JP2015218291A - POLYMER COMPOUND, ORGANIC THIN FILM AND ORGANIC SEMICONDUCTOR DEVICE CONTAINING THE POLYMER COMPOUND - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymer compound useful for manufacturing an organic transistor excellent in carrier mobility and manufacturing an organic solar cell excellent in photoelectric conversion efficiency.SOLUTION: The polymer compound contains a structural unit represented by formula (1). [In the formula, Rand Reach independently represent a 1-30C alkyl group, a 6-30C aryl group, or a 2-30C monovalent heterocyclic group; X represents a sulfur atom, N-R, or CH-R; Rrepresents a 1-30C alkyl group, a 6-30C aryl group, a 1-30C alkoxy group, a hydroxyl group, a 1-30C acyl group, or a 1-30C substituted amino group; Rrepresents a 1-30C alkyl group, a 6-30C aryl group, or a 2-30C monovalent heterocyclic group; and ring A and ring B each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring.]

Description

  The present invention relates to a polymer compound having a specific structural unit, an organic thin film containing the polymer compound, and an organic semiconductor element.

  A compound in which two aromatic hydrocarbon rings or heteroaromatic rings are cross-linked in a planar manner has a flatness fixed by cross-linking, and π conjugation spreads, and a soluble substituent can be introduced into the cross-linking site. It is known that the polymer compound is useful as an organic transistor material or an organic solar cell material (Patent Document 1, Non-Patent Document 1, Non-Patent Document 1, Non-Patent Document 1, Patent Document 2).

Special table 2009-506519

Macromolecular Chemistry and Physics 2011, 212, 428-443. Journal of Science: Part A: Polymer Chemistry, 2009, 47, 2073-2092.

  Studies have been made to improve the carrier mobility of organic transistors and the photoelectric conversion efficiency of organic solar cells using the above-described polymer compounds.

  An object of this invention is to provide the novel high molecular compound useful for manufacture of the organic transistor which is excellent in manufacture of the organic transistor excellent in carrier mobility, or photoelectric conversion efficiency. Another object of the present invention is to provide an organic thin film and an organic semiconductor element (in particular, an organic transistor and an organic solar cell) containing the polymer compound.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.

（式中、
Ｒ^１およびＲ^２は、それぞれ独立に炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の１価の複素環基を表し、これらの基は置換基を有していてもよい。
Ｘは硫黄原子、Ｎ−Ｒ^３、またはＣＨ−Ｒ^４を表し、Ｒ^３は炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数１〜３０のアルコキシ基、ヒドロキシル基、炭素原子数１〜３０のアシル基または炭素原子数１〜３０の置換アミノ基を表し、これらの基は置換基を有していてもよく、Ｒ^４は炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の１価の複素環基を表し、これらの基は置換基を有していてもよい。
環Ａおよび環Ｂは、それぞれ独立に、芳香族炭化水素化環または複素芳香環を表し、該芳香族炭化水素化環および複素芳香環は置換基を有していてもよい。）
［２］
前記環Ａおよび環Ｂが、同一の複素芳香環を表す、請求項１に記載の高分子化合物。
［３］
前記式（１）で表される構造単位が、式（２）で表される構造単位である、請求項１または２に記載の高分子化合物。

（式中、Ｒ^１、Ｒ^２、およびXは、それぞれ前記と同じ意味を表す。)
［４］
ＸがＮ−Ｒ^３である請求項１〜３のいずれかに記載の高分子化合物。
［５］
請求項１〜４のいずれかに記載の高分子化合物を含む、有機薄膜。
［６］
第１の電極と第２の電極とを有し、
該第１の電極と該第２の電極との間に請求項５に記載の有機薄膜を有する、有機半導体素子。
［７］
光電変換素子である、請求項６に記載の有機半導体素子。
［８］
有機トランジスタである、請求項６に記載の有機半導体素子。 [1]
The high molecular compound which has a structural unit represented by Formula (1).

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups are It may have a substituent.
X represents a sulfur atom, N—R ³ or CH—R ⁴ , wherein R ³ is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. , A hydroxyl group, an acyl group having 1 to 30 carbon atoms, or a substituted amino group having 1 to 30 carbon atoms, and these groups may have a substituent, and R ⁴ has 1 to 30 carbon atoms. An alkyl group, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups optionally have a substituent.
Ring A and ring B each independently represent an aromatic hydrocarbon ring or heteroaromatic ring, and the aromatic hydrocarbon ring and heteroaromatic ring optionally have a substituent. )
[2]
The polymer compound according to claim 1, wherein the ring A and the ring B represent the same heteroaromatic ring.
[3]
The polymer compound according to claim 1 or 2, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2).

(In the formula, R ¹ , R ² , and X each have the same meaning as described above.)
[4]
The polymer compound according to claim 1, wherein X is N—R ³ .
[5]
An organic thin film comprising the polymer compound according to claim 1.
[6]
A first electrode and a second electrode;
The organic-semiconductor element which has an organic thin film of Claim 5 between this 1st electrode and this 2nd electrode.
[7]
The organic-semiconductor element of Claim 6 which is a photoelectric conversion element.
[8]
The organic-semiconductor element of Claim 6 which is an organic transistor.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the organic transistor which is excellent in the organic transistor excellent in carrier mobility, or photoelectric conversion efficiency can be provided. The present invention can further provide an organic thin film and an organic semiconductor element (in particular, an organic transistor and an organic solar cell) containing the polymer compound.

It is a schematic cross section which shows an example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows an example of the photoelectric conversion element of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  In the present specification, the “structural unit” means a unit structure present in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure present in two or more in the polymer compound).

<Polymer compound>
(First structural unit)
The polymer compound of the present invention includes a structural unit represented by the formula (1) (hereinafter sometimes referred to as “first structural unit”). The first structural unit may be contained alone or in combination of two or more in the polymer compound. The polymer compound of the present invention is preferably a conjugated polymer compound.

（式中、
Ｒ^１およびＲ^２は、それぞれ独立に炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の１価の複素環基を表し、これらの基は置換基を有していてもよい。
Ｘは硫黄原子、Ｎ−Ｒ^３、またはＣＨ−Ｒ^４を表し、Ｒ^３は炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数１〜３０のアルコキシ基、ヒドロキシル基、炭素原子数１〜３０のアシル基、炭素原子数１〜３０の置換アミノ基を表し、これらの基は置換基を有していてもよく、Ｒ^４は炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数２〜３０の１価の複素環基を表し、これらの基は置換基を有していてもよい。
環Ａおよび環Ｂは、それぞれ独立に、芳香族炭化水素化環または複素芳香環を表し、該芳香族炭化水素化環または複素芳香環は置換基を有していてもよい。）

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups are It may have a substituent.
X represents a sulfur atom, N—R ³ or CH—R ⁴ , wherein R ³ is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. , A hydroxyl group, an acyl group having 1 to 30 carbon atoms, and a substituted amino group having 1 to 30 carbon atoms, and these groups may have a substituent, and R ⁴ has 1 to 30 carbon atoms. An alkyl group, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups optionally have a substituent.
Ring A and ring B each independently represent an aromatic hydrocarbonated ring or a heteroaromatic ring, and the aromatic hydrocarbonated ring or heteroaromatic ring may have a substituent. )

R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups May have a substituent. From the viewpoint of ease of synthesis of the compound of the present invention, R ¹ and R ² preferably represent the same group, represent the same group, and represent an alkyl group having 1 to 30 carbon atoms. More preferred.

The alkyl group represented by R ¹ and R ² may be either a linear alkyl group or a branched alkyl group, or a cycloalkyl group. The number of carbon atoms of the alkyl group is usually 1 to 30 (usually 3 to 30 in the case of a cycloalkyl group), and preferably 1 to 20 (3 to 20 in the case of a cycloalkyl group). The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group, Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, and 3,7-dimethyloctyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.
The alkyl group may have a substituent, and examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The aryl group represented by R ¹ and R ² is the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the aromatic hydrocarbon which may have a substituent. It includes a group in which two or more selected from a group having a ring, a group having a condensed ring, an independent benzene ring and a condensed ring are directly bonded. The number of carbon atoms that the aryl group has is usually 6 to 30, and preferably 6 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group. 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 4-phenylphenyl group and the like, and a phenyl group is preferable.
Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, an alkylthio group, a monovalent heterocyclic group, and a halogen atom. Examples of the aryl group containing these groups include 4-hexylphenyl group, 3,5-dimethoxyphenyl group, pentafluorophenyl group and the like. When the aryl group has a substituent, the substituent is preferably an alkyl group.

The monovalent heterocyclic group represented by R ¹ and R ² is the remaining atom obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the heterocyclic compound which may have a substituent. It is a group and includes a group in which two or more selected from a group having a condensed ring, an independent heterocyclic ring and a condensed ring are directly bonded. The number of carbon atoms that the monovalent heterocyclic group has is usually 2 to 30, and preferably 3 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Specific examples of the monovalent heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group. Group, 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like, and 2-thienyl group is preferable.
Examples of the substituent that the monovalent heterocyclic group may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Examples of the monovalent heterocyclic group containing these groups include 5-octyl-2-thienyl group and 5-phenyl-2-furyl group. When the monovalent heterocyclic group has a substituent, the substituent is preferably an alkyl group.

The alkyl group, aryl group and monovalent heterocyclic group as substituents are the same as the definitions and examples of the alkyl group, aryl group and monovalent heterocyclic group represented by R ¹ and R ² .

The alkoxy group as a substituent may be either a linear alkoxy group or a branched alkoxy group, or a cycloalkoxy group. The number of carbon atoms that the alkoxy group has is usually 1 to 30 (in the case of a cycloalkoxy group, usually 3 to 30).
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n- Linear alkoxy group such as dodecyloxy group, n-hexadecyloxy group, isopropoxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, 2-butyloctyloxy group, 2- Examples thereof include branched alkoxy groups such as hexyldecyloxy group and 2-octyldodecyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.

The alkylthio group as a substituent may be either a linear alkylthio group or a branched alkylthio group, or a cycloalkylthio group. The number of carbon atoms that the alkylthio group has is usually 1 to 30 (usually 3 to 30 in the case of a cycloalkylthio group).
Specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-dodecylthio group, n -Straight chain alkylthio group such as hexadecylthio group, isopropylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, 2-ethylhexylthio group, 2-butyloctylthio group, 2-hexyldecylthio group, 2- Examples thereof include branched alkylthio groups such as octyldodecylthio group, cycloalkylthio groups such as cyclopentylthio group and cyclohexylthio group.

  Examples of the halogen atom as a substituent include an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom, and a fluorine atom is preferable.

Alkyl and aryl groups represented by R ³ in the N-R ³ in which X represents is the same as the definitions and examples of the alkyl group and aryl group represented by R ¹ and R ^2.

Alkoxy group represented by R ³ in N-R ³ in which X represents a linear alkoxy group may be either branched alkoxy group, may be a cycloalkoxy group. The number of carbon atoms that the alkoxy group has is usually 1 to 30 (in the case of a cycloalkoxy group, usually 3 to 30).
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n- Linear alkoxy group such as dodecyloxy group, n-hexadecyloxy group, isopropoxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, 2-butyloctyloxy group, 2- Examples thereof include branched alkoxy groups such as hexyldecyloxy group and 2-octyldodecyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.

Acyl group represented by R ³ in N-R ³ in which X represents a linear acyl group may be either branched acyl groups. The number of carbon atoms that the acyl group has is usually 1-30.
Specific examples of the acyl group include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group. , N-dodecylcarbonyl group, linear alkylcarbonyl group such as n-hexadecylcarbonyl group, isopropylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, 2-ethylhexylcarbonyl group, 2-butyl Branched alkylcarbonyl groups such as octylcarbonyl group, 2-hexyldecylcarbonyl group, 2-octyldodecylcarbonyl group, cycloalkylcarbonyl groups such as cyclopentylcarbonyl group, cyclohexylcarbonyl group, phenylcarbonyl Arylcarbonyl groups such as 4-methylphenylcarbonyl group, 4-butylphenylcarbonyl group, 4-hexylphenylcarbonyl group, 4-octylphenylcarbonyl group, 4-dodecylphenylcarbonyl group, 4-octyloxyphenylcarbonyl group, etc. It is done.

Substituted amino group represented by R ³ in N-R ³ in which X represents a linear alkyl group, branched alkyl amino group may be any of the aryl amino group. The substituted amino group has usually 1 to 30 carbon atoms.
Specific examples of the amino group include methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, and n-octylamino. Group, linear alkylamino group such as n-dodecylamino group, n-hexadecylamino group, isopropylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group, 2-ethylhexylamino group, 2- Branched alkylamino groups such as butyloctylamino group, 2-hexyldecylamino group, 2-octyldodecylamino group, cycloalkylamino groups such as cyclopentylamino group, cyclohexylamino group, phenylamino group, 4-methylphenylamino group, 4-butylphenylamino group, 4-hexylphenylamino group 4-octylphenyl group, 4-dodecylphenyl group, and an aryl amino group such as 4-octene Ciro hydroxyphenyl amino group.

Alkyl group represented by R ⁴ is in the CH-R ⁴ in which X represents an aryl group and monovalent heterocyclic group, a definition and examples of the alkyl group, aryl group and monovalent heterocyclic group represented by R ¹ and R ² The same.

Ring A and ring B each independently represent an aromatic hydrocarbonated ring or a heteroaromatic ring, and the aromatic hydrocarbonated ring or heteroaromatic ring may have a substituent. The number of carbon atoms in the aromatic hydrocarbonated ring is preferably 6-30, more preferably 6-14, and still more preferably 6-10. The number of carbon atoms in the heteroaromatic ring is preferably 2 to 30, more preferably 2 to 14, and further preferably 3 to 8. The number of carbon atoms does not include the number of carbon atoms of the substituent.
Ring A and ring B preferably represent the same aromatic hydrocarbonated ring or heteroaromatic ring from the viewpoint of ease of synthesis of the compound of the present invention, and a polymer obtained by polymerizing the compound of the present invention From the viewpoint of further expanding the π conjugation of the compound, it is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

  The structural unit represented by the formula (1) is preferably represented by the formula (2).

（式中、Ｒ^１、Ｒ^２、およびＸは、それぞれ前記と同じ意味を表す。）

(In the formula, R ¹ , R ² and X each have the same meaning as described above.)

  Examples of the structural unit represented by Formula (1) or the structural unit represented by Formula (2) include compounds represented by Formula (1-1) to Formula (1-18).

  Among the compounds represented by formula (1-1) to formula (1-18), compounds represented by formula (1-1) to formula (1-12) are preferable.

(Second structural unit)
The polymer compound of the present invention preferably has a structural unit different from the structural unit represented by the formula (1) in addition to the structural unit represented by the formula (1). In this case, it is preferable that the structural unit represented by the formula (1) and the structural unit different from the structural unit represented by the formula (1) form a conjugate.
Conjugation in this specification is chained in the order of unsaturated bond-single bond-unsaturated bond, two pi bonds in pi orbital are adjacent, and each pi electron is arranged in parallel, on the unsaturated bond. It refers to a state where π electrons are not localized but π electrons spread on adjacent single bonds and π electrons are delocalized. Here, the unsaturated bond refers to a double bond or a triple bond.

  Examples of the structural unit different from the structural unit represented by the formula (1) include a vinylene group, an ethynylene group, an arylene group, and a divalent heterocyclic group.

The arylene group is an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and the aromatic hydrocarbon usually has 6 to 60 carbon atoms. Yes, preferably 6-20.
The arylene group includes a group having a benzene ring, a group having a condensed ring, a group in which two or more selected from an independent benzene ring and a condensed ring are directly bonded, and two or more selected from an independent benzene ring and a condensed ring. Groups bonded through groups such as vinylene are included.

  Examples of the arylene group include arylene groups represented by the following formulas 1 to 10.

（式中、Ｒ”は水素原子、フッ素原子または炭素原子数１〜３０のアルキル基または炭素原子数１〜３０のアルキル基を有する置換基を表し、該アルキル基は、ハロゲン原子、炭素原子数１〜３０のアルコキシ基、炭素原子数１〜３０のアルキルチオ基、炭素原子数２〜３０のアルキルカルボニル基、炭素原子数２〜３０のアルコキシカルボニル基、炭素原子数２〜３０のジアルキルアミノ基、炭素原子数６〜３０のアリール基、炭素原子数２〜３０の１価の複素環基および炭素原子数３〜３０の置換シリル基から選ばれる少なくとも１つの基で置換されてもよい。複数存在するＲ”は、同一でも異なっていても良い。Ｒ”が表す炭素原子数１〜３０のアルキル基または炭素原子数１〜３０のアルキル基を有する置換基としては、前記Ｒと同じものが例示される。

(In the formula, R ″ represents a hydrogen atom, a fluorine atom, a substituent having an alkyl group having 1 to 30 carbon atoms or an alkyl group having 1 to 30 carbon atoms, and the alkyl group is a halogen atom or a carbon atom number. An alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an alkylcarbonyl group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 2 to 30 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, It may be substituted with at least one group selected from an aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group having 2 to 30 carbon atoms, and a substituted silyl group having 3 to 30 carbon atoms. R ″ may be the same or different. The substituent having the alkyl group having 1 to 30 carbon atoms or the alkyl group having 1 to 30 carbon atoms represented by R ″ is the same as the above R. Those are exemplified.

The divalent heterocyclic group is an atomic group remaining after removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound, and the number of carbon atoms of the heterocyclic compound is usually 2 to 2. 30 and preferably 3-20. Further, the divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.
Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. This includes things.
The divalent heterocyclic group includes a group in which two or more selected from a group having a condensed ring, an independent heterocyclic ring and a condensed ring are directly bonded.

  Examples of the divalent heterocyclic group include bicyclic heterocyclic groups represented by the following formulas 11 to 60.

（式中、Ｒ”は前記と同じ意味を表す。ａおよびｂは、それぞれ独立にくり返しの数を表し、通常１〜５であり、好ましくは１〜３であり、特に好ましくは１である。）

(In the formula, R ″ represents the same meaning as described above. A and b each independently represent the number of repetitions, usually 1 to 5, preferably 1 to 3, particularly preferably 1. )

The polymer compound of the present invention refers to a polymer having a weight average molecular weight of 1000 or more, and a polymer compound having a weight average molecular weight of 3000 to 1000000 is preferably used. If the weight average molecular weight is lower than 3000, defects may occur in the film formation during the production of the organic semiconductor element, and if it exceeds 1000000, solvent solubility and coating film forming processability may be deteriorated. More preferably, it is 8000-500000 as a weight average molecular weight, Most preferably, it is 10000-300000.
In addition, the weight average molecular weight in this specification refers to the weight average molecular weight of polystyrene conversion calculated using the standard sample of polystyrene using gel permeation chromatography (GPC).

  The polymer compound of the present invention has high solvent solubility. Specifically, the polymer compound of the present invention is 0.1% by weight (hereinafter sometimes referred to as “wt%”). It is preferable that it has a solubility capable of producing a solution containing the above, and more preferably a solubility capable of producing a solution containing 0.4 wt% or more.

  In the polymer compound of the present invention, the content of the structural unit represented by the formula (1) may be at least one in the polymer compound, but preferably 3 in the polymer compound. More preferably, 5 or more are contained in the polymer compound.

  The polymer compound of the present invention may be any type of copolymer, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer. From the viewpoint of further increasing the carrier mobility of the organic transistor produced using the polymer compound of the present embodiment, an alternating copolymer is more preferable.

  In the polymer compound of the present invention, if a group that is active in the polymerization reaction remains at the end of the molecular chain, the carrier mobility of an organic transistor produced using the polymer compound may be lowered. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent aromatic heterocyclic group.

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

〔式中、Ｒ^１、Ｒ^２、Ｘ、環Ａおよび環Ｂは、それぞれ前記と同じ意味を表す。
Ｚはハロゲン原子を表す。２個存在するＺは、同一でも異なっていても良い。〕
式（１００）で表される１種類以上の化合物と、必要に応じて式（２００）で表される１種類以上の化合物と、をパラジウム触媒および塩基の存在下で反応される工程を有する製造方法が挙げられる。
Ｅ^１、Ｅ^２が表すアリーレン基および２価の複素環基は、上記の前記式（１）で表される構造単位とは異なる構造単位が表すアリーレン基および２価の複素環基と同じ意味を表す。
Ｑ^１００−Ｅ^１−Ｑ^２００ （１００）
〔式中、
Ｅ^１は、ビニレン基、アリーレン基または２価の複素環基を表す。
Ｑ^１００およびＱ^２００は、それぞれ独立に、ホウ酸残基（−Ｂ（ＯＨ）_２）またはホウ酸エステル残基を表す。〕
Ｔ¹−Ｅ^２−Ｔ² （２００）
〔式中、
Ｅ²は、アリーレン基または２価の複素環基を表す。
Ｔ¹およびＴ²は、それぞれ独立に、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基またはアリールアルキルスルホネート基を表す。〕 As a method using the Suzuki coupling reaction, for example,
One or more compounds represented by formula (1 ′) (preferably, one or more compounds represented by formula (2 ′));

[Wherein R ¹ , R ² , X, ring A and ring B each have the same meaning as described above.
Z represents a halogen atom. Two Z's may be the same or different. ]
Production comprising a step of reacting one or more compounds represented by the formula (100) and, if necessary, one or more compounds represented by the formula (200) in the presence of a palladium catalyst and a base A method is mentioned.
The arylene group and divalent heterocyclic group represented by E ¹ and E ² have the same meanings as the arylene group and divalent heterocyclic group represented by a structural unit different from the structural unit represented by the above formula (1). Represents.
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
[Where,
E ¹ represents a vinylene group, an arylene group or a divalent heterocyclic group.
Q ¹⁰⁰ and Q ²⁰⁰ each independently represent a boric acid residue (—B (OH) ₂ ) or a boric acid ester residue. ]
T ¹ -E ² -T ² (200)
[Where,
E ² represents an arylene group or a divalent heterocyclic group.
T ¹ and T ² each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group. ]

  In this case, the total number of moles of one or more compounds represented by the formula (1 ′) (preferably one or more compounds represented by the formula (2 ′) is represented by the formula (100). It is preferable that the amount of the compound is excessive with respect to the total number of moles of the one or more compounds, specifically, one or more compounds represented by the formula (1 ′) (preferably represented by the formula (2 ′)). The total number of moles of the one or more compounds represented by formula (100) relative to the total number of moles of the one or more compounds represented by formula (200). 0.6 to 0.99 mol%, more preferably 0.7 to 0.95 mol%.

  Examples of the halogen atom represented by X in the formulas (1 ′) and (2 ′) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom is preferable from the viewpoint of being useful as a raw material for a polymer compound. .

  As the boric acid ester residue, the following formula:

〔式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。〕
で表される基等が例示される。

[In the formula, Me represents a methyl group, and Et represents an ethyl group. ]
The group etc. which are represented by these are illustrated.

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

Examples of the alkyl sulfonate group represented by T ¹ and T ² in the formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group represented by T ¹ and T ² in Formula (200) include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the arylalkyl sulfonate group represented by T ¹ and T ² in Formula (200) include a benzyl sulfonate group.

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

Examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (0) catalyst, Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, etc. are mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate. , Dichlorobis (triphenylphosphine) palladium, palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but it is one or more compounds represented by the formula (1 ′) (preferably represented by the formula (2 ′)). Is usually 0.0001 to 0.5 mol%, preferably 0.0003 to 0.1 mol%, based on the synthesis of the number of moles of one or more compounds.

  Examples of the palladium catalyst used in the Suzuki coupling reaction include triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tri-tert-butylphosphine, and tri-tert-butylphosphinetetrafluoro. Phosphorus compounds such as borates can be added as ligands. In this case, the addition amount of the ligand is usually 0.5 to 100 mol%, preferably 0.9 to 20 mol%, more preferably 1 to 10 mol%, based on the total number of moles of the palladium catalyst. is there.

Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, potassium phosphate, sodium carbonate, barium hydroxide and the like. Examples of the organic base include triethylamine and tributylamine. Examples of the inorganic salt include cesium fluoride.
The amount of the base added is usually relative to the total number of moles of one or more compounds represented by the formula (1 ′) (preferably one or more compounds represented by the formula (2 ′)). It is 0.5-100 mol%, Preferably it is 0.9-20 mol%, More preferably, it is 1-10 mol%.

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

  Although the temperature at which the Suzuki coupling reaction is carried out depends on the solvent, it is usually about 40 to 160 ° C., and preferably 50 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound of the present invention. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

  The Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, dichlorobis (triphenylphosphine) palladium (II), which is represented by the above formula (1 ′), is contained in this polymerization vessel. One or more compounds (preferably, one or more compounds represented by the formula (2 ′)), one or more compounds represented by the formula (100), and the formula ( 200) is added, and the polymerization vessel is sufficiently substituted with nitrogen gas, degassed, and then degassed by bubbling with nitrogen gas in advance (for example, tetrahydrofuran) is added. Thereafter, a base degassed by bubbling with nitrogen gas in advance (for example, potassium carbonate aqueous solution) was dropped into the solution, and then heated and kept warm (for example, at a reflux temperature for 3 hours, While maintaining the inert atmosphere) polymerized.

As a method using Stille coupling reaction, for example, formula (300):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (300)
[Where,
E ³ represents vinylene, an arylene group or a divalent heterocyclic group. The arylene group and the divalent heterocyclic group have the same meanings as the arylene group and the divalent heterocyclic group represented by the structural unit different from the structural unit represented by the formula (1).
Q ³⁰⁰ and Q ⁴⁰⁰ each independently represent an organotin residue. ]
One or more compounds represented by formula (1) and one or more compounds represented by formula (1 ′) (preferably one or more compounds represented by formula (2 ′) or formula (3 ′)) , Most preferably one or more compounds represented by formula (4 ′)) and, if necessary, one or more compounds represented by formula (200) in the presence of a palladium catalyst. The manufacturing method which has this. E ³ is preferably a group represented by Formula 1 to Formula 60.

Examples of the organic tin residue include a group represented by —SnR ¹⁰⁰ ₃ . Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n-pentyl group, isopentyl group, 2-methylbutyl group, 1 -Methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, Examples include chain alkyl groups such as undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and adamantyl group. Examples of the aryl group include a phenyl group and a naphthyl group.
Preferably the organotin residues, -SnMe _3, -SnEt _3, a -SnBu ₃ or -SnPh _3, more preferably -SnMe _3, a -SnEt ₃ or -SnBu _3. Here, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specific examples include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium. Palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable from the viewpoints of easy reaction (polymerization) operation and reaction (polymerization) rate.
The addition amount of the palladium catalyst used in the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but one or more kinds of compounds represented by the formula (1 ′) (preferably the formula The total number of moles of one or more compounds represented by (2 ′) or formula (3 ′), most preferably one or more compounds represented by formula (4 ′) is usually from 0.0001 to 0.5 mol%, preferably 0.0003 to 0.2 mol%.

Further, in the Stille coupling reaction, a ligand or a cocatalyst can be used as necessary. Examples of the ligand include triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, tri-tert-butylphosphine, and tri-tert-butylphosphine. Examples thereof include phosphorus compounds such as tetrafluoroborate, and arsenic compounds such as triphenylarsine and triphenoxyarsine. Examples of the cocatalyst include copper iodide, copper bromide, copper chloride, and copper (I) 2-thenoylate.
When using a ligand or a cocatalyst, the addition amount of the ligand or the cocatalyst is usually 0.5 to 100 mol%, preferably 0.9 to 20 mol%, based on the total number of moles of the palladium catalyst. More preferably, it is 1 to 10 mol%.

  The Stille coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, xylene, chlorobenzene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solvent solubility of the polymer compound of the present invention, toluene or xylene is preferable.

The temperature at which the Stille coupling reaction is performed depends on the solvent, but is usually about 40 to 160 ° C., and preferably 50 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound of the present invention. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for performing the reaction (reaction time) may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

  The Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the polymerization vessel is charged with a palladium catalyst, and one or more compounds represented by the above formula (300), One or more compounds represented by the formula (1 ′) (preferably one or more compounds represented by the formula (2 ′) or the formula (3 ′), most preferably represented by the formula (4 ′)). One or more compounds), if necessary, one or more compounds represented by the formula (200) are charged, and the polymerization vessel is sufficiently substituted with nitrogen gas, deaerated, and then preliminarily nitrogen gas. After adding a solvent (for example, toluene) degassed by bubbling with a ligand, a ligand and a cocatalyst are added as necessary, and then heated and heated (for example, at reflux temperature for 8 hours, Polymerize while maintaining an active atmosphere.

By reacting one or more compounds represented by the formula (1 ′) (preferably one or more compounds represented by the formula (2 ′)) in the presence of a zero-valent nickel compound, the formula (1) It is also possible to produce the polymer compound of the present invention having a structural unit represented by (preferably a structural unit represented by the formula (2)). As the zerovalent nickel compound, bis (cyclooctadiene) nickel or tetrakis (triphenylphosphine) nickel may be used, and a reducing metal such as zinc and a divalent nickel compound such as NiCl ₂ and NiBr ₂ . Alternatively, a method of generating a zero-valent nickel compound in the reaction system by coexisting with each other may be used.
When the reaction is carried out in the presence of a zerovalent nickel compound, examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, tetrahydrofuran and the like. The temperature at which the reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for carrying out the reaction (reaction time) may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

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

<Method for producing compound>
The compound represented by the above formula (1 ′) is
It can be produced by a method of converting a normal ketone into thiocarbonyl, imine or alkylidene, for example, a method shown in the formula (3).

（式中、
環Ａ、環Ｂ、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は前記と同じを表す。）
式（３）に示すケトン化合物は、例えば国際公表特許WO２０１３／１８３５４９に記載の方法で製造することができる。すなわち式（４）で示すように、環Aおよび環Bを含むジケトン化合物とRを有機基部分として有するグリニャール試薬またはリチウム試薬と反応させて得られたジオールを酸性条件下ピナコール転移させることで式（３）に示すケトン化合物を製造することができる。

(Where
Ring A, ring B, R ¹ , R ² , R ³ and R ⁴ represent the same as described above. )
The ketone compound represented by the formula (3) can be produced, for example, by the method described in International Publication Patent WO2013 / 183549. That is, as shown in formula (4), a diol obtained by reacting a diketone compound containing ring A and ring B with a Grignard reagent or lithium reagent having R as an organic group moiety is subjected to pinacol transfer under acidic conditions. The ketone compound shown in (3) can be produced.

<Organic semiconductor materials>
The organic semiconductor material may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds. Moreover, in order to improve carrier transport property, the organic-semiconductor material may further contain the low molecular compound or polymer compound which has carrier transport property in addition to the polymer compound of this invention. When the organic semiconductor material contains a component other than the polymer compound of the present invention, the polymer compound of the present invention is preferably contained in an amount of 30% by weight or more, more preferably 50% by weight or more.

  Compounds having carrier transport properties include arylamine derivatives, stilbene derivatives, oligothiophenes and derivatives thereof, low molecular compounds such as oxadiazole derivatives, fullerenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polyaniline and derivatives thereof, polythiophene And derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.

  The organic semiconductor material may contain a polymer compound material other than the polymer compound of the present invention as a polymer binder in order to improve the characteristics. As the polymer binder, those that do not excessively lower the carrier transportability are preferable.

  Examples of polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

<Organic semiconductor element>
Since the polymer compound of the present invention has high carrier mobility, when an organic thin film containing the polymer compound of the present invention is used for an organic semiconductor element, it means charges (electrons and holes) injected from the electrode. ) Or charge generated by light absorption can be efficiently transported. Taking advantage of these characteristics, the polymer compound of the present invention can be suitably used for various organic semiconductor elements such as photoelectric conversion elements (particularly, organic solar cells), organic transistors, and organic electroluminescence elements. Hereinafter, an organic semiconductor element having an organic thin film containing the polymer compound of the present invention will be described individually.

(Photoelectric conversion element)
The photoelectric conversion element containing the polymer compound of the present invention has one or more organic thin films containing the polymer compound of the present invention as an active layer between a pair of electrodes, at least one of which is transparent or translucent. A preferable form of the photoelectric conversion element containing the polymer compound of the present invention is formed from a composition of a pair of electrodes, at least one of which is transparent or translucent, and a p-type organic semiconductor and an n-type organic semiconductor. Has an active layer. The polymer compound of the present invention is preferably used as a p-type organic semiconductor. The operation mechanism of the photoelectric conversion element of this embodiment will be described. Light energy incident from a transparent or translucent electrode is an electron-accepting compound (n-type organic semiconductor) such as a fullerene derivative and / or an electron-donating compound (p-type organic semiconductor) such as a polymer compound of the present invention. Absorbed, producing 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 that can move independently are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

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

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

  Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, conductive materials composed of indium oxide, zinc oxide, tin oxide, and indium tin oxide (hereinafter referred to as “ITO”), indium, zinc oxide, and the like, which are composites thereof. A film prepared using, NESA, gold, platinum, silver, copper, or the like is used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

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

  As a means for improving the photoelectric conversion efficiency, an additional intermediate layer other than the above active layer may be used. Examples of the material used for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).

  The active layer may contain the polymer compound of the present invention alone or in combination of two or more. The electron donating compound and the electron accepting compound are relatively determined from the energy levels of these compounds.

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

  As the electron-accepting compound, in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof Derivatives, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof Derivatives, polyfluorenes and derivatives thereof, phenanthrene derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine), fullerenes, fullerene derivatives Body and the like, preferably, titanium oxide, carbon nanotubes, a fullerene or a fullerene derivative, more preferably a fullerene or a fullerene derivative.

The fullerene or fullerene derivative includes C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. Specific examples of the fullerene derivative include the following.

  Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C70 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C70 butyric acid methyl ester), [6,6] Phenyl-C84 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C84 butyric acid methyl ester), [6,6] Examples thereof include C60 butyric acid methyl ester ([6,6] -Thienyl C60 butyric acid methyl ester).

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

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

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

  A preferred method for producing a photoelectric conversion element is a method for producing a photoelectric conversion element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode. A step of forming an active layer on the first electrode by a coating method using a solution containing the polymer compound of the present invention and a solvent (sometimes referred to as “ink”), a second on the active layer. It is a manufacturing method including the process of forming this electrode.

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

  When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Coating methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, capillary coating, etc. can be used, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet printing method, and a spin coating method are preferable.

  From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

(Organic solar cell)
The photoelectric conversion element using the polymer compound of the present invention can be operated as an organic solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. it can. It can also be used as an organic solar cell module by accumulating a plurality of organic solar cells.

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

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

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

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

(Organic transistor)
Examples of the organic transistor include a source electrode and a drain electrode, an active layer serving as a current path between these electrodes, and a gate electrode that controls the amount of current passing through the current path. An organic thin film containing the polymer compound of the invention is used as the active layer. Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.

  A field-effect organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path. The organic transistor having an active layer and an insulating layer disposed between the gate electrode. In particular, an organic transistor in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.

  The electrostatic induction organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path And the gate electrode is provided in the active layer. In particular, an organic transistor in which a source electrode, a drain electrode, and the gate electrode are provided in contact with the active layer is preferable.

  The gate electrode only needs to have a structure in which a current path flowing from the source electrode to the drain electrode can be formed and the amount of current flowing in the current path can be controlled by a voltage applied to the gate electrode. It is done.

  FIG. 1 is a schematic cross-sectional view showing an example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the active layer 2 formed on the insulating layer 3, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 on the region between the source electrode 5 and the drain electrode 6. The gate electrode 4 is provided.

  FIG. 2 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5, and a predetermined electrode A drain electrode 6 formed on the active layer 2 with an interval, an insulating layer 3 formed on the active layer 2 and the drain electrode 6, and an insulating layer on a region between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to cover 3.

  FIG. 3 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 120 shown in FIG. 3 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to cover a part of the region of the insulating layer 3 formed, and a part of the source electrode 5 and the drain electrode 6 And an active layer 2 formed on the insulating layer 3 so as to cover the surface.

  FIG. 4 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 130 shown in FIG. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The source electrode 5 formed on the insulating layer 3 so as to cover a part of the region of the insulating layer 3 formed on the active layer 3 and the active formed on the insulating layer 3 so as to cover a part of the source electrode 5 A layer 2 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to cover a part of the active layer 2 are provided.

  FIG. 5 is a schematic cross-sectional view showing another example of the organic transistor (static induction organic transistor) of the present invention. The organic transistor 140 shown in FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality of active transistors 2 with a predetermined interval on the active layer 2. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a is the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

  FIG. 6 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 150 shown in FIG. 6 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and a part of the drain electrode 6 so as to cover part of the drain electrode 6, the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below. And a gate electrode 4 formed on the insulating layer 3 so as to partially cover each region of the insulating layer 3.

  FIG. 7 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 160 shown in FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. An active layer 2 formed so as to cover the region of the insulating layer 3 formed on the active layer 2, a source electrode 5 formed on the active layer 2 so as to cover a part of the active layer 2, and one of the active layers 2 A source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval are provided so as to cover the portion.

  FIG. 8 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 170 shown in FIG. 8 has a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, an active layer 2 formed on the insulating layer 3, and a predetermined interval on the active layer 2. A source electrode 5 and a drain electrode 6 formed in the above manner. In this case, the gate electrode 4 also serves as the substrate 1.

  FIG. 9 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. The organic transistor 180 shown in FIG. 9 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval, The active layer 2 is formed on the insulating layer 3 so as to cover a part of the source electrode 5 and the drain electrode 6.

  FIG. 10 is a schematic cross-sectional view of the photoelectric conversion element of the present invention. The photoelectric conversion element 300 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 formed on the first electrode 7a, and a second electrode formed on the active layer 2. The electrode 7b is provided.

  In the organic transistor of the present invention described above, the active layer 2 and / or the active layer 2a is constituted by a film containing the polymer compound of the present invention, and a current path (channel) between the source electrode 5 and the drain electrode 6 is formed. ) The gate electrode 4 controls the amount of current passing through the current path (channel) by applying a voltage.

  Such a field effect organic transistor can be produced by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic transistor can be produced by a known method such as the method described in Japanese Patent Application Laid-Open No. 2004-006476.

  The material of the substrate 1 may be any material that does not hinder the characteristics of the organic transistor. As the substrate, a glass substrate, a flexible film substrate, or a plastic substrate can be used.

The material of the insulating layer 3 may be any material having high electrical insulation, and SiO _x , SiN _x , Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, and the like can be used. From the viewpoint of lowering the voltage, it is preferable to use a material having a high dielectric constant.

  When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification.

  In the case of a field effect transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Therefore, the state of this interface greatly affects the carrier mobility of the transistor. Therefore, as a method for improving the interface state and improving the properties, control of the interface with a silane coupling agent has been proposed (for example, Surface Chemistry, 2007, Vol. 28, No. 5, p. 242-248). ).

Examples of silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, and fluorinated alkylalkoxysilanes. And silylamine compounds such as hexamethyldisilazane (HMDS). In addition, the surface of the insulating layer may be subjected to ozone UV treatment or O ₂ plasma treatment before treatment with the surface treatment agent.

  By such treatment, the surface energy of the silicon oxide film or the like used as the insulating layer can be controlled. Further, the surface treatment improves the orientation of the film constituting the active layer on the insulating layer, and higher carrier mobility can be obtained.

  The gate electrode 4 includes metals such as gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low-resistance polysilicon, low-resistance amorphous silicon, tin oxide, indium oxide, indium / tin oxide. A material such as (ITO) can be used. These materials may be used alone or in combination of two or more. Note that a highly doped silicon substrate can be used as the gate electrode 4. A highly doped silicon substrate has not only the performance as a gate electrode but also the performance as a substrate. When the gate electrode 4 having such a performance as a substrate is used, the substrate 1 may be omitted in the organic transistor in which the substrate 1 and the gate electrode 4 are in contact with each other.

  The source electrode 5 and the drain electrode 6 are preferably made of a low-resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.

  In the organic transistor, a layer made of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2. Examples of such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.

  In addition, after the organic transistor is manufactured, it is preferable to form a protective film on the organic transistor in order to protect the organic transistor. Thereby, an organic transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic transistor can be suppressed. Further, when a display device to be driven is formed on an organic transistor, the protective film can also reduce the influence on the organic transistor in the formation process.

Examples of the method for forming the protective film include a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON _x film, or the like. In order to effectively block the atmosphere, it is preferable to form a protective film after the organic transistor is manufactured without exposing the organic transistor to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  A field effect transistor, which is a kind of organic transistor configured as described above, can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display. The field effect transistor according to the present embodiment described above includes the polymer compound of the present invention as an active layer, and thereby includes an active layer excellent in carrier mobility. The degree will be high. Therefore, it is useful for manufacturing a display having a sufficient response speed.

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

(Mass spectrometry)
Mass spectrometry was performed using AccuTOF TLC JMS-T100TD (manufactured by JEOL Ltd.).

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

(Molecular weight analysis)
The number average molecular weight and the weight average molecular weight of the polymer compound were determined using gel permeation chromatography (GPC, manufactured by Waters, trade name: Alliance GPC 2000). The polymer compound to be measured was dissolved in orthodichlorobenzene and injected into GPC. Orthodichlorobenzene was used for the mobile phase of GPC. As the column, TSKgel GMHHR-H (S) HT (two linked, manufactured by Tosoh Corporation) was used. A UV detector was used as the detector.

窒素雰囲気下、５００ｍL三つ口フラスコに出発物質１０１を４．４ｇ（２０ｍｍｏｌ），脱水ＴＨＦを１５０ｍＬを加え、８０℃に加熱した。そこにオクチルマグネシウムブロミドの ＴＨＦ溶液を８０ｍＬ（１．０Ｍ，８０ｍｍｏｌ）を同温で加え、４時間攪拌した。その後、水５０ｍLで反応を終了し、水相を酢酸水溶液で中和した後、反応溶液をトルエンで２回抽出した。得られた有機層を飽和塩化アンモニウム水溶液で２回、飽和食塩水で１回洗浄し、無水硫酸ナトリウムで乾燥し、減圧下で溶媒を留去して、化合物１０２の粗生成体を得た。

得られた粗生成体１０２を５００ｍL四つ口フラスコに加え、酢酸１００ｍLとトリフルオロ酢酸５０ｍLを加え、８０℃で２時間加熱攪拌した。反応終了後、反応溶液を水１５０ｍLに注ぎ、トルエンで２回抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液で３回洗浄し、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をアルミナ（ヘキサン：クロロホルム＝2 : 1 ）で精製して、化合物１０３を黄色の固体として４．０２ｇ（９．３ｍｍｏｌ、収率６２％）得た。

^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）：δ（ｐｐｍ）＝７．４４（ｄ，１Ｈ）、７．３５（ｄ，１Ｈ）、７．０５（ｄ，１Ｈ）、６．９８（ｄ，１Ｈ）、２．１６（ｔ，２Ｈ）、１．７２（ｔ，２Ｈ）、１．２６−１．０７（ｂｒ，２４Ｈ）、０．８２（ｔ，６Ｈ）．

窒素雰囲気下、１００ｍＬ三つ口フラスコに化合物１０３を２．０６ｇ（３．５ｍｍｏｌ）、クロロホルムを５０ｍＬ、酢酸２０ｍＬ、ＮＢＳを３．４８ｇ（１９．５ｍｍｏｌ）を加え、８０ ℃で１時間加熱した。反応終了後、室温まで冷却し、そこに水を５０ｍＬ加え、トルエン（５０ｍＬ×２）で抽出した。得られた有機層を飽和チオ硫酸ナトリウム水溶液（５０ｍＬ）、飽和食塩水（５０ｍＬ）で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。得られた残渣をカラムクロマトグラフィ（ヘキサン：クロロホルム＝3 : 1 ）で精製し、化合物１０４をオレンジ色の固体として４．４７ｇ（７．６ｍｍｏｌ、収率８２％）得た。

^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）：δ（ｐｐｍ）＝７．３４（ｓ，１Ｈ）、６．９５（ｓ，１Ｈ）、２．１３（ｔ，２Ｈ）、１．６４（ｔ，２Ｈ）、１．２７−１．０９（ｂｒ，２４Ｈ）、０．８６（ｔ，６Ｈ）．

窒素で置換した１００ｍＬフラスコ内に、出発物質１０４を２．０６ｇ (３．５ｍｍｏｌ)、４−ヘキシルアニリンを０．８６ｇ （４．２ｍｍｏｌ）、トリエチルアミンを２．１２ｇ （２１．０ｍｍｏｌ）、脱水トルエンを３０ｍL入れ、均一溶液とした。そこに四塩化チタン（１．０M、トルエン溶液）を４．２ｍL（４．２ｍｍｏｌ）を１０分かけて滴下し、１２０℃で２０時間加熱攪拌した。その後水で反応を停止させ、有機層をトルエンで抽出し、有機層を水５０ｍLで3回洗浄した。得られた有機層を無水硫酸マグネシウムで乾燥した後に、ろ過し、減圧下で溶媒を留去した。得られた粗生物をシリカゲルカラムクロマトグラフィーで精製した（展開溶媒：ヘキサン：クロロホルム＝７：１）。精製後、化合物１０５を２．５４ｇ（３．２ｍｍｏｌ、 収率９３％)得た。

^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）：δ（ｐｐｍ）＝７．１５（ｄ，２Ｈ）、６．９５（ｓ，１Ｈ）、６．５８（ｄ，２Ｈ）、５．９２（ｓ，１Ｈ）、２．６３（ｔ，２Ｈ）、２．２２（ｔ，２Ｈ）、１．６３（ｍ，４Ｈ）、１．３１−１．１７（ｂｒ，３４Ｈ）、０．８６（ｔ，９Ｈ）．

窒素雰囲気下、還流管を取り付けた１００ｍL三つ口フラスコに化合物１０５を１５５．２ｍｇ（０．２０ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボレートを１１．６ｍｇ （２０ｍｏｌ％）、ＴＨＦを５ｍＬ(最終的に２．０ ｗｔ％)、３．０Ｍ Ｋ_３ＰＯ_４水溶液を０．７ｍＬ入れ、均一溶液とした。３０分のＡｒバブリング後、トリス（ジベンジリデンアセトン）ジパラジウム９．１ｍｇ （５．０ｍｏｌ％）、化合物１０５を７７．６ｍｇ （０．２０ ｍｍｏｌ）をジクロロメタン５．０ｍLとともに加え、得られた溶液を７０℃のオイルバスに浸し、１．５時間加熱下で攪拌した。そこに末端封止材として、フェニルボロン酸を５０ｍｇ程度加え、１時間加熱還流下で攪拌した。そこにジエチルジチオカルバミン酸ナトリウム０．３４ｇと水３．０ ｍL、オルトジクロロベンゼンを１５ｍL加え、９０ ℃で１時間攪拌を行った。水層を除去後、 有機層を水５０ ｍLで２回洗浄し、次いで、３ｗｔ％の酢酸水溶液５０ｍLで２回洗浄し、次いで、水５０ｍLで２回洗浄し、得られた溶液をアセトンに注いでポリマーを析出させた。ポリマーをろ過後、オルトジクロロベンゼン １４ｍLに再度溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された高分子化合物１を７４ｍｇ得た。（Ｍｎ．１２５０００，Ｍｗ．５３２０００） Example 1
(Synthesis of polymer compound 1)

Under a nitrogen atmosphere, 4.4 g (20 mmol) of the starting material 101 and 150 mL of dehydrated THF were added to a 500 mL three-necked flask and heated to 80 ° C. Thereto was added 80 mL (1.0 M, 80 mmol) of a solution of octylmagnesium bromide in THF at the same temperature, followed by stirring for 4 hours. Thereafter, the reaction was terminated with 50 mL of water, the aqueous phase was neutralized with an aqueous acetic acid solution, and then the reaction solution was extracted twice with toluene. The obtained organic layer was washed twice with saturated aqueous ammonium chloride solution and once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product of compound 102.

The obtained crude product 102 was added to a 500 mL four-necked flask, 100 mL of acetic acid and 50 mL of trifluoroacetic acid were added, and the mixture was heated and stirred at 80 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured into 150 mL of water and extracted twice with toluene. The obtained organic layer was washed three times with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified with alumina (hexane: chloroform = 2: 1) to obtain 4.02 g (9.3 mmol, yield 62%) of compound 103 as a yellow solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.44 (d, 1H), 7.35 (d, 1H), 7.05 (d, 1H), 6.98 (d, 1H) ), 2.16 (t, 2H), 1.72 (t, 2H), 1.26-1.07 (br, 24H), 0.82 (t, 6H).

Under a nitrogen atmosphere, 2.06 g (3.5 mmol) of Compound 103, 50 mL of chloroform, 20 mL of acetic acid, and 3.48 g (19.5 mmol) of NBS were added to a 100 mL three-necked flask and heated at 80 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, 50 mL of water was added thereto, and extracted with toluene (50 mL × 2). The obtained organic layer was washed with saturated aqueous sodium thiosulfate solution (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (hexane: chloroform = 3: 1) to obtain 4.47 g (7.6 mmol, yield 82%) of compound 104 as an orange solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.34 (s, 1H), 6.95 (s, 1H), 2.13 (t, 2H), 1.64 (t, 2H) ), 1.27-1.09 (br, 24H), 0.86 (t, 6H).

In a 100 mL flask purged with nitrogen, 2.06 g (3.5 mmol) of starting material 104, 0.86 g (4.2 mmol) of 4-hexylaniline, 2.12 g (21.0 mmol) of triethylamine, and dehydrated toluene were added. 30 mL was added to obtain a uniform solution. Thereto, 4.2 mL (4.2 mmol) of titanium tetrachloride (1.0 M, toluene solution) was added dropwise over 10 minutes, and the mixture was heated and stirred at 120 ° C. for 20 hours. Thereafter, the reaction was stopped with water, the organic layer was extracted with toluene, and the organic layer was washed with 50 mL of water three times. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane: chloroform = 7: 1). After purification, 2.54 g (3.2 mmol, 93% yield) of Compound 105 was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.15 (d, 2H), 6.95 (s, 1H), 6.58 (d, 2H), 5.92 (s, 1H ), 2.63 (t, 2H), 2.22 (t, 2H), 1.63 (m, 4H), 1.31-1.17 (br, 34H), 0.86 (t, 9H) .

Under a nitrogen atmosphere, 155.2 mg (0.20 mmol) of compound 105, 11.6 mg (20 mol%) of tri-tert-butylphosphonium tetrafluoroborate, and 5 mL of THF (final) in a 100 mL three-necked flask equipped with a reflux tube 2.0 wt%), and 0.7 mL of 3.0 M K ₃ PO ₄ aqueous solution was added to obtain a uniform solution. After 30 minutes of Ar bubbling, 9.1 mg (5.0 mol%) of tris (dibenzylideneacetone) dipalladium and 77.6 mg (0.20 mmol) of compound 105 were added together with 5.0 mL of dichloromethane, and the resulting solution was added. It was immersed in an oil bath at 70 ° C. and stirred under heating for 1.5 hours. About 50 mg of phenylboronic acid was added thereto as an end-capping material, and the mixture was stirred for 1 hour with heating under reflux. Thereto was added 0.34 g of sodium diethyldithiocarbamate, 3.0 mL of water and 15 mL of orthodichlorobenzene, and the mixture was stirred at 90 ° C. for 1 hour. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution and then twice with 50 mL of water, and the resulting solution was poured into acetone. To precipitate the polymer. The polymer was filtered, dissolved again in 14 mL of orthodichlorobenzene, and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 74 mg of purified polymer compound 1. (Mn. 125000, Mw. 532000)

窒素雰囲気下、還流管を取り付けた１００ｍL三つ口フラスコに化合物１０５を１５５．２ｍｇ（０．２０ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボレートを１１．６ｍｇ （２０ｍｏｌ％）、ジクロロメタンを５ｍＬ(最終的に２．０ ｗｔ％)、３．０Ｍ Ｋ_３ＰＯ_４水溶液を０．７ｍＬ入れ、均一溶液とした。３０分のＡｒバブリング後、トリス（ジベンジリデンアセトン）ジパラジウム９．１ｍｇ （５．０ｍｏｌ％）を加えた後、加熱を開始し（５０℃）、化合物１０７を８４．８ｍｇ （０．２０ ｍｍｏｌ）のジクロロメタン溶液５．０ｍLを１５分かけて滴下した。得られた溶液を５０℃で１．５時間加熱下で攪拌した。そこに末端封止材として、フェニルボロン酸を５０ｍｇ程度加え、１時間加熱還流下で攪拌した。そこにジエチルジチオカルバミン酸ナトリウム０．３４ｇと水３．０ ｍL、オルトジクロロベンゼンを１５ｍL加え、９０ ℃で１時間攪拌を行った。水層を除去後、 有機層を水５０ ｍLで２回洗浄し、次いで、３ｗｔ％の酢酸水溶液５０ｍLで２回洗浄し、次いで、水５０ｍLで２回洗浄し、得られた溶液をアセトンに注いでポリマーを析出させた。ポリマーをろ過後、オルトジクロロベンゼン １４ｍLに再度溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された高分子化合物２を１２０ｍｇ得た。（Ｍｎ．３１０００，Ｍｗ．２１６０００） Example 2
(Synthesis of polymer compound 2)

Under a nitrogen atmosphere, 155.2 mg (0.20 mmol) of compound 105, 11.6 mg (20 mol%) of tri-tert-butylphosphonium tetrafluoroborate, and 5 mL of dichloromethane (final) in a 100 mL three-necked flask equipped with a reflux tube 2.0 wt%), and 0.7 mL of 3.0 M K ₃ PO ₄ aqueous solution was added to obtain a uniform solution. After 30 minutes of Ar bubbling, 9.1 mg (5.0 mol%) of tris (dibenzylideneacetone) dipalladium was added, heating was started (50 ° C.), and 84.8 mg (0.20 mmol) of Compound 107 was obtained. Was added dropwise over 15 minutes. The resulting solution was stirred with heating at 50 ° C. for 1.5 hours. About 50 mg of phenylboronic acid was added thereto as an end-capping material, and the mixture was stirred for 1 hour with heating under reflux. Thereto was added 0.34 g of sodium diethyldithiocarbamate, 3.0 mL of water and 15 mL of orthodichlorobenzene, and the mixture was stirred at 90 ° C. for 1 hour. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution and then twice with 50 mL of water, and the resulting solution was poured into acetone. To precipitate the polymer. The polymer was filtered, dissolved again in 14 mL of orthodichlorobenzene, and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 120 mg of purified polymer compound 2. (Mn.31000, Mw.216000)

反応容器内に、化合物１０１を１０．０ｇ（４５．４ｍｍｏｌ）、テトラヒドロフランを２５０ｍL入れた。ここへ、メチルマグネシウムブロマイドのエーテル溶液を６１ｍＬ（３Ｍ、１８１ｍｍｏｌ）を滴下し、４時間還流させた。得られた反応溶液を水に注ぎ、トルエンで抽出した。得られたトルエン溶液を濃縮し、固体を得た。ここへ、酢酸１００ｍＬとトリフルオロ酢酸５０ｍＬを加え、８０℃で３時間反応させた。反応溶液を水に注ぎ、クロロホルムで抽出した。得られたクロロホルム溶液を濃縮し、シリカゲルカラムを用いて精製し、化合物３を得た。得量は５．２５ｇであり、収率は４６％（２ｓｔｅｐ）であった。
^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）：δ（ｐｐｍ）＝７．４７（ｄ，１Ｈ）、７．３２（ｄ，１Ｈ）、７．０７（ｍ，２Ｈ）、１．４６（ｓ，６Ｈ）．

封管内に、化合物１０９を３．００ｇ（１２．８ｍｍｏｌ）とペンタデシルマグネシウムブロマイドのテトラヒドロフラン溶液（０．４Ｍ、３２ｍＬ、５１．２ｍｍｏｌ）を入れ、１５０℃で５時間反応させた。得られた反応溶液を塩酸水溶液（３５％、２０ｍＬ）に注ぎ、トルエン（１００ｍＬ）を加えて１０分間撹拌した。水層を除去し、トルエン溶液を水で洗浄した。得られたトルエン溶液を濃縮し、シリカゲルカラムを用いて精製し、化合物１１１を得た。得量は１．６３ｇであり、収率は２８％（２ｓｔｅｐ）であった。
^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）：δ（ｐｐｍ）＝７．１９（ｄ，１Ｈ）、７．０９（ｄ，１Ｈ）、７．０５（ｄ，１Ｈ）、６．９９（ｄ，１Ｈ）、５．６５（ｔ，１Ｈ）、１．２０−１．５０（ｍ，３０Ｈ）、０．８８（ｔ，３Ｈ）．

封管内に、化合物１１１を０．８０ｇ（１．８６ｍｍｏｌ）、Ｎ−ブロモスクシンイミドを０．６６４ｇ（３．７３ｍｍｏｌ）、クロロホルムを３０ｍＬ入れ、５時間撹拌した。得られた反応溶液を水に注ぎ、クロロホルムで抽出した。得られたクロロホルム溶液を濃縮し、シリカゲルカラムを用いて精製し、化合物１１２を得た。得量は０．５７ｇであり、収率は５２％であった。

フラスコ内の気体を窒素で置換したフラスコに、化合物１１２を１５０ｍｇ（０．２５６ｍｍｏｌ）、化合物１０６を９９．３ｍｇ（０．２５６ｍｍｏｌ）、テトラヒドロフランを３０ｍＬ、トリス（ジベンジリデンアセトン）ジパラジウムを９．４ｍｇ、トリ−ｔｅｒｔ−ブチルホスホニウムテトラフルオロボレートを１１．９ｍｇ入れて撹拌した。この溶液に、２ｍｏｌ／Ｌの炭酸カリウム水溶液を１．２８ｍＬ滴下し、３時間還流させた。反応液に、フェニルボロン酸を１０．０ｍｇ加えて、１時間還流させた。次に、反応液にＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物を０．１ｇ加えて、３時間還流させた。その後、反応液を水に注ぎ、トルエンを加え、トルエン層を抽出した。トルエン溶液を酢酸水溶液及び水で洗浄した後、シリカゲルカラムを通液させて精製した。得られたトルエン溶液をアセトンに滴下し、析出物を得た。析出物をアセトンを溶媒として用いてソックスレー洗浄し、高分子化合物３を得た。得量は１ｍｇであった。 Example 3
(Synthesis of polymer compound 3)

In a reaction vessel, 10.0 g (45.4 mmol) of Compound 101 and 250 mL of tetrahydrofuran were placed. To this, 61 mL (3 M, 181 mmol) of an ether solution of methylmagnesium bromide was added dropwise and refluxed for 4 hours. The resulting reaction solution was poured into water and extracted with toluene. The obtained toluene solution was concentrated to obtain a solid. Acetic acid 100mL and trifluoroacetic acid 50mL were added here, and it was made to react at 80 degreeC for 3 hours. The reaction solution was poured into water and extracted with chloroform. The resulting chloroform solution was concentrated and purified using a silica gel column to obtain compound 3. The yield was 5.25 g, and the yield was 46% (2 step).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.47 (d, 1H), 7.32 (d, 1H), 7.07 (m, 2H), 1.46 (s, 6H) ).

In a sealed tube, 3.00 g (12.8 mmol) of Compound 109 and a tetrahydrofuran solution (0.4 M, 32 mL, 51.2 mmol) of pentadecylmagnesium bromide were placed and reacted at 150 ° C. for 5 hours. The obtained reaction solution was poured into an aqueous hydrochloric acid solution (35%, 20 mL), toluene (100 mL) was added, and the mixture was stirred for 10 minutes. The aqueous layer was removed and the toluene solution was washed with water. The obtained toluene solution was concentrated and purified using a silica gel column to obtain Compound 111. The yield was 1.63 g, and the yield was 28% (2step).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.19 (d, 1H), 7.09 (d, 1H), 7.05 (d, 1H), 6.99 (d, 1H) ), 5.65 (t, 1H), 1.20-1.50 (m, 30H), 0.88 (t, 3H).

In a sealed tube, 0.81 g (1.86 mmol) of compound 111, 0.664 g (3.73 mmol) of N-bromosuccinimide, and 30 mL of chloroform were added and stirred for 5 hours. The obtained reaction solution was poured into water and extracted with chloroform. The resulting chloroform solution was concentrated and purified using a silica gel column to obtain Compound 112. The yield was 0.57 g, and the yield was 52%.

In a flask in which the gas in the flask was replaced with nitrogen, 150 mg (0.256 mmol) of compound 112, 99.3 mg (0.256 mmol) of compound 106, 30 mL of tetrahydrofuran, 9.4 mg of tris (dibenzylideneacetone) dipalladium were added. 11.9 mg of tri-tert-butylphosphonium tetrafluoroborate was added and stirred. To this solution, 1.28 mL of a 2 mol / L potassium carbonate aqueous solution was added dropwise and refluxed for 3 hours. 10.0 mg of phenylboronic acid was added to the reaction solution, and the mixture was refluxed for 1 hour. Next, 0.1 g of sodium N, N-diethyldithiocarbamate trihydrate was added to the reaction solution, and the mixture was refluxed for 3 hours. Thereafter, the reaction solution was poured into water, toluene was added, and the toluene layer was extracted. The toluene solution was washed with an aqueous acetic acid solution and water, and then purified by passing through a silica gel column. The obtained toluene solution was added dropwise to acetone to obtain a precipitate. The precipitate was Soxhlet washed using acetone as a solvent to obtain polymer compound 3. The yield was 1 mg.

Example 4
(Production and Evaluation of Organic Solar Cell 1)
A glass substrate on which ITO with a thickness of about 150 nm formed by sputtering was patterned was washed with an organic solvent, an alkaline detergent and ultrapure water, and dried. Thereafter, the glass substrate was subjected to ultraviolet ozone (UV-O ₃ ) treatment using an ultraviolet ozone (UV-O ₃ ) apparatus.
Next, a suspension in which poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid is dissolved in water (trade name: Bytron P TP AI 4083, manufactured by HC Starck B-Tech Co., Ltd.) is filtered with a filter having a pore diameter of 0.45 μm. Filtered. The suspension after filtration was spin-coated on the ITO side of the substrate to form a film with a thickness of 40 nm. Subsequently, it was dried on the hot plate at 200 ° C. for 10 minutes in the air to form an organic layer.
Next, polymer compound 2 and fullerene C60PCBM (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name: E100)) were combined with polymer compound A and C60PCBM (by weight ratio). Polymer Compound A / C60PCBM = 1/3) was dissolved in orthodichlorobenzene to produce Ink 1 (by weight percent, the sum of Polymer Compound A and C60PCBM was 2.0 weight percent). Next, the ink 1 was spin-coated on the organic layer side of the substrate to form an active layer with a thickness of 100 nm.
Next, 97% of Titanium (IV) isopropoxide purchased from SIGMAS ALDRICH was mixed with isopropanol to a concentration of 1% by weight, and the mixture was spin-coated on the active layer side of the substrate to 10 nm. The film was formed with a film thickness of. Subsequently, Al was vacuum-deposited with a film thickness of about 70 nm, and the organic solar cell 1 which is a photoelectric conversion element was manufactured. The shape of the obtained organic solar cell 1 was a 2 mm × 2 mm square.
The obtained organic solar cell 1 is irradiated with a certain amount of light using a solar simulator (product name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined by measurement. Jsc (short circuit current density) is 8.18 mA / cm ² , Voc (open end voltage) is 0.782 V, ff (fill factor) is 0.57, and photoelectric conversion efficiency (η ) Was 3.65%.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode,
6 ... drain electrode, 7a ... first electrode, 7b ... second electrode, 100, 110, 120, 130, 140, 150, 160, 170, 180 ... organic transistor, 300 ... photoelectric conversion element.

Claims (8)

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

(Where
R ¹ and R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups are It may have a substituent.
X represents a sulfur atom, N—R ³ or CH—R ⁴ , wherein R ³ is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. , A hydroxyl group, an acyl group having 1 to 30 carbon atoms, or a substituted amino group having 1 to 30 carbon atoms, and these groups may have a substituent, and R ⁴ has 1 to 30 carbon atoms. An alkyl group, an aryl group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 2 to 30 carbon atoms, and these groups optionally have a substituent.
Ring A and ring B each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring, and the aromatic hydrocarbon ring and the heteroaromatic ring may have a substituent. )   The polymer compound according to claim 1, wherein the ring A and the ring B represent the same heteroaromatic ring. The polymer compound according to claim 1 or 2, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2).

(In the formula, R ¹ , R ² , and X each have the same meaning as described above.)
The polymer compound according to claim 1, wherein X is N—R ³ .   An organic thin film comprising the polymer compound according to claim 1. A first electrode and a second electrode;
The organic-semiconductor element which has an organic thin film of Claim 5 between this 1st electrode and this 2nd electrode.   The organic-semiconductor element of Claim 6 which is a photoelectric conversion element.   The organic-semiconductor element of Claim 6 which is an organic transistor.

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