JP5874302B2 - Polymer compound and organic photoelectric conversion device using the same - Google Patents

Description

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

  An organic semiconductor material is used for organic photoelectric conversion elements, such as an organic solar cell and an optical sensor, for example. In particular, when a polymer compound is used as the organic semiconductor material, there is an advantage that a thin film can be manufactured by an inexpensive coating method, and the manufacturing cost of the element can be reduced.

  In order to improve various characteristics of the organic photoelectric conversion element, various polymer compounds have been studied for organic semiconductor materials constituting the element. For example, a polymer compound obtained by polymerizing 9,9-dioctylfluorene-2,7-diboronate and 5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-α-pentathiophene is proposed. (Patent Document 1).

Special table 2007-529596 gazette

  However, the polymer compound has a problem that long-wavelength light is not sufficiently absorbed.

  Then, an object of this invention is to provide the high molecular compound with the large light absorbency of long wavelength light.

〔（式（Ａ）及び式（Ｂ）中、Ｒは、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、下記式（２ａ）で表される基、又は下記式（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一であっても、相異なっていてもよい。Ａｒ^１、Ａｒ^２は、置換基を有してもよい炭素数６〜６０の３価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の３価の複素環基を示す。）

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 That is, the present invention first provides a polymer compound containing a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[In the formulas (A) and (B), R represents a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the following formula (2a), or a group represented by the following formula ( The hydrogen atom contained in these groups may be substituted with a fluorine atom, and a plurality of R may be the same or different from each other Ar ¹ , Ar ² represents a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent. .)

(2a)
(In Formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

（１）
〔（式（１）中、Ｒは、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、下記式（２ａ）で表される基、又は下記式（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一であっても、相異なっていてもよい。）

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 Secondly, the present invention provides a polymer compound containing a repeating unit represented by the formula (1).

(1)
[In the formula (1), R is a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the following formula (2a), or a group represented by the following formula (2b). (The hydrogen atom contained in these groups may be substituted with a fluorine atom. A plurality of R may be the same or different.)

(2a)
(In Formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

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

  Fourthly, 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.

  The polymer compound of the present invention is extremely useful because it has a large absorbance for light having a long wavelength.

Polymer compound A and [60] PCBM ([6,6] - phenyl _{C 61} - butyric acid methyl ester) is a diagram showing the absorption spectrum of the 1/2 mixture of. Polymeric compound B and [60] PCBM ([6,6] - phenyl _{C 61} - butyric acid methyl ester) is a diagram showing the absorption spectrum of the 1/2 mixture of.

  Hereinafter, the present invention will be described in detail.

〔（式（Ａ）及び式（Ｂ）中、Ｒは、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、下記式（２ａ）で表される基、又は下記式（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一であっても、相異なっていてもよい。Ａｒ^１、Ａｒ^２は、置換基を有してもよい炭素数６〜６０の３価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の３価の複素環基を示す。）

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 <Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[In the formulas (A) and (B), R represents a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the following formula (2a), or a group represented by the following formula ( The hydrogen atom contained in these groups may be substituted with a fluorine atom, and a plurality of R may be the same or different from each other Ar ¹ , Ar ² represents a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent. .)

(2a)
(In Formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

  Examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n- Examples include a pentyl group, n-hexyl group, n-octyl group, iso-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-octadecyl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  Examples of the alkoxy group represented by R include methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

  The aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon which may have a substituent. The aryl group includes a group containing a benzene ring, a group containing a condensed ring having aromaticity, a group having a structure in which two or more benzene rings or a condensed ring having aromaticity are directly bonded, and two or more benzenes Examples include a group in which a ring or an aromatic condensed ring is bonded via a group such as vinylene. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. A hydrogen atom in the aryl group may be substituted with a fluorine atom. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the substituent that the aromatic hydrocarbon may have include a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group. Specific examples of the alkyl group and alkoxy group are the same as the specific examples of the alkyl group and alkoxy group represented by R.

  The heteroaryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound which may have a substituent. Examples of the heteroaryl group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group. The hydrogen atom in the heteroaryl group may be substituted with a fluorine atom. Examples of the substituent that the aromatic heterocyclic compound may have include a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group. Specific examples of the alkyl group and alkoxy group are the same as the specific examples of the alkyl group and alkoxy group represented by R.

  In the group represented by the formula (2a), m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 6. R 'represents an alkyl group, an aryl group or a heteroaryl group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ′ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R. A hydrogen atom in the group represented by the formula (2a) may be substituted with a fluorine atom.

  In the group represented by the formula (2b), m3 represents an integer of 0 to 6, and m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ″ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R. The hydrogen atom in the group represented by the formula (2b) may be substituted with a fluorine atom.

  When R in Formula (A) is an alkyl group or an alkoxy group, the alkyl group or the alkoxy group preferably has 1 to 20 carbon atoms from the viewpoint of the solubility of the polymer compound in the solvent. More preferably, it is -18, and it is further more preferable that it is 3-12.

  When R in Formula (B) is an alkyl group or an alkoxy group, the alkyl group or the alkoxy group preferably has 1 to 20 carbon atoms from the viewpoint of solubility of the polymer compound in a solvent. More preferably, it is -18.

In formulas (A) and (B), Ar ¹ and Ar ² may have a substituent, a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituent. A trivalent heterocyclic group having 4 to 60 carbon atoms is shown.

In Ar ¹ and Ar ² , an optionally substituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms is an aromatic carbon atom having 6 to 60 carbon atoms that may have a substituent. The trivalent group remove | excluding three hydrogen atoms on the aromatic ring in a hydrogen compound is shown. The aromatic hydrocarbon compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. A ring is more preferable, and a single ring is more preferable.

  Examples of the aromatic hydrocarbon compound include benzene, naphthalene, anthracene, fluorene, pyrene, and perylene. Of these, benzene or naphthalene is preferable, and benzene is more preferable.

  The aromatic hydrocarbon group may further have a substituent, and in this case, the whole including the substituent is an aromatic hydrocarbon group. However, in this case, the carbon number of the above-described preferred aromatic hydrocarbon group does not include the carbon number of the substituent. Examples of the substituent include those shown for R above.

  The trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent refers to three hydrogens on the heterocyclic ring in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. A trivalent group excluding atoms is shown. The heterocyclic compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. Is more preferable, and a single ring is more preferable.

  Examples of the heterocyclic compound include pyridine, thiophene, thienothiophene, dithienothiophene, benzothiophene, benzodithiophene, dibenzothiophene, pyrrole, quinoline, and indole. Of these, thiophene, thienothiophene or pyridine is preferable, and thiophene is more preferable.

  The heterocyclic group may further have a substituent. In this case, the carbon number of the preferable heterocyclic group described above does not include the carbon number of the substituent. Examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkanoyl group having 1 to 12 carbon atoms, Examples thereof include an aryloxy group having 6 to 60 carbon atoms, a heterocyclic group having 3 to 60 carbon atoms, an amino group, a nitro group, and a cyano group. Examples of these substituents include the same groups as those described above for R.

Ar ¹ and Ar ² are preferably trivalent groups excluding three hydrogen atoms on the aromatic ring in benzene or thiophene.

Examples of the repeating unit represented by the formula (A) include the following repeating units.

Examples of the repeating unit represented by the formula (B) include the following repeating units.

  From the viewpoint of photoelectric conversion efficiency, the polymer compound of the present invention preferably includes a repeating unit in which the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) are directly bonded.

  The total amount of the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) contained in the polymer compound of the present invention is that of the organic photoelectric conversion element having a functional layer containing the polymer compound. From the viewpoint of increasing the photoelectric conversion efficiency, it is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of repeating units contained in the polymer compound.

  The ratio of the number of repeating units represented by formula (A) contained in the polymer compound of the present invention to the number of repeating units represented by formula (B) is, for example, 1: 9 to 9: 1. Yes, 3: 7-7: 3 is preferred.

（１）
〔式（１）中、Ｒ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 containing a repeating unit represented by the formula (1).

(1)
[In the formula (1), R represents the same meaning as described above. ]

Examples of the repeating unit represented by the formula (1) include the following repeating units.

  The amount of the repeating unit represented by the formula (1) contained in the polymer compound of the present invention is selected from the viewpoint of increasing the photoelectric conversion efficiency of an organic photoelectric conversion device having a functional layer containing the polymer compound. The amount is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of repeating units contained in the compound.

The weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is 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 substantially conjugated.

  The polymer compound of the present invention may have a repeating unit other than the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (1). Good. Examples of the repeating unit include an arylene group and a heteroarylene group. Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group. Examples of the heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like.

<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, for example, with reference to the methods disclosed in JP-A Nos. 2006-182920 and 2006-335933.

  Examples of the polymerization by the aryl coupling reaction include polymerization by Stille coupling reaction, polymerization by Suzuki coupling reaction, polymerization by Yamamoto coupling reaction, and polymerization by 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 an organotin residue and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group. This is a polymerization in which the monomer 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 uses a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, and a ligand is added as necessary to have a boronic acid residue or a boric acid ester residue. This is a polymerization in which a monomer is reacted with a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a monomer having a sulfonate group such as a trifluoromethanesulfonate group or a 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 to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups. Polymerization.

  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, and a compound having a magnesium halide group 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 method of polymerizing by a Stille coupling reaction, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Yamamoto coupling reaction are preferable, and a Stille coupling reaction More preferred are a method of polymerizing, a method of polymerizing by a Suzuki coupling reaction, and a method of polymerizing by a Yamamoto coupling reaction using a nickel zero-valent complex.

  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, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Examples of the arylamino group include a phenylamino group and a diphenylamino group.
Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and 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 monovalent heterocyclic group having aromaticity.

（３）
（式（３）中、Ｒは、前述と同じ意味を表す。複数あるＲは、同一でも相異なっていてもよい。Ｚは、臭素原子、ヨウ素原子又は塩素原子を表す。２個あるＺは、同一でも相異なっていてもよい。） When the polymer compound of the present invention is produced using Stille coupling, for example, the polymer compound is produced by polymerizing the compound represented by the formula (3) and the compound represented by the formula (4). be able to.

(3)
(In formula (3), R represents the same meaning as described above. Plural Rs may be the same or different. Z represents a bromine atom, an iodine atom or a chlorine atom. May be the same or different.)

（４）
（式（４）中、Ｒは前述と同じ意味を表す。２個あるＲは、同一でも相異なっていてもよい。Ｚ^２は有機スズ残基を表す。）

(4)
(In formula (4), R represents the same meaning as described above. Two Rs may be the same or different. Z ² represents an organotin residue.)

  In the formula (3), Z is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom, from the viewpoint of increasing the reactivity during polymerization. The compound represented by the formula (3) can be synthesized using, for example, the method described in Journal of American Chemical Society Vol. 131 Issue 21 7206-7207.

As a compound represented by Formula (3), the following compounds are mentioned, for example.

In the formula (4), ease From the point of view of the synthesis of the compound represented by formula (4), ^{Z 2} is -SnMe _3, preferably a -SnEt ₃ or -SnBu _3. Here, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

The compound represented by the formula (4) is prepared by, for example, reacting the compound represented by the formula (5) with an organolithium compound to produce an intermediate, and then reacting the intermediate with a trialkyltin halide. Can be manufactured.

(In formula (5), R represents the same meaning as described above.)

  Examples of the organic lithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide. Of the organic lithium compounds, n-butyllithium is preferable. Examples of the trialkyltin halide include trimethyltin chloride, triethyl chloride, and tributyl chloride.

  The reaction for producing an intermediate from a compound represented by formula (5) and an organolithium compound and the reaction for producing a compound represented by formula (4) from the intermediate and trialkyltin halide are usually carried out in a solvent. Done. As the solvent, sufficiently dehydrated tetrahydrofuran, fully dehydrated 1,4-dioxane, and fully dehydrated diethyl ether are preferably used.

  The temperature at which the organolithium compound and the compound represented by formula (5) are reacted is usually -100 to 50 ° C, preferably -80 to 0 ° C. The time for reacting the organolithium compound with the compound represented by the formula (5) is usually 1 minute to 10 hours, preferably 30 minutes to 5 hours. The amount of the organolithium compound to be reacted is usually 2 to 5 molar equivalents (hereinafter, the molar equivalent is simply referred to as equivalent), preferably 2 to 3 with respect to the compound represented by the formula (5). Is equivalent.

  The temperature at the time of reacting the intermediate and the trialkyltin halide is usually −100 to 100 ° C., preferably −80 ° C. to 50 ° C. The reaction time of the intermediate and the trialkyltin halide is usually 1 minute to 30 hours, preferably 1 to 10 hours. The amount of the trialkyl tin halide to be reacted is usually 2 to 6 equivalents, preferably 2 to 3 equivalents, relative to the compound represented by the formula (5).

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (4). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (5) can be produced, for example, by reacting the compound represented by the formula (6) in the presence of an acid.

(In formula (6), R represents the same meaning as described above.)

  The acid used in the reaction for producing the compound represented by formula (5) from the compound represented by formula (6) may be Lewis acid or Bronsted acid, Hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, boron fluoride, aluminum chloride, tin chloride (IV), iron chloride (II), titanium tetrachloride, Examples include benzenesulfonic acid, p-toluenesulfonic acid and mixtures of these compounds.

  The reaction for producing the compound represented by formula (5) from the compound represented by formula (6) is preferably carried out in the presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

  Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloro Halogenated saturated hydrocarbons such as pentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, Alcohols such as tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether, methyl-te t- butyl ether, tetrahydrofuran, tetrahydropyran, and the like ethers such as dioxane. These solvents may be used alone or in combination.

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (5). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (6) can be produced, for example, by reacting the compound represented by the formula (7) with a Grignard reagent or an organolithium (Li) compound.

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

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

  The reaction for producing the compound represented by the formula (6) from the compound represented by the formula (7) and a Grignard reagent or an organolithium (Li) compound is carried out in an inert gas atmosphere such as nitrogen or argon. It is preferable to do. Moreover, it is preferable to implement this reaction in presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

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

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (6). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (7) can be produced, for example, by reacting the compound represented by the formula (8) with a peroxide.

  Examples of the peroxide include sodium perborate, m-chloroperbenzoic acid, hydrogen peroxide, and benzoyl peroxide. Preferred are sodium perborate and m-chloroperbenzoic acid, and particularly preferred is sodium perborate.

  The reaction for producing the compound represented by the formula (7) from the compound represented by the formula (8) and the peroxide is carried out in the presence of a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid and butyric acid. It is preferable.

  In order to increase the solubility of the compound represented by formula (8), a mixed solvent in which one or more solvents selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, benzene, and toluene are mixed with a carboxylic acid solvent. It is preferable to carry out the reaction. The reaction temperature is preferably 0 ° C. or higher and 50 ° C. or lower.

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (7). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by methods such as chromatographic fractionation and recrystallization.

（式中、Ｂｕはｎ−ブチル基を表す。） As a compound represented by Formula (4), the following compound is mentioned, for example.

(In the formula, Bu represents an n-butyl group.)

<Organic photoelectric conversion element>
Since the polymer compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, an organic photoelectric conversion element manufactured using the polymer compound of the present invention has a short-circuit current. Density increases. Moreover, the high molecular compound of this invention can obtain a big open end voltage.

The organic photoelectric conversion device of the present invention has a pair of electrodes and a functional layer between the electrodes, and the functional layer contains the electron-accepting compound and the polymer compound of the present invention. As an electron-accepting compound, fullerene or a fullerene derivative is preferable. As a specific example of the organic photoelectric conversion element,
1. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention;
2. An organic photoelectric conversion element comprising a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention, wherein the electron-accepting compound is a fullerene An organic photoelectric conversion element which is a derivative;
Is mentioned. In general, at least one of the pair of electrodes is transparent or translucent, and the embodiment will be described below as an example.

  1 above. In the organic photoelectric conversion element, the amount of the electron accepting compound in the functional layer containing the electron accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. Is preferable, and it is more preferable that it is 20-500 weight part. In addition, 2. In the organic photoelectric conversion element, the amount of the fullerene derivative in the functional layer containing the fullerene derivative and the polymer compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is -500 weight part. From the viewpoint of increasing the photoelectric conversion efficiency, the amount of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight, and preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, and preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer compound. More preferred.

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

  From such a viewpoint, as the organic photoelectric conversion element, the above 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. Further, in the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the functional layer in the element. 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 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.

  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. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and those metals An alloy of two or more of these metals, or one or more of those metals and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with metal, 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 of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA 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.

  As a material used for the buffer layer as an additional layer, halides or oxides of alkali metals or alkaline earth metals such as lithium fluoride can be used. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

<Organic thin film>
As the functional 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 alone or in combination of two or more. Moreover, in order to improve the hole transport property of the organic thin film, a low molecular compound and / or a high molecular compound other than the high molecular compound can be mixed and used as the electron donating compound in the organic thin film.

  Examples of the electron-donating compound that the organic thin film may contain in addition to the polymer compound of the present invention include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and its derivatives, polyvinylcarbazole and its Derivatives, polysilanes and derivatives thereof, polysiloxane derivatives having aromatic amines 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 Is mentioned.

Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and 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 And 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、アルキル基、アリール基、ヘテロアリール基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂはアルキル基又はアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).

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

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

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^a and R ^b are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.

（Ｖ）
（式（Ｖ）中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、アルキル基、アリール基又は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 formula (V), u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an alkyl group, an aryl group, or a heteroaryl group.)

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.

Specific examples of the C ₆₀ derivative include the following.

Specific examples of the C ₇₀ derivative include the following.

<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 a film formation method from a solution containing the polymer compound of the present invention, or an organic thin film may be formed by a vacuum deposition method. Good. 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 unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, 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 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.

<Application of device>
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 transistor>
The organic thin film transistor of the present invention includes a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode. The organic semiconductor layer is represented by the repeating unit represented by the formula (A) and the formula (B). A polymer compound containing a repeating unit or a polymer compound containing a repeating unit represented by formula (1).

  Since the polymer compound of the present invention has high charge mobility, the organic thin film transistor having the organic semiconductor layer containing the polymer compound of the present invention has high field effect mobility.

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

  The polystyrene equivalent weight average molecular weight of the polymer compound was determined by size exclusion chromatography (SEC).

  Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm I.d. x 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF)

化合物１ 化合物２
フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、ＷＯ２０１１／０５２７０９Ａ１に記載の方法で合成した化合物１を２５２ｍｇ（０．２３９ｍｍｏｌ）、Ｌｕｍｉｎｅｓｃｅｎｃｅ Ｔｅｃｈｎｏｌｏｇｙ社製の化合物２を１００ｍｇ（０．２４０ｍｍｏｌ）、トリス(２−トリル)ホスフィンを６．６ｍｇ（０．０２２ｍｍｏｌ）、脱水トルエン１９ｍｌを入れて均一溶液とした。なお化合物２におけるアルキル基（−Ｃ_１２Ｈ_２５）は直鎖のアルキル基である。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを３．２９ｍｇ（０．００３６ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で３時間攪拌した。その後、反応液にフェニルブロミドを１０ｍｇ加え、さらに２時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、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３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１５ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２０ｇと水２．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、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、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをｏ−ジクロロベンゼン９ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。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、精製された重合体１７ｍｇ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の分子量（ポリスチレン換算）はＭｗ＝３２０００、Ｍｎ＝１４１００であった。 Example 1
(Synthesis of polymer compound A)

Compound 1 Compound 2
In a 100 mL flask in which the gas in the flask was replaced with argon, 252 mg (0.239 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1, 100 mg (0.240 mmol) of Compound 2 manufactured by Luminescence Technology, Tris ( 6.6 mg (0.022 mmol) of 2-tolyl) phosphine and 19 ml of dehydrated toluene were added to obtain a uniform solution. In addition, the alkyl group (—C ₁₂ H ₂₅ ) in the compound 2 is a linear alkyl group. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.29 mg (0.0036 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, followed by stirring at 105 ° C. for 3 hours and further stirring at 120 ° C. for 3 hours. Thereafter, 10 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 15 mL of toluene, 0.20 g of sodium diethyldithiocarbamate and 2.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 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 again in 9 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 17 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A. The molecular weight (polystyrene conversion) of the high molecular compound A measured by GPC was Mw = 32000 and Mn = 14100.

フラスコ内の気体をアルゴンで置換した２Ｌ四つ口フラスコに、化合物（Ｈ）を７．９２８ｇ（１６．７２ｍｍｏｌ）、化合物（Ｉ）を１３．００ｇ（１７．６０ｍｍｏｌ）、トリオクチルメチ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、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml、25℃）を４．９７９ｇ、及びトルエンを４０５ｍｌ入れ、撹拌しながら反応系内を３０分間アルゴンバブリングした。フラスコ内にジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）を０．０２ｇ加え、１０５℃に昇温し、撹拌しながら２ｍｏｌ／Ｌの炭酸ナトリウム水溶液４２．２ｍｌを滴下した。滴下終了後５時間反応させ、その後、フェニルボロン酸２．６ｇとトルエン１．８ｍｌとを加え、１０５℃で１６時間撹拌した。その後、反応液にトルエン７００ｍｌ及び７．５ｗｔ％のジエチルジチオカルバミン酸ナトリウム三水和物水溶液２００ｍｌを加え、８５℃で３時間撹拌した。反応液の水層を除去後、有機層を６０℃のイオン交換水３００ｍｌで２回、６０℃の３ｗｔ％酢酸３００ｍｌで１回、さらに６０℃のイオン交換水３００ｍｌで３回洗浄した。有機層をセライト、アルミナ及びシリカを充填したカラムに通し、ろ液を回収した。その後、熱トルエン８００ｍｌでカラムを洗浄し、洗浄後のトルエン溶液をろ液に加えた。得られた溶液を７００ｍｌまで濃縮した後、濃縮した溶液を２Ｌのメタノールに加え、重合体を再沈殿させた。重合体をろ過して回収し、５００ｍｌのメタノール、５００ｍｌのアセトン、５００ｍｌのメタノールで重合体を洗浄した。重合体を５０℃で一晩真空乾燥することにより、ペンタチエニル−フルオレンコポリマー（高分子化合物Ｊ）１２．２１ｇを得た。高分子化合物Ｊのポリスチレン換算の重量平均分子量は１．１×１０⁵であった。 Reference example 1
(Synthesis of polymer compound J)

Into a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (H), 13.00 g (17.60 mmol) of compound (I), trioctylmethylammonium chloride ( 4.979 g of trade name Aliquat 336 (registered trademark), manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.) and 405 ml of toluene are added and stirred. The reaction system was bubbled with argon for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and then 2.6 g of phenylboronic acid and 1.8 ml of toluene were added and stirred at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of a 7.5 wt% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer of the reaction solution, the organic layer was washed twice with 300 ml of ion exchange water at 60 ° C., once with 300 ml of 3 wt% acetic acid at 60 ° C., and further three times with 300 ml of ion exchange water at 60 ° C. The organic layer was passed through a column packed with celite, alumina and silica, and the filtrate was recovered. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the filtrate. After the obtained solution was concentrated to 700 ml, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. The polymer was recovered by filtration, and the polymer was washed with 500 ml of methanol, 500 ml of acetone, and 500 ml of methanol. The polymer was vacuum-dried at 50 ° C. overnight to obtain 12.21 g of a pentathienyl-fluorene copolymer (polymer compound J). The weight average molecular weight in terms of polystyrene of the polymer compound J was 1.1 × 10 ⁵ .

Measurement example 1
(Measurement of absorbance of organic thin film)
Fullerene derivatives ([60] PCBM ([6,6] -phenyl C ₆₁ -butyric acid methyl ester), made by Frontier Carbon, trade name: E100), which is an electron-accepting compound, and polymer compound A, which is an electron-donating compound Were dissolved in o-dichlorobenzene so that the concentration of the mixture was 2.25 wt%. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.5 μm to prepare a coating solution 1.

  The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on 120 degreeC conditions in air | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 575 nm, 600 nm, and 625 nm.

Comparative Example 1
(Measurement of absorbance of organic thin film)
Fullerene derivative ([60] PCBM ([6,6] -phenyl C ₆₁ -butyric acid methyl ester), an electron-accepting compound, manufactured by Frontier Carbon Corporation, trade name: E100), and a polymer compound that is an electron-donating compound J was mixed at a weight ratio of 2: 1 and dissolved in o-dichlorobenzene so that the concentration of the mixture was 1.5% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.5 μm to prepare a coating solution 2.

  The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on 120 degreeC conditions in air | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 575 nm, 600 nm, and 625 nm.

Example 2
(Production and evaluation of organic thin-film solar cells)
A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by Heraeus Co., Ltd.) was applied onto the ITO film by spin coating, and heated in the atmosphere at 120 ° C. for 10 minutes to form a hole injection layer having a thickness of 50 nm. Next, the coating solution 1 was applied onto the ITO film by spin coating to obtain a functional layer of an organic thin film solar cell. The film thickness of the functional layer was 100 nm. Then, the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa in all cases. The shape of the organic thin film solar cell thus obtained was a square of 2 mm × 2 mm. The obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. did. The photoelectric conversion efficiency is 1.97%, Jsc (short circuit current density) is 4.33 mA / cm ² , Voc (open circuit voltage) is 1.00 V, and FF (fill factor) is 0.45. there were.

Claims (6)

A polymer compound comprising a repeating unit represented by formula (A) and a repeating unit represented by formula (B).

[In the formulas (A) and (B), R represents a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the following formula (2a), or a group represented by the following formula ( The hydrogen atom contained in these groups may be substituted with a fluorine atom, and a plurality of R may be the same or different from each other Ar ¹ , Ar ² represents a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent. .)

(2a)
(In Formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)] The high molecular compound containing the repeating unit represented by Formula (1).

(1)
[In the formula (1), R is a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the following formula (2a), or a group represented by the following formula (2b). (The hydrogen atom contained in these groups may be substituted with a fluorine atom. A plurality of R may be the same or different.)

(2a)
(In Formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]   An organic photoelectric conversion element having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound according to claim 1.   The organic photoelectric conversion element according to claim 3, wherein the amount of the electron-accepting compound contained in the functional layer is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound.   The organic photoelectric conversion element according to claim 3 or 4, wherein the electron-accepting compound is a fullerene derivative.   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 according to claim 1.

Images