JP5228950B2 - Fluorene polymer and organic thin film device - Google Patents

Description

  The present invention relates to a fluorene polymer compound and an organic thin film element.

  Fluorene polymer compounds are variously studied because they are useful as materials for active layers in organic thin film transistors. As this fluorene polymer compound, a polymer compound including a repeating unit having a carbylidene group substituted with a hydrocarbyl group at the 9-position of a 2,7-fluorenediyl group has been proposed (Patent Document 1).

US6169163B1

However, the polymer compound does not have sufficient charge transport properties.
Accordingly, an object of the present invention is to provide a polymer compound having excellent charge transportability.

〔式中、Ｒ¹は、置換基を有していてもよいアリール基又は置換基を有していてもよいヘテロアリール基を表す。ａは１〜３の整数を表す。Ｒ¹が複数存在する場合、それらは同一でも異なっていてもよい。〕
本発明は第二に、下記式（４）で示される化合物を縮合重合させる工程を有する前記高分子化合物の製造方法を提供する。

〔式中、Ｙ¹及びＹ²はそれぞれ独立に、縮合重合反応性基を表す。Ｒ¹は、置換基を有していてもよいアリール基又は置換基を有していてもよいヘテロアリール基を表す。ａは１〜３の整数を表す。Ｒ¹が複数存在する場合、それらは同一でも異なっていてもよい。〕
本発明は第三に、下記式（４ａ）で示される化合物を提供する。

〔式中、Ｙ³及びＹ⁴はそれぞれ独立に、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基又はアリールアルキルスルホネート基を表す。Ｒ¹は、置換基を有していてもよいアリール基又は置換基を有していてもよいヘテロアリール基を表す。ａは１〜３の整数を表す。Ｒ¹が複数存在する場合、それらは同一でも異なっていてもよい。〕
本発明は第四に、前記高分子化合物を含有する組成物、有機薄膜を提供する。
本発明は第五に、前記有機薄膜を備える有機薄膜素子を提供する。 The present invention first provides a polymer compound having a repeating unit represented by the following formula (1).

[Wherein, R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ]
Secondly, the present invention provides a method for producing the polymer compound, comprising a step of condensation polymerization of a compound represented by the following formula (4).

[Wherein Y ¹ and Y ² each independently represent a condensation polymerization reactive group. R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ]
Thirdly, the present invention provides a compound represented by the following formula (4a).

[Wherein Y ³ and Y ⁴ each independently represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group. R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ]
Fourthly, the present invention provides a composition and an organic thin film containing the polymer compound.
Fifthly, the present invention provides an organic thin film element comprising the organic thin film.

  The polymer compound of the present invention is excellent in charge transportability. Therefore, the polymer compound of the present invention is useful for the production of an organic thin film transistor as an organic thin film. In addition, a liquid crystal display, an organic EL display, a display device such as electronic paper, and a switching element such as an electronic tag are produced. Useful for.

It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) which concerns on 1st Embodiment. It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) which concerns on 2nd Embodiment. It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) concerning a 3rd embodiment. It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) which concerns on 4th Embodiment. It is a schematic cross section of the organic thin-film transistor (electrostatic induction type organic thin-film transistor) concerning a 5th embodiment. It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) concerning a 6th embodiment. It is a schematic cross section of the organic thin-film transistor (field effect type organic thin-film transistor) concerning a 7th embodiment. In the organic thin-film transistor of 7th Embodiment, it is a schematic cross section of an organic thin-film transistor when it is set as the structure which the gate electrode 4 serves as the board | substrate 1. FIG. It is a schematic cross section of the solar cell which concerns on suitable embodiment. It is a schematic cross section of the photosensor concerning a 1st embodiment. It is a schematic cross section of the optical sensor which concerns on 2nd Embodiment. It is a schematic cross section of the photosensor concerning a 3rd embodiment.

The present invention will be described below.
In the present specification, the “polymer compound having a repeating unit represented by the formula (1)” means that for each repeating unit represented by the formula (1), a substituted thienyl group in the repeating unit is a polymer compound. This means both a regioregular polymer compound regularly arranged in the same direction and a regiorandom polymer compound irregularly arranged in the same direction with respect to the main chain. The same concept applies to similar structures in the synthesis example and the comparative example.

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

In the formula (1), R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. From the viewpoint of improving the solubility in a solvent, R ¹ is a substituent. The heteroaryl group which may have is preferable.

  Examples of the substituent that the aryl group or heteroaryl group may have include an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, an aryloxy group, an arylthio group, an arylethenyl group, an arylethynyl group, Arylalkyl group, arylalkoxy group, arylalkylthio group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, heteroaryl group, A carboxyl group, a cyano group, etc. are mentioned. These groups may be further substituted.

  The unsubstituted or substituted alkyl group as the substituent may be linear, branched or cyclic, and the carbon number thereof (however, when having a substituent, the carbon number of the substituent is not included) is normal. 1-20, preferably 3-20. Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, s-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluoro An octyl group etc. are mentioned.

  The substituent alkoxy group, alkylthio group, alkenyl group, and alkynyl group each have an oxygen atom, a sulfur atom, —CH═CH—, —C≡C— at the bonding position of the alkyl group. Is.

The aryl group as the substituent preferably has 6 to 60 carbon atoms, more preferably 6 to 48 carbon atoms (provided that a substituent has no carbon number). . Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a C ₁ -C ₁₂ alkylphenyl group (“C ₁ -C ₁₂ alkyl”). "is the number of carbon atoms in the alkyl moiety is meant to be 1-12. hereinafter, the same.), C ₁ -C ₁₂ alkoxyphenyl group (" C ₁ -C ₁₂ alkoxy "carbon in the alkoxy moiety meaning. follows that the number is 1 to 12, are the same.), cited pentafluorophenyl group and the like, phenyl group, C ₁ -C ₁₂ alkylphenyl group, a C ₁ -C ₁₂ alkoxyphenyl group preferable.

  The aryloxy group, arylthio group, arylethenyl group, and arylethynyl group, which are the substituents, have an oxygen atom, a sulfur atom, —CH═CH—, and —C≡C— at the bonding position of the aryl group, respectively. It has.

The arylalkyl group as the substituent preferably has 7 to 60, more preferably 7 to 48 carbon atoms (however, when it has a substituent, the carbon number of the substituent is not included). preferable. Examples of the arylalkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, and the like.

  The arylalkoxy group and arylalkylthio group as the substituents each have an oxygen atom and a sulfur atom at the bonding position of the arylalkyl group.

The substituted amino group as the substituent preferably has 1 to 60 carbon atoms, and more preferably 2 to 48 carbon atoms. Examples of the substituted amino group include an amino group substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a heteroaryl group. A methylamino group, a dimethylamino group, and the like. , Ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, heptylamino group Octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, Pi Lysyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino groups, C ₁ -C ₁₂ alkylphenyl group, Di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, a phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino group.

The substituted silyl group as the substituent preferably has 1 to 60 carbon atoms, and more preferably 3 to 48 carbon atoms. Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a heteroaryl group. A trimethylsilyl group, a triethylsilyl group , Tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group , octyldimethylsilyl group, 2-ethylhexyl - dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl mentioned group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Torirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, dimethylphenyl silyl group, or the It is done.

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

  The acyl group as the substituent preferably has 2 to 20 carbon atoms (more preferably 2 to 18 carbon atoms if the substituent has a substituent). . 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.

  The acyloxy group which is the substituent preferably has 2 to 20 carbon atoms (more preferably 2 to 18 carbon atoms if the substituent has a substituent). . 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.

（式中、Ｍｅはメチル基を表す。以下、同じである。） The imine residue that is the substituent preferably has 2 to 20 carbon atoms (but does not include the carbon number of the substituent when it has a substituent), more preferably 2 to 18 carbon atoms. preferable. Examples of the imine residue include those represented by the following structural formulas.

(In the formula, Me represents a methyl group. The same shall apply hereinafter.)

  The amide group that is the substituent preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms (provided that the substituent does not include the carbon number of the substituent when it has a substituent). . Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditriamide group. A fluoroacetamide group, a dipentafluorobenzamide group, etc. are mentioned.

The acid imide group means a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide. The acid imide group usually has 4 to 20 carbon atoms. Examples of the acid imide group include those represented by the following structural formula.

The heteroaryl group as the substituent means an atomic group remaining after removing one hydrogen atom from an aromatic heterocyclic compound. The heteroaryl group as the substituent is the same as described and exemplified as the heteroaryl group represented by R ¹ .

  Examples of the substituted carboxyl group as the substituent include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group, or a heteroaryl group. The number of carbon atoms of the substituted carboxyl group is preferably 2 to 60, more preferably 2 to 48. Examples of the substituted carboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an i-propoxycarbonyl group, a butoxycarbonyl group, an i-butoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group. Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoro Methoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluoro Chi le oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

The aryl group which may have a substituent represented by R ¹ is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and has a condensed ring, an independent benzene ring or a condensed ring 2 This means that more than one is directly connected. The carbon number of the aryl group which may have this substituent (however, when it has a substituent, the carbon number of the substituent is not included) is preferably 6 to 60, more preferably 6 to 48. . The aryl group which may have the substituent, a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, an unsubstituted aryl group such as a pyrenyl group; C ₁ -C ₁₂ alkylphenyl group, C ₁ -C ₁₂ alkoxyphenyl group, di (C ₁ -C ₁₂ alkyl) fluorenyl group, an aryl group having a substituent such as C ₁ -C ₁₂ alkyl pyrenyl group.

The heteroaryl group which may have a substituent represented by R ¹ means the remaining atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound. The aromatic heterocyclic compound has a cyclic structure, and among aromatic organic compounds, the elements constituting the ring are not only carbon atoms, but also oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, etc. This means that a hetero atom is contained in the ring. The carbon number of the heteroaryl group which may have this substituent (however, when it has a substituent, the carbon number of the substituent is not included) is preferably 3 to 60, more preferably 3 to 20. is there. Among the heteroaryl groups which may have a substituent, a 5-membered heteroaryl group is preferable from the viewpoint of charge transportability. This is because the dihedral angle formed by the thiophene ring and R ¹ in the formula (1) is reduced, and the overlap of the π orbitals between the thiophene ring and R ¹ is increased, which is considered to improve the charge transport property. Because it is. Examples of the heteroaryl group which may have a substituent include a furyl group, a thienyl group, a thienyl thienyl group, a thienothienyl group, a dithienothienyl group, a benzothienyl group, a pyrrolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, and a pyrazyl group. An unsubstituted heteroaryl group such as a quinolyl group and an isoquinolyl group; a C ₁ -C ₁₂ alkyl thienyl group, a C ₆ -C ₂₀ aryl thienyl group, a C ₁ -C ₁₂ alkyl thienyl thienyl group, a C ₁ -C ₁₂ alkyl thienothienyl group, C ₁ -C ₁₂ alkyl di-thieno thienyl group, a heteroaryl group having C ₁ -C ₁₂ alkyl thienyl thieno thienyl group, C ₁ -C ₁₂ alkyl pyridyl group, C ₁ -C ₁₂ substituent such as an alkyl bipyridyl group And the charge transportability is further improved, so that thienyl group, thienyl thienyl group, thienothi Group, more preferably a benzothienyl group, a thienyl group are more preferable.

  In the formula (1), a is preferably 1 or 2 and more preferably 1 from the viewpoint of ease of synthesis.

Examples of the repeating unit represented by the formula (1) include the repeating units represented by the following formulas (1-1) to (1-13), and the thiophene ring in the formula (1) and R ¹ are used. From the viewpoint of improving charge transportability, R ¹ is a five-membered ring, the dihedral angle formed between the thiophene ring and R ¹ is small, and the overlap of the π orbitals between the thiophene ring and R ¹ is considered to be the following formula ( 1-4) to (1-11) are preferable, and a compound represented by the following formula (1-5) is particularly preferable.

〔式中、Ａｒは、置換基を有していてもよいアリーレン基又は置換基を有していてもよいヘテロアリーレン基を表す。〕 The polymer compound of the present invention may be a homopolymer having only the repeating unit represented by the formula (1) or a copolymer with other repeating units. Examples of the other repeating unit include a repeating unit represented by the following formula (2a).

[In formula, Ar represents the arylene group which may have a substituent, or the hetero arylene group which may have a substituent. ]

  The arylene group which may have a substituent represented by Ar is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon and has a condensed ring, an independent benzene ring or a condensed ring 2 This means that more than one is directly connected. Examples of the arylene group in the arylene group which may have a substituent include a phenylene group, a biphenylylene group, a naphthalenediyl group, a fluorenediyl group, an anthracenediyl group, and a pyrenediyl group. The substituent that the arylene group may have is the same as described and exemplified in the section of the aryl group that may be included with the substituent. Carbon number except the substituent of the arylene group which may have the said substituent becomes like this. Preferably it is 6-60, More preferably, it is 6-20.

  The heteroarylene group optionally having a substituent represented by Ar means an atomic group remaining after removing two hydrogen atoms from an aromatic heterocyclic compound. The aromatic heterocyclic compound has a cyclic structure, and among aromatic organic compounds, the elements constituting the ring are not only carbon atoms, but also oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, etc. This means that a hetero atom is contained in the ring. Examples of the heteroarylene group in the heteroarylene group which may have a substituent include a furandyl group, a thiophenediyl group, a bithiophenediyl group, a pyrrolediyl group, a pyridinediyl group, and a selenophenediyl group. The substituent that the heteroarylene group may have is the same as described and exemplified in the section of the heteroaryl group that may be included with the substituent. Carbon number except the substituent of the heteroarylene group which may have the said substituent becomes like this. Preferably it is 3-60, More preferably, it is 3-20.

〔式中、Ａ環及びＢ環はそれぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、二本の結合手はＡ環及びＢ環上に１本ずつ存在する。Ｒ²及びＲ³はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アルケニル基、アルキニル基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールエテニル基、アリールエチニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、ヘテロアリール基、カルボキシル基、置換カルボキシル基又はシアノ基を表す。〕 In the repeating unit represented by the formula (2a), R ² and R ³ are each represented by the following formula (2) in the direction out of the π plane including the A ring and the B ring because the carbon at each bond position is sp ³ carbon. From the viewpoint that 2) has a bulky structure and the solubility in a solvent is improved, it is preferably a repeating unit represented by the following formula (2).

[Wherein, A ring and B ring each independently represent an aromatic hydrocarbon ring which may have a substituent, and two bonds are present on A ring and B ring one by one. R ² and R ³ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkenyl group, alkynyl group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, Arylethenyl group, arylethynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, heteroaryl group, carboxyl group, A substituted carboxyl group or a cyano group is represented. ]

〔式中、Ｒ²及びＲ³は、前記と同じ意味を有する。〕 The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (3) from the viewpoint of ease of synthesis of the compound as a raw material.

[Wherein R ² and R ³ have the same meaning as described above. ]

In the above formulas (2) and (3), the alkyl group, alkoxy group, alkylthio group, alkenyl group, alkynyl group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl represented by R ² and R ³ Alkoxy group, arylalkylthio group, arylethenyl group, arylethynyl group, substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, heteroaryl group, substituted carboxyl The groups are the same as those explained and exemplified in the section of the substituent.

In the formulas (2) and (3), R ² and R ³ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, or an alkynyl group from the viewpoint of solubility of the polymer compound in an organic solvent. An aryl group, an aryloxy group, an arylthio group, an arylethenyl group, an arylethynyl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, and a heteroaryl group, preferably an alkyl group, an alkoxy group, an alkenyl group, An alkynyl group, an aryl group, and an aryloxy group are more preferable, and an alkyl group and an aryl group are further preferable.

Examples of the repeating unit represented by the formula (3) include repeating units represented by the following formulas (3-1) to (3-6).

  The terminal group of the polymer compound of the present invention is a stable group because if the polymerization active group remains as it is, the properties and lifetime of the resulting device may be reduced when used for device fabrication. It may be protected. The terminal group is preferably one having a conjugated bond continuous with the conjugated structure of the main chain, such as those bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond. Specifically, it is described in Chemical formula 10 of JP-A-9-45478.

〔式中、Ｒ¹及びａは前記と同じ意味を有する。Ａｒは、置換基を有していてもよいアリーレン基又は置換基を有していてもよいヘテロアリーレン基を表す。ｍ、ｐ及びｑはそれぞれ独立に、正の整数を表す。〕 When the polymer compound of the present invention is composed of only the repeating unit represented by the formula (1), for example, it is a polymer represented by the following formula (X-1) and represented by the formula (1). In the case of a copolymer of a repeating unit and another repeating unit, for example, a copolymer represented by the following formula (X-2) is preferable from the viewpoint of improving the solubility of the polymer compound. It is a copolymer represented by the following formula (X-2). The copolymer may be an alternating copolymer, a block copolymer, or a random copolymer.

[Wherein, R ¹ and a have the same meaning as described above. Ar represents an arylene group which may have a substituent or a heteroarylene group which may have a substituent. m, p and q each independently represent a positive integer. ]

（式中、ｍ、ｐ及びｑは、前記と同じ意味を有する。） Examples of the polymer compounds represented by the formulas (X-1) and (X-2) include polymer compounds represented by the following formulas (X-3) to (X-10).

(In the formula, m, p and q have the same meaning as described above.)

The polymer compound of the present invention has a polystyrene-equivalent weight average molecular weight of usually 1 × 10 ³ to 1 × 10 ⁶ , and preferably 1 × 10 ⁴ to 1 × 10 ⁶ from the viewpoint of film formability. The number average molecular weight in terms of polystyrene is usually 1 × 10 ³ to 1 × 10 ⁶ , and preferably 1 × 10 ⁴ to 1 × 10 ⁶ from the viewpoint of film formability.

<Manufacturing method>
Next, a method for producing the polymer compound of the present invention will be described.

〔式中、Ｙ¹及びＹ²はそれぞれ独立に、縮合重合反応性基を表す。Ｒ¹及びａは前記と同じ意味を有する。〕
で示される化合物を縮合重合させる工程を有する方法により製造することができ、得られる高分子化合物の分子量制御のしやすさの観点からは、下記式（４ａ）：

〔式中、Ｙ³及びＹ⁴はそれぞれ独立に、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基又はアリールアルキルスルホネート基を表す。Ｒ¹は、置換基を有していてもよいアリール基又は置換基を有していてもよいヘテロアリール基を表す。ａは１〜３の整数を表す。Ｒ¹が複数存在する場合、それらは同一でも異なっていてもよい。〕
で示される化合物が好ましい。
なお、前記式（４）、（４ａ）中、Ｒ¹及びａは、前記式（１）中のＲ¹及びａとして説明し例示したものと同じである。 Examples of the polymer compound having a repeating unit represented by the formula (1) include the following formula (4):

[Wherein Y ¹ and Y ² each independently represent a condensation polymerization reactive group. R ¹ and a have the same meaning as described above. ]
From the viewpoint of ease of molecular weight control of the resulting polymer compound, the compound represented by formula (4a):

[Wherein Y ³ and Y ⁴ each independently represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group. R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ]
The compound shown by these is preferable.
In the formulas (4) and (4a), R ¹ and a are the same as those described and exemplified as R ¹ and a in the formula (1).

  In the formula (4), examples of the condensation polymerization reactive group include a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid residue (-B (OH) 2), a boric acid ester residue, and the like. Is mentioned.

  In the formulas (4) and (4a), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the formulas (4) and (4a), examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.

  In the formulas (4) and (4a), examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group.

  In the formulas (4) and (4a), examples of the arylalkyl sulfonate group include a benzyl sulfonate group.

In the formula (4), examples of the boric acid ester residue include a dialkyl ester residue, a diaryl ester residue, a diaryl alkyl ester residue, and a group represented by the following formula.

  The condensation polymerization reactive group varies depending on the type of polymerization reaction. For example, when a zero-valent nickel complex such as a Yamamoto coupling reaction is used, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group are included. Preferably, when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used, an alkyl sulfonate group, a halogen atom, a boric acid ester residue, a boric acid residue and the like are preferable.

In the polymer compound of the present invention, the compound having a plurality of the condensation polymerization reactive groups (that is, the monomer compound) is dissolved in an organic solvent as necessary, for example, using an alkali or a suitable catalyst, It can be synthesized by condensation polymerization at a temperature of from the melting point to the boiling point. Examples of the condensation polymerization method include a method of polymerizing a monomer compound by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a nickel zero-valent complex, a method of polymerizing by an oxidizing agent such as FeCl ₃ , and electrochemical Oxidative polymerization, decomposition of an intermediate polymer having an appropriate leaving group, and the like. Examples include polymerization by a Suzuki coupling reaction, polymerization by a Grignard reaction, and polymerization by a nickel zero-valent complex. Is preferable from the viewpoint of ease of structure control. In addition, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965 "Organic Synthesis", Collective Volume VI (Collective Volume VI), pages 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.). 95, 2457 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol). Symp.), Vol. 12, p. 229 (1987), etc., can be used.

In the production method of the present invention, from the viewpoint of condensation polymerization reactivity, the condensation polymerization reactive groups are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, and the condensation polymerization However, the manufacturing method performed in presence of a nickel zerovalent complex is preferable.
In addition, when the condensation polymerization reactive groups are different from each other, the reactivity between the condensation polymerization reactive group and the nickel zero-valent complex can be different, so that a polymer compound having a controlled sequence tends to be produced. .

  Examples of the monomer compound include dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, and halogen-aryl alkyl sulfonate compounds. , Alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, aryl sulfonate-aryl alkyl sulfonate compounds, and the like.

  Among these, for example, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, aryl sulfonate-aryl alkyl sulfonate compounds are sequences. It is useful in a method for producing a polymer compound in which the above is controlled.

  In the production method of the present invention, from the viewpoint of condensation polymerization reactivity, each of the condensation polymerization reactive groups is independently a halogen atom, alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, boric acid residue, and boron. A total number (J) of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups selected from the group consisting of acid ester residues and possessed by all monomer compounds, boric acid residues and boron K / J which is a ratio expressed by the total number of moles of acid ester residues (K) is in the range of 0.7 to 1.2, and condensation polymerization is performed using a nickel catalyst or a palladium catalyst. The manufacturing method to perform is preferable. As a combination of the raw material compounds in this production method, a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound may be used. Can be mentioned.

  Examples of the monomer compound include a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boric acid compound, and an aryl sulfonate-boric acid ester compound. Arylalkyl sulfonate-boric acid compound, arylalkyl sulfonate-boric acid compound, arylalkyl sulfonate-boric acid ester compound.

  The condensation polymerization reactive group is selected from the group consisting of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid residue, and a boric acid ester residue, and a nickel catalyst or In the case of performing condensation polymerization using a palladium catalyst, for example, as a raw material compound, a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boron. The sequence is controlled by using an acid compound, an aryl sulfonate-borate compound, an arylalkyl sulfonate-borate compound, an arylalkyl sulfonate-borate compound, and an arylalkyl sulfonate-borate compound. It includes a method of producing a polymer compound is.

  Although the organic solvent used for the condensation polymerization varies depending on the monomer compound and reaction used, it is usually preferable that the solvent used is sufficiently deoxygenated and dehydrated to suppress side reactions. . However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  Examples of the organic solvent used in the condensation polymerization 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, Halogenated saturated hydrocarbons such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane; halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; methanol, ethanol, propanol and isopropanol Alcohols such as butanol and t-butyl alcohol; carboxylic acids such as formic acid, acetic acid and propionic acid; dimethyl ether, diethyl ether and methyl-t-butyl Ethers such as ether, tetrahydrofuran, tetrahydropyran and dioxane; amines such as trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine and pyridine; N, N-dimethylformamide and N, N-dimethylacetamide , N, N-diethylacetamide, amides such as N-methylmorpholine oxide, and the like, and ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable. In addition, the said organic solvent may be used individually by 1 type, or may use 2 or more types together.

  In the condensation polymerization, the alkali and catalyst used as necessary are preferably those that are sufficiently dissolved in the organic solvent. When using the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon gas or nitrogen gas, or react with the alkali or catalyst solution. What is necessary is just to add a liquid slowly.

  When the polymer compound of the present invention is used in a device or the like, since the purity affects the device performance such as mobility, the monomer compound may be polymerized after being purified by distillation, sublimation purification, recrystallization or the like. preferable. Moreover, it is preferable to perform purification treatment such as reprecipitation purification and fractionation by chromatography after the polymerization.

<Composition>
The composition of the present invention contains the polymer compound of the present invention. The polymer compound contained in the composition of the present invention may be one type or two or more types. The composition of the present invention may contain other components in addition to the polymer compound. Examples of the other components include other components exemplified in the section of the organic thin film described later.

  In the composition of the present invention, the ratio of the polymer compound to the total solid content is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. .

<Organic thin film>
The organic thin film of the present invention contains the polymer compound of the present invention, but may contain other components. Other components may be added during the production of the organic thin film, or may be a raw material compound used during the production of the polymer compound, a compound produced as a by-product, or the like. Moreover, you may use the said composition for manufacture of the organic thin film of this invention.

  The thickness of the organic thin film of the present invention is preferably 1 nm to 100 μm, more preferably 2 nm to 10 μm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm. When the organic thin film has such a thickness, it is easy to form an organic thin film element having good charge transportability and sufficient strength.

  The organic thin film of the present invention may contain a low molecular compound having hole transportability and a low molecular compound having electron transportability in order to improve hole transportability and electron transportability.

Examples of the low molecular weight compound having a hole transporting property include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, polyacene and derivatives thereof, oligothiophene and derivatives thereof, polysilane and derivatives thereof, aromatics in side chains or main chains. And polysiloxane derivatives having a group amine. Examples of the low molecular weight compound having an electron transporting property include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, fluorinated polyacene and derivatives thereof, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of its derivatives, such as fullerenes and their derivatives such as C ₆₀ and the like.

  The organic thin film of this invention may contain the high molecular compound which does not have charge transport property, in order to improve the mechanical characteristic of the organic thin film obtained. Examples of the polymer compound having no charge transporting property include a non-conjugated polymer compound. Particularly, when an organic thin film is used, the compound that does not extremely impair the charge transporting property and does not strongly absorb visible light. Is also preferable. Examples of the non-conjugated polymer compound include polystyrenes (polystyrene, isotactic polystyrene, poly (α-methylstyrene), etc.), polyethylenes (HD polyethylene, etc.), polypropylene, polyisoprene, polybutadiene, poly (4-methyl-). 1-pentene), poly (tetrafluoroethylene), polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, and the like, as well as copolymers having repeating units constituting these nonconjugated polymer compounds (random copolymers) , Block copolymers).

The organic thin film of the present invention may contain a charge generating material when it is preferable to generate a charge by light absorbed in the organic thin film. Examples of the charge generation material include azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone compounds and derivatives thereof, squarylium. compounds and their derivatives, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes such as C ₆₀ and derivatives thereof.

  In addition, the organic thin film of the present invention absorbs ultraviolet (UV) light, a sensitizer that sensitizes the function of generating charges by absorbed light, a stabilizer that improves the stability of the composition and the organic thin film. May contain a UV absorber or the like.

  The organic thin film of the present invention may be produced by any method. For example, the polymer compound of the present invention is dissolved in an organic solvent to form a solution (in some cases, a liquid composition of the present invention). Can be formed by using this solution or the like.

  As the organic solvent used when producing the organic thin film of the present invention, those that can dissolve or disperse the components desired to be contained in the organic thin film well (may be heated if necessary) are preferable, Specifically, it is the same as that described and exemplified as the organic solvent used for the condensation polymerization.

  The organic thin film of the present invention may be formed by applying the solution or the like on a substrate and removing the solvent at the same time as application or after application, if necessary. The coating method is 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 printing method, offset. A coating method such as a printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, or a capillary coating method can be used.

  The application may be performed in a heated state. By heating, it becomes possible to apply a high-concentration coating liquid, to form a more uniform thin film, and to use materials that have been difficult to apply at room temperature.

  In addition, the charge transportability may be further enhanced by imparting orientation to the organic thin film by a rubbing method, a photo-alignment method, a sharing method, a pulling coating method, or the like.

<Organic thin film element>
The organic thin film of the present invention is useful for the production of organic thin film elements such as organic thin film transistors, organic solar cells, and optical sensors.

-Organic thin film transistor-
The organic thin film transistor has a configuration including a source electrode and a drain electrode, an active layer which becomes a current path between these electrodes and includes the polymer compound of the present invention, and a gate electrode which controls the amount of current passing through the current path. The active layer is composed of the organic thin film. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

  A field-effect organic thin film transistor usually includes a source electrode and a drain electrode, an active layer that becomes a current path between these electrodes and includes the polymer compound of the present invention, a gate electrode that controls the amount of current passing through the current path, An active layer and an insulating layer disposed between the gate electrode and the active layer is composed of the organic thin film. In particular, the source electrode and the drain electrode are in contact with the active layer. It is preferable that a gate electrode be provided with an insulating layer in contact with the active layer interposed therebetween.

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

  The gate electrode has only to have 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, and is, for example, a comb electrode.

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

  FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment. An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5 and a predetermined electrode. Covers the drain electrode 6 formed on the active layer 2 with an interval, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the region of the insulating layer 3 between the source electrode 5 and the drain electrode. Thus, a gate electrode 4 formed on the insulating layer 3 is provided.

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

  FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3 formed on the active layer 2 and an active layer 2 formed on the insulating layer 3 so as to partially cover the source electrode 5. And a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to partially cover the active layer 2.

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

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

  FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a seventh embodiment. An organic thin film transistor 160 shown in FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. An active layer 2 formed so as to cover the region of the insulating layer 3 formed on the substrate, a source electrode 5 formed on the active layer 2 so as to partially cover the active layer 2, and a part of the active layer 2 A source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval are provided so as to cover the source electrode 5.

  In the organic thin film transistors according to the first to seventh embodiments described above, the active layer 2 and / or the active layer 2a are formed of an organic thin film containing the polymer compound of the present invention, and the source electrode 5 and the drain electrode 6 It becomes a current passage (channel). The gate electrode 4 controls the amount of current passing through the current path (channel) in the active layer 2 and / or the active layer 2a by applying a voltage.

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

  The substrate 1 may be any glass substrate, flexible film substrate, or plastic substrate as long as the characteristics of the organic thin film transistor are not impaired.

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

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

  In the case of an organic field effect transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Therefore, the state of this interface greatly affects the mobility of the transistor. Therefore, as a method for improving the properties on the interface, the control of the interface with a silane coupling agent is known (for example, surface chemistry Vol. 28. No. 5, pp 242-248, 2007).

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

  By such treatment, the surface energy of the silicon oxide film or the like used as the insulating layer can be controlled. In addition, the surface treatment improves the orientation of the organic thin film constituting the active layer on the insulating layer, whereby high charge transportability (mobility) is obtained.

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

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

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

  In addition, after manufacturing the organic thin film transistor as described above, it is preferable to form a protective film on the organic thin film transistor in order to protect the element. Thereby, an organic thin-film transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic thin-film transistor can be suppressed. In addition, when a display device that is driven on the organic thin film transistor is formed by the protective film, the influence on the organic thin film transistor in the formation process can be reduced.

Examples of the method for forming the protective film include a method of covering the organic thin film transistor with a UV curable resin, a thermosetting resin, an inorganic SiON _x film, or the like. In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the formation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  An organic field effect transistor which is a kind of organic thin film transistor thus configured can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display. And since the organic field effect transistor of embodiment mentioned above is equipped with the organic thin film which contains the high molecular compound of this invention as an active layer, and is excellent in charge transport property, its field effect mobility is high. Become. Therefore, it is useful for manufacturing a display having a sufficient response speed.

-Solar cell-
Next, application of the organic thin film of the present invention to a solar cell will be described.

  FIG. 9 is a schematic cross-sectional view of a solar cell according to a preferred embodiment. A solar cell 200 shown in FIG. 9 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 made of the organic thin film of the present invention formed on the first electrode 7a, and an active And a second electrode 7b formed on the layer 2.

  In the solar cell according to the present embodiment, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In order to obtain a high open circuit voltage, it is preferable to select each electrode so that the difference in work function is large. In the active layer 2 (organic thin film), a charge generating agent, a sensitizer and the like can be added in order to increase photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used. Since the active layer 2 using the organic thin film of the present invention can exhibit high charge transportability, the solar cell can generate power efficiently.

-Optical sensor-
Next, the application of the organic thin film of the present invention to an optical sensor will be described.

  FIG. 10 is a schematic cross-sectional view of the photosensor according to the first embodiment. An optical sensor 300 shown in FIG. 10 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 made of an organic thin film of the present invention formed on the first electrode 7a, and an active layer. The charge generation layer 8 formed on the layer 2 and the second electrode 7b formed on the charge generation layer 8 are provided.

  FIG. 11 is a schematic cross-sectional view of an optical sensor according to the second embodiment. An optical sensor 310 shown in FIG. 11 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8. The active layer 2 made of the organic thin film of the present invention and the second electrode 7b formed on the active layer 2 are provided.

  FIG. 12 is a schematic cross-sectional view of an optical sensor according to the third embodiment. An optical sensor 320 shown in FIG. 12 includes a substrate 1, a first electrode 7a formed on the substrate 1, an active layer 2 made of an organic thin film of the present invention formed on the first electrode 7a, and an active And a second electrode 7b formed on the layer 2.

  In the optical sensors according to the first to third embodiments, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. The charge generation layer 8 is a layer that absorbs light and generates charges. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In the active layer 2 (organic thin film), a charge generating agent, a sensitizer and the like can be added in order to increase photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  Since the active layer 2 using the organic thin film of the present invention can exhibit a high charge transporting property, the optical sensor has high sensitivity.

  Examples are given below to illustrate the present invention in more detail.

で表されるモノマー（Ａ）（８ｇ、純度９９．５％）を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ₃） δ８．５１（ｓ，１Ｈ），７．８３（ｓ，１Ｈ），７．４１〜７．６１（ｍ，５Ｈ），７．２４〜７．３１（ｍ，４Ｈ），７．０７（ｄｄ，Ｊ＝２．４Ｈｚ，２．４Ｈｚ，１Ｈ） <Example 1> (Synthesis of polymer compound (P))
Synthesis of monomer (A) To a solution obtained by mixing 2,7-dibromofluorene (6.9 g), ethanol (40 mL), and tetrahydrofuran (50 mL), potassium hydroxide (1.4 g) and water (1 mL) were mixed. The solution was added and stirred. A solution of 2,2′-bithiophene-5-carboxaldehyde (5 g) and tetrahydrofuran (50 mL) was added dropwise to the resulting reaction solution. After completion of dropping, the mixture was heated to reflux for 6 hours. After the solvent was distilled off under reduced pressure, reprecipitation was performed with tetrahydrofuran / methanol. The obtained powder was washed with water (300 mL) and reprecipitated with tetrahydrofuran / methanol to obtain the following formula (A):

A monomer (A) represented by the formula (8 g, purity 99.5%) was obtained.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.51 (s, 1H), 7.83 (s, 1H), 7.41-7.61 (m, 5H), 7.24-7.31 (m , 4H), 7.07 (dd, J = 2.4 Hz, 2.4 Hz, 1H)

（式中、ｘは重合度を表す。）
で表される高分子化合物（Ｐ）を得た。こうして得られた高分子化合物（Ｐ）の収量は０．８ｇであり、ポリスチレン換算の数平均分子量は８．１×１０⁴、重量平均分子量は２．２×１０⁵であった。 Synthesis of polymer compound (P) In an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.88 g), monomer (A) ( 0.85 g), Pd (PPh ₃ ) ₂ Cl ₂ (1.2 mg), trioctylmethylammonium chloride (0.3 g), and toluene (51 mL) were mixed and heated to 105 ° C. An aqueous sodium carbonate solution (2M, 4 mL) was added dropwise to the resulting reaction solution, and the mixture was heated to reflux for 4 hours. Thereafter, phenylboric acid (0.03 g) was added, and the mixture was further heated to reflux for 3 hours. Next, a mixed solution of sodium N, N-diethyldithiocarbamate trihydrate (0.4 g) and water (6 mL) was added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling, the obtained organic layer was washed twice with water (21 mL), twice with a 3% by weight aqueous acetic acid solution (21 mL) and twice with water (21 mL), and passed through an alumina column and a silica gel column. Purified. The obtained toluene solution was added dropwise to methanol (340 mL). The deposited precipitate was collected by filtration and dried under reduced pressure to obtain the following formula (P):

(In the formula, x represents the degree of polymerization.)
The polymer compound (P) represented by this was obtained. The yield of the polymer compound (P) thus obtained was 0.8 g, the polystyrene-equivalent number average molecular weight was 8.1 × 10 ⁴ , and the weight average molecular weight was 2.2 × 10 ⁵ .

(Number average molecular weight and weight average molecular weight)
Here, the number average molecular weight and the weight average molecular weight 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 50 μL was injected into GPC. Tetrahydrofuran was used for the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A) was used as the detector.

<Example 2> (Preparation of organic thin film transistor 1)
An organic thin film transistor 1 having a structure shown in FIG. 8 was prepared using a composition containing the polymer compound (P) as a charge transporting polymer compound.
That is, first, the surface of a highly doped n-type silicon substrate to be a gate electrode was thermally oxidized to form a 200 nm silicon oxide film. The substrate was ultrasonically cleaned with acetone for 10 minutes and then irradiated with ozone UV for 30 minutes. Thereafter, the surface of the substrate was silane-treated by immersing the substrate in an octadecyltrichlorosilane (ODTS) octane diluted solution in a glove box filled with nitrogen for 15 hours.
Further, the polymer compound (P) was dissolved in chloroform as a solvent, and this was filtered through a membrane filter to prepare a coating solution.
Thereafter, the obtained coating solution is applied onto the surface-treated substrate by a spin coating method to form a thin film (organic thin film) containing a compound represented by a polymer compound (P) having a thickness of about 60 nm. did. Then, a source electrode and a drain electrode having a channel length of 20 μm and a channel width of 2 mm (having a laminated structure in the order of fullerene and gold from the organic thin film side) were formed on the organic thin film by a vacuum deposition method using a metal mask. .

Evaluation of physical properties After the organic thin film transistor 1 was heated on a hot plate at 145 ° C. for 30 minutes, the transistor was changed under the condition that the gate voltage Vg was changed to 0 to −60 V and the source-drain voltage Vsd was changed to 0 to −60 V. Characteristics were measured. The field effect mobility of the organic thin film transistor 1 calculated from the transfer characteristics obtained by such measurement was 0.013 cm ² / Vs.

で表されるモノマー（Ｂ）（０．４ｇ、純度９９．５％）を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ₃） δ７．９３（ｓ，１Ｈ），７．７５（ｓ，１Ｈ），７．４１〜７．５７（ｍ，４Ｈ），６．７４（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），２．７８（ｄｔ，Ｊ＝７．３Ｈｚ，７．３Ｈｚ，２Ｈ），１．２０〜１．７３Ｈｚ（ｍ，１８Ｈ），０．８８（ｔ，Ｊ＝６．２Ｈｚ，３Ｈ） <Comparative Example 1> (Synthesis of polymer compound (P-2))
Synthesis of monomer (B) To a solution obtained by mixing dodecyltriphenylphosphonium bromide (4.2 g) and dehydrated tetrahydrofuran (40 ml), t-butoxypotassium (0.9 g) and dehydrated tetrahydrofuran (14 ml) were added. The resulting solution was added dropwise to a solution of 2,7-dibromofluorenone (1.3 g) in dehydrated tetrahydrofuran (20 ml). After completion of dropping, the reaction was allowed to proceed for 24 hours. Water and toluene were added to the resulting reaction solution for extraction. After the recovered oil layer was distilled off under reduced pressure, column chromatography was performed to obtain the following formula (B):

The monomer (B) (0.4g, purity 99.5%) represented by these was obtained.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.93 (s, 1H), 7.75 (s, 1H), 7.41-7.57 (m, 4H), 6.74 (t, J = 7 .3 Hz, 1 H), 2.78 (dt, J = 7.3 Hz, 7.3 Hz, 2 H), 1.20 to 1.73 Hz (m, 18 H), 0.88 (t, J = 6.2 Hz, 3H)

（式中、ｙは重合度を表す。）
で表される高分子化合物（Ｐ−２）を得た。こうして得られた高分子化合物（Ｐ−２）の収量は０．３ｇであり、ポリスチレン換算の数平均分子量は２．９×１０⁴、重量平均分子量は５．６×１０⁴であった。 Synthesis of polymer compound (P-2) Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.36 g), monomer (B ) (0.34 g), Pd (PPh ₃ ) ₂ Cl ₂ (1.4 mg), trioctylmethylammonium chloride (0.079 g), and toluene (11 mL) were mixed and heated to 105 ° C. An aqueous sodium carbonate solution (2M, 1.6 mL) was added dropwise to the resulting reaction solution, and the mixture was heated to reflux for 4 hours. Thereafter, phenylboric acid (0.012 g) was added, and the mixture was further heated to reflux for 3 hours. Next, a mixed solution of sodium N, N-diethyldithiocarbamate trihydrate (0.25 g) and water (2 mL) was added, and the mixture was stirred at 90 ° C. for 5 hours. After cooling, the obtained organic layer was washed twice with water (10 mL), twice with a 3% by weight aqueous acetic acid solution (10 mL) and twice with water (10 mL), and passed through an alumina column and a silica gel column. Purified. The obtained toluene solution was added dropwise to methanol (120 mL). The deposited precipitate was collected by filtration and dried under reduced pressure. The following formula (P-2):

(In the formula, y represents the degree of polymerization.)
The polymer compound (P-2) represented by these was obtained. The yield of the polymer compound (P-2) thus obtained was 0.3 g, the polystyrene-equivalent number average molecular weight was 2.9 × 10 ⁴ , and the weight average molecular weight was 5.6 × 10 ⁴ .

<Comparative example 2> (Preparation of organic thin film transistor 2)
In Example 2, an organic thin film transistor was obtained in the same manner as in Example 2 except that the polymer compound (P-2) represented by the formula (P-2) was used instead of the polymer compound (P). 2 was produced.

Evaluation of physical properties After the organic thin film transistor 2 was heated on a hot plate at 140 ° C. for 30 minutes, the transistor was changed under the condition that the gate voltage Vg was changed to 0 to −60 V and the source-drain voltage Vsd was changed to 0 to −60 V. Characteristics were measured. The field effect mobility of the organic thin film transistor 2 calculated from the transfer characteristics obtained by such measurement was 0.0022 cm ² / Vs.

（式中、ｚ１及びｚ２は重合度を表し、ｚ１：ｚ２＝１：４（モル比）である。）
で表される高分子化合物（Ｐ−３）を得た。こうして得られた高分子化合物（Ｐ−３）の収量は１．９ｇであり、ポリスチレン換算の数平均分子量は６．６×１０⁴、重量平均分子量は１．６×１０⁵であった。 <Comparative Example 3> (Synthesis of polymer compound (P-3))
Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (1.4 g), 2,7-dibromo-9,9-dioctylfluorene (0 .89 g), 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (0.51 g), Pd (PPh ₃ ) ₂ Cl ₂ (2 mg), trioctylmethylammonium chloride (0.8 g), And toluene (82 mL) were mixed and heated to 105 ° C. A sodium carbonate aqueous solution (2M, 6.4 mL) was added dropwise to the obtained reaction solution, and the mixture was heated to reflux for 4 hours. Thereafter, phenylboric acid (0.05 g) was added, and the mixture was further heated to reflux for 3 hours. Next, a mixed solution of sodium N, N-diethyldithiocarbamate trihydrate (0.64 g) and water (10 mL) was added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling, the obtained organic layer was washed twice with water (21 mL), twice with a 3 wt% aqueous acetic acid solution (34 mL) and twice with water (34 mL), and passed through an alumina column and a silica gel column. Purified. The obtained toluene solution was added dropwise to methanol (540 mL). The deposited precipitate was collected by filtration and dried under reduced pressure. The following formula (P-3):

(In the formula, z1 and z2 represent the degree of polymerization, and z1: z2 = 1: 4 (molar ratio).)
The high molecular compound (P-3) represented by these was obtained. The yield of the polymer compound (P-3) thus obtained was 1.9 g, the number average molecular weight in terms of polystyrene was 6.6 × 10 ⁴ , and the weight average molecular weight was 1.6 × 10 ⁵ .

<Comparative example 4> (Preparation of organic thin film transistor 3)
In Example 2, an organic thin film transistor 3 was produced in the same manner as in Example 2 except that the polymer compound represented by the formula (P-3) was used instead of the polymer compound (P).

Evaluation of physical properties After the organic thin film transistor 3 was heated on a hot plate at 135 ° C. for 30 minutes, the transistor was changed under the condition that the gate voltage Vg was changed to 0 to −60 V and the source-drain voltage Vsd was changed to 0 to −60 V. Characteristics were measured. The field effect mobility of the organic thin film transistor 3 calculated from the transfer characteristics obtained by such measurement was 0.0024 cm ² / Vs.

で表されるモノマー（Ｃ）（５．８ｇ、純度９９．５％）を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ₃） δ８．３３（ｓ，１Ｈ），７．８５（ｓ，１Ｈ），７．６２（ｓ，１Ｈ），７．４６〜７．５７（ｍ，６Ｈ），７．１８（ｓ，１Ｈ） <Comparative example 5> (Synthesis of polymer compound (P-4))
-Synthesis | combination of monomer (C) Potassium hydroxide (6g) and methanol (25mL) were mixed and dissolved. Tetrahydrofuran (200 mL) and 2,7-dibromofluorene (5 g) were added to the resulting solution. A solution of 2-thiophenecarboxaldehyde (5 g) and tetrahydrofuran (50 mL) was added dropwise to the resulting reaction solution. After completion of dropping, the mixture was heated to reflux for 6 hours. The solvent was distilled off under reduced pressure, followed by extraction with chloroform / water. The chloroform solution after extraction was concentrated, and the obtained solid was recrystallized from hot isopropanol. The following formula (C):

A monomer (C) represented by the formula (5.8 g, purity 99.5%) was obtained.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.33 (s, 1H), 7.85 (s, 1H), 7.62 (s, 1H), 7.46-7.57 (m, 6H), 7.18 (s, 1H)

（式中、ｘは重合度を表す。）
で表される高分子化合物（Ｐ−４）を得た。こうして得られた高分子化合物（Ｐ−４）の収量は０．５ｇであり、ポリスチレン換算の数平均分子量は３．４×１０⁴、重量平均分子量は４．０×１０⁵であった。 Synthesis of polymer compound (P-4) In an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.54 g), monomer (C ) (0.42 g), Pd (PPh ₃ ) ₂ Cl ₂ (0.7 mg), trioctylmethylammonium chloride (0.2 g), and toluene (30 mL) were mixed and heated to 105 ° C. A sodium carbonate aqueous solution (2 M, 2 mL) was added dropwise to the obtained reaction solution, and the mixture was heated to reflux for 4 hours. Thereafter, phenylboric acid (0.03 g) was added, and the mixture was further heated to reflux for 3 hours. Next, a mixed solution of sodium N, N-diethyldithiocarbamate trihydrate (0.2 g) and water (4 mL) was added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling, the obtained organic layer was washed twice with water (20 mL), twice with 3% by weight acetic acid aqueous solution (20 mL) and twice with water (20 mL), and passed through an alumina column and a silica gel column. Purified. The obtained toluene solution was added dropwise to methanol (200 mL). The deposited precipitate was collected by filtration and dried under reduced pressure to obtain the following formula (P-4):

(In the formula, x represents the degree of polymerization.)
The high molecular compound (P-4) represented by these was obtained. The yield of the polymer compound (P-4) thus obtained was 0.5 g, the polystyrene-equivalent number average molecular weight was 3.4 × 10 ⁴ , and the weight average molecular weight was 4.0 × 10 ⁵ .

<Comparative Example 6> (Preparation of organic thin film transistor 4)
In Example 2, an organic thin film transistor 4 was produced in the same manner as in Example 2 except that the polymer compound represented by the formula (P-4) was used instead of the polymer compound (P).

Physical property evaluation The organic thin film transistor 4 was heated on a hot plate at 145 ° C. for 30 minutes, and then the transistor was changed under the condition that the gate voltage Vg was changed to 0 to −60 V and the source-drain voltage Vsd was changed to 0 to −60 V. Characteristics were measured. The field effect mobility of the organic thin film transistor 4 calculated from the transfer characteristics obtained by such measurement was 0.00012 cm ² / Vs.

<Evaluation>
It can be seen that the organic thin film transistor fabricated in Example 2 has higher field effect mobility, which is one of the factors representing charge transportability, compared to the organic thin film transistors fabricated in Comparative Examples 2, 4, and 6. Therefore, the polymer compound of the present invention has excellent charge transport properties.

DESCRIPTION OF SYMBOLS 1 Substrate 2, 2a Active layer 3 Insulating layer 4 Gate electrode 5 Source electrode 6 Drain electrode 7a First electrode 7b Second electrode 8 Charge generation layer 100, 110, 120, 130, 140, 150, 160, 170 Organic thin film transistor 200 Solar cell 300, 310, 320 Optical sensor

Claims (11)

The high molecular compound which has a repeating unit shown by following formula (1).

[Wherein, R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ] Furthermore, the high molecular compound of Claim 1 which has a repeating unit shown by following formula (2a).

[In formula, Ar represents the arylene group which may have a substituent, or the hetero arylene group which may have a substituent. ] The polymer compound according to claim 2, wherein the repeating unit represented by the formula (2a) is a repeating unit represented by the following formula (2).

[Wherein, A ring and B ring each independently represent an aromatic hydrocarbon ring which may have a substituent, and two bonds are present on A ring and B ring one by one. R ² and R ³ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkenyl group, alkynyl group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, Arylethenyl group, arylethynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, heteroaryl group, carboxyl group, A substituted carboxyl group or a cyano group is represented. ] The polymer compound according to claim 3, wherein the repeating unit represented by the formula (2) is a repeating unit represented by the following formula (3).

[Wherein R ² and R ³ have the same meaning as described above. ] The manufacturing method of the high molecular compound as described in any one of Claims 1-4 which has the process of condensation-polymerizing the compound shown by following formula (4).

[Wherein Y ¹ and Y ² each independently represent a condensation polymerization reactive group. R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ] The Y ¹ and Y ² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, and the condensation polymerization is performed in the presence of a nickel zero-valent complex. Manufacturing method. Y ¹ and Y ² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid residue, or a boric acid ester residue, and the condensation polymerization is a nickel catalyst. Or the manufacturing method of Claim 5 performed in presence of a palladium catalyst. A compound represented by the following formula (4a).

[Wherein Y ³ and Y ⁴ each independently represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group. R ¹ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. a represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different. ]   The composition containing the high molecular compound as described in any one of Claims 1-4.   The organic thin film containing the high molecular compound as described in any one of Claims 1-4.   An organic thin film element comprising the organic thin film according to claim 10.

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