WO2011052725A1

WO2011052725A1 - Polymeric compound

Info

Publication number: WO2011052725A1
Application number: PCT/JP2010/069295
Authority: WO
Inventors: 吉村　研; 健一郎大家
Original assignee: 住友化学株式会社
Priority date: 2009-10-30
Filing date: 2010-10-29
Publication date: 2011-05-05
Also published as: JP2011116961A

Abstract

Disclosed is a polymeric compound of which the optical absorption edge has a long wavelength. Specifically disclosed is a polymeric compound having a structural unit represented by formula (1) and a structural unit that is different from the structural unit represented by formula (1). [In the formula, Q¹ and Q² independently represent -S-, -O-, -Se- or -N(R³)-; and R¹, R² and R³ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, an acid imide group, an amino group, a substituted amino group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, or a cyano group.]

Description

High molecular compound

The present invention relates to a polymer compound having a specific structure.

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 However, there is a problem that high temperature and high vacuum conditions are required.

On the other hand, the organic thin film electronic device which is one aspect of the photoelectric conversion device can omit the high temperature and high vacuum process used in the manufacturing process of the silicon-based electronic device, and can be manufactured at low cost only by the coating process. Has been. 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 (Non-Patent Document 1).

However, the polymer compound has a short light absorption terminal wavelength, and the wavelength range of sunlight that can be absorbed is not sufficient.

The present invention aims to provide a polymer compound light absorbing terminal wavelength of long wavelength.

That is, the present invention first provides a polymer compound having a structural unit represented by the formula (1) and a structural unit different from the structural unit represented by the formula (1).

[Wherein, Q ¹ and Q ² are the same or different and each represents -S-, -O-, -Se- or -N (R ³ )-, and R ¹ , R ² and R ³ are the same or Differently, hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, aryl An alkynyl group, a carboxyl group or a cyano group is represented. ]

The polymer compound of the present invention, the light absorption terminal wavelength is a long wavelength, is very useful.

Hereinafter, the present invention will be described in detail.

The polymer compound of the present invention is characterized by having a structural unit represented by the formula (1) and a structural unit different from the structural unit represented by the formula (1). The structural unit represented by the formula (1) is a divalent group.

Here, the alkyl group may be linear or branched, and may be a cycloalkyl group. The alkyl group usually has 1 to 30 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n-pentyl group, isopentyl group, 2- Methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3, 7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups, cyclopentyl group, cyclohexyl group, adamantyl group and other cycloalkyl groups Can be mentioned.

Alkyl group may be linear or branched, and may be a cycloalkyloxy group. The alkyloxy group may have a substituent. The alkyloxy group usually has about 1 to 20 carbon atoms. Specific examples of the alkyloxy group include methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, iso-butoxy group, tert -Butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, tri Examples thereof include a fluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, a perfluorooctyl group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

The alkylthio group may be linear or branched, and may be a cycloalkylthio group. The alkylthio group may have a substituent. The alkylthio group usually has about 1 to 20 carbon atoms. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an iso-propylthio group, a butylthio group, an iso-butylthio group, a tert-butylthio group, Examples include a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

Aryl group, the number of carbon atoms thereof is usually about 6 to 60, may have a substituent. Specific examples of the aryl group include a phenyl group, a C1 to C12 alkyloxyphenyl group (C1 to C12 alkyl represents an alkyl having 1 to 12 carbon atoms. C1 to C12 alkyl is preferably C1 to C8 alkyl. More preferably, it is C1 to C6 alkyl, C1 to C8 alkyl represents alkyl having 1 to 8 carbon atoms, and C1 to C6 alkyl represents alkyl having 1 to 6 carbon atoms. Specific examples of C1 to C12 alkyl, C1 to C8 alkyl and C1 to C6 alkyl include those described and exemplified for the above alkyl group, and the same applies to the following.), C1 to C12 alkylphenyl group, 1 -Naphthyl group, 2-naphthyl group, pentafluorophenyl group.

The aryloxy group usually has about 6 to 60 carbon atoms and may have a substituent on the aromatic ring. Specific examples of the aryloxy group include a phenoxy group, a C1-C12 alkyloxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.

The arylthio group usually has about 6 to 60 carbon atoms and may have a substituent on the aromatic ring. Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The arylalkyl group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkyl group include phenyl-C1-C12 alkyl group, C1-C12 alkyloxyphenyl-C1-C12 alkyl group, C1-C12 alkylphenyl-C1-C12 alkyl group, 1-naphthyl-C1-C12 alkyl And a 2-naphthyl-C1-C12 alkyl group.

The arylalkyloxy group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkyloxy group include phenyl-C1-C12 alkyloxy group, C1-C12 alkyloxyphenyl-C1-C12 alkyloxy group, C1-C12 alkylphenyl-C1-C12 alkyloxy group, 1-naphthyl- Examples thereof include C1-C12 alkyloxy group and 2-naphthyl-C1-C12 alkyloxy group.

The arylalkylthio group usually has about 7 to 60 carbon atoms and may have a substituent. Specific examples of the arylalkylthio group include a phenyl-C1-C12 alkylthio group, a C1-C12 alkyloxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, and a 1-naphthyl-C1-C12 alkylthio group. And a 2-naphthyl-C1-C12 alkylthio group.

Acyl groups usually have about 2 to 20 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

Acyloxy groups usually have about 2 to 20 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The amide group usually has about 2 to 20 carbon atoms. An amide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an amide. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

The acid imide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide. Specific examples of the acid imide group include a succinimide group and a phthalimide group.

The substituted amino group usually has about 1 to 40 carbon atoms. Specific examples of the substituent amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert-Butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyloctylamino, laurylamino , Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 al Ruoxyphenylamino group, di (C1-C12 alkyloxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkyloxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 Alkylamino group, di (C1-C12 alkyloxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group, 2- Naphthyl-C1-C 2 alkylamino group.

Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, and tri-p-xylylsilyl group. , Tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-iso-propylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, Examples thereof include a tri-p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-iso-propylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, Examples thereof include a tri-p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-iso-propylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, Tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group Di (tri-n-propylsilyl) amino group, di (tri-iso-propylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p -Xylylsilyl) amino group, (Tribenzylsilyl) amino group, di (diphenylmethyl silyl) amino, di (tert- butyldiphenylsilyl) amino group, di (dimethylphenylsilyl) and amino group.

Specific examples of the monovalent heterocyclic group 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, indazole Heterocycles such as naphthyridine, quinoxaline, quinazoline, quinazoline, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine A group obtained by removing one hydrogen atom from a compound can be mentioned. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable.

Examples of the heterocyclic oxy group and the heterocyclic thio group include a group in which an oxygen atom or a sulfur atom is bonded to the monovalent heterocyclic group.
The heterocyclic oxy group usually has about 4 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
The heterocyclic thio group usually has about 4 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

The arylalkenyl group usually has 7 to 20 carbon atoms, and specific examples of the arylalkenyl group include a styryl group.

The arylalkynyl group usually has 7 to 20 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

From the viewpoint of solubility in a solvent, at least one of R ¹ and R ² is preferably an alkyl group.

Q ¹ and Q ² are preferably —S— or —O— from the viewpoint of making the light absorption terminal wavelength longer wavelength absorption. Among these, at least one of Q ¹ and Q ² is preferably —S—.

Examples of the structural unit represented by Formula (1) include structural units represented by Formula 301 to Formula 351. The structural units represented by Formula 301 to Formula 351 are divalent groups.

In Formula 301 to Formula 351, R ¹⁰ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. Definition of alkyl group, aryl group, arylalkyl group, monovalent heterocyclic group, specific examples include definition of alkyl group, aryl group, arylalkyl group, monovalent heterocyclic group represented by R ¹ described above The same as the specific example. R ¹⁰ is preferably an alkyl group.
X ¹⁰ represents a halogen atom. Specific examples of the halogen atom are the same as the specific examples of the halogen atom represented by R ¹ described above. R ³ represents the same meaning as described above.

Among the structural units represented by Formula 301 to Formula 351, the structural units represented by Formula 301 to Formula 306 are preferable, the structural units represented by Formula 302 and Formula 303 are more preferable, and the structural unit is particularly preferable. This is a structural unit represented by Formula 302.

Moreover, the preferable one aspect | mode of the structural unit represented by Formula (1) is a structural unit (divalent group) represented by Formula (3).

(In the formula, R ⁵⁰ represents an alkyl group.)

The polymer compound of the present invention has a structural unit different from the structural unit represented by the formula (1) in addition to the structural unit represented by the formula (1). It is preferable that the structural unit represented by the formula (1) and the structural unit different from the structural unit represented by the formula (1) form a conjugate. Conjugation in the present invention is chained in the order of unsaturated bond-single bond-unsaturated bond, two π bonds of π orbitals are adjacent to each other, and each π electron is arranged in parallel. It refers to a state in which π electrons are not localized on the bond but are spread and delocalized on the adjacent single bond. Here, the unsaturated bond refers to a double bond or a triple bond.
The structural unit different from the structural unit represented by the formula (1) includes a divalent group, and examples of the divalent group include an arylene group and a divalent heterocyclic group. Preferably, the structural unit different from the structural unit represented by the formula (1) is an arylene group or a divalent aromatic heterocyclic group.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the number of carbon atoms constituting the ring is usually about 6 to 60, preferably 6 to 20. Here, aromatic hydrocarbons include those having a benzene ring, those having a condensed ring, those having two or more independent benzene rings or condensed rings directly bonded, or bonded via a group such as vinylene. It is.

Examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the figure below), a naphthalenediyl group (formulas 4 to 13 in the figure below), an anthracenediyl group (formulas 14 to 19 in the figure below), and a biphenyl-diyl group (formula in the figure below). 20-25), a terphenyl-diyl group (formulas 26 to 28 in the following figure), a condensed ring compound group (formulas 29 to 38 in the following figure) and the like. The fused ring compound group includes a fluorene-diyl group (formulas 36 to 38 in the following figure).

The divalent heterocyclic group means an atomic group remaining after removing two hydrogen atoms from a heterocyclic compound, and the number of carbon atoms constituting the ring is usually about 3 to 60.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things.

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

In the formulas 1 to 143, R represents a hydrogen atom or a substituent. A plurality of R may be the same or different, and may be bonded to each other to form a ring. When R is a substituent, examples of the substituent include alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, aryl Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group, And a group selected from a cyano group. The hydrogen atom contained in these substituents may be substituted with a fluorine atom.

An alkyl group represented by R, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a substituted amino group, Definition of substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, specific examples are the alkyl group, alkyloxy group, alkylthio group, aryl group represented by R ¹ described above, Aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent Definition of the heterocyclic group of, the same as the specific example It is.

As the substituted carboxyl group, those having 2 to 20 carbon atoms are usually used, and examples thereof include a group having a methyl ester structure, a group having an ethyl ester structure, and a group having a butyl ester structure.

A and b are the same or different and represent the number of repetitions, and are usually 1 to 5, preferably 1 to 3, and particularly preferably 1.

The structural unit different from the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (A-1) to the formula (H-1) from the viewpoint of photoelectric conversion efficiency.

[In formulas (A-1) to (H-1), Q ³ to Q ¹⁵ are the same or different and represent —S—, —O—, —Se—, or —N (R ³ ) —. R ⁴⁰ to R ⁵² are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group , Acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, complex A ring thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented. R ⁴⁰ and R ⁴¹ _, R ⁴² and R ⁴³ may be connected to each other to form a cyclic structure. Y ¹ to Y ⁶ are the same or different and each represents a nitrogen atom or ═CH—. ]

Specific examples of the cyclic structure formed by connecting R ⁴⁰ and R ⁴¹ _, R ⁴² and R ⁴³ include a cyclic structure represented by the formula (I) and a cyclic structure represented by the formula (II).

In formula (I) and formula (II), R ³² and R ³³ are the same or different and represent a hydrogen atom or a substituent. When R ³² or R ³³ is a substituent, the substituent is preferably a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, butyl group, hexyl group, octyl group, dodecyl group, methoxy group, ethoxy group, butoxy group, hexyloxy group, octyloxy group Groups, alkyloxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group. X ³² represents a sulfur atom or a selenium atom. X ³² is preferably a sulfur atom. Y ³⁶ to Y ³⁹ are the same or different and each represents a nitrogen atom or ═CH—. Y ³⁶ to Y ³⁹ are preferably nitrogen atoms.

As the structural units represented by formula (A-1) to formula (H-1), groups represented by formula (500) to formula (525) are preferable.

(Wherein R represents the same meaning as R in formulas 1 to 143)

Among the structural units represented by Formula (500) to Formula (525), Formula (500), Formula (504), Formula (505), Formula (506), Formula (511), Formula (523), Formula ( 524) and a structural unit represented by the formula (525) are preferable.

The polymer compound in the present invention refers to a polymer having a weight average molecular weight (Mw) of 1000 or more, and a polymer compound having a weight average molecular weight of 3,000 to 10,000,000 is preferably used. If the weight average molecular weight is lower than 3000, defects may occur in film formation during device fabrication, and if it exceeds 10000000, solubility in a solvent and applicability during device fabrication may be degraded. The weight average molecular weight is more preferably 8000 to 5000000, and particularly preferably 10,000 to 1000000.
In addition, the weight average molecular weight in this invention points out the weight average molecular weight of polystyrene conversion calculated using the standard sample of polystyrene using gel permeation chromatography (GPC).

The content of the structural unit represented by the formula (1) in the polymer compound of the present invention may be at least one in the compound. Preferably, the polymer compound contains an average of 2 or more per polymer chain, more preferably an average of 3 or more per polymer chain.

In addition, when the polymer compound of the present invention is used in an element, it is desirable that the solubility in a solvent is high in terms of ease of device production. Specifically, the polymer compound of the present invention preferably has a solubility capable of producing a solution containing 0.01% by weight (wt)% or more of the polymer compound, and a solution containing 0.1% by weight or more is produced. It is more preferable that it has the solubility which can be made, and it is further more preferable that it has the solubility which can produce the solution containing 0.4 wt% or more.

The polymer compound of the present invention is characterized by having a structural unit represented by the formula (1). For example, the polymer compound represented by the formula (1-2) is a raw material. It can be synthesized by using as one.

[Wherein W ¹ and W ² are the same or different and are a hydrogen atom, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid ester residue, a sulfonium methyl group, a phosphonium methyl group, or a phosphonate. It represents a methyl group, a monohalogenated methyl group, a boric acid residue, a formyl group, a vinyl group or an organotin residue. R ¹ and R ² represent the same meaning as described above. ]

The compound represented by the formula (1-2) can be produced by introducing a substituent into the compound represented by the formula (1-3) by a known Wittig reaction or the like.

[Wherein W ¹ and W ² represent the same meaning as described above. ]

For the Wittig reaction, a known method can be used. For example, in the presence of a Wittig reagent, in a solvent such as aromatic hydrocarbons, ethers, halogenated hydrocarbons, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, The reaction can be carried out under cooling or heating. The Wittig reagent can be obtained, for example, by reacting the corresponding phosphonium salt with a base such as alkyllithium such as potassium carbonate, tert-butoxypotassium, sodium hydride or n-butyllithium.

The polymer compound of the present invention can be produced by increasing the molecular weight of the compound represented by the formula (1-2). The method for producing the polymer compound of the present invention is not particularly limited, but a method using a Suzuki coupling reaction or a Stille coupling reaction is preferable from the viewpoint of ease of synthesis of the polymer compound.

As a method using the Suzuki coupling reaction, for example, the formula (100):
Q ¹⁰⁰ -E ¹ -Q ²⁰⁰ (100)
[Wherein E ¹ represents a divalent group containing an aromatic ring. Q ¹⁰⁰ and Q ²⁰⁰ are the same or different and represent a boric acid residue or a boric acid ester residue. ]
One or more compounds represented by formula (200):
T ¹ -E ² -T ² (200)
Wherein, E ² represents a structural unit containing a group represented by the formula (1). T ¹ and T ² are the same or different and each represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an arylalkyl sulfonate group. ]
The manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. E ¹ is preferably a divalent aromatic group, and more preferably 1 to 141 described above.
In this case, the total number of moles of one or more compounds represented by formula (200) used in the reaction is excessive with respect to the total number of moles of one or more compounds represented by formula (100). Is preferred. When the total number of moles of one or more compounds represented by formula (200) used in the reaction is 1 mole, the total number of moles of one or more compounds represented by formula (100) is 0.6 to 0.00. The amount is preferably 99 mol, more preferably 0.7 to 0.95 mol.

As the borate ester residue, the following formula:

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

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

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

Specifically, the method for carrying out the Suzuki coupling reaction includes a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is carried out in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, etc. , Dichlorobis (triphenylphosphine) palladium, palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (100). The amount is preferably 0.0003 mol to 0.1 mol.

When palladium acetates are used as the palladium catalyst used in the Suzuki coupling reaction, for example, a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine is added as a ligand. can do. In this case, the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst. is there.

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

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

The temperature at which the Suzuki coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

The Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the compound represented by the formula (100), the compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) was charged, the polymerization vessel was sufficiently replaced with nitrogen gas, degassed, and then degassed by adding a degassed solvent such as toluene by bubbling with nitrogen gas in advance. Thereafter, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution, is dropped into this solution, and then heated and heated, for example, while maintaining an inert atmosphere at the reflux temperature for 8 hours. Polymerize.

As a method using the Stille coupling reaction, for example, the formula (300):
Q ³⁰⁰ -E ³ -Q ⁴⁰⁰ (300)
[Wherein E ³ represents a divalent group containing an aromatic ring. Q ³⁰⁰ and Q ⁴⁰⁰ are the same or different and represent an organotin residue. ]
And a method of reacting one or more compounds represented by the formula (200) with one or more compounds represented by the formula (200) in the presence of a palladium catalyst. E ³ is preferably a divalent aromatic group, more preferably a group represented by the above formulas 1 to 141.

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

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

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

Specifically, examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst.
Examples of the palladium catalyst used in the Stille coupling reaction include Pd (0) catalyst, Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium can be mentioned, and from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, palladium [Tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst used for the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (100). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.

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

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

The temperature at which the Stille coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for carrying out the reaction (reaction time) may be the end point when the desired degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.

The Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the polymerization vessel is charged with a compound represented by the formula (300), a compound represented by the formula (200), A palladium catalyst is charged, and the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene, and then coordinate as necessary. After adding the catalyst and the cocatalyst, the mixture is heated and heated, for example, and polymerized while maintaining an inert atmosphere at the reflux temperature for 8 hours.

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

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

In the polymer compound of the present invention, the light absorption terminal wavelength is preferably a long wavelength. The light absorption terminal wavelength can be determined by the following method.
For the measurement, a spectrophotometer (for example, JASCO-V670, UV-visible near infrared spectrophotometer manufactured by JASCO Corporation) operating in the wavelength region of ultraviolet, visible and near infrared is used. When JASCO-V670 is used, the measurable wavelength range is 200 to 1500 nm. Therefore, measurement is performed in this wavelength range. First, the absorption spectrum of the substrate used for measurement is measured. As the substrate, a quartz substrate, a glass substrate, or the like is used. Next, a thin film containing the first compound is formed on the substrate from a solution containing the first compound or a melt containing the first compound. In film formation from a solution, drying is performed after film formation. Thereafter, an absorption spectrum of the laminate of the thin film and the substrate is obtained. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the thin film.
In the absorption spectrum of the thin film, the vertical axis represents the absorbance of the first compound, and the horizontal axis represents the wavelength. It is desirable to adjust the thickness of the thin film so that the absorbance at the largest absorption peak is about 0.5 to 2. The absorbance of the absorption peak with the longest wavelength among the absorption peaks is defined as 100%, and the intersection of the absorption peak and a straight line parallel to the horizontal axis (wavelength axis) including the absorbance of 50% of the absorption peak. The intersection point that is longer than the peak wavelength is taken as the first point. The intersection point between the absorption peak and a straight line parallel to the wavelength axis containing 25% of the absorbance, which is longer than the peak wavelength of the absorption peak, is defined as a second point. The intersection of the straight line connecting the first point and the second point and the reference line is defined as the light absorption terminal wavelength. Here, the reference line is the intersection of the absorption peak and the straight line parallel to the wavelength axis including the absorbance of 10% at the absorption peak of the longest wavelength, where the absorbance of the absorption peak is 100%. The third point on the absorption spectrum that is 100 nm longer than the reference wavelength and the absorption spectrum that is 150 nm longer than the reference wavelength with reference to the wavelength of the intersection that is longer than the peak wavelength of the absorption peak A straight line connecting the top and the fourth point.

Since the polymer compound of the present invention can exhibit high electron and / or hole transport properties, when an organic thin film containing the compound is used in a device, electrons or holes injected from an electrode, or light absorption. The generated charge can be transported. Taking advantage of these characteristics, it can be suitably used for various devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.

<Photoelectric conversion element>
The photoelectric conversion element having the polymer compound of the present invention has one or more active layers containing the polymer compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.
A preferred form of the photoelectric conversion element having the polymer compound of the present invention is formed from a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. Having an active layer. The polymer compound of the present invention is preferably used as a p-type organic semiconductor. The operation mechanism of the photoelectric conversion element of this embodiment will be described. Light energy incident from a transparent or translucent electrode is an electron-accepting compound (n-type organic semiconductor) such as a fullerene derivative and / or an electron-donating compound (p-type organic semiconductor) such as a polymer compound of the present invention. Absorbed, producing excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface, Electric charges (electrons and holes) that can move independently are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.
The photoelectric conversion element manufactured using the polymer compound of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

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

Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, 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, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

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

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

<Active layer>
The active layer 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 active layer, compounds other than the polymer compound of this invention can also be mixed and used as an electron-donating compound and / or an electron-accepting compound in the said active layer. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

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

As the electron-accepting compound, in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and Derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinolines and derivatives thereof, polyquinoxalines and Derivatives thereof, polyfluorene and derivatives thereof, phenanthrene derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproin), fullerenes, fullerene derivatives, Mashiku are titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Examples of fullerene and fullerene derivatives include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ and derivatives thereof. Specific examples of the fullerene derivative include the following.

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

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

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

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

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

The solvent used for film formation from a solution, 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, 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 be dissolved usually the solvent to 0.1% by weight or more.

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Application methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, capillary coating, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet coating method, and a spin coating method are preferable.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

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

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

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

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

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

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

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

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

Hereinafter, examples will be shown to describe the present invention in more detail, but the present invention is not limited to these examples.

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

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

Reference example 1
(Synthesis of Compound 1)

In a 1000 mL four-necked flask purged with argon, 13.0 g (80.0 mmol) of 3-bromothiophene and 80 mL of diethyl ether were added to obtain a uniform solution. While maintaining the solution at −78 ° C., a hexane solution of n-butyllithium (n-BuLi) (2.6 M, 31 mL, 80.6 mmol) was added dropwise. After reacting at −78 ° C. for 2 hours, a solution obtained by dissolving 8.96 g (80.0 mmol) of 3-thiophenaldehyde in 20 mL of diethyl ether was added dropwise. It was stirred 30 min at -78 ° C. After the dropwise addition, further stirred at room temperature for 30 minutes (25 ° C.). The reaction solution was cooled again to −78 ° C., and a hexane solution of n-BuLi (2.6 M, 62 mL, 161 mmol) was added dropwise over 15 minutes. After the dropwise addition, the reaction solution was stirred at −25 ° C. for 2 hours, and further stirred at room temperature (25 ° C.) for 1 hour. Thereafter, the reaction solution was cooled to −25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes. After dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours, and 50 mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After extracting the reaction product with diethyl ether, the reaction product was dried with magnesium sulfate, filtered, and the filtrate was concentrated to obtain 35 g of a crude product. The crude product was purified by recrystallization using chloroform to obtain 28 g of Compound 1.

Reference example 2
(Synthesis of Compound 2)

10.5 g (23.4 mmol) of bisiodothienylmethanol (Compound 1) synthesized in Reference Example 1 and 150 mL of methylene chloride were added to a 300 mL four-necked flask to obtain a uniform solution. To the solution, 7.50 g (34.8 mmol) of pyridinium chlorochromate was added and stirred at room temperature (25 ° C.) for 10 hours. The reaction solution was filtered to remove insoluble matters, and then the filtrate was concentrated to obtain 10.0 g (22.4 mmol) of Compound 2.

Reference example 3
(Synthesis of Compound 3)

In a 300 mL flask purged with argon, 10.0 g (22.4 mmol) of Compound 2 synthesized in Reference Example 2, 6.0 g (94.5 mmol) of copper powder, dehydrated N, N-dimethylformamide (hereinafter referred to as DMF). 120 mL) was added and stirred at 120 ° C. for 4 hours. After the reaction, the flask was cooled to room temperature (25 ° C.), and the reaction solution was passed through a silica gel column to remove insoluble components. Thereafter, 500 mL of water was added, and the reaction product was extracted with chloroform. The organic layer as a chloroform solution was dried over magnesium sulfate, the organic layer was filtered, and the filtrate was concentrated to obtain a crude product. The composition was purified with a silica gel column (developing solution: chloroform) to obtain 3.26 g of compound 3.

Reference example 4
(Synthesis of Compound 4)

2) 2.27 g (11.8 mmol) of Compound 3 synthesized in Reference Example 3 and 48 mL of dehydrated DMF were placed in a 200 mL four-necked flask purged with argon to obtain a uniform solution. The flask was kept at 0 ° C. and 4.86 g (26.0 mmol) of N-bromosuccinimide was added. After stirring at 0 ° C. for 2 hours, the reaction was stopped by adding 200 mL of 1N aqueous sodium thiosulfate solution. The organic layer was extracted with chloroform, and the organic layer was dried over magnesium sulfate. The organic layer was filtered and the filtrate was concentrated to obtain a crude product. This was purified by a silica gel column (developing solution: chloroform) to obtain 3.88 g (11.1 mmol) of the target compound 4.

Reference Example 5
(Synthesis of Compound 5)

In a 200 mL four-necked flask purged with argon, 0.700 g (1.30 mmol) of triphenyl (tetradecyl) phosphonium bromide and 10 mL of dehydrated tetrahydrofuran were added to obtain a homogeneous solution. The flask was kept at −78 ° C., and 0.48 mL (1.25 mmol) of n-butyllithium (2.6 M hexane solution) was added. After stirring at −78 ° C. for 1 hour, a solution of 0.350 g (1.00 mmol) of Compound 4 synthesized in Reference Example 4 in 5 mL of tetrahydrofuran (THF) was added dropwise. After reacting at −78 ° C. for 3 hours, the reaction was stopped by adding 50 mL of water, and the organic layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off from the filtrate. Purification with a silica gel column (eluent: hexane) gave 350 mg (0.648 mmol) of Compound 5.

Example 1
(Synthesis of polymer A)

In a 100-mL flask purged with argon, 150 mg (0.282 mmol) of compound 5 synthesized in Reference Example 5 and compound 6 (4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxabolan- 2-yl) -2,1,3-benzothiadiazole) (Aldrich) 107 mg (0.276 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), Aldrich) 100 mg was added, and toluene 5 mL was dissolved in the obtained toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.0 mg of palladium acetate, 10.0 mg of tris (2-methoxyphenyl) phosphine (0.0 mg) and 4.0 mL of an aqueous sodium carbonate solution (16.7 wt%) were added, and the mixture was stirred at 100 ° C. for 5 hours. Went. Thereafter, 30 mg of phenylboric acid was added, and the mixture was further reacted at 100 ° C. for 2 hours. Thereafter, 1 g of sodium diethyldithiocarbamate and 10 mL of water were added, and the mixture was stirred under reflux for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 20 ml of water, twice with 20 mL of an acetic acid aqueous solution (3 wt%) and further twice with 20 mL of water, and poured into methanol to precipitate a polymer. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene 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 102 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer A. The molecular weight (polystyrene conversion) of the polymer A measured by GPC was Mw = 8200 and Mn = 3200. It was 865 nm when the light absorption terminal wavelength of the polymer A was measured.

Comparative Example 1
(Synthesis of polymer B)
Journal of Materials Chemistry, Vol. The polymer B having the following structure was produced by the method described in 12, 2887-2892 (2002), and the light absorption terminal wavelength was measured and found to be 650 nm.

Reference Example 6
(Synthesis of Compound 8)

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.00 g (1.89 mmol) of Compound 5 and 50 mL of dehydrated THF were added to obtain a uniform solution. The solution was kept at −78 ° C., and 1.81 mL (4.71 mmol) of a 2.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After dropping, the mixture was stirred at -78 ° C for 3 hours. Thereafter, 1.69 g (5.20 mmol) of tributyltin chloride was added while keeping the flask at −78 ° C. After the addition, it stirred for 30 minutes at -78 ° C., then stirred at room temperature for 5 hours (25 ° C.). Thereafter, the reaction by adding water 200ml was stopped, the reaction product was extracted with ethyl acetate. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate and filtered, and then the filtrate was concentrated with an evaporator and the solvent was distilled off. The resulting oily substance was purified by silica gel column (developing solvent: hexane). As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 1.14 g (1.20 mmol) of Compound 8 was obtained.

Example 2
(Synthesis of polymer C)

In a 100 mL flask in which the gas in the flask was replaced with argon, 300 mg (0.316 mmol) of Compound 8 and 88 mg of Compound 9 (4,7-dibromo-2,1,3-benzothiazole) (Aldrich) were added (0. 299 mmol) and 19 ml of toluene to make a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.33 mg (0.00473 mmol) of tris (dibenzylideneacetone) dipalladium and 8.6 mg (0.0284 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 5 hours. Thereafter, 500 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 200 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 o-dichlorobenzene, 2 g of sodium diethyldithiocarbamate and 50 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 wt% aqueous acetic acid solution, then twice with 50 mL of water, and then 50 mL of 5% aqueous potassium fluoride solution. And then washed 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 obtained polymer was redissolved 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 C. The molecular weight (polystyrene conversion) of the polymer C measured by GPC was Mw = 23000 and Mn = 13000. The light absorption terminal wavelength of the polymer C was 865 nm.

Claims

A polymer compound having a structural unit represented by formula (1) and a structural unit different from the structural unit represented by formula (1).

[Wherein, Q 1 and Q 2 are the same or different and each represents -S-, -O-, -Se- or -N (R 3 )-, and R 1 , R 2 and R 3 are the same or Differently, hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, aryl An alkynyl group, a carboxyl group or a cyano group is represented. ]
The polymer compound according to claim 1, wherein the structural unit different from the structural unit represented by the formula (1) is a divalent aromatic group.
2. The polymer compound according to claim 1, wherein the structural unit different from the structural unit represented by the formula (1) is a group represented by the formula (A-1) to the formula (H-1).

[In formulas (A-1) to (H-1), Q 3 to Q 15 are the same or different and represent —S—, —O—, —Se—, or —N (R 3 ) —. R 40 to R 52 are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group , Acyl group, acyloxy group, amide group, acid imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, complex A ring thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented. R 40 and R 41 , R 42 and R 43 may be connected to each other to form a cyclic structure. Y 1 to Y 6 are the same or different and each represents a nitrogen atom or ═CH—. ]
2. The polymer compound according to claim 1, wherein at least one of Q 1 and Q 2 is —S—.
The polymer compound according to claim 1, wherein at least one of R 1 and R 2 is an alkyl group.
The polymer compound according to claim 5, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (3).

(In the formula, R 50 represents an alkyl group.)
The polymer compound according to claim 1 the weight average molecular weight in terms of polystyrene is 3000 or more.