JP2010111830A - Polymer compound, method for producing the same and organic electronic device containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound which is soluble in an organic solvent and hardly agglomerates and from which a uniform thin film can be formed and to provide an organic electronic device which is obtained by using the polymer compound and is excellent in degree of charge transfer and has high heat resistance. <P>SOLUTION: The polymer compound has at least one repeating unit shown by general formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>and R<SP>4</SP>to R<SP>9</SP>are each independently a hydrogen atom or a same or different substituent (except for a sulfo group, a carboxy group, a phosphoryl group and a hydroxy group); R<SP>1</SP>and R<SP>2</SP>can be bonded to each other to form a ring; and R<SP>3</SP>is ≥1C non-substituted or substituted monovalent alkyl group having substituents except for an amino group and an aryl group) in a polymer chain thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic semiconductor material that can be easily formed by coating or the like, and an organic electronic device using the material. More specifically, the present invention relates to an organic semiconductor material made of a polymer compound having a phenazacillin skeleton.

  In recent years, electronic devices using organic semiconductor materials, that is, organic electronic devices, have been widely developed, and these organic electronic devices include organic transistors, organic electroluminescence, organic solar cells, organic semiconductor lasers, and the like. . In order for organic electronic devices to be used at a practical level, it is necessary for organic semiconductor layers made of organic semiconductor materials to exhibit stable charge mobility over a wide operating temperature range, and to easily form a uniform thin film over a wide area. It is necessary to be able to produce it. In particular, it is desirable that film formation by coating formation is possible instead of conventional film formation by vapor deposition or the like, and that the characteristic stability in the environment during film formation is excellent. Such an organic electronic device is promising as a technique for forming an integrated circuit on a glass or plastic substrate at a low cost.

  Hitherto, polymer compounds useful as organic semiconductor materials that can be formed by coating have been proposed. For example, polythiophenes such as poly (3-hexylthiophene) are known. Since these polymer compounds have some solubility in organic solvents, there is an advantage that film formation using various coating and printing means is possible.

  However, an organic semiconductor layer formed of polythiophenes such as poly (3-hexylthiophene) has a drawback that it is easily oxidized by oxygen in the atmosphere exposed during the film forming process. An organic transistor having an oxidized organic semiconductor layer has a problem that an off-current increases and an on / off ratio decreases. For such a problem, for example, Patent Document 1 proposes poly [5,5′-bis (3-dodecyl-2-thienyl) -2,2′-dithiophene]. Since this polymer compound is soluble in an organic solvent, it is possible to form a film using various coating and printing means, and it is difficult to oxidize and to prevent problems due to oxidation. However, there is a problem that the device lifetime has not reached the practical level.

For example, in organic electroluminescence, Patent Documents 2 to 5 propose using a phenazacillin derivative for an organic semiconductor layer (charge transport layer) as an organic semiconductor material that can be formed by coating. However, there is a problem that the practical use level has not been reached with respect to solubility and heat resistance in organic solvents.
JP 2003-221434 A JP 2000-313739 A JP 2001-316457 A JP 2002-069161 A JP 2002-275249 A

  Organic semiconductor materials that can form organic transistors that can be used in large-area flexible displays, etc., and organic transistors that can be used in displays such as LCDs and electronic papers at practical levels are easily soluble in solvents. It is desirable to be able to form a coating solution, to have stable characteristics in the environment during film formation, and to be able to form a film that exhibits stable charge mobility over a wide range of operating temperatures including normal temperature. Development of satisfactory organic semiconductor materials is expected.

  The present invention provides a new polymer compound that solves the above-mentioned conventional problems, and an object of the present invention is to provide an organic semiconductor that is excellent in stability in an environment during film formation and can be easily formed by coating or the like. To provide materials. Another object of the present invention is to provide an organic electronic device made of such an organic semiconductor material.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer compound is soluble in an organic solvent and has no cohesiveness, and can form a uniform thin film. Thus, it was found that an organic electronic device having excellent charge mobility and high heat resistance was obtained, and the present invention was completed.

That is, the present invention provides the following [1] to [10].
[1] A polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.

（式中、Ｒ^１、Ｒ^２、Ｒ^４〜Ｒ^９は、各々独立して水素原子もしくは互いに同一であっても異なっていてもよい置換基（ただし、スルホ基、カルボキシル基、ホスホリル基及びヒドロキシル基を除く）を示す。Ｒ^１とＲ^２は互いに結合して環を形成してもよい。Ｒ^３は炭素数１以上の無置換もしくは置換されてもよい一価のアルキル基を示す。ただし、Ｒ^３で表されるアルキル基上の置換基としてアミノ基及びアリール基を除く。）

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. )

[2] In the general formula (1), R ¹ and R ² are unsubstituted or substituted monovalent linear or branched alkyl groups having 1 to 6 carbon atoms, or unsubstituted 3 to 8 carbon atoms. Alternatively, the polymer compound according to [1], which is a cyclic alkyl group which may be substituted.
[3] In the general formula (1), R ¹ and R ² are aryl groups, and R ³ is a monovalent alkyl group having 2 or more carbon atoms which may be unsubstituted or substituted. Molecular compound.
[4] In the general formula (1), one of R ¹ and R ² is an aryl group, and the other is an unsubstituted or optionally substituted monovalent linear or branched alkyl group having 1 to 6 carbon atoms. The polymer compound according to [1].
[5] An organic semiconductor material comprising the polymer compound according to any one of [1] to [4].
[6] An organic semiconductor material, which can be used in a state where the polymer compound according to any one of [1] to [4] is dissolved in an organic solvent.
[7] An organic transistor having an organic semiconductor layer, wherein the organic semiconductor layer contains at least one polymer compound according to any one of [1] to [4].
[8] Organic electroluminescence obtained by sandwiching at least one layer containing at least one polymer compound according to any one of [1] to [4] between a pair of electrodes.
[9] An organic solar battery comprising an organic thin film layer disposed between a pair of electrodes, wherein the organic thin film layer contains at least one polymer compound according to any one of [1] to [4]. Organic solar cell.

  [10] The method for producing a polymer compound according to [1], wherein the phenazacillin compound represented by the general formula (2) is polymerized using a nickel catalyst.

（式中、Ｒ^１、Ｒ^２、Ｒ^４〜Ｒ^９は、各々独立して水素原子もしくは互いに同一であっても異なっていてもよい置換基（ただし、スルホ基、カルボキシル基、ホスホリル基及びヒドロキシル基を除く）を示す。Ｒ^１とＲ^２は互いに結合して環を形成してもよい。Ｒ^３は炭素数１以上の無置換もしくは置換されてもよい一価のアルキル基を示す。ただし、Ｒ^３で表されるアルキル基上の置換基としてアミノ基及びアリール基を除く。Ｘ^１はハロゲン原子を表す。）

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group as a substituent on the alkyl group represented by R ³ , X ¹ represents a halogen atom.)

  [11] The method for producing a polymer compound according to [1], wherein the phenazacillin compound represented by the general formula (2) and the phenazacillin compound represented by the general formula (3) are polymerized using a palladium catalyst. .

（式中、Ｒ^１、Ｒ^２、Ｒ^４〜Ｒ^９は、各々独立して水素原子もしくは互いに同一であっても異なっていてもよい置換基（ただし、スルホ基、カルボキシル基、ホスホリル基及びヒドロキシル基を除く）を示す。Ｒ^１とＲ^２は互いに結合して環を形成してもよい。Ｒ^３は炭素数１以上の無置換もしくは置換されてもよい一価のアルキル基を示す。ただし、Ｒ^３で表されるアルキル基上の置換基としてアミノ基及びアリール基を除く。Ｘ^１はハロゲン原子を表す。）

（式中、Ｒ^１、Ｒ^２、Ｒ^４〜Ｒ^９は、各々独立して水素原子もしくは互いに同一であっても異なっていてもよい置換基（ただし、スルホ基、カルボキシル基、ホスホリル基及びヒドロキシル基を除く）を示す。Ｒ^１とＲ^２は互いに結合して環を形成してもよい。Ｒ^３は炭素数１以上の無置換もしくは置換されてもよい一価のアルキル基を示す。ただし、Ｒ^３で表されるアルキル基上の置換基としてアミノ基及びアリール基を除く。Ｘ^２はボロン酸基、ボロン酸エステル基、もしくはトリアルキルスタニル基を表す。）

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group as a substituent on the alkyl group represented by R ³ , X ¹ represents a halogen atom.)

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. X ² represents a boronic acid group, a boronic acid ester group, or a trialkylstannyl group.

  According to the present invention, it is possible to provide a polymer compound that is soluble in an organic solvent, has no cohesiveness, and can form a uniform thin film. In addition, a polymer compound suitable for an organic electronic device and an organic electronic device having excellent charge mobility and high heat resistance can be provided.

Hereinafter, the present invention will be described in detail.
The polymer compound of the present invention is a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. )

In the general formula (1), R ¹ , R ² , and R ^{4 to} R ⁹ each independently include a hydrogen atom or a substituent that may be the same as or different from each other.

R ¹ , R ² , and R ^{4 to} R ⁹ include a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms. Group or an aryl group having 4 to 20 carbon atoms which may be unsubstituted or substituted.
R ¹ , R ² , R ^{4 to} R ⁹ are preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or unsubstituted or substituted having 4 to 20 carbon atoms. Represents an aryl group, more preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an unsubstituted or substituted aryl group having 4 to 10 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl Group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3, 5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexyl Heptyl group, n-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, cyclohexylmethyl group, ( 1-isopropylcyclohexyl) methyl group, 2-cyclohexylethyl group, bornel group, isobornel group, 1-norbornyl group, 2-norbornanemethyl group, 1-bicyclo [2.2.2] octyl group, 1-adamantyl group, 3 -Noradamantyl group, 1-adamantylmethyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl Group, 2,5-di Tilcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2, 6-diisopropylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclo Tetradecyl group,

Methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3 -(N-hexyloxy) propyl group, 3- (2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (n- Decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n -Propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyl Xylbutyl, 4-n-decyloxybutyl, 4-n-dodecyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-n-propoxypentyl, 6-ethoxyhexyl, 6-iso Propoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8 -Methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, tetrahydrofurfuryl group,
2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 2-allyloxyethyl group, 2- (4′-pentenyloxy) ethyl group, 3-allyloxypropyl group, 3- (2′-hexenyloxy) propyl group, 3- (2′-heptenyloxy) propyl group, 3 -(1'-cyclohexenyloxy) propyl group, 4-allyloxybutyl group,

Benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- (4 ′) -Fluorobenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (Benzyloxymethoxy) ethyl group, 2- (4′-methylbenzyloxymethoxy) ethyl group,
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxy Sibutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- (2 ′ -Phenyloxyethoxy) butyl group,
n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2- (2 ′ -Methoxyethylthio) ethyl group, 4- (3'-ethoxypropylthio) butyl group, 2- (2'-ethylthioethylthio) ethyl group, 2-allylthioethyl group, 2- N-dithioethyl group, 3- (4′-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2- (2′-benzyloxyethylthio) ethyl group, 3- (3′-benzylthiopropylthio) propyl group ,
2-phenylthioethyl group, 2- (4′-methoxyphenylthio) ethyl group, 2- (2′-phenyloxyethylthio) ethyl group, 3- (2′-phenylthioethylthio) propyl group,

Fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, difluoromethyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro -N-propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n -Decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro-n-tetradecyl group, 1 1-dihydro-perfluoro-n-hexadecyl group, perfluoro-n-hexyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chloro Octyl group, 2,2,2-trichloroethyl group,
2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, 5-hydroxyheptyl group, 8-hydroxyoctyl group, 10- Examples thereof include a linear, branched or cyclic alkyl group which may be unsubstituted or substituted, such as a hydroxydecyl group, a 12-hydroxydodecyl group and a 2-hydroxycyclohexyl group.
Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include linear, branched or cyclic alkoxy groups derived from the above-described alkyl group.

Examples of the unsubstituted or substituted aryl group having 4 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-phenyl-1-naphthyl group, and a 6-phenyl-2-naphthyl group. Group, 2-anthracenyl group, 9-anthracenyl group, 9-methyl-10-anthracenyl group, 9-phenyl-10-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 9-methyl-10-phenanthryl group, 9-phenyl-10-phenanthryl group, 1-methyl-9-phenanthryl group, 1-phenyl-9-phenanthryl group, 2-methyl-9-phenanthryl group, 2-phenyl-9-phenanthryl group, 1,8-dimethyl-9-phenanthryl group, 1,8 Diphenyl-9-phenanthryl group, 2-chloro-9-phenanthryl group, 2-fluoro-9-phenanthryl group, 2,7-dichloro-9-phenanthryl group, 2,7-dimethyl-9-phenanthryl group, 2,7 -Diphenyl-9-phenanthryl group, 2,7,9-trimethyl-10-phenanthryl group, 2,7,9-triphenyl-10-phenanthryl group, 1,2,3,4-tetrahydronaphthalen-6-yl group ,
1-pyrenyl group, 2-pyrenyl group, 1-phenyl-2-pyrenyl group, 1-methyl-2-pyrenyl group, 2-phenyl-1-pyrenyl group, 2-methyl-1-pyrenyl group, 4,5- Dimethyl-1-pyrenyl group, 6-phenyl-1-pyrenyl group, 6-methyl-1-pyrenyl group, 6-tert-butyl-1-pyrenyl group, 6-cyclohexyl-1-pyrenyl group, 7-phenyl-1 -Pyrenyl group, 7-methyl-1-pyrenyl group, 7-phenyl-2-pyrenyl group, 7-methyl-2-pyrenyl group, 7-tert-butyl-2-pyrenyl group, 1,8-diphenyl-2- Pyrenyl group, 1,8-dimethyl-2-pyrenyl group, 5,9-dicyclohexyl-2-pyrenyl group, 3,6-diphenyl-1-pyrenyl group, 3,6-dimethyl-1-pyrenyl group, 3,6 -Di-tert-butyl-1-pyret Nyl group, 8-methyl-1-pyrenyl group, 8-tert-butyl-1-pyrenyl group, 8-phenyl-1-pyrenyl group, 9-phenyl-1-pyrenyl group, 9-phenyl-2-pyrenyl group, 9-methyl-2-pyrenyl group, 10-phenyl-1-pyrenyl group, 10-methyl-1-pyrenyl group, 10-phenyl-2-pyrenyl group, 10-methyl-2-pyrenyl group, 9-methyl-1 -Pyrenyl group, 3,6,8-trimethyl-1-pyrenyl group, 3,6,8-triphenyl-1-pyrenyl group, 3,6-dimethyl-8-phenyl-1-pyrenyl group, 9,10- Dimethyl-1-pyrenyl group, 9,10-diphenyl-1-pyrenyl group, 4,9-dimethyl-1-pyrenyl group, 4,9-diphenyl-1-pyrenyl group, 9,5-dimethyl-2-pyrenyl group 4,5,9,10-teto Methyl-2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, 4-quinolinyl group, 3-quinolinyl group, 2-quinolinyl group, 1-phenyl-isoquinolin-3-yl group, 2-phenyl-7-naphthyridinyl group, 2-phenanthrolinyl group, 4-pyridinyl group, 3-pyridinyl group, 2- Pyridinyl group, 2-phenyl-5-pyridyl group, 2-phenyl-4-pyridyl group, 2,5-diphenyl-4-pyridyl group, 2- (2′-pyridyl) -5-pyridyl group, 2,5- Di (2′-pyridyl) -4-pyridyl group, 2-ethyl-6-phenyl-4-pyridyl group, 2,3,4-triphenyl-6-pyridyl group, 3-ethyl-4-pyridyl group, 2 - Midinyl group, 2-phenyl-5-pyrimidinyl group, 2- (2 ′, 6′-dimethylphenyl) -5-pyrimidinyl group, 4,5-diphenyl-2-pyrimidinyl group, 2-pyridazinyl group, 2-pyrazinyl group 4,6-diphenyl-1,3,5-triazin-2-yl group, 4,6-di (2′-naphthyl) -1,3,5-triazin-2-yl group, 4,6-di (1′-naphthyl) -1,3,5-triazin-2-yl group, 3-furanyl group, 2-furanyl group, 3-thienyl group, 2-thienyl group, 2-benzofuranyl group, 2-benzothiophenyl Group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4- ethyl Phenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 2-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tertbutylphenyl group, 4-n- Pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 3-n-hexylphenyl group, 4- (2'-ethylbutyl) Phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2′-ethylhexyl) phenyl group, 4-tert-octyl Phenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl Group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2, 4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobuty Phenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2 -Methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group,

4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl Group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n- Pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-nepentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2 '-Ethylbutyloxy) phenyl group, 4-n-octyloxyphenyl group, 4-n-de Siloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy -1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy- 2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 2-methyl-4-methoxyphenyl group, 2-methyl -5-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl Group, 2-phenyloxyphenyl group, 3-phenyloxyphenyl group, 4-phenyloxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 3 , 5-diphenylphenyl group, 2,4-diphenylphenyl group, 2,3-diphenylphenyl group, 2,5-diphenyl Phenyl group, 3,4-diphenylphenyl group, 2,4,6-triphenylphenyl group, 3,4,5-triphenylphenyl group, 2,4,5-triphenylphenyl group, 2- (2′- Pyridyl) phenyl group, 3- (2′-pyridyl) phenyl group, 4- (2′-pyridyl) phenyl group, 4- (4′-methylphenyl) phenyl group, 4- (3′-methylphenyl) phenyl group 4- (4′-methoxyphenyl) phenyl group, 4- (4′-n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4- (4′-chlorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 2-ethyl-4-phenylphenyl group, 3-fluoro-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, 2- (1′-naphthyl) phenyl 2- (2′-naphthyl) phenyl group, 3- (1′-naphthyl) phenyl group, 3- (2′-naphthyl) phenyl group, 4- (1′-naphthyl) phenyl group, 4- (2 ′ -Naphthyl) phenyl group, 4- (2'-naphthyl) -1-naphthyl group, 2-phenyl-1-naphthyl group, 1-phenyl-2-naphthyl group, 4- (1'-naphthyl) -1-naphthyl Group, 6- (2′-naphthyl) -2-naphthyl group, 6- (1′-naphthyl) -2-naphthyl group, 6-N, N-diphenylamino-2-naphthyl group, 4-N, N— Diphenylamino-1-naphthyl group, 4-cyanophenyl group, 3-cyanophenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2- Chlorophenyl group, 4-bromoph An phenyl group, a 3-bromophenyl group, a 2-bromophenyl group, a 4-chloro-1-naphthyl group, a 4-chloro-2-naphthyl group, a 6-bromo-2-naphthyl group, a 2,3-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5- Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6- Dichloro-2-naphthyl group, 2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, -Fluoro-4-methylphenyl group, 2-methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2 -Chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-methyl-4-chlorophenyl group, 2-chloro- 4,6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3- Fluoro-4-ethoxyphenyl group, 3-chloro-4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6 Chlorophenyl group, 5-chloro-2,4-dimethoxyphenyl group, 3-N, N-diphenylaminophenyl group, 4-N, N-diphenylaminophenyl group, 9,9-dimethyl-9H-fluoren-2-yl Group, 9,9-diethyl-9H-fluoren-2-yl group, 9,9-di-n-hexyl-9H-fluoren-2-yl group, 9,9-di-n-octyl-9H-fluorene- 2-yl group, 9,9-diphenyl-9H-fluoren-2-yl group, 9,9-dicyclohexyl-9H-fluoren-2-yl group, 9,9-dibenzyl-9H-fluoren-2-yl group, 7-N, N-diphenylamino-9,9-dimethyl-9H-fluoren-2-yl group, dibenzofuran-2-yl group, dibenzofuran-4-yl group, dibenzofuran-3-yl group, Examples thereof include a dibenzofuran-2-yl group, a dibenzothiophen-4-yl group, a dibenzothiophen-3-yl group, and a dibenzothiophen-2-yl group.

The polymer compound of the present invention is required to have high heat resistance against heat generated during the process or when an element such as an organic electronic device is moved. From the viewpoint of heat resistance, in the general formula (1), R ¹ and R ² may be a monovalent alkyl group having 1 to 6 carbon atoms which may be unsubstituted or substituted, and examples thereof include a methyl group and an ethyl group. N-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1- Methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, cyclobutyl group, cyclopentyl group, 4-methylcyclopentyl group, cyclohexyl group, cyclooctyl group, methoxymethyl group, ethoxy Examples thereof include linear, branched or cyclic alkyl groups such as methyl group and n-butoxymethyl group.
R ¹ and R ² may be bonded to each other to form a ring, and when R ¹ and R ² are combined to form a ring, they may be unsubstituted or substituted having 3 to 8 carbon atoms. It is preferable to form a cyclic alkyl group.

Alternatively, the polymer compound of the present invention is required to have high charge mobility in an organic electronic device. In general, the longer the π conjugate length of the main chain, the higher the charge mobility. Therefore, from the viewpoint of charge mobility, in general formula (1), R ¹ and R ² are preferably aryl groups, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, 2 -Anthracenyl group, 9-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-fluoro-9-phenanthryl group, 1-biphenyleneyl group, 2 -Biphenyleneyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 5-acenaphthylenyl group, 3-fluoranthenyl group, 1-triphenylenyl group, 2-triphenylenyl group, 1-naphthacenyl Group, 2-naphthacenyl group, 9-naphthacenyl group, 3-perylenyl group, 4-quinolyl group, 2 Quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrazinyl group, 3- Furyl, 2-furyl, 2-benzofuryl, 4-dibenzofuranyl, 2-dibenzofuranyl, 3-thienyl, 2-thienyl, dibenzothiophen-4-yl, dibenzothiophen-2- Yl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzoimidazolyl group, carbazol-3-yl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, Examples thereof include substituted or unsubstituted aryl groups such as m-terphenyl-4-yl group and m-terphenyl-3-yl group. Further, in the general formula (1), when R ¹ and R ² are aryl groups, R ³ may be an unsubstituted or optionally substituted monovalent alkyl group having 2 or more carbon atoms, preferably A monovalent alkyl group having 2 to 20 carbon atoms which may be unsubstituted or substituted is preferable. Examples of R ³ include linear, branched or cyclic alkyl groups having 2 to 20 carbon atoms, which are exemplified as specific examples of R ¹ , R ² and R ^{4 to} R ⁹ .

Next, in the general formula (1), R ³ includes a monovalent alkyl group having 1 or more carbon atoms which may be unsubstituted or substituted. The monovalent alkyl group is not particularly limited, but is an unsubstituted or substituted linear, branched or cyclic monovalent alkyl group such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4- Methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3 5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n -Hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc. .
Examples of the substituent on the monovalent alkyl group of R ³ include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms.
As a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms exemplified as specific examples of R ¹ , R ² and R ^{4 to} R ⁹ And linear, branched or cyclic alkoxy groups derived from
Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, β-methylphenethyl group, and α, α-dimethylbenzyl group. , Α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-ethylbenzyl group, 2-ethylbenzyl group, 4-isopropylbenzyl group 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4-tert-octylbenzyl group, 4-allyl Benzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4- (4′-methylphenyl) ) Benzyl group, 4-methoxybenzyl group, 2-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-heptyloxybenzyl group, 4-n-decyloxybenzyl group, 4- n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutoxymethylbenzyl group, 4-allyloxybenzyl group, 4- Vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl group, 4-phenyloxybenzyl group, 3-phenyloxybenzyl group,
4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl And an aralkyl group such as a group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group.
However, it is preferable to remove an amino group and an aryl group as a substituent on the alkyl group represented by R ³ .

  Further, the number average molecular weight of the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain is not particularly limited, but is 1000 to 1000000 in terms of polystyrene. Preferably it is 3000-500000. More preferably, it is 4000-200000.

  In addition, a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain has a terminal functional group substituted or unsubstituted carbocyclic aromatic group, disubstituted amino group, The terminal treatment may be performed by substitution with a chain, branched or cyclic alkyl group, an alkyloxy group having a linear, branched or cyclic alkyl group, a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, or the like.

  Specific examples of the polymer compound represented by the general formula (1) of the present invention are illustrated below, for example, but the present invention is not limited to these specific examples.

Next, the manufacturing method of the high molecular compound which has at least one repeating unit represented by General formula (1) of this invention in a polymer chain is demonstrated.
The polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain is produced, for example, by polymerizing the phenazacillin compound represented by the general formula (2) using a nickel catalyst. can do.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group as a substituent on the alkyl group represented by R ³ , X ¹ represents a halogen atom.)

In the general formula ^{(2), R 1, R} 2, R 4 ~R 9 are respectively the same as ^{R 1, R 2, R 4} ~R 9 in the general formula (1) described above.

Next, in the general formula (2), R ³ are each the same as R ³ in the general formula (1) described above.
In the general formula (2), X ¹ represents a halogen atom. Examples of the halogen atom for X ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain is represented by, for example, the phenazacillin compound represented by the general formula (2) and the general formula (3). The phenazacillin compound produced can be polymerized using a palladium catalyst.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. X ² represents a boronic acid group, a boronic acid ester group, or a trialkylstannyl group.

In the general formula ^{(3), R 1, R} 2, R 4 ~R 9 are respectively the same as ^{R 1, R 2, R 4} ~R 9 in the general formula (1) described above.

Next, in the general formula (3), R ³ are each the same as R ³ in the general formula (1) described above.
In the general formula (3), X ² represents a boronic acid group, a boronic acid ester group, or a trialkylstannyl group.

The polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in the polymer chain can be used as an organic semiconductor material.
As an organic semiconductor material, it is suitable for organic electroluminescent material, organic transistor material, and organic solar cell material.

Further, the polymer compound of the present invention can be used in a state dissolved in an organic solvent.
Organic solvents include hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene and other hydrocarbon solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents, dichloromethane, chloroform, tetrachloromethane Halogenated hydrocarbon solvents such as dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol, pentanol, Alcohol solvents such as hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, fluorine-containing alcohol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide A polar solvent such as can be used.
These organic solvents may be used alone or in combination.

In organic electronic devices, organic semiconductor materials are required to have high heat resistance. As an index indicating the heat resistance of the organic semiconductor material, a glass transition temperature can be given. The glass transition temperature tends to be higher as the alkyl chain length of R ¹ and R ² is shorter. Therefore, in the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, the one having a smaller number of carbon atoms in the alkyl groups of R ¹ and R ² is excellent in heat resistance.
In organic electronic devices, organic semiconductor materials are required to have high charge mobility. In this organic semiconductor material, generally, the longer the π-conjugated length of the main chain, the higher the charge mobility. Therefore, in the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, it is more chargeable that R ¹ or R ² is an aryl group and the π conjugate length of the main chain is increased. Excellent mobility.
Furthermore, in an organic electronic device, the organic semiconductor material is required to have excellent solubility. In the polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain, it is generally more soluble that R ^{1 to} R ⁹ are long chains or branched chains. Is excellent.

Although said glass transition temperature can be evaluated using well-known techniques, such as DSC (differential scanning calorimetry) and TMA (thermomechanical analysis), it evaluated using the method of DSC.
The charge mobility can be evaluated using a known technique such as an FET method (electric field transistor), a time-of-flight method, or an SCLC (space charge limited current method). Evaluated.

  According to the present invention, it is possible to obtain a polymer compound that is soluble in an organic solvent, has no cohesiveness, and can form a uniform thin film. In addition, a polymer compound suitable for an organic electronic device and an organic electronic device having excellent charge mobility and high heat resistance can be obtained.

Next, the organic transistor of the present invention will be described.
The organic transistor of the present invention includes at least one layer containing at least one polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in a polymer chain between a pair of electrodes. It is something that is sandwiched.

Embodiments of the organic transistor of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of the organic transistor of the present invention.
In the form of this organic transistor, a gate electrode 21 is provided on a substrate 11, a gate insulating layer 31 is laminated on the gate electrode, and a source electrode 61 and a drain electrode formed on the gate electrode at predetermined intervals. 41 is formed, and an organic semiconductor layer 51 is further stacked thereon (bottom gate / bottom contact structure).

  In the form of the organic transistor shown in FIG. 2, the gate electrode 22 is provided on the substrate 12, the gate insulating layer 32 is laminated on the gate electrode, and the organic semiconductor layer 52 is laminated thereon. Further, a source electrode 62 and a drain electrode 42 are formed at a predetermined interval thereon (bottom gate / top contact structure).

  In the form of the organic transistor shown in FIG. 3, the source electrode 63 and the drain electrode 43 are formed on the substrate 13 at a predetermined interval, and the organic semiconductor layer 53 is laminated thereon, A gate insulating layer 33 is laminated thereon, and a gate electrode 23 is further provided thereon (top gate / bottom contact structure).

  In the form of the organic transistor shown in FIG. 4, the organic semiconductor layer 54 is laminated on the substrate 14, and the source electrode 64 and the drain electrode 44 are formed on the substrate 14 at a predetermined interval. A gate insulating layer 34 is laminated thereon, and a gate electrode 24 is further provided thereon (top gate / top contact structure).

  In the transistor having such a structure, the organic semiconductor layer forms a channel region, and an on / off operation is performed by controlling a current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode. .

  The organic semiconductor layer containing a polymer compound having at least one repeating unit represented by the general formula (1) in the polymer chain may be subjected to a doping treatment. Doping means introducing an electron accepting molecule (acceptor) or an electron donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the polymer compound of the present invention and a dopant. Either an acceptor or a donor can be used as the dopant used in the present invention.

As the donor dopant in the present invention, any donor dopant can be used as long as it plays the role of donating electrons to the organic compound molecules of the organic semiconductor layer. Particularly suitable examples include alkali metals such as Li, Na, K, Rb, and Cs, alkaline earth metals such as Ca, Sr, and Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, and Tb. , Dy, Ho, Er, Yb, and other rare earth metals, ammonium ions, R ₄ P ⁺ , R ₄ As ⁺ , R ₃ S ⁺ , and acetylcholine.

Any acceptor dopant may be used in the present invention as long as it serves to remove electrons from the organic compound molecules of the organic semiconductor layer. Particularly preferred examples include halogens such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF, Lewis such as PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BC1 ₃ , BBr ₃ and SO _3. Acids, HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H and other protic acids, acetic acid, formic acid, organic acids such as amino acids, FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoCl ₅ , WF ₅ , WCl ₆ , UF ₆ , LnCl ₃ (Lantanoids such as Ln = La, Ce, Nd, Pr, and Y) Transition metal compounds, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₅ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , electrolyte anions such as sulfonate anions, and the like.

  As a method for doping these dopants, it is possible to use either a method in which a thin film of an organic semiconductor is prepared in advance and a dopant is introduced later, or a method in which a dopant is introduced at the time of forming a thin film of an organic semiconductor. As the doping of the former method, gas phase doping using a dopant in a gas state, liquid phase doping in which a solution or liquid dopant is brought into contact with the thin film, and diffusion doping in which a solid state dopant is brought into contact with the thin film Examples of solid phase doping can be given. In liquid phase doping, the efficiency of doping can be adjusted by applying electrolysis. In the latter method, a mixed solution or dispersion of an organic semiconductor compound and a dopant may be simultaneously applied and dried. As other methods, any of chemical doping such as electrochemical doping, photoinitiation doping, and physical doping such as ion implantation can be used.

  The method for forming the organic thin film is not particularly limited, and a conventionally known general thin film forming method can be used. Specifically, dry deposition methods such as vacuum deposition, sputtering, plasma, ionization deposition, ion plating, and cluster ion beam, and solutions such as spin coating, dip coating, flow coating, cast, bar coating, roll coating, and inkjet Any of the coating methods can be applied. The organic semiconductor layer containing the polymer compound of the present invention used in the present organic transistor is preferably applied by a coating method such as dip coating, spin coating, casting, bar coating, roll coating or the like of a solution dissolved in a solvent.

  The film thickness of the organic semiconductor layer in the present invention is not particularly limited, but in general, if the film thickness is too thin, defects such as pinholes are likely to occur, and conversely, if the film thickness is too thick, the channel length may be long depending on the structure of the transistor, In some cases, a high applied voltage is required. In this case, the driving speed and the on / off ratio are reduced. Therefore, it is generally preferable to set in the range of several nm or more and several tens of μm or less, and more preferably 5 nm or more and 1 μm or less.

  Further, the substrate used in the organic transistor of the present invention is not particularly limited, but any substrate may be used. In general, it is possible to use a plastic substrate in addition to a glass such as quartz or a silicon wafer. Furthermore, a composite substrate can also be used for these, and a single layer structure or a multilayer structure may be used. Examples of plastic substrates include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include substrates made of triacetate (TAC), cellulose acetate propionate (CAP), and the like.

  In the organic transistor of the present invention, materials that can be used for the source electrode, the drain electrode, and the gate electrode are not particularly limited as long as they are conductive materials. Indium tin oxide alloy (ITO), tin oxide (NESA) , Indium zinc oxide (IZO), molybdenum oxide, gold, silver, platinum, copper, indium, aluminum, magnesium, nickel, chromium, iron, tin, tantalum, palladium, tellurium, iridium, ruthenium, germanium, tungsten, lithium, beryllium , Sodium, potassium, calcium, zinc, magnesium / indium alloy, magnesium / copper alloy, magnesium / silver alloy, magnesium / aluminum alloy, aluminum / lithium alloy, aluminum / scandium / lithium alloy, sodium / potassium Other metals and alloys such as gold, fluorine-doped zinc oxide, carbon, graphite, glassy carbon, silver paste and carbon paste is used. In particular, platinum, gold, silver, copper, aluminum, indium, ITO and carbon are preferable. In addition, a known conductive polymer whose conductivity is improved by doping or the like, for example, polyaniline, polypyrrole, polythiophene, a complex of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), or the like is also preferably used. Among the source electrode and drain electrode, those having low electrical resistance at the contact surface with the organic thin film layer are preferable.

  As a method for forming an electrode in the organic transistor of the present invention, a method of forming a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material by using a known photolithography method or a lift-off method, aluminum There is a method of etching using a resist such as thermal transfer or ink jet on a metal foil such as copper or copper. Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from a coating film by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.

  Although various insulators can be used as a material used for the insulator layer which is a gate insulating layer in the organic transistor of the present invention, an inorganic oxide or an organic compound having a high relative dielectric constant is particularly preferable. Inorganic oxides include silicon oxide, silicon nitride, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, titanium Strontium acid, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, pentoxide tantalum, titanium dioxide, trioxide yttrium and the like. Of these, silicon oxide, silicon nitride, aluminum oxide, tantalum oxide, and titanium oxide are preferable.

  As a method for forming the inorganic oxide, a dry process such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, Examples include wet processes such as spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, and other coating methods, and printing and inkjet patterning methods. Can be used depending on the material.

  Examples of the organic compound used for the gate insulating layer include polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photo cation polymerization type photo curable resin, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, A novolak resin, polyvinylidene fluoride (PVF), cyanoethyl pullulan, or the like can also be used. As the method for forming the organic compound, the wet process is preferable.

An embodiment of the organic electroluminescence of the present invention will be described.
The organic electroluminescence of the present invention comprises at least a layer containing at least one polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in a polymer chain between a pair of electrodes. It is sandwiched further.

  Organic electroluminescence is usually composed of a single-layer or multilayer organic thin film between a pair of electrodes. In the case of a single-layer element, a light emitting layer is provided between a pair of electrodes. The light emitting layer contains at least one kind of light emitting material, and additionally contains a hole injection / transport material or an electron injection / transport material for transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. Also good. Multi-layer type devices are (A) anode / hole injection / transport layer / light emitting layer / cathode, (B) anode / light emitting layer / electron injection / transport layer / cathode, (C) anode / hole injection / transport layer / light emitting layer. There is an organic electroluminescent element laminated in a multilayer structure of / electron injection / transport layer / cathode. Further, the hole blocking layer is laminated between the light emitting layer and the electron injection / transport layer. (D) Anode / hole injection / transport layer / light emitting layer / hole blocking layer / electron injection / transport layer / cathode. You can also.

  The organic electroluminescence of the present invention is not limited to these element configurations, and each type of element can be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. Further, in each type of device, light emission is performed between the hole injection / transport layer and the light emitting layer, between the hole injection / transport material and the light emitting material, and / or between the light emitting layer and the electron injection / transport layer. A mixed layer of a material and an electron injection / transport material can also be provided.

  The polymer compound of the present invention can be used in any device configuration. The polymer compound of the present invention can also be used as a hole / transport material in a hole / transport layer. The hole / transport material has the function of injecting electrons from the cathode to the organic layer and the function of transporting the injected electrons and injecting them into the light-emitting layer. It can be used for halls and transport layers.

  Since the thin film formed of the polymer compound of the present invention is amorphous, it is advantageous in terms of long-term storage when the thin film is formed, light emission life when the element is driven, and the like. In addition, since the polymer compound of the present invention has good adhesion to the metal electrode and the ionization potential of the thin film is low, it is advantageous for hole injection from the anode. In this case, it is more advantageous to use the polymer compound of the present invention for the hole / transport layer on the ITO electrode (anode) side.

  Here, the hole injection / transport layer, the light emitting layer, or the electron injection / transport layer may be formed of two or more layers.

  The hole injection / transport material has a function of injecting holes from the anode, a function of injecting holes into the light emitting layer or the light emitting material, and an electron injection / transport layer of excitons generated in the light emitting layer or Examples thereof include compounds that prevent movement to an electron injection / transport material and have excellent thin film forming ability. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyarylalkane, stilbene, butadiene, There are benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine, and their derivatives, and conductive polymers such as polyvinylcarbazole, polysilane, polythiophene, and polyaniline. Absent. Hole injection / transport materials may be used alone or in combination.

  Among the hole injection / transport materials that can be used in the organic electroluminescence of the present invention, more effective hole injection / transport materials are aromatic tertiary amine derivatives or phthalocyanine derivatives. Specifically, the aromatic tertiary amine derivatives include triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl. -4,4'-diamine (TPD), 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl (α-NPD), N, N, N ', N'-( 4-methylphenyl) -1,1′-phenyl-4,4′-diamine, N, N, N ′, N ′-(4-methylphenyl) -1,1′-biphenyl-4,4′-diamine N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-(methylphenyl) -N, N ′-(4-n-butyl Phenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tri) Aminophenyl) -4-phenyl - there is cyclohexane, or an oligomer or polymer such as having these aromatic tertiary amine skeletons, though not particularly limited thereto.

Examples of phthalocyanine (Pc) derivatives include H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, VOPc, Examples include, but are not limited to, phthalocyanine derivatives such as TiOPc, MoOPc, GaPc-O-GaPc, and naphthalocyanine derivatives.

  When the polymer compound according to the present invention is used for the hole injecting / transporting layer, the usable electron injecting / transporting material has a function of injecting electrons from the cathode, and injects electrons into the light emitting layer or the light emitting material. And a compound that prevents the excitons generated in the light emitting layer from moving to the hole injection / transport layer or the hole injection / transport material and has an excellent thin film forming ability.

  Specifically, quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadiazole, thiadiazole, tetrazole, Examples include perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives. The electron injection / transport material may be used alone or in combination.

In the organic electroluminescence of the present invention, a more effective electron injection / transport material is a metal complex compound. Among these, for example, organoaluminum complexes represented by the general formulas (a) to (c) are preferable.
(Q) ₃ -Al (a)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand)
(Q) ₂ -Al-OL (b)
(In the formula, Q represents a substituted 8-quinolinolate ligand, OL represents a phenolate ligand, and L represents a hydrocarbon group having 6 to 24 carbon atoms including a phenyl moiety)
(Q) _2- Al-O-Al- (Q) ₂ (c)
(Wherein Q represents a substituted 8-quinolinolate ligand)

Specific examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand include, for example, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl- 8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, bis ( 2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum Bis (2-methyl 8-quinolinolato) (4-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum Bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolato) aluminum, bis (2-methyl-8-quinolinolato) ) (2,6-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenol) Lato) aluminum, bis (2-methyl-8-quinori) Lat) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2 , 4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,4 5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4 -Dimethyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2
, 4-Dimethyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) ) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum -Μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-Methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo -Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) ) Aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum. Of course, these organometallic complexes may be used alone or in combination.

  Examples of the light emitting material or doping material that can be used for the organic electroluminescence of the present invention include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenyl. Butadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, triphenylamine , Benzidine type triphenylamine, styrylamine type triphenylamine, diamine type trif Niruaminpiran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, there are rubrene and derivatives thereof, but is not limited thereto.

  Examples of the light emitting material that can be used for the organic electroluminescence of the present invention include phosphorescent (triplet light emission) compounds. Specifically, tris (2-phenylpyrimidyl) iridium complex, tris [2- (2′-fluorophenyl) pyridyl] iridium complex, bis (2-phenylpyridyl) acetylacetonatoiridium complex, bis [2- (2 ′, 4′-difluorophenyl) pyridyl] acetylacetonatoiridium complex, 2,3,7,8,12,13,17,18-octaethyl-21H, 23H porphyrin platinum complex and the like.

  Suitable conductive materials for use in organic electroluminescent anodes have work functions greater than 4 eV, such as carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and the like These alloys, metal oxides such as indium tin oxide alloy (ITO) and tin oxide (NESA), as well as known conductive polymers such as polythiophene and polypyrrole, such as polyethylenedioxythiophene (PEDOT) and polystyrenesulfonic acid (PSS) Or the like. These conductive materials may be used alone or in combination.

  The anode may have a single layer structure or a multilayer structure.

  The sheet electrical resistance of the anode is preferably set to several hundred Ω / □ or less, more preferably 5Ω / □ or more and 50Ω / □ or less.

  The thickness of the anode is generally set to about 5 nm to 1000 nm, more preferably about 10 nm to 500 nm, although it depends on the conductive material used.

  Conductive materials used for the cathode are suitable to have a work function smaller than 4 eV, such as magnesium, calcium, tin, lead, titanium, yttrium, lithium, lithium fluoride, ruthenium, manganese, and alloys thereof. Used. Examples of the alloy include lithium / indium, magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the heating temperature, atmosphere, and degree of vacuum, and an appropriate ratio is selected. These conductive materials may be used alone or in combination.

  The cathode may have a single layer structure or a multilayer structure.

  The sheet electrical resistance of the cathode is preferably set to several hundred Ω / □ or less.

  Although the thickness of the cathode depends on the conductive material to be used, it is generally set to about 5 nm to 1000 nm, more preferably about 10 nm to 500 nm.

  The formation method of the organic electroluminescence electrode (anode, cathode) according to the present invention is not particularly limited, and a conventionally known general thin film formation method can be used. Specifically, any of dry deposition methods such as vacuum deposition, sputtering, plasma, ionization deposition, ion plating, cluster ion beam, and solution coating methods such as spin coating, dipping, flow coating, casting, bar coating, and inkjet Some methods can be applied.

  In organic electroluminescence, in order to emit light efficiently, it is desirable that at least one is sufficiently transparent in the light emission wavelength region of the device. The substrate is also preferably transparent. The transparent electrode is set so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering using the conductive material. It is desirable that the electrode on the light emitting surface has a light transmittance of 50% or more, preferably 70% or more. The substrate is not limited as long as it has a mechanical and thermal strength and is transparent, but examples thereof include glass substrates, transparent polymers such as polyethylene, polyethersulfone, and polypropylene.

  The organic electroluminescence can be prevented from being reduced in luminance and life due to quenching by having a multilayer structure. If necessary, a light emitting material, a doping material, a hole injecting / transporting material for injecting carriers, and an electron injecting / transporting material can be used in combination. In addition, the hole injection / transport layer, the light emitting layer, and the electron injection / transport layer may each be formed of two or more layers, and an element in which holes or electrons are efficiently injected from the electrode and transported in the layer. A structure is selected.

  The formation method of each layer (hole injection / transport layer, light emitting layer, electron injection / transport layer) of the organic electroluminescence according to the present invention is not particularly limited, and a conventionally known general thin film formation method is used. Is possible. Specifically, any of dry deposition methods such as vacuum deposition, sputtering, plasma, ionization deposition, ion plating, cluster ion beam, and solution coating methods such as spin coating, dipping, flow coating, casting, bar coating, and inkjet Some methods can be applied.

  The film thickness is not particularly limited, but each layer needs to be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. In general, the thickness is preferably about 1 nm to 1 μm, more preferably about 10 nm to 0.2 μm.

  When the layer containing the polymer compound of the present invention is a hole injecting and transporting layer, it is preferable to use a solution coating method as a method for forming the hole injecting and transporting layer. Method, casting method, micro gravure coating method, gravure coating method, bar coating method, wire bar coating method, dip coating method, roll coating method, spray coating method, Langmuir-Blodget method, screen printing method, flexographic printing method, offset Examples thereof include a printing method and an inkjet printing method.

  Moreover, as a formation method of a light emitting layer, a vacuum evaporation method, an ionization evaporation method, or a solution coating method can be used. When the light emitting layer contains the polymer compound of the present invention or when it contains a polymer compound having a light emitting function, the light emitting layer is preferably formed using a solution coating method. When the light emitting layer contains a compound having a light emitting function, it can be formed by using a vacuum vapor deposition method, an ionization vapor deposition method, or a solution coating method. Furthermore, as a method for forming the electron injecting and transporting layer, a vacuum deposition method, an ionization deposition method or a solution coating method can be used.

  When forming each layer using the solution coating method, the material for forming each layer or the material and the binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of binder resins that can be used in the hole injection / transport layer, light emitting layer, and electron injection / transport layer include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, and polymethyl. Examples thereof include insulating polymers such as methacrylate, polymethyl acrylate, and cellulose, photoconductive polymers such as polyvinyl carbazole (PVK) and polysilane, and conductive polymers such as polythiophene, polypyrrole, and polyaniline. Binder resins may be used alone or in combination.

  When forming each layer using the solution coating method, the material for forming each layer or the material and binder resin are carbonized with an appropriate organic solvent (for example, hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, etc.). Hydrogen solvents, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, for example, halogenated carbonization such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene Hydrogen solvents, for example, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol Alcohol solvents such as methyl cellosolve, ethyl cellosolve, ethylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2 A polar solvent such as pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide) and / or water can be dissolved or dispersed to form a coating solution, and a thin film can be formed by various coating methods.

  The dispersing method is not particularly limited, and for example, it can be dispersed in the form of fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like.

  The concentration of the coating solution is not particularly limited, and can be set to a concentration range suitable for forming a desired thickness by a coating method to be performed. In general, the solution concentration is about 0.1 wt% or more and 50 wt% or less, preferably about 1 wt% or more and 30 wt% or less. In the case of using a binder resin, the amount used is not particularly limited, but in general, the material for forming each layer (in the case of forming a single-layer element, the total amount of each component). E) 5 wt% or more and 99.9 wt% or less, preferably 10 wt% or more and 99.9 wt% or less, more preferably 15 wt% or more and 90 wt% or less.

  It is preferable to provide a protective layer (sealing layer) for the purpose of preventing contact with oxygen and moisture on the fabricated device, and in the device inert material (for example, paraffin, liquid paraffin, silicon oil, Fluorocarbon oil, zeolite-containing fluorocarbon oil, etc.) can be enclosed and protected.

  As a material used for the protective layer, for example, an organic polymer material (for example, fluorinated resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyphenylene oxide), inorganic materials (for example, diamond thin films, amorphous silica, electrically insulating glass, metal oxides, metal nitrides, metal carbonides, metal sulfides), and photocurable resins. Moreover, the material used for a protective layer may be used independently, or may be used together. The protective layer may have a single layer structure or a multilayer structure.

  The organic electroluminescence of the present invention can usually be used as a direct current drive type element, but can also be used as an alternating current drive type element. Further, the organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or an MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. The organic electroluminescent element of the present invention includes a panel-type light source (for example, a backlight for a clock, a liquid crystal panel, etc.), various light-emitting elements (for example, an alternative to a light-emitting element such as an LED), and various display elements [for example, information display Element (PC monitor, mobile phone / mobile terminal display element)], various signs, various sensors, and the like.

An embodiment of the organic solar cell of the present invention will be described.
The organic solar cell of the present invention comprises at least a layer containing at least one polymer compound having at least one repeating unit represented by the general formula (1) of the present invention in a polymer chain between a pair of electrodes. It is sandwiched further.
The organic solar cell of the present invention is usually composed of a single-layer or multilayer organic thin film between a pair of electrodes. In the case of a single-layer element, an active layer is provided between a pair of electrodes. Here, the active layer is formed by mixing at least an organic p-type semiconductor and an organic n-type semiconductor. The multilayer element includes (A) electrode / organic p-type semiconductor layer / active layer / electrode, (B) electrode / active layer / organic n-type semiconductor layer / electrode, and (C) electrode / organic p-type semiconductor layer / active layer. There are organic solar cells stacked in a multilayer configuration of: / organic n-type semiconductor layer / electrode. Here, the organic p-type semiconductor layer or the organic n-type semiconductor layer may be formed of two or more layers.

  The polymer compound of the present invention can be used in any device configuration. The polymer compound of the present invention can be used as a hole transport material in either the active layer or the organic p-type semiconductor layer. The hole transport material of the present invention has a function of injecting holes from the active layer into the organic p-type semiconductor layer and a function of transporting the injected holes and injecting them into the electrode, so that there are two or more organic p-type semiconductor layers. Even in this case, it can be used for any organic n-type and p-type semiconductor layers.

  When the compound according to the present invention is used in the active layer, examples of the organic p-type semiconductor that can be used include compounds having a function of transporting holes from the active layer and a function of injecting holes into the electrode. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyarylalkane, stilbene, butadiene, There are benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, etc. and their derivatives, and conductive polymers such as polyvinylcarbazole (PVK), polysilane, polythiophene, and polyaniline. It is not something. Organic p-type semiconductors may be used alone or in combination.

  Examples of the organic n-type semiconductor include compounds having a function of transporting electrons from the active layer and a function of injecting electrons into the electrode. Specifically, quinoline metal complex, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, 2,4,7-trinitrofluorenone, anthraquinodimethane, diphenoquinone, naphthoquinone, anthraquinone, stilbenequinone, thiopyran Examples include, but are not limited to, dioxide, oxadiazole, thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, fullerene, silole, and the like. Organic n-type semiconductors may be used alone or in combination.

  The formation method of the organic-semiconductor layer in the organic solar cell of this invention is not specifically limited, It is possible to use a conventionally well-known general thin film formation method. Specifically, any of dry deposition methods such as vacuum deposition, sputtering, plasma, ionization deposition, ion plating, cluster ion beam, and solution coating methods such as spin coating, dipping, flow coating, casting, bar coating, and inkjet Some methods can be applied.

  The film thickness of the organic semiconductor layer in the organic solar cell of the present invention is not particularly limited, but in general, if the film thickness is too thin, the light absorption efficiency decreases, and conversely, if it is too thick, carriers generated in the active layer are transported to the electrode. In some cases, the conversion efficiency is lowered. Therefore, it is usually preferable to set the film thickness in the range of several nm to 1 μm.

  The method for forming the organic thin film in the organic solar cell of the present invention is not particularly limited, and a conventionally known general thin film forming method can be used. Specifically, dry deposition methods such as vacuum deposition, sputtering, plasma, ionization deposition, ion plating, and cluster ion beam, and solutions such as spin coating, dip coating, flow coating, cast, bar coating, roll coating, and inkjet Any of the coating methods can be applied. The organic semiconductor layer containing the polymer compound of the present invention used in the present organic solar cell is preferably applied by a coating method such as dip coating, spin coating, casting, bar coating, or roll coating of a solution dissolved in a solvent.

  When forming each layer using the solution coating method, the material for forming each layer or the material and the binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of binder resins that can be used in the organic p-type semiconductor layer, active layer, and organic n-type semiconductor layer include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, and polymethyl. Examples thereof include insulating polymers such as methacrylate, polymethyl acrylate, and cellulose, photoconductive polymers such as polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, and polyaniline. Binder resins may be used alone or in combination.

  When forming each layer using the solution coating method, the material for forming each layer or the material and binder resin are carbonized with an appropriate organic solvent (for example, hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, etc.). Hydrogen solvents, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, for example, halogenated carbonization such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene Hydrogen solvents, for example, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol Alcohol solvents such as methyl cellosolve, ethyl cellosolve, ethylene glycol, for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2 A polar solvent such as pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide) and / or water can be dissolved or dispersed to form a coating solution, and a thin film can be formed by various coating methods.

    The dispersing method is not particularly limited, and for example, it can be dispersed in the form of fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like.

  As a material that can be used for the electrode in the present invention, an electrode material having a high work function and an electrode material layer having a low work function are used in combination. By combining an electrode material layer having a high work function and an electrode material layer having a low work function, a built-in electric field can be applied to the organic thin film. Examples of electrode materials having a large work function include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and alloys thereof, indium tin oxide alloy (ITO), tin oxide (NESA), etc. Typical examples include metal oxides, and known conductive polymers such as polythiophene and polypyrrole, such as complexes of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), but are not limited thereto. Absent. These electrode materials may be used alone or in combination.

  As an electrode material having a small work function, magnesium, calcium, tin, lead, titanium, yttrium, lithium, lithium fluoride, ruthenium, manganese, or an alloy thereof is used. Examples of the alloy include lithium / indium, magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the heating temperature, atmosphere, and degree of vacuum, and an appropriate ratio is selected. These electrode materials may be used alone or in combination.

  Although the film thickness of an electrode is based also on the electroconductive material to be used, it is 1 nm or more and 500 nm or less normally, Preferably it is 10 nm or more and 200 nm or less. If the film thickness is too thin, the sheet resistance of the electrode becomes too large, and the generated photocharge cannot be sufficiently transmitted to the external circuit. If it is too thick, the transmittance of the irradiated light is deteriorated, so that the conversion efficiency is lowered.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example.
(Example 1)

Under a nitrogen stream, bis (1,5-cyclooctadiene) nickel (2.19 g, 7.98 mmol), 1,5-cyclooctadiene (1 mL), and 2,2′-bipyridyl (1.25 g, 7.98 mmol) was suspended in toluene (60 mL), heated to 60 ° C., and stirred for 1 hour. Subsequently, 2,8-dibromo-5,10-dihydro-10,10-di-n-hexyl-5-methylphenazacillin (3.00 g, 5.58 mmol) was added, followed by stirring at 60 ° C. for 14 hours. did. Further, bromobenzene (175 mg, 1.10 mmol) was added, the reaction was stirred for 3.5 hours, the reaction was filtered through Celite, and the filtrate was concentrated under reduced pressure to give a colorless transparent oil (30 g). It was. This colorless transparent oil was discharged into methanol, and the precipitate was collected by filtration to obtain a white solid (28 g). This white solid was washed with 2M hydrochloric acid (200 mL), methanol (200 mL) and hexane (200 mL) in this order, and dried under reduced pressure at 70 ° C. to obtain poly (5,10-dihydro-10,10-di-n-hexyl). 1.83 g of (-5-methylphenazacillin) was obtained as a white solid.
Molecular weight: 36600
In this example, the glass transition temperature Tg of the polymer compound was evaluated using a DSC method. When the temperature elevation rate was measured at 10 ° C./min, a value of Tg = 130.1 ° C. was obtained. The glass transition temperature of this example was higher than that of the conventional compound.

(Example 2)
Ultrasonic cleaning of patterned glass substrate with 150 nm thick ITO transparent electrode (sputtered film product; sheet resistance 15 Ω) with neutral detergent, semi-coclean (Furuuchi Chemical), ultrapure water, acetone, isopropyl alcohol After washing in this order, it was dried with nitrogen blow, and finally ultraviolet ozone cleaning was performed. Next, PEDOT / PSS (Formula 4) was formed into a film with a thickness of 65 nm by spin coating, and dried under reduced pressure (200 degrees, 1 hour) on a hot plate to form a first hole injecting and transporting layer. Next, a toluene solution (1.5% by weight) of the polymer compound synthesized in Example 1 was formed into a film having a thickness of 50 nm by spin coating, and heat treatment was performed in a nitrogen atmosphere on a hot plate (180 1 hour), a second hole injection transport layer was formed.

  Next, after rinsing the second hole injecting and transporting layer with toluene, a xylene solution (1.2% by weight) of polyfluorene (formula 5) is formed into a film having a thickness of 60 nm by a spin coating method. A light emitting layer was formed by drying under reduced pressure (140 degrees, 30 minutes) on the plate. Next, the glass substrate is fixed to the substrate holder of the vapor deposition apparatus, lithium fluoride (LiF) is deposited on the light emitting layer, and the film thickness is 0.5 nm at a vapor deposition rate of 0.2 nm / second using a molybdenum boat. Then, aluminum (Al) was heated with a tungsten boat to form an aluminum layer having a thickness of 100 nm at a deposition rate of 2.0 nm / sec to complete the cathode. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. In this organic electroluminescence device, light emission was observed through a glass substrate by applying a direct current voltage using ITO as an anode and LiF / Al as a cathode. The luminance was measured with a Topcon luminance meter BM-8.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.0 V and luminance of 350 cd / cm ² was confirmed. When continuous driving was performed for 200 hours from an initial luminance of 500 cd / cm ² , the luminance reduction rate was 12%.

(Example 3)
A thermal oxide film (SiO ₂ ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 Ω · cm as a gate electrode. Here, the silicon substrate itself becomes the gate electrode, and the SiO ₂ layer formed on the surface of the silicon substrate becomes the gate insulating layer. On top of this, an organic semiconductor layer having a thickness of 50 nm was formed by spin coating using the dichloroethane solution of the compound synthesized in Example 1. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source electrode and drain electrode had a thickness of 40 nm, a channel width of 5 mm, and a channel length of 20 μm.
The organic transistor manufactured as described above exhibited characteristics as a p-type transistor element. When charge mobility was determined from the saturation region of the current-voltage (IV) characteristics of the organic transistor, a value of 7.7 × 10 ⁻² (cm ² / Vs) was obtained. Furthermore, when the drain bias was −50 V, the drain current value was measured when the gate bias was −50 V and 0 V, and the current on / off ratio was determined, a value of 2.8 × 10 ⁵ was obtained. The charge mobility of this example was superior to the conventional compound.

The polymer compound of the present invention is soluble in an organic solvent, has no cohesiveness, and can form a homogeneous thin film. By using the compound, an organic electronic device having excellent charge mobility and high heat resistance Is obtained.
The organic transistor using the polymer compound of the present invention has high charge mobility, a large current on / off ratio, and excellent storage stability. The liquid crystal display element, organic electroluminescent element, electronic paper, various types Can be used for sensors and the like.

It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention.

Explanation of symbols

11: Substrate 21: Gate electrode 31: Gate insulating layer 41: Drain electrode 51: Organic semiconductor layer 61: Source electrode

12: Substrate 22: Gate electrode 32: Gate insulating layer 42: Drain electrode 52: Organic semiconductor layer 62: Source electrode

13: Substrate 23: Gate electrode 33: Gate insulating layer 43: Drain electrode 53: Organic semiconductor layer 63: Source electrode

14: Substrate 24: Gate electrode 34: Gate insulating layer 44: Drain electrode 54: Organic semiconductor layer 64: Source electrode

Claims (11)

A polymer compound having at least one repeating unit represented by the general formula (1) in a polymer chain.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. ) In the general formula (1), R ¹ and R ² are monovalent linear or branched alkyl groups having 1 to 6 carbon atoms which may be unsubstituted or substituted, or unsubstituted or substituted having 3 to 8 carbon atoms. The polymer compound according to claim 1, which is a cyclic alkyl group which may be present. The polymer compound according to claim 1, wherein R ¹ and R ² in the general formula (1) are aryl groups, and R ³ is an unsubstituted or substituted monovalent alkyl group having 2 or more carbon atoms. In the general formula (1), one of R ¹ and R ² is an aryl group, and the other is an unsubstituted or substituted monovalent linear or branched alkyl group having 1 to 6 carbon atoms, Item 5. The polymer compound according to Item 1.   An organic semiconductor material comprising the polymer compound according to claim 1.   An organic semiconductor material which can be used in a state where the polymer compound according to claim 1 is dissolved in an organic solvent.   An organic transistor having an organic semiconductor layer, wherein the organic semiconductor layer contains at least one polymer compound according to any one of claims 1 to 4.   Organic electroluminescence formed by sandwiching at least one layer containing at least one polymer compound according to any one of claims 1 to 4 between a pair of electrodes.   An organic solar battery comprising an organic thin film layer disposed between a pair of electrodes, wherein the organic thin film layer contains at least one polymer compound according to claim 1. The method for producing a polymer compound according to claim 1, wherein the phenazacillin compound represented by the general formula (2) is polymerized using a nickel catalyst.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group as a substituent on the alkyl group represented by R ³ , X ¹ represents a halogen atom.) The method for producing a polymer compound according to claim 1, wherein the phenazacillin compound represented by the general formula (2) and the phenazacillin compound represented by the general formula (3) are polymerized using a palladium catalyst.

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group as a substituent on the alkyl group represented by R ³ , X ¹ represents a halogen atom.)

(Wherein R ¹ , R ² , R ^{4 to} R ⁹ are each independently a hydrogen atom or a substituent which may be the same or different from each other (however, a sulfo group, a carboxyl group, a phosphoryl group and a hydroxyl group). R ¹ and R ² may be bonded to each other to form a ring, and R ³ represents a monovalent alkyl group having 1 or more carbon atoms, which may be unsubstituted or substituted. And an amino group and an aryl group are excluded as a substituent on the alkyl group represented by R ^3. X ² represents a boronic acid group, a boronic acid ester group, or a trialkylstannyl group.

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