JP5834682B2 - Polymer compound and electronic device using the same - Google Patents

Description

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

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

  On the other hand, organic thin-film solar cells, which are one embodiment of electronic devices, can omit the high-temperature and high-vacuum processes used in the production process of silicon-based solar cells, and can be manufactured at low cost by only the coating process. It is coming. As a polymer compound used for an organic thin film solar cell, a polymer compound composed of a repeating unit (A) and a repeating unit (B) is described (Patent Document 1).

繰り返し単位（Ａ） 繰り返し単位（Ｂ）

Repeating unit (A) Repeating unit (B)

Special table 2009-506519

  However, the organic photoelectric conversion element using the polymer compound has a problem that the open-circuit voltage is low.

  Then, an object of this invention is to provide the high molecular compound which can manufacture an organic photoelectric conversion element with a high open end voltage.

（１）
〔式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。環Ａｒ^１及び環Ａｒ^２は、それぞれ独立に、置換基を有してもよい炭素原子数６〜６０の芳香族炭化水素環又は置換基を有してもよい炭素原子数４〜６０の複素環を示す。Ａは、炭素原子、珪素原子又はゲルマニウム原子を表す。〕

（２）
〔式中、Ｙは、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^３）−又は−Ｃ（Ｒ^４）＝Ｃ（Ｒ^５）−を表す。Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。〕 That is, the present invention first provides a polymer compound comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).

(1)
[Wherein, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. Ring Ar ¹ and Ring Ar ² are each independently an aromatic hydrocarbon ring having 6 to 60 carbon atoms which may have a substituent or a heterocycle having 4 to 60 carbon atoms which may have a substituent. Indicates a ring. A represents a carbon atom, a silicon atom, or a germanium atom. ]

(2)
[Wherein, Y represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ³ )-or -C (R ⁴ ) = C (R ⁵ )-. R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. ]

（３）
〔式中、Ｙは、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^３）−又は−Ｃ（Ｒ^４）＝Ｃ（Ｒ^５）−を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。環Ａｒ^１及び環Ａｒ^２は、置換基を有してもよい炭素原子数６〜６０の芳香族炭化水素環又は置換基を有してもよい炭素原子数４〜６０の複素環を表す。〕 Secondly, the present invention provides a polymer compound containing a repeating unit represented by the formula (3).

(3)
[Wherein, Y represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ³ )-or -C (R ⁴ ) = C (R ⁵ )-. R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. The ring Ar ¹ and the ring Ar ² represent an aromatic hydrocarbon ring having 6 to 60 carbon atoms which may have a substituent or a heterocyclic ring having 4 to 60 carbon atoms which may have a substituent. ]

（４）
〔式中、Ｒ^６及びＲ^７は、それぞれ独立に、炭素原子数６〜１０のアルキル基を表す。〕 Thirdly, this invention provides the high molecular compound containing the repeating unit represented by Formula (4).

(4)
[Wherein, R ⁶ and R ⁷ each independently represents an alkyl group having 6 to 10 carbon atoms. ]

  Fourthly, the present invention provides an electronic device comprising the polymer compound.

  Fifth, the present invention provides an organic photoelectric conversion device having a pair of electrodes and an active layer provided between the electrodes, wherein the active layer includes an electron accepting compound and the polymer compound.

  6thly this invention provides the said organic photoelectric conversion element whose quantity of the electron-accepting compound contained in an active layer is 10-1000 weight part with respect to 100 weight part of high molecular compounds.

  Seventhly, the present invention provides the organic photoelectric conversion element, wherein the electron-accepting compound is a fullerene derivative.

  Eighth, the present invention provides an organic thin film transistor comprising a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode, wherein the organic semiconductor layer includes the polymer compound.

  Since the organic photoelectric conversion element using the polymer compound of the present invention has a high open-circuit voltage, the present invention is extremely useful.

（１）
〔式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。環Ａｒ^１及び環Ａｒ^２は、それぞれ独立に、置換基を有してもよい炭素原子数６〜６０の芳香族炭化水素環又は置換基を有してもよい炭素原子数４〜６０の複素環を示す。Ａは、炭素原子、珪素原子又はゲルマニウム原子を表す。〕

（２）
〔式中、Ｙは、硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^３）−又は−Ｃ（Ｒ^４）＝Ｃ（Ｒ^５）−を表す。Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。〕 Hereinafter, the present invention will be described in detail.
The polymer compound of the present invention includes a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).

(1)
[Wherein, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. Ring Ar ¹ and Ring Ar ² are each independently an aromatic hydrocarbon ring having 6 to 60 carbon atoms which may have a substituent or a heterocycle having 4 to 60 carbon atoms which may have a substituent. Indicates a ring. A represents a carbon atom, a silicon atom, or a germanium atom. ]

(2)
[Wherein, Y represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ³ )-or -C (R ⁴ ) = C (R ⁵ )-. R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. ]

In the formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an optionally substituted alkyl group, an optionally substituted alkoxy group, and an optionally substituted alkylthio. Group, aryl group which may be substituted, aryloxy group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted and heteroaryl group which may be substituted Is mentioned.

The alkyl group represented by R ¹ and R ² may be linear or branched, and may be a cycloalkyl group. The carbon number of an alkyl group is 1-30 normally, and 1-20 are preferable. The alkyl group may have a substituent, and examples of the substituent include a fluorine atom. Specific examples of the alkyl group which may be substituted include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2- Methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl Examples thereof include chain alkyl groups such as a group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group and an adamantyl group.

The alkyl part of the alkoxy group represented by R ¹ and R ² may be linear, branched or cyclic. The carbon atom number of an alkoxy group is 1-30 normally, and 1-20 are preferable. The alkoxy group may have a substituent, and examples of the substituent include a fluorine atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the optionally substituted alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluoro Examples include a hexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

The alkyl part of the alkylthio group represented by R ¹ and R ² may be linear or branched, and may be cyclic. The number of carbon atoms of the alkylthio group is usually 1-30, preferably 1-20. The alkylthio group may have a substituent, and examples of the substituent include a fluorine atom. Specific examples of the alkylthio group which may be substituted include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and trifluoromethylthio group.

The aryl group represented by R ¹ and R ² is an atomic group obtained by removing one hydrogen atom from an unsubstituted aromatic hydrocarbon, having a benzene ring, having a condensed ring, an independent benzene ring Alternatively, a structure in which two or more condensed rings are bonded directly or via a group such as vinylene is also included. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 30. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent. As an aryl group, a phenyl group, 1-naphthyl group, and 2-naphthyl group are mentioned, for example. Examples of the substituent that the aryl group may have include a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and an optionally substituted alkylthio group. The number of carbon atoms and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, and the optionally substituted alkylthio group are the substituted groups represented by the aforementioned R ¹ and R ^2. The number of carbon atoms of the alkyl group which may be substituted, the alkoxy group which may be substituted and the alkylthio group which may be substituted is the same as the specific examples. Examples of the substituted aryl group include a C1-C12 alkoxyphenyl group, a C1-C12 alkylphenyl group, and a pentafluorophenyl group.
Here, “C” represents a carbon atom, and the number attached represents the number of carbon atoms in the group described immediately after. That is, the “C1 to C12 alkylphenyl group” represents a group having an alkyl group having 1 to 12 carbon atoms, and the “C1 to C12 alkoxyphenyl group” has 1 carbon atom. It represents a group having ~ 12 alkoxy groups. The same applies to the following. The number of carbon atoms in the alkyl group and the number of carbon atoms in the alkoxy group are preferably 1-8, more preferably 1-6.

The aryloxy group represented by R ¹ and R ² usually has 6 to 60 carbon atoms, and preferably 6 to 20 carbon atoms. The aryl part of the aryloxy group may have a substituent. Examples of the substituent include a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and a substituted group. There may be mentioned a good alkylthio group. The number of carbon atoms and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, and the optionally substituted alkylthio group are the substituted groups represented by the aforementioned R ¹ and R ^2. The number of carbon atoms of the alkyl group which may be substituted, the alkoxy group which may be substituted and the alkylthio group which may be substituted is the same as the specific examples. Specific examples of the optionally substituted aryloxy group include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group. Can be mentioned.

The arylalkyl group represented by R ¹ and R ² usually has 7 to 60 carbon atoms, and preferably 7 to 20 carbon atoms. The aryl part of the arylalkyl group may have a substituent. Examples of the substituent include a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and a substituted group. There may be mentioned a good alkylthio group. The number of carbon atoms and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, and the optionally substituted alkylthio group are the substituted groups represented by the aforementioned R ¹ and R ^2. The number of carbon atoms of the alkyl group which may be substituted, the alkoxy group which may be substituted and the alkylthio group which may be substituted is the same as the specific examples. Specific examples of the optionally substituted arylalkyl group include phenyl-C1-C12 alkyl group, C1-C12 alkoxyphenyl-C1-C12 alkyl group, C1-C12 alkylphenyl-C1-C12 alkyl group, 1-naphthyl. -C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group are mentioned.

The arylalkoxy group represented by R ¹ and R ² usually has 7 to 60 carbon atoms, and preferably 7 to 20 carbon atoms. The aryl part of the arylalkoxy group may have a substituent. Examples of the substituent include a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and a substituted group. There may be mentioned a good alkylthio group. The number of carbon atoms and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, and the optionally substituted alkylthio group are the substituted groups represented by the aforementioned R ¹ and R ^2. The number of carbon atoms of the alkyl group which may be substituted, the alkoxy group which may be substituted and the alkylthio group which may be substituted is the same as the specific examples. Specific examples of the optionally substituted arylalkoxy group include a phenyl-C1 to C12 alkoxy group, a C1 to C12 alkoxyphenyl-C1 to C12 alkoxy group, a C1 to C12 alkylphenyl-C1 to C12 alkoxy group, and 1-naphthyl. -C1-C12 alkoxy group and 2-naphthyl-C1-C12 alkoxy group are mentioned.

The heteroaryl group represented by R ¹ and R ² is an atomic group obtained by removing one hydrogen atom from an unsubstituted aromatic heterocyclic compound, having a single ring, having a condensed ring, independently And those obtained by bonding two or more monocyclic or condensed rings directly or via a group such as vinylene are also included. Examples of the aromatic heterocyclic compound include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, Oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman , Isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, indazo , Naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine and phenazine It is done. Examples of the substituent that the heteroaryl group may have include, for example, a fluorine atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and a substituted group. Examples thereof include an aryl group which may be substituted, an aryloxy group which may be substituted, an arylalkyl group which may be substituted, and an arylalkoxy group which may be substituted. The optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the optionally substituted aryl group, the optionally substituted aryloxy group, the substituted The definition and specific examples of the arylalkyl group which may be substituted and the arylalkoxy group which may be substituted are as follows. The alkyl group which may be substituted represented by the aforementioned R ¹ and R ² and the alkoxy which may be substituted Group, optionally substituted alkylthio group, optionally substituted aryl group, optionally substituted aryloxy group, optionally substituted arylalkyl group and optionally substituted arylalkoxy group. Definitions and specific examples are the same.

R ¹ and R ² are preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group and an arylalkyl group from the viewpoint of improving the photoelectric conversion characteristics of the organic photoelectric conversion device containing the polymer compound of the present invention. A group and an aryl group are more preferable, and an alkyl group is more preferable.

  In formula (1), A represents a carbon atom, a silicon atom, or a germanium atom. From the viewpoint of improving the photoelectric conversion efficiency of the organic photoelectric conversion element containing the polymer compound of the present invention, a carbon atom is preferable.

In formula (1), ring Ar ¹ and ring Ar ² are each independently an aromatic hydrocarbon ring having 6 to 60 carbon atoms which may have a substituent or carbon atoms which may have a substituent. Represents ~ 60 heterocycles. The heterocyclic ring that may have a substituent is preferably an aromatic heterocyclic ring that may have a substituent.

  Examples of the aromatic hydrocarbon ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, perylene ring, tetracene ring, and pentacene ring. The aromatic carbocycle is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

  Examples of the aromatic heterocycle include pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, acridine ring, phenanthroline ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, Thiophene oxide ring, benzothiophene oxide ring, dibenzothiophene oxide ring, thiophene dioxide ring, benzothiophene dioxide ring, dibenzothiophene dioxide ring, furan ring, benzofuran ring, dibenzofuran ring, pyrrole ring, indole ring, dibenzopyrrole ring, Examples include a silole ring, a benzosilole ring, a dibenzosilole ring, a borol ring, a benzoborol ring, and a dibenzoborol ring. The aromatic heterocyclic ring is preferably a thiophene ring, a furan ring or a pyrrole ring, more preferably a thiophene ring or a furan ring, and even more preferably a thiophene ring.

Examples of the substituent that the aromatic hydrocarbon ring and the heterocyclic ring may have include a fluorine atom, a cyano group, a nitro group, an amino group, and a monovalent organic group. Specific examples of the monovalent organic group are the same as the specific examples of the monovalent organic group represented by R ¹ and R ² . From the viewpoint of increasing the solubility of the polymer compound in the organic solvent, the aromatic hydrocarbon ring and the heterocyclic ring may be an alkyl group which may be substituted, an alkoxy group which may be substituted, or an aryl which may be substituted. It preferably has one or more substituents selected from the group consisting of an oxy group and an optionally substituted aryl group.

Specific examples of the repeating unit represented by formula (1) include the repeating units represented by formula (101) to formula (130).

In formula (101) to formula (130), R ¹ and R ² represent the same meaning as described above. R represents a substituent.

Examples of the substituent represented by R include a fluorine atom, a cyano group, a nitro group, an amino group, and a monovalent organic group. Specific examples of the monovalent organic group are the same as the specific examples of the monovalent organic group represented by R ¹ and R ² . From the viewpoint of increasing the solubility of the polymer compound in the organic solvent, the aromatic hydrocarbon ring and the heterocyclic ring may be an alkyl group which may be substituted, an alkoxy group which may be substituted, or an aryl which may be substituted. It preferably has one or more substituents selected from the group consisting of an oxy group and an optionally substituted aryl group.

  The repeating unit represented by the formula (101) to the formula (130) includes a repeating unit represented by the formula (101), a repeating unit represented by the formula (106), a repeating unit represented by the formula (111), The repeating unit represented by the formula (116), the repeating unit represented by the formula (121), and the repeating unit represented by the formula (126) are preferable. The repeating unit represented by the formula (101), the formula (106) The repeating unit represented by formula (111) and the repeating unit represented by formula (111) are more preferred, and the repeating unit represented by formula (101) is more preferred.

  Specific examples of the repeating unit represented by formula (2) include the repeating units represented by formula (201) to formula (205).

（式中、Ｒ^３、Ｒ^４及びＲ^５は、前述と同じ意味を表す。）

(In the formula, R ³ , R ⁴ and R ⁵ represent the same meaning as described above.)

  The repeating unit represented by the formula (201) to the formula (205) includes the repeating unit represented by the formula (201), the repeating unit represented by the formula (202), the repeating unit represented by the formula (204), and The repeating unit represented by formula (205) is preferred, the repeating unit represented by formula (201) and the repeating unit represented by formula (202) are more preferred, and the repeating unit represented by formula (201) is further preferable.

  When the total of the number of repeating units represented by the formula (1) and the number of repeating units represented by the formula (2) of the polymer compound of the present invention is 100, the polymer compound of the present invention has 20-80 are preferable and, as for the number of the repeating units represented by Formula (1), 40-60 are more preferable.

（３）
〔式中、Ｙ、Ｒ^１、Ｒ^２、環Ａｒ^１及び環Ａｒ^２は、前述と同じ意味を表す。〕 Another embodiment of the polymer compound of the present invention is a polymer compound having a repeating unit represented by the formula (3).

(3)
[Wherein, Y, R ¹ , R ² , ring Ar ¹ and ring Ar ² represent the same meaning as described above. ]

As a repeating unit represented by Formula (3), the repeating unit represented by Formula (301)-Formula (388) is mentioned, for example.

In formula (301) to formula (388), R ³ , R ⁴ and R ⁵ represent the same meaning as described above.

（４）
〔式中、Ｒ^６及びＲ^７は、それぞれ独立に、炭素原子数６〜１０のアルキル基を表す。〕 The repeating unit represented by the formula (3) is preferably a repeating unit represented by the formula (4).

(4)
[Wherein, R ⁶ and R ⁷ each independently represents an alkyl group having 6 to 10 carbon atoms. ]

The polymer compound of the present invention has a polystyrene-equivalent weight average molecular weight of preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ^{7, and} still more preferably 10 ³ to 10 ⁶ .

  The polymer compound of the present invention is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound in which atoms constituting the main chain of the polymer compound are conjugated.

<Method for producing polymer compound>
The polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like. The synthesis of the monomer can be performed with reference to, for example, methods disclosed in JP-T-2009-506519 and WO2011 / 060526A1.

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

  Polymerization by Stille coupling reaction is necessary using palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride as catalysts. Depending on the ligand, ligands such as triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine A monomer having a substituted stannyl group and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a sulfonic acid residue such as a trifluoromethanesulfonate group or a p-toluenesulfonate group. Polymerization in which a monomer having a group is reacted. The details of the polymerization by the Stille coupling reaction are described in, for example, Angewante Chemie International Edition, 2005, Vol. 44, p. 4442-4489.

Polymerization by Suzuki coupling reaction is a monomer having a dihydroxyboryl group or a borate ester residue using a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, adding a ligand as necessary. And a monomer having a halogen atom such as bromine atom, iodine atom or chlorine atom, or a monomer having a sulfonic acid residue such as trifluoromethanesulfonate group or p-toluenesulfonate group.
Examples of the inorganic base include sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate and potassium fluoride. Examples of the organic base include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetraethylammonium hydroxide. Examples of the palladium complex include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, and bis (triphenylphosphine) palladium dichloride. Examples of the nickel complex include bis (cyclooctadiene) nickel. Examples of the ligand include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine. It is done.
Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry (Part A: Polymer Chemistry), 2001, Vol. 39, p. 1533-1556.

Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent, and has monomers having a halogen atom, monomers having a sulfonic acid residue such as a trifluoromethanesulfonate group, or monomers having a halogen atom and a sulfonic acid residue. This is a polymerization in which a monomer is reacted.
Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel. A catalyst comprising a nickel complex other than a nickel zero-valent complex such as dichloride and a ligand such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, if necessary. . Examples of the reducing agent include zinc and magnesium. Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system.
Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.

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

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

  Among the polymerizations by the aryl coupling reaction, from the viewpoint of reactivity, a polymerization method by a Stille coupling reaction, a polymerization method by a Suzuki coupling reaction, and a polymerization method by a Yamamoto coupling reaction are preferable.

  The lower limit of the reaction temperature of the aryl coupling reaction is preferably −100 ° C., more preferably −20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.

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

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

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

<Electronic element>
The polymer compound of the present invention can be used for an organic layer contained in an electronic device. Examples of the electronic element include an organic photoelectric conversion element, an organic thin film transistor, and an organic electroluminescence element.

<Organic photoelectric conversion element>
The organic photoelectric conversion device of the present invention has a pair of electrodes, an active layer between the electrodes, and the active layer is represented by the formula (1) and the repeating unit represented by the formula (2) And a polymer compound containing an electron-accepting compound. As an electron-accepting compound, fullerene and a fullerene derivative are preferable. As a specific example of the organic photoelectric conversion element,
1. A pair of electrodes and an active layer between the electrodes, the active layer including an electron-accepting compound, a repeating unit represented by formula (1), and a repeating unit represented by formula (2) An organic photoelectric conversion element containing a molecular compound;
2. A pair of electrodes and an active layer between the electrodes, the active layer including an electron-accepting compound, a repeating unit represented by formula (1), and a repeating unit represented by formula (2) An organic photoelectric conversion element containing a molecular compound, wherein the electron-accepting compound is a fullerene derivative;
Is mentioned. In general, at least one of the pair of electrodes is transparent or translucent. Hereinafter, this case will be described as an example.

  1 above. In the organic photoelectric conversion element, the amount of the electron-accepting compound contained in the active layer is preferably 10 to 1000 parts by weight when the amount of the polymer compound contained in the active layer is 100 parts by weight, It is more preferably 20 to 500 parts by weight. In addition, 2. In the organic photoelectric conversion element, the amount of the fullerene derivative contained in the active layer is preferably 10 to 1000 parts by weight when the amount of the polymer compound contained in the active layer is 100 parts by weight. More preferably, it is 500 parts by weight. From the viewpoint of increasing the photoelectric conversion efficiency of the organic photoelectric conversion element, the amount of the fullerene derivative contained in the active layer is 20 to 400 parts by weight when the amount of the polymer compound contained in the active layer is 100 parts by weight. Preferably, it is 40 to 250 parts by weight, more preferably 80 to 120 parts by weight. From the viewpoint of increasing the short circuit current density of the organic photoelectric conversion element, the amount of the fullerene derivative contained in the active layer is 20 to 250 parts by weight when the amount of the polymer compound contained in the active layer is 100 parts by weight. It is preferably 40 to 120 parts by weight.

  As the organic photoelectric conversion element, the above-described 1. , 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. In the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the active layer. Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material of the substrate include glass, a polymer compound, 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.

As a material for the pair of electrodes, a metal, a conductive polymer, or the like can be used. The material of one of the pair of electrodes is preferably a material having a low work function. Examples of materials having a low work function include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And an alloy of two or more of these metals, or one or more of these metals, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, An alloy with one or more metals of tin, graphite, a graphite intercalation compound, or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
Examples of the material for the transparent or translucent electrode include conductive metal oxides and translucent metal thin films. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

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

<Organic thin film>
As the active layer in the organic photoelectric conversion element of the present invention, for example, an organic thin film containing the polymer compound of the present invention and an electron-accepting compound can be used.

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

  The organic thin film may contain the polymer compound of the present invention alone or in combination of two or more. Moreover, in order to improve the hole transport property of the said organic thin film, high molecular compounds other than a low molecular weight compound and / or the high molecular compound of this invention can also be mixed and used as an electron-donating compound in the said organic thin film.

  Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains. And polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C _60, carbon nanotube, Examples include phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.

  The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

Fullerenes and derivatives thereof include C ₆₀ , C ₇₀ , C ₈₄ and derivatives thereof. A fullerene derivative represents a compound in which at least a part of fullerene is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）

（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又はエステル構造を有する基を表す。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂは置換されていてもよいアルキル基又は置換されていてもよいアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV). It is done.

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

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

Definitions and specific examples of the optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted heteroaryl group represented by R ^a and R ^b are represented by R ¹ and R ² . The definition and specific examples of the alkyl group which may be substituted with the fluorine atom, the aryl group which may be substituted and the heteroaryl group which may be substituted are the same.

（Ｖ）
（式中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、置換されていてもよいアルキル基、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

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

Definitions and specific examples of the optionally substituted alkyl group represented by R ^c , the optionally substituted aryl group and the optionally substituted heteroaryl group are the substitution represented by R ¹ and R ² The definition and specific examples of the alkyl group which may be substituted, the aryl group which may be substituted and the heteroaryl group which may be substituted are the same.

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

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

<Method for producing organic thin film>
The organic thin film may be produced by any method. For example, the organic thin film may be produced by film formation from a solution containing the polymer compound of the present invention and a solvent, or an organic thin film is formed by vacuum deposition. May be. Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.

  The solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound of the present invention. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane. And halogenated hydrocarbon solvents such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  For film formation from solution, 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, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

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

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

<Organic thin film transistor>
The polymer compound of the present invention can also be used for organic thin film transistors. Examples of the organic thin film transistor include a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between these electrodes, and a gate electrode that controls the amount of current passing through the current path. The organic semiconductor layer contains a polymer compound containing a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

  A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and between the organic semiconductor layer and the gate electrode. It is preferable to provide an insulating layer disposed on the surface. In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer, and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.

  The electrostatic induction type organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, and a gate electrode for controlling an amount of current passing through the current path, and the gate electrode is in the organic semiconductor layer. Is preferably provided. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned.

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

化合物１

５００ｍｌフラスコに、４，５−ジフルオロ−１，２−ジアミノベンゼン（東京化成工業製）を１０．２ｇ（７０．８ｍｍｏｌ）、ピリジンを１５０ｍＬ入れて均一にした。フラスコを０℃に保ったまま、フラスコ内に塩化チオニルを１６．０ｇ（１３４ｍｍｏｌ）滴下した。滴下後、フラスコを２５℃に温めて、６時間反応を行った。その後、反応液に、水２５０ｍｌを加え、さらにクロロホルムを加えて反応生成物を含む有機層を抽出した。有機層を硫酸ナトリウムで乾燥させ、濾過した。濾液をエバポレーターで濃縮し、析出した固体を再結晶で精製した。再結晶の溶媒には、メタノールを用いた。精製後、化合物１を１０．５ｇ（６１．０ｍｍｏｌ）得た。 Reference example 1
(Synthesis of Compound 1)

Compound 1

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

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

化合物１ 化合物２

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

Compound 1 Compound 2

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

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

化合物３ 化合物２

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、特表２００９−５０６５１９号公報に記載の方法で合成した化合物３を５００ｍｇ（０．５１０ｍｍｏｌ）、化合物２を１５５ｍｇ（０．４７０ｍｍｏｌ）、トルエンを３３ｍｌ入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを７．００ｍｇ（０．００７６４ｍｍｏｌ）、トリス(２−トルイル)ホスフィンを１４．０ｍｇ（０．０４６０ｍｍｏｌ）加え、１００℃で６時間攪拌した。その後、反応液にフェニルブロミドを８９ｍｇ加え、さらに５時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール３００ｍＬに注いだ。析出したポリマーを濾過して回収し、得られたポリマーを、円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒濾紙内に残ったポリマーを、トルエン１００ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム２ｇと水４０ｍＬを加え、８時間還流下で攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３重量%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、次いで、５重量％フッ化カリウム水溶液５０ｍLで２回洗浄し、次いで、水５０ｍLで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、得られたポリマーをｏ−ジクロロベンゼン５０ｍＬに溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーを濾過後、乾燥させ、精製された重合体１８５ｍｇを得た。以下、この重合体を高分子化合物Ａと呼称する。ＧＰＣで測定した高分子化合物Ａのポリスチレン換算の分子量は、重量平均分子量が３５０００であり、数平均分子量が１３５００であった。 Example 1
(Synthesis of polymer compound A)

Compound 3 Compound 2

In a 200 mL flask in which the gas in the flask was replaced with argon, 500 mg (0.510 mmol) of Compound 3 synthesized by the method described in JP-T-2009-506519, 155 mg (0.470 mmol) of Compound 2, 33 mL of toluene A uniform solution was obtained. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 7.00 mg (0.00764 mmol) of tris (dibenzylideneacetone) dipalladium and 14.0 mg (0.0460 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, 89 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 5 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 2 g of sodium diethyldithiocarbamate and 40 mL of water were added, and the mixture was stirred under reflux for 8 hours. After removing the aqueous layer, the organic layer is washed twice with 50 ml of water, then twice with 50 mL of a 3% by weight aqueous acetic acid solution, then twice with 50 mL of water and then 5% by weight potassium fluoride. The resultant was washed twice with 50 mL of an aqueous solution and then twice with 50 mL of water, and the resulting solution was poured into methanol to precipitate a polymer. The polymer was filtered and dried, and the resulting polymer was dissolved in 50 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 185 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A. The molecular weight in terms of polystyrene of the polymer compound A measured by GPC was a weight average molecular weight of 35000 and a number average molecular weight of 13500.

Example 2
(Production and evaluation of organic thin-film solar cells)
Fullerene derivative C60PCBM (Phenyl C61-butyric acid methyl ester, product name: E100), which is an electron-accepting compound, and polymer compound A, which is an electron-donating compound, in a weight ratio of 3: 1. The mixture was dissolved in o-dichlorobenzene so that the concentration of the mixture was 2% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 1.0 μm to prepare a coating solution 1.
A glass substrate on which an ITO film having a thickness of 150 nm was formed by a sputtering method was cleaned using an ultraviolet ozone cleaning apparatus. Next, a PEDOT: PSS solution (manufactured by HC Starck, CleviosP VP AI4083) is applied onto the ITO film by spin coating, and heated in the atmosphere at 120 ° C. for 10 minutes to form a hole with a thickness of 50 nm. An injection layer was produced. Next, the coating solution 1 was applied onto the hole injection layer by spin coating to obtain an active layer of an organic thin film solar cell. The thickness of the active layer was 100 nm. Then, the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm on an active layer with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm then. The degree of vacuum during vapor deposition was 1 to 9 × 10 ⁻³ Pa in all cases. The shape of the organic thin film solar cell was a 2 mm × 2 mm square. The obtained organic thin-film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), photoelectric conversion efficiency, short-circuit current density The open circuit voltage and the fill factor were determined.

化合物４ 化合物５

フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、特表２００９−５０６５１９号公報に記載の方法で合成した化合物４を５６１ｍｇ（１．００ｍｍｏｌ）、化合物５（４,７−ｂｉｓ(４,４,５,５−ｔｅｔｒａｍｅｔｈｙｌ−１,３,２−ｄｉｏｘａｂｏｒｏｌａｎ−２−ｙｌ)−２,１,３−ｂｅｎｚｏｔｈｉａｄｉａｚｏｌｅ）（Ａｌｄｒｉｃｈ社製）を３８８．１ｍｇ（１．００ｍｍｏｌ）、メチルトリアルキルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、アルドリッチ社製）を２０２ｍｇ加え、トルエン２０ｍｌに溶解させ、得られたトルエン溶液をアルゴンで３０分バブリングした。その後、反応液に酢酸パラジウムを２．２５ｍｇ、トリス(２−メトキシフェニル)ホスフィンを１２．３ｍｇ、１６．７重量％の炭酸ナトリウム水溶液を６．５ｍＬ加え、１００℃で５時間攪拌を行った。その後、反応液にフェニルホウ酸５０ｍｇを加え、さらに７０℃で２時間反応させた。その後、反応液にジエチルジチオカルバミン酸ナトリウム２ｇと水２０ｍＬを加え、２時間還流下で攪拌を行った。水層を除去後、有機層を水２０ｍｌで２回洗浄し、次いで、３重量%の酢酸水溶液２０ｍＬで２回洗浄し、さらに水２０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、得られたポリマーをｏ−ジクロロベンゼン３０ｍＬに溶解させ、アルミナ／シリカゲルカラムに通し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、精製された重合体２８０ｍｇを得た。以下、この重合体を高分子化合物Ｂと呼称する。ＧＰＣで測定した高分子化合物Ｂのポリスチレン換算の分子量は、重量平均分子量が３００００であり、数平均分子量が１４０００であった。 Reference example 3
(Synthesis of polymer compound B)

Compound 4 Compound 5

In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of Compound 4 synthesized by the method described in JP-T-2009-506519, Compound 5 (4,7-bis (4,4, 388.1 mg (1.00 mmol) of 5,5-tetramethyl-1,3,2-dioxaboralan-2-yl) -2,1,3-benzothiazole) (manufactured by Aldrich), methyltrialkylammonium chloride (trade name) 202 mg of Aliquat 336 (registered trademark, manufactured by Aldrich) was added and dissolved in 20 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine, and 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, followed by stirring at 100 ° C. for 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and the mixture was further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 20 ml of water, then twice with 20 mL of a 3% by weight acetic acid aqueous solution and further twice with 20 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer. The polymer was filtered and dried to obtain 280 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound B. The molecular weight in terms of polystyrene of the polymer compound B measured by GPC was a weight average molecular weight of 30,000 and a number average molecular weight of 14,000.

Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
In Example 2, an organic thin film solar cell was prepared in the same manner except that the polymer compound B was used instead of the polymer compound A, and the photoelectric conversion efficiency, the short-circuit current density, the open-end voltage, and the fill factor were obtained.

Table 1

Claims (7)

The high molecular compound containing the repeating unit represented by Formula (3).

(3)
[Wherein, Y represents a sulfur atom, an oxygen atom, a selenium atom, -N (R ³ )-or -C (R ⁴ ) = C (R ⁵ )-. R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. The ring Ar ¹ and the ring Ar ² represent an aromatic hydrocarbon ring having 6 to 60 carbon atoms which may have a substituent or a heterocyclic ring having 4 to 60 carbon atoms which may have a substituent. ] The high molecular compound containing the repeating unit represented by Formula (4).

(4)
[Wherein, R ⁶ and R ⁷ each independently represents an alkyl group having 6 to 10 carbon atoms. ] Electronic device comprising the polymer compound according to claim 1 or 2. A pair of electrodes, and an active layer disposed between the electrodes, the organic photoelectric conversion element active layer comprising a polymer compound according to claim 1 or 2 and an electron-accepting compound. The organic photoelectric conversion device according to claim 4 , wherein the amount of the electron-accepting compound contained in the active layer is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. Electron-accepting compound, an organic photoelectric conversion device according to claim 4 or 5 is a fullerene derivative. A source electrode, a drain electrode, comprising an organic semiconductor layer, a gate electrode, an organic thin film transistor comprising the polymer compound according to claim 1 or 2 wherein the organic semiconductor layer.