JP2008095074A - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

（式中、Ｒ¹〜Ｒ⁸は、水素原子又は置換基を表す。）で表される繰り返し単位と、下記式（７０）：

〔式中、Ｃ環及びＤ環は、芳香環を表す。Ｃ環及びＤ環は、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基ほかからなる群から選ばれる置換基を有していてもよい。Ｅは、Ｏ又はＳである。〕で表される繰り返し単位とを有する高分子化合物。
【選択図】なしThe present invention provides a novel polymer compound having strong fluorescence intensity that is useful as a light-emitting material, and a polymer light-emitting device using the polymer compound.
The following formula (1):

(Wherein R ^{1 to} R ⁸ represent a hydrogen atom or a substituent) and the following formula (70):

[In formula, C ring and D ring represent an aromatic ring. The C ring and D ring may have a substituent selected from the group consisting of an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, and the like. E is O or S. ] The high molecular compound which has a repeating unit represented by these.
[Selection figure] None

Description

  The present invention relates to a polymer compound and a polymer light-emitting device using the polymer compound.

  High-molecular-weight light-emitting materials are variously studied because they are useful as materials used for the light-emitting layer of light-emitting elements. Specific examples thereof include poly (p-phenylene) (Non-Patent Document 1), poly (m-phenylene) (Non-Patent Document 2), and polymers such as poly (p-biphenylene) (Non-Patent Document 3). It is disclosed.

Makromol. Chem. 191, 1991-2003 (1990) Polymer Preprints, 44 (1), 1035-1036 (2003) Polymer Preprints, 34 (1), 1009-1010 (1993)

  However, these compounds still have insufficient fluorescence intensity.

  An object of the present invention is to provide a novel polymer compound having strong fluorescence intensity that is useful as a light-emitting material, and a polymer light-emitting device using the polymer compound.

（式中、Ｒ¹〜Ｒ⁸はそれぞれ独立に、水素原子又は置換基を表す。）
で表される繰り返し単位と、下記式（７０）：

〔式中、Ｃ環及びＤ環は、それぞれ独立に、芳香環を表す。Ｃ環及びＤ環は、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、アシル基、アシルオキシ基、置換カルボキシル基及びシアノ基からなる群から選ばれる置換基を有していてもよい。置換基が複数存在する場合には、それらは同一であっても異なっていてもよい。Ｅは、Ｏ又はＳである。〕
で表される繰り返し単位とを有する高分子化合物を提供する。 The present invention provides the following formula (1):

(Wherein R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent)
A repeating unit represented by the following formula (70):

[In formula, C ring and D ring represent an aromatic ring each independently. C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group It may have a substituent selected from the group consisting of a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group and a cyano group. When a plurality of substituents are present, they may be the same or different. E is O or S. ]
The high molecular compound which has a repeating unit represented by these is provided.

  The polymer compound of the present invention is useful as a light emitting material and has strong fluorescence intensity. It is also useful for thin films, organic transistors, solar cells and the like. Since a polymer light emitting device using the polymer compound has high performance, it is useful for a planar light source, a display device and the like.

Hereinafter, the present invention will be described in detail. Note that in the formulas representing the repeating units in the present specification, parentheses may or may not be added, but both are synonymous.
<Polymer compound>
-Repeating unit represented by Formula (1) The polymer compound of the present invention has a repeating unit represented by Formula (1) and a repeating unit represented by Formula (70), and is converted into polystyrene. Have a number average molecular weight of 10 ³ to 10 ⁸ . Each of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (70) may contain only one kind or two or more kinds.

Substituent represented by -R ¹ to R ⁸ -
In the formula (1), the substituents represented by R ^{1 to} R ⁸ are each independently an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group. Group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, acyl group, acyloxy group, substituted carboxyl group or cyano group. These groups may have a substituent.

  The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i -Butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, etc. Pentyl, hexyl, octyl, 2-ethylhexyl, decyl and 3,7-dimethyloctyl are preferred.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, the methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group I-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy A pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, the methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i -Butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc. And a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

  The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms, specifically, methylsilyl group, ethylsilyl group, propylsilyl group, i-propylsilyl group, butylsilyl. Group, i-butylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctyl Silyl group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyl Dimethylsilyl Octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, etc., pentylsilyl group, hexylsilyl Group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl The group 3,7-dimethyloctyl-dimethylsilyl group is preferred.

  The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms, specifically, methylamino group, dimethylamino group Group, ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group Octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, and the like. Pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino Group, decylamino group, 3,7-dimethyloctylami Group is preferred.

  The aryl group usually has about 6 to 60 carbon atoms. Specific examples of the aryl group include a phenyl group which may have a substituent, a 1-naphthyl group which may have a substituent, a 2-naphthyl group which may have a substituent, and the like. Can be mentioned. Examples of the substituent of the phenyl group which may have the substituent include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, Examples thereof include an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group, and a cyano group. When a plurality of substituents are present, they may be the same or different. When the phenyl group which may have a substituent has a substituent, the number of the substituent is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When the phenyl group which may have the substituent has a substituent, and the substituent is an alkyl group, the phenyl group having the substituent has a carbon number of 1 to 1 as a substituent on the phenyl ring. A phenyl group into which 12 alkyl groups have been introduced (hereinafter referred to as “C ₁ -C ₁₂ alkylphenyl group”. “C ₁ -C ₁₂ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms. The same applies hereinafter).
Examples of the C _{1 to} C ₁₂ alkylphenyl group include a methyl substituted phenyl group, an ethyl substituted phenyl group, a propyl substituted phenyl group, an i-propyl substituted phenyl group, a butyl substituted phenyl group, an i-butyl substituted phenyl group, and a t-butyl. Substituted phenyl group, pentyl substituted phenyl group, hexyl substituted phenyl group, cyclohexyl substituted phenyl group, heptyl substituted phenyl group, octyl substituted phenyl group, 2-ethylhexyl substituted phenyl group, nonyl substituted phenyl group, decyl substituted phenyl group, 3,7- Examples include dimethyloctyl substituted phenyl group, lauryl substituted phenyl group, trifluoromethyl substituted phenyl group, pentafluoroethyl substituted phenyl group, perfluorobutyl substituted phenyl group, perfluorohexyl substituted phenyl group, perfluorooctyl substituted phenyl group, etc. Among them, from the viewpoint of solubility of the polymer compound in the solvent, butyl-substituted phenyl group, i-butyl-substituted phenyl group, t-butyl-substituted phenyl group, hexyl-substituted phenyl group, heptyl-substituted phenyl group, octyl-substituted phenyl Group, 2-ethylhexyl substituted phenyl group, nonyl substituted phenyl group, decyl substituted phenyl group, 3,7-dimethyloctyl substituted phenyl group are preferable. These C _{1 to} C ₁₂ alkylphenyl groups may further have a substituent.

When the phenyl group which may have the substituent has a substituent, and the substituent is an alkoxy group, the phenyl group having the substituent may have 1 to 1 carbon atoms as a substituent on the phenyl ring. A phenyl group into which 12 alkoxy groups have been introduced (hereinafter referred to as “C ₁ -C ₁₂ alkoxyphenyl group”. “C ₁ -C ₁₂ alkoxy” indicates that the alkoxy moiety has 1 to 12 carbon atoms. The same applies hereinafter).
The C ₁ -C ₁₂ alkoxyphenyl group include a methoxy-substituted phenyl group, an ethoxy-substituted phenyl group, propyloxy-substituted phenyl group, i- propyloxy-substituted phenyl group, butoxy-substituted phenyl group, i- butoxy-substituted phenyl group, t -Butoxy substituted phenyl group, pentyloxy substituted phenyl group, hexyloxy substituted phenyl group, cyclohexyloxy substituted phenyl group, heptyloxy substituted phenyl group, octyloxy substituted phenyl group, 2-ethylhexyloxy substituted phenyl group, nonyloxy substituted phenyl group, decyloxy Substituted phenyl group, 3,7-dimethyloctyloxy substituted phenyl group, lauryloxy substituted phenyl group, trifluoromethoxy substituted phenyl group, pentafluoroethoxy substituted phenyl group, perfluorobutoxy substitution Examples include a phenyl group, a perfluorohexyloxy-substituted phenyl group, a perfluorooctyloxy-substituted phenyl group, a methoxymethyloxy-substituted phenyl group, and a 2-methoxyethyloxy-substituted phenyl group. From the viewpoint of, butoxy-substituted phenyl group, i-butoxy-substituted phenyl group, t-butoxy-substituted phenyl group, pentyloxy-substituted phenyl group, hexyloxy-substituted phenyl group, heptyloxy-substituted phenyl group, octyloxy-substituted phenyl group, 2- An ethylhexyloxy substituted phenyl group, a nonyloxy substituted phenyl group, a decyloxy substituted phenyl group, a 3,7-dimethyloctyloxy substituted phenyl group, and a lauryloxy substituted phenyl group are preferred. These C _{1 to} C ₁₂ alkoxyphenyl groups may further have a substituent.

  When the phenyl group which may have the substituent has a substituent and the substituent is an acyl group, the phenyl group having the substituent has 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms. And a phenyl group substituted with 15 acyl groups, specifically, an acetyl substituted phenyl group, a propionyl substituted phenyl group, a butyryl substituted phenyl group, an isobutyryl substituted phenyl group, a pivaloyl substituted phenyl group, a trifluoroacetyl substituted phenyl group. Etc.

  When the phenyl group which may have the substituent has a substituent and the substituent is an acyloxy group, the phenyl group having the substituent has 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms. 15 acyloxy groups, specifically, acetoxy-substituted phenyl group, propionyloxy-substituted phenyl group, butyryloxy-substituted phenyl group, isobutyryloxy-substituted phenyl group, pivaloyloxy-substituted phenyl group, trifluoroacetyloxy-substituted phenyl group, etc. Is mentioned.

  When the phenyl group which may have the substituent has a substituent, and the substituent is a substituted carboxyl group, the phenyl group having the substituent includes an alkyl group, an aryl group, an arylalkyl group or Examples thereof include a phenyl group having a carboxyl group substituted with a monovalent heterocyclic group (the number of carbon atoms is usually about 2 to 30, preferably about 2 to 15) as a substituent. From the viewpoint, a phenyl group having a carboxyl group substituted with an alkyl group as a substituent is preferable. Specific examples of the phenyl group having the substituent include a methoxycarbonyl substituted phenyl group, an ethoxycarbonyl substituted phenyl group, a propoxycarbonyl substituted phenyl group, an i-propoxycarbonyl substituted phenyl group, a butoxycarbonyl substituted phenyl group, and an i-butoxycarbonyl substituted. Phenyl group, t-butoxycarbonyl substituted phenyl group, pentyloxycarbonyl substituted phenyl group, hexyloxycarbonyl substituted phenyl group, cyclohexyloxycarbonyl substituted phenyl group, heptyloxycarbonyl substituted phenyl group, octyloxycarbonyl substituted phenyl group, 2-ethylhexyl Siloxycarbonyl substituted phenyl group, nonyloxycarbonyl substituted phenyl group, decyloxycarbonyl substituted phenyl group, 3,7-dimethyloctyloxycarbonyl substituted Phenyl group, dodecyloxycarbonyl substituted phenyl group, trifluoromethoxycarbonyl substituted phenyl group, pentafluoroethoxycarbonyl substituted phenyl group, perfluorobutoxycarbonyl substituted phenyl group, perfluorohexyloxycarbonyl substituted phenyl group, perfluorooctyloxycarbonyl substituted phenyl Group, a phenoxycarbonyl-substituted phenyl group, and the like.

The aryloxy group generally has about 6 to 60 carbon atoms, and specifically includes a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, 2 - naphthyloxy group and the like are exemplified, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

The arylalkyl group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group or the like are exemplified, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy group, etc. are exemplified, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The arylalkenyl group usually has about 8 to 60 carbon atoms. Specifically, the phenyl-C _{2 to} C ₁₂ alkenyl group (“C _{2 to} C ₁₂ alkenyl” has 2 to 2 carbon atoms in the alkenyl moiety. indicates a 12. the same applies is less.), C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl group, etc. are exemplified, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkynyl groups, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl groups, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl group, etc. are exemplified, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The arylamino group has a carbon number of usually about 6 to 60, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di ( C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group and the like are exemplified, and C ₁ -C ₁₂ alkylphenylamino group, di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable.

The monovalent heterocyclic group usually has about 4 to 60 carbon atoms, and specifically includes thienyl group, C _{1 to} C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C _{1 to} C ₁₂ is alkylpyridyl group and the thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable. The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.

  The acyl group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. It is. Specific examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyl group. Siloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooxy group Chill oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like. In addition, these groups may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

（式中、Ｒ’は独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜６０のアリール基、又は炭素数４〜６０の１価の複素環基を表す。） When the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a hetero atom or a group containing a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom or the group containing a hetero atom include the following groups.

(In the formula, R ′ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, or a monovalent heterocyclic group having 4 to 60 carbon atoms.)

In the above formula, the alkyl group, aryl group, and monovalent heterocyclic group represented by R ′ are the same as those described and exemplified as the substituents represented by R ^{1 to} R ⁸ .

（式中、Ｒ¹⁷及びＲ¹⁸は、それぞれ独立に置換基を表す。）
で表されるものが好ましく、該式（８）中のＲ¹⁷、Ｒ¹⁸が、それぞれ独立に、アルキル基又はアルコキシ基であるものがより好ましく、Ｒ¹⁷、Ｒ¹⁸が共にアルキル基であるもの又は共にアルコキシ基であるものがさらに好ましい。 As the repeating unit represented by the formula (1), from the viewpoint of ease of synthesis of the polymer compound, the following formula (8):

(In the formula, R ¹⁷ and R ¹⁸ each independently represent a substituent.)
In the formula (8), R ¹⁷ and R ¹⁸ are each independently preferably an alkyl group or an alkoxy group, and both R ¹⁷ and R ¹⁸ are both alkyl groups. Or it is more preferable that both are alkoxy groups.

In the formula (8), the substituents represented by R ¹⁷ and R ¹⁸ are the same as those described and exemplified as the substituents represented by R ^{1 to} R ⁸ .

-Repeating unit represented by said Formula (70) In said Formula (70), C ring and D ring represent an aromatic ring each independently. C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group It may have a substituent selected from the group consisting of a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group and a cyano group. When a plurality of substituents are present, they may be the same or different. E is O or S.

  In the formula (70), examples of the aromatic ring represented by C ring and D ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring; pyridine Heteroaromatic rings such as a ring, a bipyridine ring, a phenanthroline ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, and a pyrrole ring are exemplified, but a benzene ring is preferable from the viewpoint of ease of synthesis of the polymer compound.

When the C ring and the D ring have the substituent, an alkyl group and an alkoxy group are preferable from the viewpoint of ease of synthesis of the polymer compound and solubility of the polymer compound. Further, when a plurality of substituents are present, they may be the same or different. The said substituent is the same as what was demonstrated and illustrated as a substituent represented by R < ¹ > -R < ⁸ > in said Formula (1).

（式中、ＸはＯ又はＳを表し、Ｒ^aは置換基を表し、ｍは独立に０〜５の整数を表し、ｎは独立に０〜３の整数を表す。Ｒ^aが複数存在する場合には、それらは同一であっても異なっていてもよい。）
のいずれかで表されるものが挙げられる。 Examples of the repeating unit represented by the formula (70) include the following formulas (2a) to (2d):

(In the formula, X represents O or S, R ^a represents ^a substituent, m independently represents an integer of 0 to 5, and n independently represents an integer of 0 to 3. A plurality of R ^a are present. In some cases, they may be the same or different.)
The thing represented by either of these is mentioned.

The substituent represented by R ^a is the same as described and exemplified as the substituent represented by R ^{1 to} R ⁸ . Moreover, from the viewpoint of solubility of the polymer compound, m is preferably an integer of 1 to 3, and n is preferably 1 or 2.

〔式中、Ｙは、Ｏ又はＳを表す。Ｒ^j及びＲ^kは、それぞれ独立に、水素原子、アルキル基、アルコキシ基又はアリール基を表す。〕
で表されるものであることが、高分子化合物の合成の容易さや高分子化合物の蛍光強度の観点から好ましい。 The repeating unit represented by the formula (2a) is represented by the following formula (2E):

[Wherein Y represents O or S. R ^j and R ^k each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. ]
It is preferable from the viewpoint of the ease of synthesis of the polymer compound and the fluorescence intensity of the polymer compound.

In the formula (2E), R ^j and R ^k are the same (that is, both are a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group) in view of the ease of synthesis of the polymer compound. An alkoxy group is preferable. The alkyl group and aryl group represented by R ^j and R ^k are the same as those described and exemplified as the substituent represented by R ^{1 to} R ⁸ in the formula (1). Examples of the alkoxy group represented by R ^j and R ^k include a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, from the viewpoint of the solubility and fluorescence intensity of the polymer compound. Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group are preferred, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl An oxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are more preferable.

（式中、Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、アシル基、アシルオキシ基、置換カルボキシル基又はシアノ基を表す。）
等が挙げられ、高分子化合物の耐熱性や高分子量化の観点からは、

（式中、Ｒは前記と同じ意味を有する。）
が好ましい。 As the repeating unit represented by the formula (70), for example,

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, An arylalkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group, or a cyano group is represented.)
From the viewpoint of heat resistance and high molecular weight of the polymer compound,

(In the formula, R has the same meaning as described above.)
Is preferred.

In the above formula, one structural formula has a plurality of Rs, which may be the same or different. In the above formula, the group represented by R is the same as described and exemplified as the substituent represented by R ^{1 to} R ⁸ .

（式中、Ａｒ₁は、前記式（７０）で表されない２価の複素環基、又は２価の芳香族アミン基を表す。これらの基は、置換基を有していてもよい。）
で表される繰り返し単位を有していてもよい。この繰り返し単位は、一種のみ含んでいても二種以上含んでいてもよい。 Other Repeating Units From the viewpoint of ease of charge injection and luminous efficiency of the electroluminescent device, the polymer compound of the present invention is further represented by the above formula (70) even in the repeating unit represented by the above formula (1). The following formula (2) which is not a repeating unit:

(In the formula, Ar ₁ represents a divalent heterocyclic group not represented by the formula (70) or a divalent aromatic amine group. These groups may have a substituent.)
It may have a repeating unit represented by This repeating unit may contain only 1 type, or may contain 2 or more types.

In Formula (2), Ar ₁ represents a divalent heterocyclic group not represented by Formula (70) or a divalent aromatic amine group. These groups are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, 1 It may have a substituent such as a valent heterocyclic group, an acyl group, an acyloxy group, or a substituted carboxyl group. When Ar ₁ has a plurality of substituents, they may be the same or different.

  In the formula (2), the divalent heterocyclic group means the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. A heterocyclic compound means an organic compound having a cyclic structure in which the elements constituting the ring contain not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. . As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable.

  Examples of the divalent heterocyclic group include the following. Among these, from the viewpoint of ease of charge injection and light emission efficiency of the polymer light emitting device, phenoxazine-diyl group containing nitrogen and oxygen (the following formula L) as a hetero atom, and nitrogen and sulfur as a hetero atom A phenothiazine-diyl group (formula M) is preferred.

  A group containing nitrogen as a heteroatom; diazaphenylene group (formula 45 to 48), quinoline diyl group (formula 49 to 63), quinoxaline diyl group (formula 64 to 68), acridine diyl group (formula 69 to 72), bipyridyldiyl groups (the following formulas 73 to 75), phenanthroline diyl groups (the following formulas 76 to 78), and the like.

  5-membered ring heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (the following formulas 94 to 98) and the like.

  5-membered condensed heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (the following formulas 99 to 108) and the like.

  A 5-membered ring heterocyclic group containing sulfur or the like as a hetero atom, a group bonded to the α position of the hetero atom to form a dimer or oligomer: (Formula 109 to 110) and the like.

  5-membered ring heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as heteroatoms, which are bonded to the phenyl group at the α-position of the heteroatoms: (the following formulas 111 to 117) and the like.

（上式４５〜７８、式９４〜１０８、式１１０〜１１７、Ｌ、Ｍ中、Ｒは、前記と同じ意味を有する。） A phenoxazine-diyl group containing nitrogen and oxygen as a hetero atom (the following formula L), a phenothiazine-diyl group containing nitrogen and sulfur as a hetero atom (the following formula M), and the like.

(In the above formulas 45 to 78, formulas 94 to 108, formulas 110 to 117, L and M, R has the same meaning as described above.)

（式中、Ａｒ₅及びＡｒ₇はそれぞれ独立に、置換基を有していてもよいアリーレン基、一般式（４）で表される基、又は一般式（５）で表される基を表す。Ａｒ₆は、置換基を有していてもよいアリール基、一般式（６）で表される基又は一般式（７）で表される基を表す。また、Ａｒ₅とＡｒ₆の間、Ａｒ₅とＡｒ₇の間、又はＡｒ₆とＡｒ₇の間に環を形成していてもよい。

（式中、Ａｒ₈及びＡｒ₉は、それぞれ独立に、置換基を有していてもよいアリーレン基を表す。Ｒ₇及びＲ₈は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｌは、０又は１である。）

（式中、Ａｒ₁₀及びＡｒ₁₁は、それぞれ独立に、置換基を有していてもよいアリーレン基を表す。Ａｒ₁₂は、置換基を有していてもよいアリール基を表す。また、Ａｒ₁₀とＡｒ₁₂の間、Ａｒ₁₀とＡｒ₁₁の間、又はＡｒ₁₁とＡｒ₁₂の間に環を形成していてもよい。）

（式中、Ａｒ₁₃は、置換基を有していてもよいアリーレン基を表す。Ａｒ₁₆及びＡｒ₁₇は、それぞれ独立に、置換基を有していてもよいアリール基を表す。また、Ａｒ₁₃とＡｒ₁₆の間、Ａｒ₁₃とＡｒ₁₇の間、又はＡｒ₁₆とＡｒ₁₇の間に環を形成していてもよい。）

（式中、Ａｒ₁₄は、置換基を有していてもよいアリーレン基を示す。Ａｒ₁₅は、置換基を有していてもよいアリール基を表す。Ｒ₁₁及びＲ₁₂は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｒは０又は１である。） In said Formula (2), a bivalent aromatic amine group means the remaining atomic groups remove | excluding two hydrogen atoms from aromatic amine, and carbon number is about 4-60 normally. The carbon number does not include the carbon number of the substituent. Examples of the divalent aromatic amine group include a group represented by the following general formula (3).

(In the formula, Ar ₅ and Ar ₇ each independently represent an arylene group which may have a substituent, a group represented by the general formula (4), or a group represented by the general formula (5). Ar ₆ represents an aryl group which may have a substituent, a group represented by the general formula (6), or a group represented by the general formula (7), and between Ar ₅ and Ar ₆ . , Ar ₅ and Ar ₇ , or Ar ₆ and Ar ₇ may form a ring.

(In the formula, Ar ₈ and Ar ₉ each independently represent an arylene group which may have a substituent. R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, 1 Represents a valent heterocyclic group or a cyano group, and l is 0 or 1.)

(Wherein, Ar ₁₀ and Ar ₁₁ are each independently, .Ar ₁₂ which represents an arylene group optionally having a substituent, represents an aryl group which may have a substituent. In addition, Ar _A ring may be formed between ₁₀ and Ar ₁₂ , between Ar ₁₀ and Ar ₁₁ , or between Ar ₁₁ and Ar _12. )

(In the formula, Ar ₁₃ represents an arylene group which may have a substituent. Ar ₁₆ and Ar ₁₇ each independently represents an aryl group which may have a substituent. Ar _A ring may be formed between ₁₃ and Ar ₁₆ , between Ar ₁₃ and Ar ₁₇ , or between Ar ₁₆ and Ar _17. )

(In the formula, Ar ₁₄ represents an arylene group which may have a substituent. Ar ₁₅ represents an aryl group which may have a substituent. R ₁₁ and R ₁₂ are each independently Represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, and r is 0 or 1.)

In the above formula, the arylene group represented by Ar ₅ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₃ , Ar ₁₄ has usually 6 to 60 carbon atoms, Specific examples include a phenylene group, naphthalenediyl group, anthracenylene group, biphenylene group, triphenylene group, fluorene-diyl group, stilbenediyl group and the like. From the viewpoint of ease of synthesis of the polymer compound, a phenylene group is preferable.

In the above formula, the aryl group represented by Ar ₆ , Ar ₁₂ , Ar ₁₅ , Ar ₁₆ , Ar ₁₇ has usually 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl and the like. From the viewpoint of ease of synthesis of the polymer compound, a phenylene group is preferable.

In the above formula, the alkyl group, aryl group, and monovalent heterocyclic group represented by R ₇ , R ₈ , R ₁₁ , and R ₁₂ are explained and exemplified as the substituent represented by R ^{1 to} R ⁸ . Is the same.

Ar _{5 to} Ar ₁₇ in the above formula are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group , An arylamino group, a monovalent heterocyclic group, a cyano group and the like.

（上記式１１８〜１２２中、Ｒは、前記と同じ意味を有する。） Specific examples of the divalent aromatic amine group include the following groups.

(In the above formulas 118 to 122, R has the same meaning as described above.)

（式中、Ｒは前記と同じ意味を有する。） Specific examples of the repeating unit represented by the formula (2) include those represented by the following formula.

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

と、前記式（７０）で表される繰り返し単位である

とを、それぞれ１種類以上の組み合わせて有するものが挙げられる。さらに、前記式（１）で表される繰り返し単位である

と、前記式（７０）で表される繰り返し単位である

と、前記式（２）で表される繰り返し単位である

とを、それぞれ１種類以上の組み合わせて有するものが挙げられる。 A specific example of the polymer compound of the present invention is a repeating unit represented by the formula (1).

And a repeating unit represented by the formula (70).

And those having one or more types in combination. Furthermore, it is a repeating unit represented by the formula (1).

And a repeating unit represented by the formula (70).

And a repeating unit represented by the formula (2).

And those having one or more types in combination.

  In the polymer compound of the present invention, the ratio (total) of the repeating units represented by the formula (1) is usually 0.1 to 90 mol% of all repeating units of the polymer compound, and is heat resistant. From this point of view, it is preferably 1 to 50 mol% of all repeating units of the polymer compound.

  In the polymer compound of the present invention, the ratio (total) of the repeating units represented by the formula (70) is usually 10 to 99.9 mol% of all repeating units of the polymer compound, and the fluorescence intensity From this point of view, it is preferably 50 to 90 mol% of all repeating units of the polymer compound.

  In the polymer compound of the present invention, when it has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (70), and further a repeating unit represented by the formula (2), The ratio of the repeating unit represented by the formula (2) is usually 2 to 50 mol% of all repeating units of the polymer compound, and from the viewpoint of ease of charge injection and luminous efficiency of the polymer light emitting device. Is preferably 5 to 50 mol% of all repeating units of the polymer compound.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is usually 1.0 × 10 ^{3 to} 1.0 × 10 ⁸ , preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁷ . When the number average molecular weight in terms of polystyrene is less than 1.0 × 10 ^3, it is difficult to obtain a tough thin film, and when it exceeds 1.0 × 10 ⁸ , the solubility is lowered and the production of the thin film is difficult. . Moreover, the weight average molecular weight of polystyrene conversion is 1.1 * 10 < ³ > -1.1 * 10 < ⁸ > normally, Preferably it is 2.2 * 10 < ³ > -1.1 * 10 < ⁷ >.

Others In the polymer compound of the present invention, the repeating unit represented by the formula (1), the repeating unit represented by the formula (70), and the repeating unit represented by the formula (2) are the same repeating unit. Units or different repeating units may be directly bonded to each other or may be bonded via a vinylene group or the like.

  The terminal group of the polymer compound of the present invention is a stable group because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and life of the device obtained when used for device preparation may be reduced. It may be protected. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group may be used. Specifically, substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.

  The polymer compound of the present invention may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer, or a polymer having an intermediate structure thereof, for example, a block property It may be a random copolymer having a color. From the viewpoint of obtaining a polymer compound having a high fluorescence quantum yield, a random copolymer having a blocking property, a block copolymer, or a graft copolymer is preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  Examples of the good solvent for the polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

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

As a method for producing the polymer compound of the present invention, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, a polymerization by an oxidizing agent such as FeCl ₃ And a method by electrochemical oxidation polymerization, a method by decomposition of an intermediate polymer having an appropriate leaving group, and the like.

  Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, and the method of polymerizing by Ni (0) catalyst are preferable because the structure can be easily controlled.

  Specifically, a compound having a plurality of reactive substituents, which is a monomer, is dissolved in an organic solvent as necessary, and, for example, reacted with an appropriate catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. Can do.

  The organic solvent varies depending on the compound and reaction used. In general, in order to suppress side reactions, it is preferable that the solvent used be sufficiently deoxygenated to allow the reaction to proceed under an inert atmosphere. Similarly, it is preferable to perform a dehydration treatment (however, this is not the case in the case of a two-phase reaction with water such as a Suzuki coupling reaction).

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  More specifically, the reaction conditions will be described.

  In the case of Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates, etc. are used as catalysts, inorganic bases such as potassium carbonate, sodium carbonate and barium hydroxide, organic bases such as triethylamine, An inorganic salt such as cesium fluoride is added in an equivalent amount or more, preferably 1 to 20 equivalents, and more preferably 1 to 10 equivalents to the monomer. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. The base may be added as an aqueous solution and reacted in a two-phase system (in the case of reacting in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added if necessary). Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 0.1 to 200 hours, preferably about 0.5 to 50 hours. The reaction is carried out under an inert atmosphere such as argon gas or nitrogen gas under conditions that do not deactivate the catalyst.

  In the case of the Grignard reaction, a halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane or the like to form a Grignard reagent solution, and this is mixed with a monomer solution prepared separately, and a nickel catalyst or An example is a method in which a palladium catalyst is added while paying attention to excess reaction, and then reacted while heating to reflux. Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method. The reaction is performed in an inert atmosphere such as argon gas or nitrogen gas.

  When a zerovalent nickel complex is used, the halide is used in an ether solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, 1,4-dioxane, or an aromatic hydrocarbon solvent such as toluene. The method of making it react using a zerovalent nickel complex is illustrated. Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, and the like. (1,5-cyclooctadiene) nickel (0) is preferred. In this case, it is preferable to add a neutral ligand from the viewpoint of improving the yield of the polymer compound and increasing the molecular weight.

  Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as: triphenylphosphine, tritolylphosphine, tributylphosphine, triphenoxyphosphine, and other third phosphine ligands, etc., and nitrogen-containing ligands are preferred in terms of versatility and low cost, 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of increasing the molecular weight of the polymer, a system in which 2,2'-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable.

  The amount of the zero-valent nickel complex is not particularly limited as long as it does not inhibit the polymerization reaction, but if it is too small, the polymerization reaction time becomes long, and if it is too much, post-treatment becomes difficult. Therefore, the amount is usually 0.1 mol or more, preferably 1 mol or more per 1 mol of the monomer. If the amount used is too small, the molecular weight tends to be small. The upper limit is not limited, but if the amount is too large, the post-treatment tends to be difficult, so 5.0 mol or less is preferable.

  When using a neutral ligand, the amount used is usually about 0.5 to 10 moles per mole of zero-valent nickel complex, and cost performance (high yield and low cost input) From the viewpoint of (amount), 0.9 to 1.1 mol is preferable. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method. The reaction is carried out under an inert atmosphere such as argon gas or nitrogen gas under conditions that do not deactivate the catalyst.

  When the polymer compound of the present invention is used as a light-emitting material of a polymer light-emitting device, the purity affects the light-emitting properties, and therefore, the monomer before polymerization is polymerized after being purified by methods such as distillation, sublimation purification, and recrystallization. It is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography after the synthesis.

<Liquid composition>
The liquid composition of the present invention is useful for production of light-emitting elements such as polymer light-emitting elements and organic transistors. The liquid composition comprises the polymer compound and a solvent. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

  In addition to the polymer compound, the liquid composition of the present invention is a low molecular light emitting material, a hole transport material, an electron transport material, a stabilizer (such as an antioxidant), an additive for adjusting viscosity and / or surface tension. An agent or the like may be included. Each of these optional components may be used alone or in combination of two or more.

  Examples of the low molecular luminescent material that may be contained in the liquid composition of the present invention include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, Metal complexes having a metal complex of 8-hydroxyquinoline as a ligand, metal complexes having an 8-hydroxyquinoline derivative as a ligand, other luminescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene Derivative, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivative, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, Emitting material of low molecular weight compounds of acetylene-based, and the like. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  Further, the low-molecular light-emitting material includes a metal complex that emits light from a triplet excited state (triplet light-emitting complex: usually a complex containing a central metal and a ligand, such as phosphorescent light In addition to this phosphorescence emission, a complex in which fluorescence emission is observed, or a polymer complex compound in which a partial structure of a complex exhibiting emission from a triplet excited state is present in the side chain, main chain, and terminal of the polymer compound is included. ) Can be used. Examples of the triplet light-emitting complex include Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001). ), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852 etc. Has been.

  The central metal of the triplet light-emitting complex is usually a metal having an atomic number of 50 or more, and the complex has a spin-orbit interaction and can cause an intersystem crossing between the singlet state and the triplet state. . Examples of the central metal include rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and lanthanoids such as europium, terbium, thulium, dysprosium, samarium, praseodymium, gadolinium, and tungsten, and rhenium, Iridium, platinum, gold and europium are preferred, rhenium, iridium, platinum and gold are more preferred, and iridium is particularly preferred.

  Examples of the ligand of the triplet light-emitting complex include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, 2-phenyl- Examples include benzoxazole and its derivatives, porphyrin and its derivatives.

  Specific examples of the triplet light-emitting complex include the following (PL-1 to PL-37).

  Here, R has the same meaning as described above, but preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group. A group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, and a cyano group, and an alkyl group and an alkoxy group are more preferable from the viewpoint of enhancing the solubility in a solvent. A plurality of R may be the same or different.

で表される金属錯体が特に好ましい The triplet light emitting complex has the following formula:

Particularly preferred is a metal complex represented by

  Examples of the hole transport material that the liquid composition of the present invention may contain include, for example, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, Arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Derivatives and the like.

  Examples of the electron transport material that may be contained in the liquid composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, etc. Can be mentioned.

  Examples of the stabilizer that may be contained in the liquid composition of the present invention include an antioxidant. The antioxidant is not particularly limited as long as it does not inhibit light emission and charge transport. When the composition contains a solvent, it is usually soluble in the solvent. For example, a phenol-based antioxidant, phosphorous And system antioxidants. By using this antioxidant, the storage stability of the polymer compound and the solvent can be improved.

  As an additive for adjusting the viscosity and / or surface tension which the liquid composition of the present invention may contain, for example, a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a viscosity A low molecular weight compound for lowering, a surfactant for lowering surface tension, and the like may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport, and is usually soluble in the solvent of the liquid composition. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener.

  When the liquid composition of the present invention contains a hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 wt% to 80 wt%, preferably 5 wt% to 60% by weight. When the liquid composition of the present invention contains an electron transport material, the ratio of the electron transport material in the liquid composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %.

When forming a film using this liquid composition in the preparation of a polymer light emitting device, it is only necessary to remove the solvent by drying after applying the liquid composition, and also to mix the charge transport material and the light emitting material. In this case, the same technique can be applied, which is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

  For film formation using a liquid composition, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing A coating method such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. In the case of the liquid composition passing through the discharge device, such as an ink jet printing method, In order to prevent flight bending, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the liquid composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole , Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent contained in the liquid composition is preferably two or more, more preferably two to three, and more preferably two from the viewpoints of film forming properties and device characteristics. Further preferred.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. In this case, it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of less than 180 ° C. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition dissolved at 60 ° C. in the solvent. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

<Application>
The polymer compound of the present invention can be used not only as a light emitting material but also as a conductive material by thin film, organic semiconductor material, organic transistor, optical material, solar cell or doping.

-Thin film-
The thin film of the present invention will be described. This thin film is formed using the polymer compound. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

  The light-emitting thin film preferably has a quantum yield of light emission of 50% or more, more preferably 60% or more, and further preferably 70% or more from the viewpoint of the brightness of the device, the light emission voltage, and the like. .

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.

The organic semiconductor thin film has a higher electron mobility or hole mobility, preferably 10 ⁻⁵ cm ² / V / second or more, more preferably 10 ⁻³ cm ² / V / second or more, More preferably, it is 10 ^-1 cm ² / V / second or more. In addition, an organic transistor can be manufactured using an organic semiconductor thin film. Specifically, an organic transistor can be formed by forming an organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like. .

-Organic transistors (polymer field effect transistors)-
Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.

  The polymer compound of the present invention can be suitably used as a material for a polymer field effect transistor, particularly as a material for an active layer. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the support substrate is not particularly limited as long as the characteristics as a field effect transistor are not hindered, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The polymer field effect transistor can be produced by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer compound. For film formation from a solution in which an organic solvent-soluble polymer compound is dissolved in a solvent, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method Application methods such as dip coating, spray coating, screen printing, flexographic printing, offset printing, and ink jet printing can be used.

  A sealed polymer field effect transistor obtained by sealing after producing a polymer field effect transistor is preferred. Thereby, the polymer field effect transistor is shielded from the atmosphere, and deterioration of the characteristics of the polymer field effect transistor can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the polymer field effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

-Organic solar cells-
Next, an organic solar cell will be described. A solid photoelectric conversion element utilizing the photovoltaic effect as an organic photoelectric conversion element which is one embodiment of an organic solar battery will be described.

  The polymer compound of the present invention is used as a material of an organic photoelectric conversion element, particularly as an organic semiconductor layer of a Schottky barrier type element utilizing an interface between an organic semiconductor and a metal, and between an organic semiconductor and an inorganic semiconductor or between organic semiconductors. It can be suitably used as an organic semiconductor layer of a pn heterojunction element utilizing an interface.

  Furthermore, as an electron-donating polymer and an electron-accepting polymer in a bulk heterojunction device with an increased donor-acceptor contact area, an organic photoelectric conversion device using a polymer / low-molecular composite system, for example, electron accepting It can be suitably used as an electron donating conjugated polymer (dispersion support) of a bulk heterojunction organic photoelectric conversion element in which a fullerene derivative is dispersed as a body.

  As the structure of the organic photoelectric conversion element, for example, in a pn heterojunction type element, a p-type semiconductor layer is formed on an ohmic electrode, for example, ITO, and an n-type semiconductor layer is further stacked thereon. It is sufficient that an ohmic electrode is provided.

  The organic photoelectric conversion element is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as the organic photoelectric conversion element are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic photoelectric conversion element can be produced by a known method, for example, the method described in Synth. Met., 102, 982 (1999) or the method described in Science, 270, 1789 (1995).

<Polymer light emitting device>
Next, the polymer light emitting device of the present invention will be described.

  The polymer light emitting device of the present invention has an electrode composed of an anode and a cathode, and a light emitting layer provided between the electrodes and containing the polymer compound.

  Further, as the polymer light-emitting device of the present invention, (1) a polymer light-emitting device in which an electron transport layer is provided between the cathode and the light-emitting layer, and (2) a hole transport layer is provided between the anode and the light-emitting layer. Examples thereof include a polymer light emitting device provided, and (3) a polymer light emitting device in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

More specifically, the following structures a) to d) are exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

  Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, The method by the film-forming from a solution is illustrated.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, and an ink jet printing method can be used.

  When forming a film from a solution by using the polymer compound of the present invention at the time of preparing a polymer light emitting device, it is only necessary to remove the solvent by drying after coating this solution, and charge transport materials and light emitting materials can be used. Even in the case of mixing, the same technique can be applied, which is very advantageous in production.

  The film thickness of the light emitting layer varies depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, the film thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 200 nm.

  In the polymer light emitting device of the present invention, a light emitting material other than the polymer compound may be mixed and used in the light emitting layer. In the polymer light emitting device of the present invention, a light emitting layer containing a light emitting material other than the polymer compound may be laminated with a light emitting layer containing the polymer compound.

  As the light emitting material other than the polymer compound, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-type, xanthene-type, coumarin-type and cyanine-type pigments, 8-hydroxyquinoline and metal complexes of its derivatives, aromatic amines, and the like. , Tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and the like can be used. Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393, metal complexes showing light emission from the triplet excited state can be used. .

  When the polymer light-emitting device of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, and polysiloxane having an aromatic amine in the side chain or main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thieni Lembinylene) and its derivatives are exemplified. Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, Examples described in JP-A-3-7992 and JP-A-3-152184 are exemplified.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, polyaniline and derivatives thereof A polymer hole transport material such as polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, more preferably polyvinyl carbazole and derivatives thereof, Polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole and derivatives thereof are obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review, Vol. 89, page 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since the polysiloxane derivative has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  For film formation from solution, spin coating method from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing A coating method such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer light-emitting device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and Derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and Examples thereof include polyfluorene and derivatives thereof. Specifically, JP-A 63-70257, 63-175860, JP 2-135359, 2-135361, 2-209988, 3-37992, Examples described in JP-A-3-152184 are exemplified.

  Of these, oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinones and derivatives thereof, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof are preferable. More preferred are-(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, the vacuum evaporation method from powder, or the method by film formation from a solution or molten state, the polymer electron transport material is a solution or melt. Each method is exemplified by film formation from the state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  For film formation from solution or molten state, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing A coating method such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Further, among the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly the charge injection layers (hole injection layers). , An electron injection layer).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be stacked, and the thickness of each layer may be appropriately selected in consideration of light emission efficiency and element lifetime.

  In the present invention, a polymer light emitting device provided with a charge injection layer (electron injection layer, hole injection layer) is a polymer light emitting device provided with a charge injection layer adjacent to the cathode, or a charge injection adjacent to the anode. Examples thereof include a polymer light emitting device provided with a layer.

For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode
f) Anode / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
h) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
k) Anode / charge injection layer / light emitting layer / charge transport layer / cathode
l) Anode / light-emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
n) Anode / charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) Anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having a value ionization potential, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an intermediate value of electron affinity between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, and leakage between light emitting pixels in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like, and examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion, and the like.

  The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon, etc. .

  The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Examples of the polymer light emitting device provided with the insulating layer include a polymer light emitting device provided with an insulating layer adjacent to the cathode and a polymer light emitting device provided with an insulating layer adjacent to the anode.

Specific examples include the following structures q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode
ab) Anode / insulating layer / hole transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode

  The substrate for forming the polymer light-emitting device of the present invention may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include substrates such as glass, plastic, polymer film, and silicon. It is done. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  In the present invention, it is usually preferred that at least one of the anode and cathode electrodes is transparent or translucent, and the anode side is transparent or translucent.

  As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and their composite films made of conductive glass made of indium, tin, oxide (ITO), indium, zinc, oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as this anode.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. It is.

  In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. .

  As a material for the cathode, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like Two or more alloys, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. In addition, a layer made of a conductive polymer, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer. The protective layer which protects may be mounted | worn. In order to stably use the polymer light emitting device for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the device from the outside.

  As the protective layer, resins, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

  The polymer light-emitting device of the present invention can be used in a display device such as a planar light source, a segment display device, a dot matrix display device, a liquid crystal display device (for example, a backlight).

  In order to obtain planar light emission using the polymer light emitting device of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light, a method of forming either one of the anode or the cathode, or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples. In this example, the number average molecular weight and the weight average molecular weight were determined as polystyrene-reduced number average molecular weight and weight average molecular weight by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

で表される４，４’−ジオクチルオキシビフェニル １０５ｇを得た。 <Synthesis Example 1> (Synthesis of 4,4′-dioctyloxybiphenyl)
56 g of 4,4′-dihydroxybiphenyl was dissolved in 500 g of ethanol. To this solution, 40 g of potassium hydroxide was added (partially added) and reacted. Next, this solution was heated and 128 g of 1-bromooctane was added dropwise at 70 ° C. After the dropping, the reaction was continued at 70 ° C. for 7 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this reaction solution was cooled, and the generated precipitate was collected by filtration. The precipitate was then washed with 500 ml of methanol. Next, this precipitate was washed with a mixed solvent of 500 ml of methanol / 300 ml of ion-exchanged water, and further washed with a mixed solvent of 500 ml of acetone / 300 ml of ion-exchanged water. The precipitate is dried under reduced pressure and the following structural formula:

105 g of 4,4′-dioctyloxybiphenyl represented by the formula:

で表される３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ２０ｇを得た。 <Synthesis Example 2> (Synthesis of 3,3′-dibromo-4,4′-dioctyloxybiphenyl)
20.5 g of 4,4′-dioctyloxybiphenyl was dissolved in 650 g of chloroform. To this solution, 16.8 g of bromine was added dropwise with care so that the reaction temperature did not exceed 30 ° C. After the dropping, the reaction was continued at room temperature for 45 hours. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution to treat unreacted bromine. Next, this solution was allowed to stand and a separated chloroform solution was recovered. The chloroform solution was washed 3 times with ion exchange water and then filtered to remove insolubles. Next, the obtained chloroform solution was passed through an alumina column for purification. Next, the solvent was distilled off from the obtained solution under reduced pressure to obtain a crude product. This crude product was recrystallized and purified using a mixed solvent of 100 g of toluene / 85 g of methanol. The resulting precipitate was dried under reduced pressure and the following structural formula:

20 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl represented by the formula:

で表される単量体（１） ０．６１ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．２８ｇと２，２’−ビピリジル ０．７０ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）７０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．２４ｇを加え、室温で１０分間攪拌した後、６０℃で５時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Example 1> (Synthesis of polymer compound 1)
The following structural formula:

After charging 0.61 g of monomer (1), 0.23 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.70 g of 2,2′-bipyridyl in a reaction vessel The inside of the reaction system was replaced with nitrogen gas. To this was added 70 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.24 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 5 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled to room temperature, and then a methanol 40 ml / ion-exchanged water 40 ml mixed solution was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. This toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with about 5 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.29 g of a polymer. This polymer is referred to as polymer compound 1. The number average molecular weight in terms of polystyrene of the polymer compound 1 was 1.1 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 3.9 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 1 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 1 estimated from the charge is C / D = 7/3.)
CD

<Comparative example 1> (Synthesis of polymer compound 2)
A reaction vessel was charged with 0.61 g of the monomer (1), 0.26 g of 3,3′-dioctyloxy-4,4′-dibromobiphenyl and 0.66 g of 2,2′-bipyridyl, and then reacted. The system was replaced with nitrogen gas. To this was added 70 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled to room temperature, and then a methanol 40 ml / ion-exchanged water 40 ml mixed solution was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. This toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with about 5 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.07 g of a polymer. This polymer is referred to as polymer compound 2. The polymer compound 2 had a polystyrene-equivalent number average molecular weight of 1.6 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 3.5 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is shown below.
(Note that the molar ratio of the repeating units contained in the polymer compound 2 estimated from preparation is K / L = 7/3.)
K L

で表される単量体（２） ０．５４ｇと、下記構造式：

で表される単量体（３） ０．３１ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．０８５ｇと２，２’−ビピリジル ０．６３ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．１１ｇを加え、室温で１０分間攪拌した後、室温で２０時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Example 2> (Synthesis of polymer compound 3)
The following structural formula:

0.54 g of the monomer (2) represented by the following structural formula:

After charging 0.31 g of monomer (3), 0.03 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.63 g of 2,2′-bipyridyl in a reaction vessel The inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.11 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with a 5 wt% aqueous acetic acid solution and then allowed to stand to collect the separated toluene solution. Next, this toluene solution was washed with about 5 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was passed through an alumina column for purification. Next, the obtained toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.2 g of a polymer. This polymer is referred to as polymer compound 3. The number average molecular weight in terms of polystyrene of the polymer compound 3 was 2.0 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 1.1 × 10 ⁵ .

The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 3 estimated from the charge is M / N / O = 6/3/1.)
M N O

<Comparative Example 2> (Synthesis of Polymer Compound 4)
Monomer (2) 0.54 g, Monomer (3) 0.31 g, 3,3′-Dioctyloxy-4,4′-dibromobiphenyl 0.085 g and 2,2′-bipyridyl 0.63 g Was charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.11 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with a 5 wt% aqueous acetic acid solution and then allowed to stand to collect the separated toluene solution. Next, this toluene solution was washed with about 5 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was passed through an alumina column for purification. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.24 g of a polymer. This polymer is referred to as polymer compound 4. The polymer compound 4 had a polystyrene-equivalent number average molecular weight of 2.1 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 6.3 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 4 estimated from the charge is P / Q / R = 6/3/1.)
P Q R

で表される単量体（４） ０．２１ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．０８５ｇと２，２’−ビピリジル ０．６３ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．１１ｇを加え、室温で１０分間攪拌した後、室温で２１時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Example 3> (Synthesis of polymer compound 5)
Monomer (1) 0.52 g and the following structural formula:

After charging 0.21 g of the monomer (4), 0.03 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.63 g of 2,2′-bipyridyl in a reaction vessel The inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.11 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at room temperature for 21 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with a 5 wt% aqueous acetic acid solution and then allowed to stand to collect the separated toluene solution. Next, this toluene solution was washed with 4% by weight ammonia water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water, then allowed to stand and separated to recover the toluene solution. Next, this toluene solution was passed through an alumina column for purification. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.25 g of a polymer. This polymer is referred to as polymer compound 5. The polymer compound 5 had a polystyrene-equivalent number average molecular weight of 1.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 5.4 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 5 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 5 estimated from the charge is S / T / U = 6/3/1.)
S T U

<Comparative Example 3> (Synthesis of Polymer Compound 6)
Monomer (1) 0.52 g, Monomer (4) 0.21 g, 3,3′-Dioctyloxy-4,4′-dibromobiphenyl 0.085 g and 2,2′-bipyridyl 0.63 g Was charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.11 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at room temperature for 21 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with a 5 wt% aqueous acetic acid solution and then allowed to stand to collect the separated toluene solution. Next, this toluene solution was washed with 4% by weight ammonia water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was passed through an alumina column for purification. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.24 g of a polymer. This polymer is referred to as polymer compound 6. The polymer compound 6 had a polystyrene-equivalent number average molecular weight of 1.6 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 4.0 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 6 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 6 estimated from the charge is V / W / X = 6/3/1.)
V W X

で表される単量体（５） ０．３７ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．２８ｇと２，２’−ビピリジル ０．６６ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．１５ｇを加え、室温で２０時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Comparative Example 4> (Synthesis of Polymer Compound 7)
The following structural formula:

After charging 0.37 g, 0.33 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.66 g of 2,2′-bipyridyl in a reaction vessel The inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and reacted at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the solvent was distilled off from this solution under reduced pressure. Toluene was added to the resulting precipitate, stirred and dissolved. The toluene solution was filtered to remove insoluble matters, and the obtained toluene solution was washed with about 5% by weight of an acetic acid aqueous solution and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with 4 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was passed through an alumina column for purification. Next, after concentrating the obtained toluene solution under reduced pressure, methanol was added thereto for reprecipitation, and the generated precipitate was recovered.

Next, this precipitate was washed with methanol and then dried under reduced pressure to obtain 0.01 g of a polymer. This polymer is referred to as polymer compound 7. The polymer compound 7 had a polystyrene-equivalent number average molecular weight of 6.5 × 10 ³ and a polystyrene-equivalent weight average molecular weight of 1.6 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 7 estimated from the preparation is shown below.
(Note that the molar ratio of the repeating units contained in the polymer compound 7 estimated from preparation is A / B = 7/3.)
A B

で表される単量体（６） ０．４３ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．２８ｇと２，２’−ビピリジル ０．６６ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．１５ｇを加え、室温で２０時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Comparative Example 5> (Synthesis of Polymer Compound 8)
The following structural formula:

After charging 0.43 g of the monomer (6) represented by the following formula: 0.28 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.66 g of 2,2′-bipyridyl The inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and reacted at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the solvent was distilled off from this solution under reduced pressure. Toluene was added to the resulting precipitate, stirred and dissolved. The toluene solution was filtered to remove insoluble matters, and the obtained toluene solution was washed with about 5% by weight of an acetic acid aqueous solution and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with 4 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was passed through an alumina column for purification. Next, after concentrating this toluene solution under reduced pressure, methanol was added to the toluene solution for reprecipitation, and the generated precipitate was recovered.

Next, this precipitate was washed with methanol and then dried under reduced pressure to obtain 0.17 g of a polymer. This polymer is called polymer compound 8. The polymer compound 8 had a polystyrene-equivalent number average molecular weight of 5.4 × 10 ³ and a polystyrene-equivalent weight average molecular weight of 8.7 × 10 ³ .

The structure of the repeating unit contained in the polymer compound 8 estimated from the preparation is shown below.
(Note that the molar ratio of the repeating units contained in the polymer compound 8 estimated from preparation is E / F = 7/3.)
E F

<Comparative Example 6> (Synthesis of Polymer Compound 9)
0.37 g of the monomer (6), 0.31 g of the monomer (3), 3,3′-dibromo-4,4′-dioctyloxybiphenyl 0.085 g and 2,2′-bipyridyl 0.66 g Were charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and reacted at room temperature for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, a mixed solution of 40 ml of methanol / 40 ml of ion exchange water was poured into this solution and stirred for about 1 hour. Next, the solvent was distilled off from this solution under reduced pressure. Toluene was added to the resulting precipitate, stirred and dissolved. The toluene solution was filtered to remove insoluble matters, and the obtained toluene solution was washed with about 5% by weight of an acetic acid aqueous solution and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with 4 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, the obtained toluene solution was passed through an alumina column for purification. Next, after concentrating the obtained toluene solution under reduced pressure, methanol was added thereto for reprecipitation, and the generated precipitate was recovered.

Next, this precipitate was washed with methanol and then dried under reduced pressure to obtain 0.21 g of a polymer. This polymer is called polymer compound 9. The polymer compound 9 had a polystyrene-equivalent number average molecular weight of 8.3 × 10 ³ and a polystyrene-equivalent weight average molecular weight of 1.6 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 9 estimated from the preparation is shown below.
(The molar ratio of the repeating units contained in the polymer compound 9 estimated from the preparation is G / H / I = 6/3/1.)
G H I

<Evaluation method> (Evaluation of fluorescence characteristics of polymer compound)
A 0.8 wt% toluene solution of the polymer compound was spin-coated on a quartz plate to prepare a polymer compound thin film. The fluorescence spectrum of this thin film was measured using a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, trade name: Fluorolog) at an excitation wavelength of 350 nm. In order to obtain the relative fluorescence intensity in the thin film, the spectrophotometer (trade name: Cary5E, manufactured by Varian) was obtained by integrating the fluorescence spectrum plotted in wavenumber with the intensity of Raman line of water as standard. The value assigned by the absorbance at the excitation wavelength was measured using.

  Table 1 shows the measurement results of the fluorescence peak wavelength and fluorescence intensity of the polymer compounds 1-6. It is recognized that the polymer compound 1 (Example) exhibits stronger fluorescence than the polymer compound 2 (Comparative Example). It is recognized that the polymer compound 3 (Example) exhibits stronger fluorescence than the polymer compound 4 (Comparative Example). It is recognized that the polymer compound 5 (Example) exhibits stronger fluorescence than the polymer compound 6 (Comparative Example). It is recognized that the polymer compound 1 (Example) exhibits stronger fluorescence than the polymer compounds 7 and 8 (Comparative Example). It is recognized that the polymer compound 3 (Example) exhibits stronger fluorescence than the polymer compound 9 (Comparative Example).

<Example 4> (Creation and evaluation of device)
Polymer compound 1 was dissolved in xylene to prepare xylene solution A having a polymer concentration of 1.0% by weight.
A 0.2 μm membrane of a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, trade name: BaytronP CH8000) on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering. A thin film having a thickness of 60 nm was formed by spin coating using the liquid filtered through a filter, and dried on a hot plate at 200 ° C. for 10 minutes.
Next, the xylene solution A was used to form a film at a rotation speed of 600 rpm by spin coating. The film thickness after film formation was about 70 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then barium was deposited as a cathode at about 5 nm and then aluminum was deposited at about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
By applying a voltage to the EL element, EL light emission having a peak at 435 nm was obtained from this element. The intensity of EL emission was almost proportional to the current density. The device started to emit light at 4.3 V, and the maximum light emission efficiency was 0.82 cd / A. The obtained results are shown in Table 2.

<Comparative Example 7>
Polymer compound 2 was dissolved in xylene to prepare xylene solution B having a polymer concentration of 1.0% by weight. In Example 4, an EL device was produced in the same manner as in Example 4 except that the xylene solution B was used instead of the xylene solution A. The film thickness after the film formation using the xylene solution B was about 72 nm.
By applying a voltage to the EL element, EL light emission having a peak at 450 nm was obtained from the element. The intensity of EL emission was almost proportional to the current density. The device started to emit light at 4.7 V, and the maximum light emission efficiency was 0.70 cd / A. The obtained results are shown in Table 2.

で表される化合物Ｓ１を５重量％添加した混合物の、１．３重量％キシレン溶液Ｃを調製した。
スパッタ法により１５０ｎｍの厚みでＩＴＯ膜を付けたガラス基板に、ポリ（エチレンジオキシチオフェン）／ポリスチレンスルホン酸の溶液（バイエル社、商品名：Ｂａｙｔｒｏｎ）を用いてスピンコートにより５０ｎｍの厚みで成膜し、ホットプレート上で２００℃で１０分間乾燥した。
次に、キシレン溶液Ｃを用いてスピンコートにより８００ｒｐｍの回転速度で成膜した。膜厚は約６３ｎｍであった。これを窒素ガス雰囲気下１３０℃で１時間乾燥した後、陰極としてバリウムを約５ｎｍ、次いでアルミニウムを約８０ｎｍ蒸着して、ＥＬ素子を作製した。なお、真空度が、１×１０^-4Ｐａ以下に到達した後に金属の蒸着を開始した。
前記ＥＬ素子に電圧を引加することにより、この素子から５１０ｎｍにピークを有するＥＬ発光が得られた。該素子は５．６５Ｖから発光が開始し、 ８．４Ｖで１００ｃｄ／ｍ²の発光を示し、最大発光効率は１．８ｃｄ／Ａであった。得られた結果を表２に示す。 <Example 5>
Polymer compound 1 has the following structural formula:

A 1.3% by weight xylene solution C of a mixture to which 5% by weight of the compound S1 represented by formula (1) was added was prepared.
A glass substrate with an ITO film with a thickness of 150 nm formed by sputtering is spin-coated to form a film with a thickness of 50 nm using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, trade name: Baytron). And dried on a hot plate at 200 ° C. for 10 minutes.
Next, the xylene solution C was used to form a film at a rotational speed of 800 rpm by spin coating. The film thickness was about 63 nm. This was dried at 130 ° C. for 1 hour in a nitrogen gas atmosphere, and then barium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
By applying a voltage to the EL element, EL light emission having a peak at 510 nm was obtained from this element. The device started to emit light at 5.65 V, showed light emission of 100 cd / m ^{2 at} 8.4 V, and had a maximum light emission efficiency of 1.8 cd / A. The obtained results are shown in Table 2.

<Comparative Example 8>
A 1.3 wt% xylene solution D of a mixture obtained by adding 5 wt% of the compound S1 to the polymer compound 2 was prepared.
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed into a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, trade name: Baytron). And dried on a hot plate at 200 ° C. for 10 minutes.
Next, the xylene solution D was used to form a film at a rotational speed of 800 rpm by spin coating. The film thickness was about 67 nm. This was dried at 130 ° C. for 1 hour in a nitrogen gas atmosphere, and then barium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
By applying a voltage to the EL element, EL light emission having a peak at 520 nm was obtained from the element. The device started to emit light at 6.7 V, showed light emission of 100 cd / m ² at 9.8 V, and had a maximum light emission efficiency of 0.64 cd / A. The obtained results are shown in Table 2.

で表される単量体（１０） ０．５８ｇと３，３’−ジブロム−４，４’−ジオクチルオキシビフェニル ０．２６ｇと２，２’−ビピリジル ０．６６ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）７０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）１．１５ｇを加え、室温で１０分間攪拌した後、６０℃で３時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Comparative Example 9> (Synthesis of Polymer Compound 10)
The following structural formula:

After charging 0.58 g of the monomer (10) represented by the following formula: 0.26 g of 3,3′-dibromo-4,4′-dioctyloxybiphenyl and 0.66 g of 2,2′-bipyridyl The inside of the reaction system was replaced with nitrogen gas. To this was added 70 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, stirred at room temperature for 10 minutes, and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled to room temperature, and then a mixed solution of methanol 60 ml / ion exchanged water 60 ml was poured into this solution, followed by stirring for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with a 1N hydrochloric acid aqueous solution and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with about 5 wt% aqueous ammonia and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was washed with ion-exchanged water and then allowed to stand to collect a separated toluene solution. Next, this toluene solution was poured into methanol and reprecipitated.

Next, the precipitate produced by reprecipitation was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.17 g of a polymer. This polymer is referred to as polymer compound 10. The polymer compound 10 had a polystyrene-equivalent number average molecular weight of 1.3 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 5.3 × 10 ⁴ .

The structure of the repeating unit contained in the polymer compound 10 estimated from the preparation is shown below.
(Note that the molar ratio of the repeating units contained in the polymer compound 10 estimated from the charge is C ′ / D ′ = 7/3.)
C'D '

<Comparative Example 10> (Element creation and evaluation of polymer compound 10)
A 1.0 wt% xylene solution E of a mixture obtained by adding 5 wt% of the compound S1 to the polymer compound 10 was prepared.
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed into a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, trade name: Baytron). And dried on a hot plate at 200 ° C. for 10 minutes.
Next, the xylene solution E was used to form a film at a rotational speed of 800 rpm by spin coating. The film thickness was about 77 nm. This was dried at 130 ° C. for 1 hour in a nitrogen gas atmosphere, and then barium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
By applying a voltage to the EL element, EL light emission having a peak at 510 nm was obtained from this element, but strong light emission derived from the polymer compound 10 was observed. The device started to emit light at 6.8 V, showed light emission of 100 cd / m ² at 13 V, and the maximum light emission efficiency was 0.05 cd / A. The obtained results are shown in Table 2.

  The device produced using the polymer compound 1 which is the polymer compound of the present invention exhibits higher luminous efficiency than the device produced using the polymer compounds 2 and 10 which are not the polymer compound of the present invention. Was recognized.

Claims (16)

Following formula (1):

(Wherein R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent)
A repeating unit represented by the following formula (70):

[In formula, C ring and D ring represent an aromatic ring each independently. C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group It may have a substituent selected from the group consisting of a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group and a cyano group. When a plurality of substituents are present, they may be the same or different. E is O or S. ]
A polymer compound having a repeating unit represented by: The repeating unit represented by the formula (1) is represented by the following formula (8):

(In the formula, R ¹⁷ and R ¹⁸ each independently represent a substituent.)
The polymer compound according to claim 1, which is represented by: The polymer compound according to claim 2, wherein R ¹⁷ and R ¹⁸ are each independently an alkyl group or an alkoxy group. The repeating unit represented by the formula (70) is represented by the following formulas (2a) to (2d):

(In the formula, X represents O or S, R ^a represents ^a substituent, m independently represents an integer of 0 to 5, and n independently represents an integer of 0 to 3. A plurality of R ^a are present. In some cases, they may be the same or different.)
The high molecular compound as described in any one of Claims 1-3 represented by either. The repeating unit represented by the formula (2a) is represented by the following formula (2E):

[Wherein Y represents O or S. R ^j and R ^k each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. ]
The polymer compound according to claim 4, which is represented by:   The repeating unit represented by the formula (1) is a repeating unit represented by the formula (8), and the repeating unit represented by the formula (70) is a repeating unit represented by the formula (2E). The polymer compound according to claim 5. Furthermore, the following formula (2):

(In the formula, Ar ₁ represents a divalent heterocyclic group not represented by the formula (70) or a divalent aromatic amine group. These groups may have a substituent.)
The high molecular compound as described in any one of Claims 1-6 which has a repeating unit represented by these. The polymer compound according to any one of claims 1 to 7, which has a polystyrene-equivalent number average molecular weight of 1.0 x 10 ^{3 to} 1.0 x 10 ⁸ .   The polymer light emitting element which has an electrode which consists of an anode and a cathode, and the light emitting layer which is provided between this electrode and contains the polymer compound as described in any one of Claims 1-8.   A planar light source comprising the polymer light emitting device according to claim 9.   A display device comprising the polymer light emitting device according to claim 9.   A liquid composition comprising the polymer compound according to any one of claims 1 to 8 and a solvent.   Furthermore, the liquid composition of Claim 12 containing a low molecular fluorescent material.   The thin film containing the high molecular compound as described in any one of Claims 1-8.   The organic transistor containing the high molecular compound as described in any one of Claims 1-8.   The solar cell containing the high molecular compound as described in any one of Claims 1-8.