent photo-electric conversion efficiency in the case of using in an organic photo-electric conversion element. <P>SOLUTION: The polymer compound contains a constitutional unit expressed by chemical formula (in the formula; R is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a univalent heterocyclic group, a carboxy group, a substituted carboxy group, a cyano group or a nitro group; R<SP>1</SP>is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group; Ar<SB>1</SB>is an arylene group or a bivalent heterocyclic group; Z is an oxygen atom or a sulfur atom; and m and n are each independently an integer of 2-4). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In recent years, studies on organic photoelectric conversion elements (organic solar cells, organic photosensors, etc.) using organic semiconductor materials for active layers have been actively conducted. In particular, if a polymer compound is used as an organic semiconductor material, an active layer can be produced by an inexpensive coating method. Therefore, various studies have been made on organic photoelectric conversion elements using a polymer compound having excellent solubility in an organic solvent. Has been. For example, an organic solar cell (non-patent document 1) using a polymer compound containing the following repeating unit (N) is known.

繰り返し単位（Ｎ）

Repeating unit (N)

Applied Physics Letters Vol.84, No.10 1653-1655 (2004)

  However, even when the polymer compound is used in an organic photoelectric conversion element, there is a problem that the photoelectric conversion efficiency is not always sufficient.

  Then, an object of this invention is to provide the high molecular compound which is excellent in photoelectric conversion efficiency, when it uses for an organic photoelectric conversion element.

（１）
（式中、Ｒは、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表す。複数個のＲは、同一であっても異なっていてもよい。Ｒ¹は、水素原子、アルキル基、アルコキシ基、アリール基またはシアノ基を表す。複数個のＲ¹は同一であっても異なっていてもよい。Ａｒ₁はアリーレン基または２価の複素環基を表す。Ｚは、酸素原子または硫黄原子を表す。複数個のＺは、同一であっても異なっていてもよい。ｍおよびｎは、それぞれ独立に、２〜４の整数を表す。） The present invention first provides a polymer compound containing a structural unit represented by the following formula (1).

(1)
(Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group) Group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or a nitro group. a plurality of R may optionally be the same or different .R ¹ is a hydrogen atom, an alkyl group, an alkoxy group,. a plurality of R ¹ representing an aryl group or a cyano group are the same .Ar ₁ may be different even represents an arylene group or a divalent heterocyclic group .Z represents an oxygen atom or sulfate Represents an atom. Plurality of Z may be .m and n be different even identical, each independently represents an integer of 2 to 4.)

  Secondly, the present invention provides a composition containing a polymer compound having the structural unit represented by the formula (1).

  Thirdly, this invention provides the liquid composition containing the high molecular compound which has a structural unit represented by said Formula (1).

  Fourthly, the present invention provides an organic thin film containing a polymer compound having a structural unit represented by the formula (1).

  Fifthly, the present invention provides an organic photoelectric conversion element having an organic layer containing a polymer compound containing the structural unit represented by the formula (1).

  Sixth, the present invention provides a pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing the polymer compound between the electrodes, and adjacent to the first organic layer. There is provided an organic photoelectric conversion device having a second organic layer containing the obtained electron donating compound.

  Seventhly, the present invention provides a pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing an electron-accepting compound between the electrodes, and adjacent to the first organic layer. There is provided an organic photoelectric conversion device having a second organic layer containing the obtained polymer compound.

  Eighth, the present invention provides an organic photoelectric conversion device having a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing the polymer compound and the electron donating compound between the electrodes.

  Ninthly, the present invention provides an organic photoelectric conversion device having a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing an electron-accepting compound and the polymer compound between the electrodes.

  10thly this invention provides the organic electroluminescent element which has an organic layer containing the high molecular compound containing the structural unit represented by said Formula (1).

（４）
（式中、Ｒは、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表す。複数個のＲは、同一であっても異なっていてもよい。Ｒ¹は、水素原子、アルキル基、アルコキシ基、アリール基またはシアノ基を表す。複数個のＲ¹は同一であっても異なっていてもよい。Ａｒ₁はアリーレン基または２価の複素環基を表す。Ｚは、酸素原子または硫黄原子を表す。複数個のＺは、同一であっても異なっていてもよい。ｍおよびｎは、それぞれ独立に、２〜４の整数を表す。Ｔは、縮合重合に関与する置換基を表す。複数個のＴは、同一でも異なっていてもよい。） Eleventhly, the present invention provides a compound represented by the following formula (4).

(4)
(Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group) Group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or a nitro group. a plurality of R may optionally be the same or different .R ¹ is a hydrogen atom, an alkyl group, an alkoxy group,. a plurality of R ¹ representing an aryl group or a cyano group are the same .Ar ₁ may be different even represents an arylene group or a divalent heterocyclic group .Z represents an oxygen atom or sulfate A plurality of Z may be the same or different, m and n each independently represents an integer of 2 to 4. T represents a substituent involved in condensation polymerization. A plurality of T may be the same or different.)

  The organic photoelectric conversion element using the polymer compound of the present invention is excellent in photoelectric conversion efficiency.

  Hereinafter, the present invention will be described in detail.

<Polymer compound>
The polymer compound of the present invention has a structural unit represented by the formula (1).

  In the formula (1), R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, Represents a cyano group or a nitro group. A plurality of R may be the same or different.

  In the formula (1), the alkyl group represented by R may be linear or branched, and may be a cycloalkyl group. Carbon number is about 1-20 normally, As a specific example of an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, s-butyl group, 3-methylbutyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 3,7-dimethyl An octyl group, n-lauryl group, etc. are mentioned. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  In the formula (1), the alkoxy group represented by R may be linear or branched, and may be a cycloalkyloxy group. The number of carbon atoms is usually about 1 to 20, and specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, s-butoxy group. Group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group 3,7-dimethyloctyloxy group, n-lauryloxy group and the like. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, and a perfluorooctyl group.

  In the formula (1), the alkylthio group represented by R may be linear or branched, and may be a cycloalkylthio group. The number of carbon atoms is usually about 1 to 20, and specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t- Butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio Group, n-laurylthio group and the like. A hydrogen atom in the alkylthio group may be substituted with a fluorine atom. Examples of the alkylthio group substituted with a fluorine atom include a trifluoromethylthio group.

（６）
（式中、ａ１は１から６の整数を表し、ａ２は０から５の整数を表す。） In the formula (1), the aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, having a benzene ring, having a condensed ring, an independent benzene ring Alternatively, a structure in which two or more condensed rings are bonded directly or via a group such as vinylene is also included. The aryl group may have a substituent. Examples of the substituent include a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, or a carbon number. Examples thereof include an alkoxy group having 1 to 20 cycloalkyl groups in its structure and a group represented by the following formula (6). The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples of the aryl group include phenyl group, C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9- anthracenyl group, pentafluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclohexyloxy N-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, n-lauryloxy and the like. C ₁ -C ₁₂ specifically alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, n- propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, n- butylphenyl group, isobutyl Phenyl group, s-butylphenyl group, t-butylphenyl group, n-pentylphenyl group, isoamylphenyl group, hexylphenyl group, n-heptylphenyl group, n-octylphenyl group, n-nonylphenyl group, n-decyl Examples thereof include a phenyl group and an n-dodecylphenyl group. A hydrogen atom in the aryl group may be substituted with a fluorine atom.

(6)
(In the formula, a1 represents an integer of 1 to 6, and a2 represents an integer of 0 to 5.)

In the formula (1), the aryloxy group represented by R usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples of the aryloxy group include phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ ~ C ₁₂ alkylphenoxy group are preferable. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclohexyloxy N-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, n-lauryloxy and the like. Specific examples of the C ₁ -C ₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, an n-propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, n-butylphenoxy group, isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, n-pentylphenoxy group, isoamylphenoxy group, n-hexylphenoxy group, n-heptylphenoxy group, n-octylphenoxy group, An n-nonylphenoxy group, an n-decylphenoxy group, an n-dodecylphenoxy group, and the like can be given.

In the formula (1), the arylthio group represented by R may have a substituent and usually has about 6 to 60 carbon atoms. Specific examples of the arylthio group include a phenylthio group, C ₁ -C ₁₂ alkoxy phenylthio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, Toriajiruchio group is Can be mentioned.

In the formula (1), the arylalkyl group represented by R may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples of the arylalkyl group include phenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group , 2-naphthyl-C ₁ -C ₁₂ alkyl group and the like.

In the formula (1), the arylalkoxy group represented by R may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples of the arylalkoxy group include phenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy group , 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like.

In the formula (1), the arylalkylthio group represented by R may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples of the arylalkylthio group include phenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group , 2-naphthyl-C ₁ -C ₁₂ alkylthio group and the like.

In the formula (1), arylalkenyl group represented by R has a carbon number of usually about 8 to 60, specific arylalkenyl group, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, a C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl group are preferred.

In the formula (1), arylalkynyl group represented by R has a carbon number of usually about 8 to 60, specific arylalkynyl group, a phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ ~ C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl group and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferred.

In the formula (1), the substituted amino group represented by R includes an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. And the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is about 1-60 normally without including the carbon number of this substituent, Preferably it is C2-48. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, diisopropylamino group, and n-butylamino group. , S-butylamino group, isobutylamino group, t-butylamino group, n-pentylamino group, n-hexylamino group, cyclohexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group N-nonylamino group, n-decylamino group, 3,7-dimethyloctylamino group, n-laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrid Fluoromethylamino group Arylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2 - naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups and the like.

In the formula (1), the substituted silyl group represented by R is a silyl substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Groups. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri n-propylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, t-butylsilyldimethylsilyl group, n-pentyldimethylsilyl group, n-hexyldimethylsilyl group, n-heptyldimethylsilyl group, n-octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, n-nonyldimethylsilyl group, n-decyldimethylsilyl group, a 3,7-- dimethylsilyl group, n- lauryl dimethyl silyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1- Fuchiru -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzyl Examples thereof include a silyl group, a diphenylmethylsilyl group, a t-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

  In the formula (1), examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the formula (1), the acyl group represented by R usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the acyl group include an acetyl group and a propionyl group. , Butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group and the like.

  In the formula (1), the acyloxy group represented by R usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the acyloxy group include an acetoxy group and propionyloxy. Group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

  In the formula (1), the imine residue represented by R means an imine compound (that is, an organic compound having —N═C— in the molecule. Examples thereof include aldimine, ketimine, and these A compound in which a hydrogen atom on N is substituted with an alkyl group, etc.)) and a residue obtained by removing one hydrogen atom. The number of carbon atoms of the imine residue is usually about 2 to 20, preferably 2 to 18. Specific examples of the imine residue include groups represented by the following structural formulas.

（式中、Ｍｅはメチル基を表す。また、波線は、結合手を表し、イミン残基の種類によっては、シス体、トランス体等の幾何異性体を持つ場合があることを意味する。）

(In the formula, Me represents a methyl group. Further, a wavy line represents a bond, and it may have a geometric isomer such as a cis isomer or a trans isomer depending on the type of imine residue.)

  In the formula (1), the amide group represented by R usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. 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, a dibenzamide group. , Ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

  In the formula (1), the acid imide group represented by R includes a residue obtained by removing one hydrogen atom bonded to the nitrogen atom from the acid imide, and has about 4 to 20 carbon atoms. is there. Specific examples of the acid imide group include the groups shown below.

In the formula (1), the monovalent heterocyclic group represented by R refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The carbon number of the monovalent heterocyclic group is usually about 4 to 60, preferably 4 to 20. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, etc. Say. Specific examples of the monovalent heterocyclic group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group etc., and a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  In the formula (1), examples of the substituted carboxyl group represented by R include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group is usually about 2 to 60, preferably 2 to 48. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent. Specific examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl. Group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, n-dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyl Alkoxycarbonyl group, a perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

  From the viewpoint of ease of monomer synthesis, R in the formula (1) is preferably a hydrogen atom, an alkyl group, an alkoxy group or an aryl group, and preferably a hydrogen atom or an alkyl group.

  From the viewpoint of photoelectric conversion efficiency and the like of the organic photoelectric conversion element containing the polymer compound of the present invention, at least one R in R in the formula (1) is preferably an alkyl group, and has 1 to 10 carbon atoms. The alkyl group is more preferably.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cyano group. A plurality of R ¹ may be the same or different.

In the formula (1), examples of the alkyl group represented by R ¹ include the same groups as the alkyl groups described for R.

In the formula (1), examples of the alkoxy group represented by R ¹ include the same groups as the alkoxy groups described for R.

In the formula (1), examples of the aryl group represented by R ¹ include the same groups as the aryl group described for R above.

From the viewpoint of ease of monomer synthesis, R ¹ in the formula (1) is preferably a hydrogen atom, an alkyl group, an aryl group, or a cyano group.

In the formula (1), Ar ₁ represents an arylene group or a divalent heterocyclic group.

In the above formula (1), the arylene group represented by Ar ₁ is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having a condensed ring, an independent benzene ring or two condensed rings. Those in which the above are bonded directly or via a group such as vinylene are also included. The arylene group may have a substituent. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.

In the formula (1), examples of the arylene group represented by Ar ₁ include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (for example, the following formulas 4 to 13), an anthracene-diyl group (for example, The following formulas 14 to 19), biphenyl-diyl groups (for example, the following formulas 20 to 25), terphenyl-diyl groups (for example, the following formulas 26 to 28), condensed ring compound groups (for example, the following formulas 29 to 35), Fluorene-diyl group (for example, the following formulas 36 to 38), stilbene-diyl group (the following formulas 39 to 42), distilben-diyl group (for example, the following formulas 43 and 44), benzofluorene-diyl group (for example, the following formula 45-47), dibenzofluorene-diyl groups (for example, the following formula 48) and the like.

（式中、Ｒは、前記式（１）で定義したＲと同じ基が挙げられる。複数個のＲは、同一でも異なっていてもよい。）

(In the formula, R includes the same group as R defined in the formula (1). A plurality of R may be the same or different.)

In the formula (1), the divalent heterocyclic group represented by Ar ₁ refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic in the ring. Say. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable. Carbon number of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group represented by Ar ₁ include a pyridine-diyl group (for example, the following formulas 49 to 54), a diazaphenylene group (for example, the following formulas 55 to 58), and a quinoline diyl group (for example, Formula 59-73), quinoxaline diyl group (for example, Formula 74-78), acridine diyl group (for example, Formula 79-82), bipyridyldiyl group (for example, Formula 83-85), phenanthroline diyl group ( For example, divalent heterocyclic groups containing a nitrogen atom as a hetero atom such as the following formulas 86 to 88) and groups having a carbazole structure (for example, the following formulas 89 to 91); oxygen, silicon, nitrogen, 5-membered ring heterocyclic groups containing atoms such as sulfur and selenium (for example, the following formulas 92 to 96); 5-membered condensed heterocycles containing atoms such as oxygen, silicon, nitrogen, selenium, boron and phosphorus as heteroatoms Groups (for example, the following formulas 97 to 121); 6-membered condensed heterocyclic groups containing atoms such as oxygen, silicon, and nitrogen as heteroatoms (for example, the following formulas 122 to 124); oxygen, silicon, as heteroatoms, A 5-membered heterocyclic group containing atoms such as nitrogen, sulfur, selenium and the like, which is bonded at the α-position of the heteroatom to form a dimer or oligomer (for example, the following formulas 125 to 126); oxygen as a heteroatom A 5-membered ring heterocyclic group containing atoms such as silicon, nitrogen, sulfur, selenium and the like, which is bonded to the phenyl group at the α-position of the heteroatom (for example, the following formulas 127 to 133); oxygen as a heteroatom , A group in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing atoms such as nitrogen and sulfur (for example, the following formulas 134 to 139), and the like.

（式中、Ｒは、前記式（１）で定義したＲと同じ基があげられる。複数個のＲは、同一でも異なっていてもよい。）

(In the formula, R is the same group as R defined in the formula (1). A plurality of R may be the same or different.)

In the formula (1), Ar ₁ is preferably a fluorene-diyl group or a benzofluorene-diyl group from the viewpoint of photoelectric conversion efficiency and the like of the organic photoelectric conversion element containing the polymer compound of the present invention.

  In the formula (1), Z represents an oxygen atom or a sulfur atom. A plurality of Z may be the same or different. From the viewpoint of the photoelectric conversion efficiency of the organic photoelectric conversion element containing the polymer compound of the present invention, a sulfur atom is preferable.

  In said formula (1), m and n represent the integer of 2-4 each independently. From the viewpoint of ease of synthesis of the monomer, both m and n are preferably 2.

The structural unit represented by the formula (1) has geometric isomerism. Specifically, it has cis isomer or trans isomerism at the site of two carbon-carbon double bonds adjacent to Ar ₁ in the formula. The polymer compound used in the present invention may have only the structural unit represented by the formula (1) having cis isomerism, and only the structural unit represented by the formula (1) having trans isomerism. The structural unit represented by the formula (1) having cis isomerism and the structural unit represented by the formula (1) having trans isomerism may be included.

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

（２）
（式中、Ｒ、Ｒ¹、Ａｒ₁は前述と同じ意味を表す）
で表されるものが好ましい。 As the structural unit represented by the formula (1), from the viewpoint of the photoelectric conversion efficiency of the organic photoelectric conversion element containing the polymer compound of the present invention, the following formula (2):

(2)
(Wherein R, R ¹ and Ar ₁ represent the same meaning as described above)
The thing represented by these is preferable.

From the viewpoint of solubility of the polymer compound in a solvent, the polymer compound of the present invention preferably further has a structural unit represented by the following formula (3).
−Ar ₂ − (3)
(In the formula, Ar ₂ represents an arylene group, a divalent heterocyclic group, a divalent aromatic amine group, or a divalent group having a metal complex structure.)

In the formula (3), examples of the arylene group represented by Ar ₂ include the same groups as the arylene group described above for Ar ₁ .

In the formula (3), examples of the divalent heterocyclic group represented by Ar ₂ include the same groups as the divalent heterocyclic group described above for Ar ₁ .

（７）
[式中、Ａｒ₃、Ａｒ₄、Ａｒ₅およびＡｒ₆は、それぞれ独立に、アリーレン基または２価の複素環基を表す。Ａｒ₇、Ａｒ₈およびＡｒ₉は、それぞれ独立に、アリール基または１価の複素環基を表す。Ａｒ₃、Ａｒ₅およびＡｒ₉が複数個ある場合、それらは同一でも異なっていてもよい。ｘおよびｙは、それぞれ独立に、０または正の整数である。] In the formula (3), examples of the divalent aromatic amine group represented by Ar ₂ include a group represented by the following formula (7).

(7)
[Wherein Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ each independently represent an arylene group or a divalent heterocyclic group. Ar ₇ , Ar ₈ and Ar ₉ each independently represent an aryl group or a monovalent heterocyclic group. When there are a plurality of Ar ₃ , Ar ₅ and Ar ₉ , they may be the same or different. x and y are each independently 0 or a positive integer. ]

In the formula (7), examples of the arylene group represented by Ar ₃ , Ar ₄ , Ar _5, and Ar ₆ include the same groups as the arylene group described above for Ar ₁ .

In the formula (7), examples of the divalent heterocyclic group represented by Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ include the same groups as the divalent heterocyclic group described above for Ar _1. .

In the formula (7), examples of the aryl group represented by Ar ₇ , Ar _8, and Ar ₉ include the same groups as the aryl group described in the above R.

In the formula (7), examples of the monovalent heterocyclic group represented by Ar ₇ , Ar ₈ and Ar ₉ include the same groups as the monovalent heterocyclic group described in the above R.

  Specific examples of the divalent aromatic amine group represented by the formula (7) include groups represented by the following formulas 140 to 147.

（式中、Ｒは、それぞれ独立に、前記式（１）で定義したＲと同じ基があげられる。）

(In the formula, each R is independently the same group as R defined in the formula (1).)

  In the formula (7), x is preferably 0 or 1 and y is preferably 0 or 1 from the viewpoint of ease of monomer synthesis.

In the formula (3), examples of the divalent group having a metal complex structure represented by Ar ₂ include groups represented by the following formulas 148 to 154.

（式中、Ｒは、前記式（１）で定義したＲと同じ基があげられる。複数個のＲは、同一でも異なっていてもよい。）

(In the formula, R is the same group as R defined in the formula (1). A plurality of R may be the same or different.)

  When the polymer compound of the present invention has the structural unit represented by the formula (1) and the structural unit represented by the formula (3), the structural unit represented by the formula (1) and the formula (3) ), The constitutional unit represented by the formula (1) is usually in the range of 10 to 90 mol, and the constitution represented by the formula (3). The unit is usually in the range of 10 mol to 90 mol.

The polymer compound of the present invention has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ from the viewpoint of photoelectric conversion efficiency characteristics when used in an organic photoelectric conversion element and solubility in an organic solvent. Is preferably 1 × 10 ⁴ to 1 × 10 ⁷ . The weight average molecular weight in terms of polystyrene is preferably 1 × 10 ³ to 1 × 10 ⁸ , and more preferably 1 × 10 ⁴ to 1 × 10 ⁷ . In addition, from the viewpoint of improving the film formability of the organic thin film containing the polymer compound of the present invention, the dispersity defined by the weight average molecular weight / number average molecular weight is preferably 3 or less.

  In the present invention, the polystyrene-equivalent number average molecular weight and weight average molecular weight can be determined by gel permeation chromatography (GPC).

  In addition, if the polymerization active group remains at the terminal of the polymer compound of the present invention, the photoelectric conversion efficiency when the organic photoelectric conversion element is formed may be lowered. Therefore, the terminal of the polymer compound is stable. It may be protected with a protecting group. As the protecting group, those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include those having a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond. It is done. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  Examples of the good solvent for the polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the polymer compound, the polymer compound can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  The structural unit of the polymer compound of the present invention may be linked by a non-conjugated structure, or the structural unit may contain the non-conjugated structure. Examples of this non-conjugated structure include those shown below, and combinations of two or more thereof.

（式中、Ｒは、前記式（１）で定義したＲと同じ基があげられる。Ａｒは、ヘテロ原子を含んでいてもよい炭素数６〜６０の炭化水素基を表す。Ｒが複数個存在する場合には、それらは同一であっても異なっていてもよい。）

(In the formula, R is the same group as R defined in the formula (1). Ar represents a hydrocarbon group having 6 to 60 carbon atoms which may contain a hetero atom. If present, they may be the same or different.)

  In the above formula, examples of the hetero atom include oxygen, sulfur, nitrogen, silicon, boron, phosphorus, and selenium.

  The polymer compound of the present invention may be any of a random polymer compound, a graft polymer compound, and an alternating polymer compound. Also included are cases where the main chain is branched and there are 3 or more terminal groups and dendrimers.

<Composition>
The composition of the present invention is a composition containing the polymer compound of the present invention, and is at least one selected from the group consisting of an electron donating compound, an electron accepting compound, a light emitting material, a hole transporting material, and an electron transporting material. Examples thereof include a composition containing at least one kind of material and at least one polymer compound of the present invention, and a composition containing at least two kinds of polymer compounds of the present invention. .

  Examples of the electron donating compound that may be contained in the composition of the present invention include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof. Derivatives, polysiloxane derivatives having an aromatic amine 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, and the like.

Examples of the electron-accepting compound that may be contained in the composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane 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, polyfluorene and derivatives thereof, C Examples include fullerenes such as ₆₀ and derivatives thereof, phenanthrene derivatives such as bathocuproine, and carbon nanotubes. Fullerenes and derivatives thereof are particularly preferable.

Examples of fullerenes include C ₆₀ , C ₇₀ and derivatives thereof. Specific examples of the derivative include the following.

  Examples of the light-emitting material that may be contained in the composition of the present invention include a low-molecular fluorescent material, a polymer compound not having the structural unit represented by the formula (1), or a compound that emits light from a triplet excited state. Is mentioned.

  The low-molecular fluorescent material that may be contained in the composition of the present invention usually has a photoluminescence emission peak in the wavelength range of 400 to 700 nm. The molecular weight of the low-molecular fluorescent material is usually less than 3000, preferably about 100 to 1000, and more preferably about 100 to 500.

  Examples of the low-molecular fluorescent material include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, and metal complexes of 8-hydroxyquinoline as ligands. Metal complexes having 8-hydroxyquinoline derivatives as ligands, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene derivatives, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene Of low molecular weight compounds such as derivatives, stilbene, silicon-containing aromatics, oxazoles, furoxanes, thiazoles, tetraarylmethanes, thiadiazoles, pyrazoles, metacyclophanes, acetylenes, etc. Light resistance materials. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  Examples of the polymer compound not having the structural unit represented by the formula (1) that may be contained in the composition of the present invention include a polymer compound having only the structural unit represented by the formula (3). can give.

  The compound that exhibits light emission from the triplet excited state that may be contained in the composition of the present invention is usually a compound that exhibits light emission from the triplet excited state at room temperature (ie, 25 ° C.), such as phosphorescence. In addition to this phosphorescence emission, a complex in which fluorescence emission is observed is also included.

Examples of the compound exhibiting light emission from the triplet excited state include metal complexes in which the central metal is a transition metal or a lanthanoid, and specifically, for example, Ir (ppy) ₃ , Btp ₂ Ir having iridium as the central metal. (acac), PtOEP with platinum as the central metal, Eu (TTA) ₃ phen with europium as the central metal, and the like.

  Among compounds exhibiting light emission from a triplet excited state, as a complex compound (hereinafter sometimes abbreviated as “triplet luminescent complex compound”), for example, conventionally used as a low molecular EL light-emitting material The metal complex compound which has been mentioned is mention | raise | lifted. These include, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 ( Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Adv. Mater. , (1999), 11 (10), 852, and the like.

  The central metal of the triplet light emitting complex compound is usually a metal having an atomic number of 50 or more, which has a spin-orbit interaction, and can cause an intersystem crossing between the singlet state and the triplet state. Examples include rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and the lanthanoids europium, terbium, thulium, dysprosium, samarium, praseodymium, gadolinium, and the like, rhenium, iridium, platinum, Gold, europium and terbium are preferred.

  Examples of the ligand of the triplet light-emitting complex compound include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, 2-phenyl- Examples thereof include benzoxazole and derivatives thereof, porphyrin and derivatives thereof.

  When the composition of the present invention contains a compound that emits light from a triplet excited state, the ratio between the polymer compound and the compound that emits light from a triplet excited state is the type of polymer compound to be combined, and is desired to be optimized. Since it varies depending on the characteristics, it is not particularly limited, but the compound that exhibits light emission from the triplet excited state with respect to 100 parts by weight of the polymer compound is usually 0.01 to 50 parts by weight, preferably 0.1 to 0.1 parts by weight. 40 parts by weight.

  Examples of the hole transport material that the composition of the present invention may contain include, for example, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, aryl Amine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Etc.

  Examples of the electron transport material that may be contained in the composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthra. Quinodimethane 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, polyfluorene and derivatives thereof, and the like It is done.

  When the composition of the present invention contains a hole transport material, the ratio of the hole transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %. When the composition of the present invention contains an electron transport material, the proportion of the electron transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. is there.

  In addition, the composition of the present invention may contain a solvent, a stabilizer, an additive for adjusting viscosity and / or surface tension, an antioxidant, and the like. Each of these optional components may be used alone or in combination of two or more.

  Examples of the stabilizer that may be contained in the composition of the present invention include phenolic antioxidants and phosphorus antioxidants.

  Examples of the additive for adjusting the viscosity and / or surface tension that may be contained in the composition of the present invention include a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, and a decrease in viscosity. A low molecular weight compound for reducing the surface tension and a surfactant for reducing the surface tension may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport. When the composition contains a solvent, it is usually soluble in the solvent. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener. That is, when the composition of the present invention contains a solvent (that is, a liquid composition described later), the viscosity of the composition can be increased by adding a small amount of a poor solvent to the solid content in the composition. Can be increased. When a poor solvent is added for this purpose, the type and amount of the poor solvent may be selected as long as the solid content in the composition does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50% by weight or less, more preferably 30% by weight or less based on the entire composition.

  The antioxidant that may be contained in the composition of the present invention is not limited as long as it does not inhibit light emission and charge transport. When the composition contains a solvent, it is usually soluble in the solvent. . Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the composition and solvent of the present invention can be improved.

<Liquid composition>
The composition of the present invention is particularly useful as a liquid composition for an organic photoelectric conversion device, an organic electroluminescence device or the like. The liquid composition is one in which the composition of the present invention contains a solvent as necessary. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

When forming an organic thin film by forming a film using this liquid composition (for example, a composition in a solution state) at the time of manufacturing an element, the solvent is removed by drying after applying the liquid composition. In addition, since a similar method can be applied even when a charge transport material or a light emitting material is mixed, it is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

The film formation method from a liquid composition includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, and capillary coating. Coating methods such as coating methods, spray coating methods, nozzle coating methods, gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reverse printing methods, and ink jet printing methods can be used. A printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method is preferable in that pattern formation and multicolor coating are easy.
Moreover, the inkjet printing method, the nozzle coat method, and the dispenser method are preferable at the point of the use efficiency of a solution.
Furthermore, from the viewpoint of film formation speed, a micro gravure coating method, a spin coating method, a flexographic printing method, and an offset printing method are preferable.

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. If the liquid composition such as the ink jet printing method passes through a discharge device, clogging or flight during discharge In order to prevent bending, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole , Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  When the liquid composition of the present invention is used in an organic electroluminescence device, the type of solvent contained in the liquid composition is preferably two or more from the viewpoints of film formability and device characteristics. ~ 3 types are more preferable, and two types are more preferable.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. It is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition dissolves.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of less than 180 ° C. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of less than 180 ° C. From the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition at 60 ° C. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

  When the liquid composition of the present invention is used for an organic electroluminescence device, the solvent contained in the liquid composition includes a combination of anisole and bicyclohexyl, a combination of anisole and cyclohexylbenzene, xylene from the viewpoint of viscosity and film-forming property. And combinations of bicyclohexyl, xylene and cyclohexylbenzene, mesitylene and methylbenzoate.

  When the liquid composition of the present invention is used in an organic electroluminescence device, it is included in the solubility parameter of the solvent and the composition of the present invention from the viewpoint of solubility in a solvent of components other than the solvent included in the liquid composition. The difference from the solubility parameter of the polymer compound is preferably 10 or less, and more preferably 7 or less. These solubility parameters can be determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

  The manufacturing method of the organic thin film of this invention is not limited to the film-forming from a solution, For example, you may form a thin film by a vacuum evaporation method.

<Compound>
The compound of the present invention is represented by the formula (4). In the formula (4), R is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group. , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano Represents a group or a nitro group. A plurality of R may be the same or different. Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, Specific examples of the acyl group, the acyloxy group, the imine residue, the acid imide group, the monovalent heterocyclic group, and the substituted carboxyl group include the same groups as those described for R in the above formula (1).

  From the viewpoint of easy synthesis of the compound, R in the formula (4) is preferably a hydrogen atom, an alkyl group, an alkoxy group or an aryl group, and preferably a hydrogen atom or an alkyl group.

In Formula (4), R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cyano group. A plurality of R ¹ may be the same or different. Specific examples of the alkyl group, alkoxy group, and aryl group include the same groups as those described for R ¹ in the above formula (1).

From the viewpoint of ease of synthesis of the compound, R ¹ in the formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, or a cyano group.

In formula (4), Ar ₁ represents an arylene group or a divalent heterocyclic group. Specific examples of the arylene group and the divalent heterocyclic group include the same groups as those described for Ar ₁ in the above formula (1).

  In formula (4), Z represents an oxygen atom or a sulfur atom. Plural Zs may be the same or different. Moreover, m and n represent the integer of 2-4 each independently.

  From the viewpoint of easy synthesis of the compound, both m and n are preferably 2.

In formula (4), T represents a substituent involved in condensation polymerization. Specific examples of substituents involved in condensation polymerization include halogen atoms, alkylsulfo groups, arylsulfo groups, arylalkylsulfo groups, boric acid ester groups, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, and monohalogenated methyl groups. Group, -B (OH) ₂ , formyl group, cyano group or vinyl group.

  Examples of the alkylsulfo group include a methanesulfo group, an ethanesulfo group, and a trifluoromethanesulfo group. Examples of the arylsulfo group include a benzenesulfo group and a p-toluenesulfo group. Examples of the arylalkylsulfo group include a benzylsulfo group.

  Examples of the borate group include groups represented by the following formula.

（式中、Ｍｅはメチル基を示し、Ｅｔはエチル基を示す。）

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

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(In the formula, X represents a halogen atom, Me represents a methyl group, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
-CH ₂ P ⁺ Ph ₃ X ^-
(In the formula, X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonate methyl group include groups represented by the following formula.
-CH ₂ PO (OR ') ₂
(In the formula, R ′ represents an alkyl group, an aryl group or an arylalkyl group. Specific examples of the alkyl group, the aryl group and the arylalkyl group include the alkyl group and the aryl group described in the above-mentioned formula (1) R). Or the group similar to an arylalkyl group is mentioned.)

  Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

A preferable substituent as a substituent involved in the condensation polymerization varies depending on the kind of the polymerization reaction. For example, when a zero-valent nickel complex (Ni (0) complex) such as a Yamamoto coupling reaction is used, a halogen atom, an alkylsulfo group, An arylsulfo group or an arylalkylsulfo group is mentioned. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkylsulfo group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

（５）
（式中、Ｒ、Ｒ¹、Ａｒ₁、Ｔは前述と同じ意味を表す） Specific examples of the structure of the compound represented by the formula (4) include a compound represented by the following formula (5).

(5)
(In the formula, R, R ¹ , Ar ₁ and T represent the same meaning as described above)

下式で表される、ビチオフェン化合物とウイッティヒ・ホーナー反応を行うことで合成できる。

<Method for producing compound>
Next, the manufacturing method of the compound represented by said Formula (5) is demonstrated.
As a compound synthesis method, for example, bromomethylation of a compound represented by H—Ar ₁ —H is carried out to obtain a bis (bromomethyl) compound, and then the obtained bis (bromomethyl) compound and triethyl phosphite are obtained. To obtain a phosphonate represented by the following formula,

It can be synthesized by performing a Wittig-Horner reaction with a bithiophene compound represented by the following formula.

<Method for producing polymer compound>
Next, the manufacturing method of the high molecular compound of this invention is demonstrated.
As a method for synthesizing a polymer compound, for example, in the case of synthesizing a polymer compound composed of a structural unit represented by the above formula (1) and a structural unit represented by the above formula (3), The polymer represented by the present invention and the compound represented by T ¹ -Ar ₂ -T ² can be used as raw materials, and this can be subjected to condensation polymerization to produce the polymer compound of the present invention (wherein Ar ₂ represents the above formula) Examples include the same group as Ar ₂ defined in (3), wherein T ¹ and T ² each independently represent a substituent involved in condensation polymerization, and specific examples of the substituent involved in condensation polymerization are described above. And the same groups as the substituents involved in the condensation polymerization described in T.)

  Specifically, the method for producing a polymer compound of the present invention comprises dissolving a compound that is a monomer and having two substituents involved in condensation polymerization in an organic solvent, if necessary, for example, alkali or an appropriate catalyst. Can be used at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Volume 6. (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Macro Rekyura Symposium (Macromol.Chem., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

In the method for producing a polymer compound of the present invention, a known condensation reaction can be used depending on the substituent involved in the condensation polymerization. For example, a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a zerovalent nickel complex, a method of polymerizing by an oxidizing agent such as FeCl _3, a method of electrochemical oxidative polymerization Or a method by decomposition of an intermediate polymer having an appropriate leaving group. Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, and the method of polymerizing by zero-valent nickel complex are preferable because the structure can be easily controlled.

In the method for producing a polymer compound of the present invention, substituents (T, T ¹ , T ² ) involved in condensation polymerization are independently selected from a halogen atom, an alkylsulfo group, an arylsulfo group, or an arylalkylsulfo group. A production method in which condensation polymerization is performed in the presence of a zerovalent nickel complex is preferred. Examples of the raw material compound include dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, and halogen-aryl alkyl sulfonates. Compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds. Among these, as raw material compounds, for example, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, or aryl sulfonate-aryl alkyls. The method of manufacturing the high molecular compound which controlled the sequence by using a sulfonate compound is mentioned.

In the method for producing a polymer compound of the present invention, substituents (T, T ¹ , T ² ) involved in condensation polymerization are independently halogen atoms, alkylsulfo groups, arylsulfo groups, arylalkylsulfo groups. , Boric acid group (—B (OH) ₂ ), or boric acid ester group, and the total number of moles of halogen atoms, alkylsulfo groups, arylsulfo groups, and arylalkylsulfo groups possessed by all raw material compounds (J ) And the total number of moles of boric acid groups and boric acid ester groups (K), the ratio K / J is substantially 1 (usually in the range of 0.7 to 1.2), nickel catalyst or palladium A production method in which condensation polymerization is performed using a catalyst is preferred. Specific examples of the combination of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. . Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates An acid compound and an arylalkyl sulfonate-borate ester compound are mentioned. Among these, as raw material compounds, for example, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid. The method of manufacturing the high molecular compound which controlled the sequence by using an ester compound, an arylalkyl sulfonate-boric acid compound, and an arylalkyl sulfonate-boric acid ester compound is mentioned.

Although the solvent used for the reaction varies depending on the compound used and the reaction, it is generally preferable to perform sufficient deoxygenation treatment in order to suppress side reactions. The reaction is preferably allowed to proceed under an inert atmosphere. Similarly, the solvent used in the reaction is preferably subjected to dehydration treatment.
However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, decalin, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-butylbenzene, xylene, tetralin, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbons such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol , Alcohols such as isopropanol, butanol and t-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether Ethers such as ter, methyl-t-butyl ether, tetrahydrofuran, tetrahydropyran and dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, Examples include amides such as N, N-dimethylacetamide, N, N-diethylacetamide, and N-methylmorpholine oxide. These solvents may be used alone or in combination. Of these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. Examples of the alkali include inorganic bases such as potassium carbonate and sodium carbonate; organic bases such as triethylamine; inorganic salts such as cesium fluoride. Examples of the catalyst include palladium [tetrakis (triphenylphosphine)] and palladium acetates. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound of the present invention is used for an organic solar battery or the like, the purity affects the performance of the device such as photoelectric conversion efficiency. Therefore, the monomer before polymerization is purified by a method such as distillation, sublimation purification, and recrystallization. It is preferable to polymerize later. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

<Organic photoelectric conversion element>
The organic photoelectric conversion element containing the polymer compound of the present invention has a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing the polymer compound of the present invention between the electrodes. The polymer compound of the present invention can be used as an electron accepting compound or an electron donating compound, but is preferably used as an electron donating compound. In this case, the electron-donating compound is not particularly limited as long as the polymer compound of the present invention and the electron-accepting compound have adjacent heterojunction interfaces.

  Next, the operation mechanism of the organic photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound to generate excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface. Electric charges (electrons and holes) that can move are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

One embodiment of the organic photoelectric conversion device of the present invention includes a pair of electrodes, a layer containing an electron-accepting compound and a layer containing an electron-donating compound between the electrodes, and both layers are adjacent to each other in a heterojunction. Examples include an element forming an interface. Another embodiment of the organic photoelectric conversion device of the present invention includes a device having a pair of electrodes and a layer in which an electron-accepting compound and an electron-donating compound are mixed between the electrodes. In particular,
1. A pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing the polymer compound of the present invention as an electron-accepting compound between the electrodes, and adjacent to the first organic layer An organic photoelectric conversion device having a second organic layer containing the obtained electron donating compound;
2. A pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing an electron-accepting compound between the electrodes, and the polymer compound provided adjacent to the first organic layer An organic photoelectric conversion element having a second organic layer containing;
3. An organic photoelectric conversion element having at least one organic layer containing a pair of electrodes, at least one of which is transparent or translucent, and the polymer compound and the electron donating compound between the electrodes;
4). An organic photoelectric conversion device having a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing an electron-accepting compound and the polymer compound between the electrodes;
5). An organic photoelectric conversion element comprising at least one organic layer containing a pair of electrodes, at least one of which is transparent or translucent, and an electron-accepting compound and the polymer compound between the electrodes, wherein the electron-accepting compound comprises: An organic photoelectric conversion element which is a fullerene derivative;
Is given.

  In addition, said 5. In the organic photoelectric conversion element, the ratio of the fullerene derivative in the organic layer containing the fullerene derivative and the polymer compound used in the present invention is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. Preferably, it is 50-500 weight part.

  In order for the organic photoelectric conversion element to have high conversion efficiency, the electron-accepting compound and the electron-donating compound have an absorption region that can efficiently absorb a desired incident light spectrum, It is important that the junction interface includes many heterojunction interfaces in order to efficiently separate excitons, and that the junction interface has a charge transport property for quickly transporting the charges generated by the heterojunction interface to the electrode.

  From such a viewpoint, the organic photoelectric conversion device of the present invention includes the above-mentioned 3, and 4. Or 5. From the viewpoint of including many heterojunction interfaces, 5. Is more preferable. In the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the organic layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons.

  When the polymer compound used in the present invention is an electron donor, the electron acceptor suitably used for the organic photoelectric conversion element has an electron acceptor whose HOMO energy is higher than that of the polymer compound, The LUMO energy of the acceptor is higher than the LUMO energy of the polymer compound. Further, when the polymer compound is an electron acceptor, the electron donor suitably used for the organic photoelectric conversion element is such that the electron donor has a HOMO energy lower than that of the polymer compound and an electron donor. The LUMO energy of the polymer is lower than the LUMO energy of the polymer compound.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when an electrode is formed and an 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.

  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 composites, indium tin oxide (ITO), a film made using a conductive compound such as indium zinc zinc oxide (NESA) Etc.), gold, platinum, silver, copper and the like are 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material. Furthermore, as the electrode material, a metal, a conductive polymer, or the like can be used. Preferably, one of the pair of electrodes is preferably a material having a small work function. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and two of them One or more alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or a graphite intercalation compound are used. It is done. 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, calcium-aluminum alloy and the like.

  As materials used for the charge transport layer as the additional layer, that is, the hole transport layer and the electron transport layer, an electron donating compound and an electron accepting compound described later can be used, respectively. As a material used as a buffer layer as an additional layer, an alkali metal such as lithium fluoride, a halide of an alkaline earth metal, an oxide, or the like can be used. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

  As said organic layer in the organic photoelectric conversion element of this invention, the organic thin film containing the high molecular compound containing the structural unit represented by the said Formula (1) can be used, for example.

  The organic thin film has a thickness of usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The said organic thin film may contain the high molecular compound used for this invention individually by 1 type, or may contain it in combination of 2 or more types. In addition, in order to increase the hole transport property of the organic thin film, a low molecular compound and / or a high molecular compound other than the high molecular compound is mixed as an electron donating compound and / or an electron accepting compound in the organic thin film. It can also be used.

  By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

<Organic electroluminescence element>
Next, the structure of the layer of the organic electroluminescence element of the present invention (hereinafter sometimes referred to as “organic EL element”) will be described.

  In addition to having an anode, a light emitting layer and a cathode as essential components, the organic EL device of the present invention has another layer between the anode and the light emitting layer and / or between the light emitting layer and the cathode. Can have.

  Examples of the layer that can be provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer. When both the electron injection layer and the electron transport layer are provided, the layer close to the cathode is the electron injection layer, and the layer close to the light emitting layer is the electron transport layer.

The electron injection layer is a layer having a function of improving electron injection efficiency from the cathode, and the electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer or the electron transport layer closer to the cathode. is there. In addition, when the electron injection layer or the electron transport layer has a function of blocking hole transport, these layers may also serve as the hole blocking layer.
Having the function of blocking hole transport makes it possible, for example, to produce an element that allows only hole current to flow, and confirm the blocking effect by reducing the current value.

  Examples of what is provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer. When both the hole injection layer and the hole transport layer are provided, the layer close to the anode is the hole injection layer, and the layer close to the light emitting layer is the hole transport layer.

The hole injection layer is a layer having a function of improving the hole injection efficiency from the anode, and the hole transport layer is a hole injection layer from the anode, the hole injection layer or the hole transport layer closer to the anode. It is a layer having a function of improving. In addition, when the hole injection layer or the hole transport layer has a function of blocking electron transport, these layers may also serve as an electron block layer.
Having the function of blocking electron transport makes it possible, for example, to manufacture an element that allows only electron current to flow and to confirm the blocking effect by reducing the current value.

  In the organic EL device of the present invention, one light emitting layer is usually provided, but the present invention is not limited to this, and two or more light emitting layers may be provided.

  Note that the electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.

More specifically, the organic EL device of the present invention can have any of the following layer configurations:
a) Anode / hole transport layer / light emitting layer / cathode b) Anode / light emitting layer / electron transport layer / cathode c) Anode / hole transport layer / light emitting layer / electron transport layer / cathode d) Anode / charge injection layer / Emissive layer / cathode e) anode / emission layer / charge injection layer / cathode f) anode / charge injection layer / emission layer / charge injection layer / cathode g) anode / charge injection layer / hole transport layer / emission layer / cathode h ) Anode / hole transport layer / light emitting layer / charge injection layer / cathode i) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode j) Anode / charge injection layer / light emitting layer / charge transport Layer / cathode k) anode / light emitting layer / electron transport layer / charge injection layer / cathode l) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / hole transport Layer / light emitting layer / charge transport layer / cathode n) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode o) anode / charge injection layer / Hole transport layer / light emitting layer / electron transporting layer / charge injection layer / cathode (wherein, / indicates that each layer is laminated adjacently. Hereinafter the same.)

Furthermore, the organic EL device of the present invention may have two or more light emitting layers. Specifically, as an organic EL element having two light emitting layers,
p) Layer structure of anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / electrode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode The thing which has is mentioned.
Further, as an organic EL device having three or more light emitting layers, specifically, an electrode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer as one stacked repeating unit,
q) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / stacking repeating unit / stacking repeating unit ... / cathode and including two or more layers of the stacking repeating unit The thing which has a layer structure is mentioned.
In the layer structures p and q, each layer other than the anode, the electrode, the cathode, and the light emitting layer can be deleted as necessary.
Here, the electrode is a layer that generates holes and electrons by applying an electric field. Examples thereof include vanadium oxide, indium / tin / oxide, and molybdenum oxide.

  The organic EL device of the present invention can further have a substrate, and each of the layers can be provided on the substrate. The organic EL device of the present invention can further have a sealing member on the opposite side of the substrate with the above layers interposed therebetween. The organic EL device having the substrate and the above layer structure usually has a substrate on the anode side, but the present invention is not limited to this, and the substrate may be on either the anode or cathode side.

  In the organic EL device of the present invention, in order to emit light from the light emitting layer, all the layers on either side of the light emitting layer are usually transparent. Specifically, for example, in the case of an organic EL device having a configuration of substrate / anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode / sealing member, the substrate, anode, charge All of the injection layer and hole transport layer are transparent, so-called bottom emission type elements, or all of the electron transport layer, charge injection layer, cathode and sealing member are transparent, so-called top emission Type element. In the case of an organic EL device having the structure of substrate / cathode / charge injection layer / electron transport layer / light emitting layer / hole transport layer / charge injection layer / anode / sealing member, the substrate, cathode, charge injection layer and electron All of the transport layers are transparent, so-called bottom emission type elements, or all of the hole transport layer, charge injection layer, cathode and sealing member are transparent, so-called top emission type elements can do. Here, the term “transparent” means that the visible light transmittance from the light emitting layer to the light emitting layer is 40% or more. In the case of an element that requires light emission in the ultraviolet region or infrared region, a device having a transmittance of 40% or more in the region is preferable.

In the organic EL device of the present invention, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode in order to improve adhesion with the electrode or improve charge injection from the electrode. In addition, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer in order to improve the adhesion of the interface or prevent mixing.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

  Next, the material and forming method of each layer constituting the organic EL element of the present invention will be described more specifically.

<Board>
The organic EL device of the present invention usually has a substrate. The substrate may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed. For example, glass, plastic, a polymer film, a silicon substrate, or a laminate of these is used. As this board | substrate, a commercially available thing can be obtained or it can manufacture by a well-known method.

<Anode>
As the anode of the organic EL element of the present invention, it is preferable to use a transparent or translucent electrode because an element that emits light through the anode can be configured. As such a transparent electrode or a semi-transparent electrode, a metal oxide, metal sulfide or metal thin film having high electrical conductivity can be used, and a high transmittance can be suitably used. And use. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
A material that reflects light may be used for the anode, and the material is preferably a metal, metal oxide, or metal sulfide having a work function of 3.0 eV or more.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

<Hole injection layer>
The hole injection layer can be provided between the anode and the hole transport layer or between the anode and the light emitting layer. As the hole injection layer, the polymer compound of the present invention can be used.
In the organic EL device of the present invention, the material for forming the hole injection layer other than the polymer compound includes phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, etc. Oxides, amorphous carbon, polyaniline, polythiophene derivatives, and the like.

<Hole transport layer>
As the hole transport layer, the polymer compound of the present invention may be used. In other cases, the material constituting the hole transport layer includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a side chain. Or a polysiloxane derivative having an aromatic amine in the main chain, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, Examples include poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, polyarylamine or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, and more preferred Is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Light emitting layer>
The light-emitting layer includes the polymer compound of the present invention, the composition of the present invention, a compound that emits fluorescence, a compound that emits light from a triplet excited state, and the like. Further, a dopant material may be further included.

  Examples of low molecular weight compounds that emit fluorescence include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, and pyrrole derivatives. , Thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, pyrazoline dimers, and other pigment materials, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzooxa Central metals such as zolyl zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex have rare earth metals such as Al, Zn, Be etc. or Tb, Eu, Dy etc. , It can be exemplified oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, a metal complex having a quinoline structure.

  Polymer compounds that emit fluorescence include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and the above dye bodies and metal complex light emitting materials. And the like.

  A dopant can be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. In addition, the thickness of such a light emitting layer is about 20-2000 mm normally.

<Method for forming light emitting layer>
As a method for forming a light emitting layer containing an organic substance, a method of applying a solution containing a light emitting material on or above a substrate, a vacuum deposition method, a transfer method, or the like can be used. Specific examples of the solvent used for the film formation from the solution include the same solvents as those for dissolving the hole transport material when forming the hole transport layer from the above solution.
As a method for applying a solution containing a light emitting material on or above a substrate, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method Coating methods such as slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, inkjet printing, etc. are used. be able to. A printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method is preferable in that pattern formation and multicolor coating are easy. In the case of a sublimable low-molecular compound, a vacuum deposition method can be used. Furthermore, a method of forming a light emitting layer only at a desired place by laser transfer or thermal transfer can be used.

<Electron transport layer>
As the electron transport layer, known materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof. , Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method of forming the electron transport layer, but in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, a polymer binder may be used in combination. Examples of the method for forming an electron transport layer from a solution include the same film formation method as the method for forming a hole transport layer from a solution described above.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Electron injection layer>
The electron injection layer is provided between the electron transport layer and the cathode or between the light emitting layer and the cathode. Depending on the type of the light-emitting layer, the electron injection layer may be an alkali metal, an alkaline earth metal, an alloy containing one or more of the above metals, an oxide, a halide and a carbonate of the metal, or a mixture of the substances. Etc. Examples of alkali metals or oxides, halides and carbonates thereof include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, rubidium oxide. , Rubidium fluoride, cesium oxide, cesium fluoride, lithium carbonate and the like. Examples of alkaline earth metals or oxides, halides and carbonates thereof include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, barium fluoride, Examples include strontium oxide, strontium fluoride, and magnesium carbonate. The electron injection layer may be a laminate of two or more layers. Specifically, LiF / Ca etc. are mentioned. The electron injection layer is formed by vapor deposition, sputtering, printing, or the like. The thickness of the electron injection layer is preferably about 1 nm to 1 μm.

<Cathode material>
As a material for the cathode used in the organic EL device of the present invention, a material having a small work function and easy electron injection into the light emitting layer and / or a material having high electrical conductivity and / or a material having high visible light reflectivity are preferable. As the metal, an alkali metal, an alkaline earth metal, a transition metal, or a group III-B metal can be used. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or the above metals Or an alloy of one or more of them with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or a graphite or graphite layer A compound or the like is used. 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, calcium-aluminum alloy, and the like. In addition, a transparent conductive electrode can be used as the cathode, and for example, a conductive metal oxide or a conductive organic material can be used. Specifically, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) and indium zinc oxide (IZO) which are composites thereof as conductive metal oxides, and polyaniline as conductive organic substances Alternatively, an organic transparent conductive film such as a derivative thereof, polythiophene or a derivative thereof may be used. Note that the cathode may have a laminated structure of two or more layers. In some cases, the electron injection layer is used as a cathode.

  The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.

<Insulating layer>
An insulating layer having a film thickness of 2 nm or less that can be optionally included in the organic EL device of the present invention has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Organic EL elements having an insulating layer having a thickness of 2 nm or less are provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, and those having an insulating layer having a thickness of 2 nm or less adjacent to the anode. Can be mentioned.

  The organic EL element of the present invention can be used as a backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device.

  In order to obtain planar light emission using the organic EL element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately applying a plurality of types of light emitting materials having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and 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.

  In the following examples, the molecular weight of the polymer compound was determined by the polystyrene-equivalent number average molecular weight by GPC (trade name: LC-10Avp) manufactured by Shimadzu Corporation or GPC (PL-GPC2000) manufactured by GPC Laboratory. The polymer compound was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 50 μL was injected into GPC. Tetrahydrofuran was used as the GPC mobile phase, 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.

（３）単量体化合物（Ｂ）の合成
次に、反応容器に、前記原料化合物（Ａ）７．８ｇと５−ブロム−２，２’−ビチオフェン−５’−カルボキシアルデヒド６．７ｇとを仕込み、反応系内を窒素ガス置換した後、テトラヒドロフラン（脱水）１５０ｇを加え、溶解させた。得られた溶液に、あらかじめカリウム−ｔ−ブトキシド４．９ｇをテトラヒドロフラン（脱水）５０ｍｌに溶解した溶液を滴下した。滴下後、引き続き室温で３０時間反応させた。なお、反応は窒素ガス雰囲気下で行なった。
次に、得られた反応溶液に酢酸を加え中和した後、この溶液をメタノール中に注ぎ込んだ。得られた溶液から、減圧下、溶媒を留去して、粘調固形物を得た。得られた粘調固形物を、トルエン／へキサン＝３０／１００（重量比）を展開溶媒とするアルミナカラムで精製することにより、粗生成物３．５ｇを得た。
次に、得られた粗生成物をメタノールで洗浄し、減圧乾燥した後、トルエン１０ｍｌに溶解した。このトルエン溶液をメタノール中に滴下し再沈、得られた沈殿物を回収した。この沈殿物を減圧乾燥して、下記構造式：

（Ｂ）
で示される単量体化合物（Ｂ）１．１ｇを得た。 <Example 1> Synthesis of compound (B) (1) Synthesis of bis (bromomethyl) compound of 9,9-dioctylfluorene To 65 g of acetic acid, 21.0 g of 9,9-dioctylfluorene and 9.0 g of paraformaldehyde were added. . To the obtained mixed solution, 196 g of a 25% hydrobromic acetic acid solution was added at room temperature, followed by reaction at 80 ° C. for 10 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, the reaction solution was cooled to room temperature, and then the reaction solution was allowed to stand to collect a separated lower layer. Next, 200 ml of hexane was added to the obtained recovered material. This hexane solution was washed 7 times with ion exchange water. Next, the solvent was distilled off from the obtained hexane solution under reduced pressure to obtain a viscous solid. By purifying the resulting viscous solid with a silica gel column using toluene / hexane = 2/8 (volume ratio) as a developing solvent, 8.3 g of a bis (bromomethyl) compound of 9,9-dioctylfluorene is obtained. Got.
(2) Synthesis of phosphonate ester Next, 8.0 g of the 9,9-dioctylfluorene bis (bromomethyl) compound and 25 g of triethyl phosphite were charged in a reaction vessel, and the temperature was raised to 140 ° C. For 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, unreacted triethyl phosphite was distilled off at 120 ° C. under reduced pressure to obtain 8.2 g of phosphonic acid ester {raw material compound (A)}.

(3) Synthesis of monomer compound (B) Next, 7.8 g of the raw material compound (A) and 6.7 g of 5-bromo-2,2′-bithiophene-5′-carboxaldehyde were added to a reaction vessel. After charging and replacing the inside of the reaction system with nitrogen gas, 150 g of tetrahydrofuran (dehydrated) was added and dissolved. A solution prepared by previously dissolving 4.9 g of potassium t-butoxide in 50 ml of tetrahydrofuran (dehydrated) was added dropwise to the obtained solution. After the dropping, the reaction was continued at room temperature for 30 hours. The reaction was performed in a nitrogen gas atmosphere.
Next, after acetic acid was added to the obtained reaction solution for neutralization, this solution was poured into methanol. From the obtained solution, the solvent was distilled off under reduced pressure to obtain a viscous solid. The obtained viscous solid was purified with an alumina column using toluene / hexane = 30/100 (weight ratio) as a developing solvent, to obtain 3.5 g of a crude product.
Next, the obtained crude product was washed with methanol, dried under reduced pressure, and then dissolved in 10 ml of toluene. This toluene solution was dropped into methanol and reprecipitated, and the resulting precipitate was recovered. The precipitate is dried under reduced pressure to obtain the following structural formula:

(B)
1.1 g of the monomer compound (B) represented by

（Ｃ−１）

で表される化合物（Ｃ−１）（1.19g）を得た。 <Synthesis Example 1>
6.65 g of 2,7-dibromo-9-fluorenone was placed in a nitrogen-substituted 500 ml three-necked flask and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid: chloroform = 1: 1 (weight basis). To the resulting solution was added sodium perborate monohydrate and stirred for 20 hours. The reaction solution was filtered through celite and washed with toluene. The filtrate was washed with water, sodium bisulfite, and saturated brine in that order, and then dried over sodium sulfate. After distilling off the solvent, 6.11 g of crude product was obtained.
The crude product is recrystallized from toluene and further recrystallized from chloroform.

(C-1)

The compound (C-1) (1.19g) represented by these was obtained.

・ C ₈ H ₁₇ MgBr solution preparation
In a 100 ml three-necked flask, 1.33 g of magnesium was taken, flame dried, and purged with argon. To this, 10 ml of THF and 2.3 ml of 1-bromooctane were added and heated to start the reaction. After refluxing for 2.5 hours, the mixture was allowed to cool to room temperature to prepare a C ₈ H ₁₇ MgBr solution.

（Ｃ−２）

で表される化合物（Ｃ−２）（1.30g）を得た。 Grignard reaction 1.00 g of compound (C-1) was placed in a nitrogen-substituted 300 ml three-necked flask and suspended in 10 ml of tetrahydrofuran. After cooling to 0 ° C., the C ₈ H ₁₇ MgBr solution prepared above was added. The cold bath was removed and the mixture was stirred for 5 hours under reflux. After allowing the reaction solution to cool, 10 ml of water and hydrochloric acid were added. It was a suspension before the addition of hydrochloric acid, but it became a two-phase solution after the addition. After separation, the organic phase was washed with water and saturated brine in this order. The organic phase thus obtained was dried over sodium sulfate and the solvent was distilled off to obtain 1.65 g of a crude product. Purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1 (volume basis)), the following formula:

(C-2)

The compound (C-2) (1.30g) represented by these was obtained.

（Ｃ−３）
で表される化合物（Ｃ−３）（0.14g）を得た。 0.20 g of compound (C-2) was placed in a nitrogen-substituted 25 ml two-necked flask and dissolved in 4 ml of toluene. To this solution, 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 100 ° C. for 11 hours. The resulting reaction solution was allowed to cool, then washed with water, 4N aqueous sodium hydroxide solution, water and saturated brine in this order, and the solvent was distilled off to obtain the following formula:

(C-3)
The compound (C-3) (0.14g) represented by these was obtained.

で表される化合物（Ｃ）（0.28g）を得た。 Under a nitrogen atmosphere, 1.0 g (1.77 mmol) of compound (C-3), 0.945 g (3.72 mmol) of bis (pinacolato) diboron, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride 0.078 g in a reaction vessel (0.11 mmol), 0.059 g (0.11 mmol) of 1,1′-bis (diphenylphosphino) ferrocene and 15 ml of 1,4-dioxane were added, and argon gas was bubbled for 30 minutes. Thereafter, 1.043 g (10.6 mmol) of potassium acetate was added, and the mixture was reacted at 95 ° C. for 13.5 hours under a nitrogen atmosphere. After completion of the reaction, the obtained reaction solution was filtered to remove insoluble matters. It refine | purified with the alumina short column, after removing the solvent, it was made to melt | dissolve in toluene, activated carbon was added, and it stirred and filtered. The obtained filtrate was purified again with an alumina short column, activated carbon was added, and the mixture was stirred and filtered. After completely removing toluene from the obtained filtrate, 2.5 ml of hexane was added and recrystallized to obtain the following formula:

The compound (C) (0.28g) represented by these was obtained.

<Example 2> Synthesis of polymer compound 1 0.929 g of the compound (B), 0.659 g of the compound (C) and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.23 g and dichlorobis (triphenylphosphine) palladium (II) 1.9 mg were charged into the reaction vessel. Was replaced with argon gas. To this reaction vessel, 40 ml of toluene deaerated in advance by bubbling argon gas was added.
Next, 8 ml of a 16.7 wt% aqueous sodium carbonate solution previously deaerated by bubbling with an argon gas was dropped into this solution, and then the temperature was raised and the mixture was refluxed for 50 minutes.
Next, after cooling this reaction solution to near room temperature, 25 ml of toluene deaerated in advance by bubbling argon gas was added. A solution prepared by dissolving 0.14 g of 4-t-butylphenylboric acid in 1 ml of tetrahydrofuran was added to the reaction solution, and the temperature was raised and the mixture was refluxed for 1 hour. The reaction was performed in an argon gas atmosphere.
After the reaction, the reaction solution was cooled to near room temperature, and 15 ml of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated gel-like toluene solution was recovered.
Next, this gel-like toluene solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. Next, this precipitate was dried under reduced pressure and then dissolved in chloroform. Next, this chloroform solution was filtered to remove insoluble matters, and then this chloroform solution was passed through an alumina column for purification. Next, this chloroform solution was poured into methanol and reprecipitated, and the generated precipitate was collected. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.22 g of a polymer compound (hereinafter, this polymer compound is referred to as “polymer compound 1”). The polymer compound 1 had a polystyrene equivalent weight average molecular weight of 3.3 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 1.1 × 10 ⁴ .

化合物Ｄ、０．９４９ｇと化合物Ｅ、１．２５３ｇとメチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．３０ｇと、ジクロロビス（トリフェニルホスフィン）パラジウム（II） ３．４ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで置換した。この反応容器に、予めアルゴンガスをバブリングして、脱気したトルエン ４５ｍｌを加えた。次に、この溶液に、攪拌下、予めアルゴンガスでバブリングして、脱気した１６．７重量％炭酸ナトリウム水溶液 １０ｍｌを滴下し、１２時間還流した。次に、反応溶液を冷却し、フェニルホウ酸０．１ｇ／テトラヒドロフラン０．５ｍｌ混合溶液を加え、２時間還流した。なお、反応はアルゴンガス雰囲気下で行った。反応終了後、反応溶液を冷却した後、この反応溶液にトルエン６０ｇを加えた。この反応溶液を静置し、分液して、トルエン溶液を回収した。次に、このトルエン溶液を濾過し、不溶物を除去した。次に、このトルエン溶液を、アルミナカラムを通し、精製した。次に、このトルエン溶液をメタノール中に注ぎ込み、再沈精製し、生成した沈殿を回収した。次に、この沈殿を、減圧乾燥した後、再びトルエンに溶解した。次に、このトルエン溶液をろ過した後、このトルエン溶液を、アルミナカラムを通し、精製した。次に、このトルエン溶液をメタノール中に注ぎ込み、再沈精製し、生成した沈殿を回収した。この沈殿をメタノールで洗浄した後、減圧乾燥して高分子化合物（以下、この高分子化合物を「高分子化合物２」という）、０．５ｇを得た。高分子化合物２のポリスチレン換算の重量平均分子量は９．９×１０⁴であり、ポリスチレン換算の数平均分子量は６．１×１０⁴であった。 Synthesis example 2
(Synthesis of polymer compound 2)

Compound D, 0.949 g and Compound E, 1.253 g and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 C., trademark of Henkel Corporation) 0.30 g and dichlorobis (triphenylphosphine) palladium (II) 3.4 mg were charged into a reaction vessel, and the inside of the reaction vessel was replaced with argon gas. To this reaction vessel, 45 ml of toluene deaerated by bubbling argon gas in advance was added. Next, 10 ml of a 16.7 wt% sodium carbonate aqueous solution deaerated by bubbling with argon gas in advance under stirring was added dropwise to the solution and refluxed for 12 hours. Next, the reaction solution was cooled, a mixed solution of 0.1 g of phenylboric acid / 0.5 ml of tetrahydrofuran was added, and the mixture was refluxed for 2 hours. The reaction was performed in an argon gas atmosphere. After completion of the reaction, the reaction solution was cooled, and 60 g of toluene was added to the reaction solution. The reaction solution was allowed to stand and separated to collect a toluene solution. Next, this toluene solution was filtered to remove insoluble matters. Next, this toluene solution was purified through an alumina column. Next, this toluene solution was poured into methanol and purified by reprecipitation, and the generated precipitate was recovered. Next, this precipitate was dried under reduced pressure and then dissolved again in toluene. Next, after filtering this toluene solution, this toluene solution was purified by passing through an alumina column. Next, this toluene solution was poured into methanol and purified by reprecipitation, and the generated precipitate was recovered. The precipitate was washed with methanol and dried under reduced pressure to obtain 0.5 g of a polymer compound (hereinafter, this polymer compound is referred to as “polymer compound 2”). The polymer compound 2 had a polystyrene equivalent weight average molecular weight of 9.9 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 6.1 × 10 ⁴ .

前記化合物（Ｂ）０．４７５ｇと上記化合物（Ｆ）０．２８３ｇとメチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．１４ｇと、ジクロロビス（トリフェニルホスフィン）パラジウム（II）１．７ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで置換した。この反応容器に、予めアルゴンガスをバブリングして脱気したトルエン ４５ｇを加えた。
次に、この溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％炭酸ナトリウム水溶液 １０ｍｌを滴下した後、昇温し、１２時間還流した。
次に、この反応溶液を室温付近まで冷却した後、この反応溶液に、予めフェニルホウ酸０．０５ｇをテトラヒドロフラン１ｍｌに溶解した溶液を加えた後、昇温し、１時間還流した。なお、反応はアルゴンガス雰囲気下で行った。
反応後、前記反応溶液を室温付近まで冷却した後、前記反応溶液にトルエン１５ｍｌを加えた。この反応溶液を静置し、分液したトルエン溶液を回収した。
次に、得られたトルエン溶液を、アルミナカラムに通し、精製した。得られたトルエン溶液を、メタノール中に注ぎ込み、再沈し、生成した沈殿を回収した。次に、この沈殿を、減圧乾燥した後、トルエンに溶解した。得られたトルエン溶液をろ過し、不溶物を除去した後、このトルエン溶液をアルミナカラムに通し、精製した。次に、得られたトルエン溶液をメタノール中に注ぎ込み、再沈し、生成した沈殿を回収した。得られた沈殿をメタノールで洗浄した後、減圧乾燥して、高分子化合物（以下、この高分子化合物を「高分子化合物３」という）０．０７ｇを得た。高分子化合物３のポリスチレン換算の重量平均分子量は２．１×１０⁴であり、ポリスチレン換算の数平均分子量は１．３×１０⁴であった。 Example 3
(Synthesis of polymer compound 3)

0.475 g of the compound (B), 0.283 g of the compound (F) and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.14 g and dichlorobis (triphenylphosphine) palladium (II) 1.7 mg were charged into the reaction vessel, and the inside of the reaction vessel was replaced with argon gas. To this reaction vessel, 45 g of toluene deaerated in advance by bubbling argon gas was added.
Next, 10 ml of a 16.7% by weight aqueous sodium carbonate solution deaerated by bubbling with an argon gas in advance was added dropwise to the solution, and then the temperature was raised and refluxed for 12 hours.
Next, after cooling this reaction solution to near room temperature, a solution prepared by previously dissolving 0.05 g of phenylboric acid in 1 ml of tetrahydrofuran was added to this reaction solution, and the temperature was then raised to reflux for 1 hour. The reaction was performed in an argon gas atmosphere.
After the reaction, the reaction solution was cooled to near room temperature, and 15 ml of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered.
Next, the obtained toluene solution was passed through an alumina column for purification. The obtained toluene solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. Next, this precipitate was dried under reduced pressure and then dissolved in toluene. The obtained toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, the obtained toluene solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.07 g of a polymer compound (hereinafter, this polymer compound is referred to as “polymer compound 3”). The polymer compound 3 had a polystyrene equivalent weight average molecular weight of 2.1 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 1.3 × 10 ⁴ .

（２）化合物（Ｈ）の合成
次に、反応容器に、前記原料化合物（Ｇ）４．１８ｇと５−ブロム−２，２’−ビチオフェン−５’−カルボキシアルデヒド３．０ｇとを仕込み、反応系内を窒素ガスで置換した後、テトラヒドロフラン（脱水）５５ｇを加え、溶解させた。得られた溶液に、あらかじめカリウム−ｔ−ブトキシド２．２４ｇをテトラヒドロフラン（脱水）１２ｇに溶解した溶液を滴下した。滴下後、引き続き室温で２０時間反応させた。なお、反応は窒素ガス雰囲気下で行なった。
次に、得られた反応溶液に酢酸を加え中和した後、得られた溶液をメタノール中に注ぎ込み、再沈し、生成した沈殿を回収した。得られた沈殿を減圧乾燥した後、トルエンに溶解した。
次に、得られたトルエン溶液をろ過し、不溶物を除去した後、得られたトルエン溶液をアルミナカラムに通し、精製した。次に、得られたトルエン溶液をメタノール中に注ぎ込み、再沈し、生成した沈殿を回収した。得られた沈殿をメタノールで洗浄した後、減圧乾燥して、下記構造式：

で示される単量体化合物（Ｈ）２．２ｇを得た
<Example 4> Synthesis of Compound (H) (1) Synthesis of phosphonate ester of bis (bromomethyl) compound of 3,4-bis (4- (3,7-dimethyloctyloxy) phenyl) thiophene To 60 g of acetic acid, 20.4 g of 3,4-bis (4- (3,7-dimethyloctyloxy) phenyl) thiophene and 5.5 g of paraformaldehyde were added. To the obtained mixed solution, 120 g of a 25% hydrobromic acetic acid solution was added at room temperature, followed by reaction at room temperature for 18 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, the reaction solution was allowed to stand, and the separated lower layer was recovered. Next, 250 ml of hexane was added to the obtained recovered material. This hexane solution was washed 7 times with ion exchange water. Next, the solvent was distilled off from the obtained hexane solution under reduced pressure to obtain 16.4 g of a solid.
Next, 16.4 g of the solid obtained above and 25 g of triethyl phosphite were charged in a reaction vessel, and then the temperature was raised and reacted at 130 ° C. for 4 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, excess triethyl phosphite was distilled off at 120 ° C. under reduced pressure.
The obtained reaction product was cooled and then dissolved in toluene. The obtained solution was purified with a silica gel column using toluene and subsequently chloroform as a developing solvent, to obtain 9.8 g of a phosphonic acid ester {raw material compound (G)}.

(2) Synthesis of Compound (H) Next, 4.18 g of the raw material compound (G) and 3.0 g of 5-bromo-2,2′-bithiophene-5′-carboxaldehyde were charged into a reaction vessel and reacted. After replacing the system with nitrogen gas, 55 g of tetrahydrofuran (dehydrated) was added and dissolved. A solution prepared by dissolving 2.24 g of potassium tert-butoxide in 12 g of tetrahydrofuran (dehydrated) in advance was added dropwise to the resulting solution. After the dropping, the reaction was continued at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.
Next, after acetic acid was added to the resulting reaction solution for neutralization, the resulting solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. The obtained precipitate was dried under reduced pressure and then dissolved in toluene.
Next, the obtained toluene solution was filtered to remove insoluble matters, and then the obtained toluene solution was passed through an alumina column for purification. Next, the obtained toluene solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain the following structural formula:

2.2 g of the monomer compound (H) represented by

Example 5
(Synthesis of polymer compound 4)

0.544 g of the compound (H), 0.329 g of the compound (C) and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.70 g, palladium (II) acetate 2.5 mg and tris (2-methoxyphenyl) phosphine 11.9 mg were charged into the reaction vessel, and the reaction vessel was filled with argon gas. Replaced. To this reaction vessel, 20 ml of toluene deaerated in advance by bubbling argon gas was added.
Next, 5 ml of a 16.7 wt% aqueous sodium carbonate solution previously deaerated by bubbling with an argon gas was added dropwise to the resulting solution, and then the temperature was raised to a temperature at which the solvent was refluxed, and refluxed for 20 minutes.
Next, after cooling the obtained reaction solution, a mixed solution of 0.10 g of phenylboric acid / 0.5 ml of tetrahydrofuran was added to this reaction solution, and then the temperature was raised and refluxed for 1 hour.
Next, after cooling the reaction solution, 20 ml of toluene deaerated by bubbling argon gas in advance was added to the reaction solution, and the temperature was raised and refluxed for 3 hours. The reaction was performed in an argon gas atmosphere.
After completion of the reaction, the resulting reaction solution was cooled, and then 40 g of toluene was added. Next, the obtained reaction solution was allowed to stand, and the separated gel-like toluene layer was recovered.
Next, this gel-like toluene layer was poured into methanol and re-precipitated, and the generated precipitate was recovered. Next, this precipitate was dried under reduced pressure and then dissolved in toluene. Next, the obtained toluene solution was filtered to remove insoluble matters, and then the obtained toluene solution was passed through an alumina column for purification. Next, the obtained toluene solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was recovered. The obtained precipitate was washed with methanol and then dried under reduced pressure to obtain 0.03 g of a polymer (hereinafter, this polymer is referred to as “polymer compound 4”). The polymer compound 4 had a polystyrene equivalent weight average molecular weight of 2.8 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 8.7 × 10 ³ .

The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is as follows.

Example 6
(Production and evaluation of organic thin-film solar cells)
Polymer compound 1 as an electron donor was dissolved in orthodichlorobenzene at a concentration of 0.75% (% by weight). Thereafter, 3 times the weight of PCBM (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name E100) was mixed with the solution as an electron acceptor. Subsequently, it filtered with the Teflon (trademark) filter with the hole diameter of 1.0 micrometer, and produced the application | coating solution.

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, the coating solution was applied by spin coating to obtain an active layer (film thickness of about 80 nm) of the organic thin film solar cell. Then, lithium fluoride was vapor-deposited with a thickness of 4 nm by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm. The degree of vacuum at the time of vapor deposition was all 1 to 9 × 10 ⁻³ Pa. Moreover, the shape of the obtained organic thin-film solar cell was a regular square of 2 mm × 2 mm. The photoelectric conversion efficiency of the obtained organic thin-film solar cells is generated by irradiating a certain amount of light using a solar simulator (product name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ). The current and voltage were measured and determined. The measurement results are shown in Table 1.

Comparative Example 1
An organic thin film solar cell was produced in the same manner as in Example 6 except that the polymer compound 2 was used as the electron donor, and the photoelectric conversion efficiency was measured. The measurement results are shown in Table 1.

Example 7
An organic thin film solar cell was produced in the same manner as in Example 6 except that the polymer compound 3 was used as an electron donor, and the photoelectric conversion efficiency was measured. The measurement results are shown in Table 1.

Example 8
An organic thin film solar cell was produced in the same manner as in Example 6 except that the polymer compound 4 was used as the electron donor, and the photoelectric conversion efficiency was measured. The measurement results are shown in Table 1.

-Evaluation-
As can be seen from Table 1, the organic thin film solar cells (Examples 6, 7 and 8) formed using the polymer compounds 1 and 3 and the polymer compound 4 are organic thin film solar cells formed using the polymer compound 2. The photoelectric conversion efficiency was higher than that of the battery (Comparative Example 1).

Claims (15)

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

(1)

(Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group) Group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or a nitro group. a plurality of R may optionally be the same or different .R ¹ is a hydrogen atom, an alkyl group, an alkoxy group,. a plurality of R ¹ representing an aryl group or a cyano group are the same .Ar ₁ may be different even represents an arylene group or a divalent heterocyclic group .Z represents an oxygen atom or sulfate Represents an atom. Plurality of Z may be .m and n be different even identical, each independently represents an integer of 2 to 4.) The polymer compound according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (2).

(Wherein R, R ¹ and Ar ¹ represent the same meaning as described above) Furthermore, the high molecular compound of Claim 1 or 2 which has a structural unit represented by following formula (3).
−Ar ₂ − (3)
(In the formula, Ar ₂ represents an arylene group, a divalent heterocyclic group, a divalent aromatic amine group, or a divalent group having a metal complex structure.)   The composition containing the high molecular compound in any one of Claims 1-3.   The liquid composition containing the polymer compound in any one of Claims 1-3.   The organic thin film containing the high molecular compound in any one of Claims 1-3.   The organic photoelectric conversion element which has an organic layer containing the high molecular compound in any one of Claims 1-3.   A pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing the polymer compound according to any one of claims 1 to 3 between the electrodes, and adjacent to the first organic layer And an organic photoelectric conversion element having a second organic layer containing an electron donating compound.   A pair of electrodes, at least one of which is transparent or translucent, a first organic layer containing an electron-accepting compound between the electrodes, and provided adjacent to the first organic layer. An organic photoelectric conversion device comprising a second organic layer containing the polymer compound according to any one of the above.   An organic photoelectric conversion device comprising a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing the polymer compound and the electron donating compound according to claim 1 between the electrodes.   An organic photoelectric conversion device comprising a pair of electrodes, at least one of which is transparent or translucent, and an organic layer containing an electron-accepting compound and the polymer compound according to claim 1 between the electrodes.   The organic photoelectric conversion device according to claim 9 or 11, wherein the electron-accepting compound is a fullerene derivative.   The organic electroluminescent element which has an organic layer containing the high molecular compound in any one of Claims 1-3. A compound represented by the following formula (4).

(4)
(Wherein, R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group) Group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or a nitro group. a plurality of R may optionally be the same or different .R ¹ is a hydrogen atom, an alkyl group, an alkoxy group,. a plurality of R ¹ representing an aryl group or a cyano group are the same .Ar ₁ may be different even represents an arylene group or a divalent heterocyclic group .Z represents an oxygen atom or sulfate A plurality of Z may be the same or different, m and n each independently represents an integer of 2 to 4. T represents a substituent involved in condensation polymerization. A plurality of T may be the same or different.) The compound according to claim 14, wherein the compound represented by the formula (4) is a compound represented by the following formula (5).

(5)
(In the formula, R, R ¹ , Ar ₁ and T represent the same meaning as described above)