JP2006328387A - High-molecular compound and high-molecular luminescent device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-molecular compound capable of providing an electronic element excellent in element performance when used as a material for electronic element. <P>SOLUTION: This high-molecular compound is characterized by including at least one residue of a compound represented by the formula [wherein A, B and C rings are each an aromatic or nonaromatic ring; Z<SB>1</SB>, Z<SB>2</SB>, Z<SB>3</SB>, Z<SB>4</SB>, and Z<SB>5</SB>are each C-(Q)<SB>z</SB>or a nitrogen atom; Q is a substituent or hydrogen; z is 0 or 1]. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 and charge transport materials are variously studied because they are soluble in a solvent and can form an organic layer in a light-emitting element by a coating method. Polyfluorenes are known as polymer compounds that can be used for light-emitting materials and charge transport materials in electronic devices such as polymer light-emitting devices (polymer LEDs) (Patent Document 1).
International Publication No. 99/54385 Pamphlet

However, the device performance of the device using the polymer compound as a light emitting material, a charge transporting material or the like has not yet been practically satisfactory.
For example, a polymer LED using the above-described polymer compound has not yet been in a satisfactory level in terms of device performance such as light emission efficiency and color tone of light emission.
An object of the present invention is to provide a polymer compound that can provide an electronic device having excellent device performance when used as a material for an electronic device.

〔式中、Ａ環、Ｂ環およびＣ環はそれぞれ独立に置換基を有していてもよい芳香族環または非芳香族環を表し、Ｚ₁、Ｚ₂、Ｚ₃、Ｚ₄、およびＺ₅はそれぞれ独立に、Ｃ−（Ｑ）ｚまたは窒素原子を表し、Ｑは、置換基または水素原子を表し、ｚは０または１を表し、Ａ環とＢ環は互いに、それぞれの環を構成するＺ₅以外の原子を共有していてもよく、Ａ環、Ｂ環およびＣ環の一つ以上二つ以下は非芳香族環である。〕 That is, the present invention provides a polymer compound containing at least one residue of a compound represented by the following formula (1).
(Formula 1)

[Wherein, A ring, B ring and C ring each independently represents an aromatic ring or a non-aromatic ring optionally having a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ independently represents C- (Q) z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, and ring A and ring B constitute each ring. Atoms other than Z ₅ may be shared, and one or more of A ring, B ring and C ring are non-aromatic rings. ]

  When used as a material for an electronic device, the polymer compound of the present invention provides an electronic device with excellent device performance.

In the formula (1), A ring, B ring and C ring each independently represent an aromatic ring or a non-aromatic ring which may have a substituent.

Examples of the aromatic ring include those having 4n + 2 π electrons in the ring structure. Specific examples include aromatic hydrocarbon rings such as benzene ring and cyclodecanpentaene ring; aromatic heterocycles such as furan ring, thiophene ring, pyrrole ring, pyridine ring, pyrimidine ring and pyridazine ring.
Non-aromatic rings include cyclopentane ring, cyclopentene ring, cyclopentadiene ring, cyclohexane ring, cyclohexene ring, cyclohexadiene ring, cycloheptane ring, cycloheptene ring, cycloheptadiene ring, cycloheptatriene ring, cyclooctane ring, cyclooctane ring, Octene ring, cyclooctadiene ring, cyclooctatriene ring, cyclooctatetraene ring, cyclononane ring, cyclononane ring, cyclononanediene ring, cyclononanetriene ring, cyclodecane ring, cyclodecene ring, cyclodecandiene ring, cyclodecanetriene ring , Cyclodecane tetraene ring, cyclododecane ring, cyclododecane ring, cyclododecane diene ring, cyclododecane triene ring, cyclododecane tetraene ring, cyclododecanpentaene ring, cycloundecane , Cycloundecane ring, cycloundecandiene ring, cycloundecantriene ring, cycloundecane tetraene ring, cycloundecanpentaene ring, cycloundecane hexaene ring, etc .; non-aromatic such as pyran ring, thiopyran ring, etc. Family heterocycles.

When the aromatic ring or the non-aromatic ring has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, Arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, fluorine atom, acyl group, acyloxy group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro And an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and an arylalkylthio group are more preferable.

  Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methyl group and an ethyl group. Propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, and the like, such as pentyl group, isoamyl group, hexyl group, An octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferred.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and 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 group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyl Examples include oxy group, pentyloxy group, Aryloxy group, octyloxy group, 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, and a 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 -A dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group etc. are mentioned, A pentylthio group, a hexylthio group, an octylthio group, 2-ethylhexylthio group, a decylthio group, and a 3,7- dimethyloctylthio group are preferable.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or through a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl groups, C _{1 to} C ₁₂ alkoxyphenyl groups (C _{1 to} C ₁₂ are carbon atoms). indicates that 1-12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group And a pentafluorophenyl group are exemplified, and a C ₁ -C ₁₂ alkoxyphenyl group and a C ₁ -C ₁₂ alkylphenyl group are preferred. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and a C _{1 to} C ₁₂ alkylphenoxy group. , 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, and C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group, Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

Arylthio group has a carbon number of usually about 3 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio group, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

Arylalkyl group is usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include 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 groups and the like, 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 usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, a phenylpentyloxy group, a phenyl group. hexyloxy group, a phenyl heptene Chiro alkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy groups such as phenyl Ok Chiro alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl - C ₁ -C ₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy The group C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy is preferred.

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl-C ₁ -C ₁₂ alkylthio groups, C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group are exemplified is, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₂ -C ₁₂ alkenyl group, a 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 groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

Arylalkynyl group has a carbon number of usually about 8 to 60, and examples thereof include phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, 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 groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is about 1-60 normally without including the carbon number of this substituent, Preferably it is C2-48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino 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, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, 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 groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, Examples include a fluoroacetyl group and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, Examples include benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group. And pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and has about 4 to 20 carbon atoms. Specific examples include the groups shown below. .

上記式において、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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。
中でも、チエニル基、Ｃ₁〜Ｃ₁₂アルキルチエニル基、ピロリル基、フリル基、ピリジル基、Ｃ₁〜Ｃ₁₂アルキルピリジル基、ピペリジル基、キノリル基、イソキノリル基などが好ましく、チエニル基、Ｃ₁〜Ｃ₁₂アルキルチエニル基、ピリジル基、Ｃ₁〜Ｃ₁₂アルキルピリジル基がさらに好ましい。 The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, the following structure is shown.

In the above formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group.
Among them, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group are preferable, a thienyl group, C ₁ ~ C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group more preferred.

  The substituted carboxyl group means 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 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl 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, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. Can be mentioned. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

In the above formula (1), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent C- (Q) z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z Represents 0 or 1.
Examples of the substituent in Q include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a substituted amino group, Examples include substituted silyl groups, fluorine atoms, acyl groups, acyloxy groups, amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, cyano groups, and nitro groups. , Similar to those described above.

A ring and B ring may share a ring atom other than Z ₅ constituting each ring, and one or more of A ring, B ring and C ring are non-aromatic rings.
Preferably, the ring A and the ring B share one ring atom other than Z ₅ . Moreover, the case where there is one non-aromatic ring is preferable.

式（１−１） 式（１−２） 式（１−３）

〔式中、Ａ環、Ｂ環およびＣ環はそれぞれ独立に置換基を有していてもよい芳香族環または非芳香族環を表し、Ｚ₁、Ｚ₂、Ｚ₃、Ｚ₄およびＺ₅はそれぞれ独立にＣ−（Ｑ）ｚまたは窒素原子を表し、Ｑは、置換基または水素原子を表し、ｚは０または１を表し、Ａ環とＢ環はＺ₅以外の環の原子を共有していてもよくまた、各環の置換基同士が結合して、さらに環を形成していてもよく、Ａ環、Ｂ環、Ｃ環のうち、結合手を持たない環の１つ以上が非芳香族環である。〕
Moreover, it is preferable that the high molecular compound of this invention contains the repeating unit shown by following formula (1-1)-(1-3) as a repeating unit.

Formula (1-1) Formula (1-2) Formula (1-3)

[Wherein, A ring, B ring and C ring each independently represents an aromatic ring or a non-aromatic ring which may have a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ Each independently represents C- (Q) z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, and ring A and ring B share a ring atom other than Z ₅ In addition, substituents of each ring may be bonded to each other to form a ring, and one or more of the rings having no bond among A ring, B ring and C ring It is a non-aromatic ring. ]

Specific examples of the repeating unit represented by the formula (1-1) include

等およびこれらが置換基を有するものが挙げられる。

And those having a substituent.

等およびこれらが置換基を有するものが挙げられる。 Specific examples of the repeating unit represented by the formula (1-2) include

And those having a substituent.

等およびこれらが置換基を有するものが挙げられる。 Specific examples of the repeating unit represented by the formula (1-3) include

And those having a substituent.

Among the repeating units represented by the above formulas (1-1) to (1-3), atoms constituting the A ring, the B ring and the C ring (the “atoms constituting the ring” form a ring skeleton) May refer to atoms other than carbon atoms, such as nitrogen, oxygen, sulfur, silicon, selenium, etc., but from the viewpoint of adjusting charge transportability, A ring, B ring and C ring It is preferable that all the constituent atoms are carbon atoms.

From the viewpoint of increasing the solubility of the polymer compound, the viewpoint of adjusting the emission wavelength, and the viewpoint of adjusting the charge transport property, it is preferable that any one of the A ring, the B ring, and the C ring has a substituent.

Furthermore, from the viewpoint of charge transportability, a repeating unit having a structure represented by the above formulas (1-1) and (1-2) is preferable. From the viewpoint of easy synthesis, the above formula (1-1) The structure shown is more preferred.

式（２−１）

〔式中、Ｒ₁およびＲ₂はそれぞれ独立に置換基を表し、Ｄ環は置換基を有していてもよい非芳香族環を表し、ａは０〜２の整数を表し、ｂは０〜３の整数を表し、Ｒ₁およびＲ₂がそれぞれ複数存在する場合、それらは同一でも異なっていてもよく、Ｒ₁とＲ₂は互いに結合して環を形成していてもよい。また、Ｒ₁および／またはＲ₂はＤ環と結合して環を形成していてもよく、Ｑおよびｚは前記と同じ意味を表す。〕
Furthermore, the above formula (1-1) is more preferably the following formula (2-1).

Formula (2-1)

[Wherein, R ₁ and R ₂ each independently represents a substituent, the D ring represents a non-aromatic ring which may have a substituent, a represents an integer of 0 to 2, and b represents 0 Represents an integer of ˜3, and when there are a plurality of R ₁ and R ₂ , they may be the same or different, and R ₁ and R ₂ may be bonded to each other to form a ring. R ₁ and / or R ₂ may be bonded to the D ring to form a ring, and Q and z represent the same meaning as described above. ]

式（３−１）

〔式中、Ｒ₁、Ｒ₂、Ｄ環、Ｑ、ｚ、ａおよびｂは前記と同じ意味を表す。〕
The repeating unit containing the above formula (2-1) is preferably a repeating unit represented by the following formula (3-1).

Formula (3-1)

[Wherein, R ₁ , R ₂ , D ring, Q, z, a and b represent the same meaning as described above. ]

式（４−１） 式(４-２)

式（４−３） 式（４‐４）

〔式中、Ｒ_1a、Ｒ_1b、Ｒ_2a〜Ｒ_2cおよびＲ_3a〜Ｒ_3gは置換基を表す。式（４−１）〜（４−３）において、Ｒ_2cとＲ_3gは互いに結合して環を形成しても良い。式（４−４）において、Ｒ_2cとＲ_3eは互いに結合して環を形成していても良い。〕
互いに結合して形成される環としては、芳香族環、非芳香族環等があげられその具体例等は、前記に記載と同様である。

なお、式（4−1）〜（4-３）の単位は、式（3-1）でｚ＝１の場合に含まれ、
式（4-4）の単位は、式（3-1）でｚ＝０の場合に含まれる。
Among the repeating units represented by the formula (3-1), from the viewpoint of adjusting the charge transport property, the following formulas (4-1), (4-2), (4-3) and (4-4) More preferred are those shown.

Formula (4-1) Formula (4-2)

Formula (4-3) Formula (4-4)

[In formula, R _<1a> , R _<1b> , R < _2a > -R <_2c> and R < _3a > -R < _3g > represent a substituent. In formulas (4-1) to (4-3), R _2c and R _3g may be bonded to each other to form a ring. In formula (4-4), R _2c and R _3e may be bonded to each other to form a ring. ]
Examples of the ring formed by bonding to each other include an aromatic ring and a non-aromatic ring, and specific examples thereof are the same as described above.

The units of the formulas (4-1) to (4-3) are included when z = 1 in the formula (3-1),
The unit of the formula (4-4) is included when z = 0 in the formula (3-1).

  As a specific example of the repeating unit represented by the above formula (4-1),

が挙げられる。

Is mentioned.

Specific examples of the repeating unit represented by the formula (4-2) include

が挙げられる。

Is mentioned.

Specific examples of the repeating unit represented by the formula (4-3) include

が挙げられる。

Is mentioned.

Specific examples of the repeating unit represented by the above formula (4-4) include

が挙げられる。

Is mentioned.

In the formula, Me represents a methyl group, and Et represents an ethyl group.

  The above formulas (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and The total of repeating units having the structure represented by (4-4) is usually 1 mol% or more and 100 mol% or less, and 5 mol% or more and 100 mol% of the total of all repeating units of the polymer compound of the present invention. The following is preferable.

  The polymer compound of the present invention has the above formulas (1-1), (1-2), (1-3), from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, improving the heat resistance, and the like. In addition to the repeating units represented by (2-1), (3-1), (4-1), (4-2), (4-3) and (4-4), 1 Copolymers containing more than one type are preferred.

−Ａｒ₄−Ｘ₂− （７）
−Ｘ₃− （８）
式中、Ａｒ₁、Ａｒ₂、Ａｒ₃およびＡｒ₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｘ₁、Ｘ₂およびＸ₃はそれぞれ独立に−ＣＲ₉＝ＣＲ₁₀−、−Ｃ≡Ｃ−、−Ｎ（Ｒ₁₁）−、または−（ＳｉＲ₁₂Ｒ₁₃）_m−を示す。Ｒ₉およびＲ₁₀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、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₁₁、Ｒ₁₂およびＲ₁₃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、アリールアルキル基または置換アミノ基を示す。ｆｆは１または２の整数を示す。mは１〜１２の整数を示す。Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂およびＲ₁₂がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。 The above formulas (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and The repeating unit other than the repeating unit represented by (4-4) is preferably a repeating unit represented by the following formula (5), formula (6), formula (7) or formula (8).

-Ar _1- (5)

—Ar ₄ —X ₂ — (7)
-X _3- (8)
In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₉ ═CR ₁₀ —, —C≡C—, —N (R ₁₁ ) —, or — (SiR ₁₂ R ₁₃ ) _m —. R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents an integer of 1 or 2. m represents an integer of 1 to 12. When there are a plurality of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₂ , they may be the same or different.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings directly or a group such as vinylene. Which are connected via The arylene group may have a substituent.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and cyano group.
Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.
Examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalenediyl group (formulas 4 to 13 in the following figure), an anthracene-diyl group (formulas 14 to 19 in the following figure), and a biphenyl-diyl group (in the following figure). Formulas 20 to 25), fluorene-diyl groups (formulas 36 to 38 in the following diagram), terphenyl-diyl groups (formulas 26 to 28 in the diagram below), condensed ring compound groups (formulas 29 to 35 in the diagram below), stilbene-diyl ( Examples are formulas A to D) and distilben-diyl (formulas E and F below). Of these, a phenylene group, a biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferable.

The divalent heterocyclic group in Ar ₁ , Ar ₂ , Ar _3, and Ar ₄ refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the group has a substituent. May be.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and cyano group.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups containing silicon, nitrogen, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure).
5-membered ring condensed hetero groups containing silicon, nitrogen, selenium and the like as a hetero atom: (Formulas 99 to 100 and 102 to 110 in the following figure).
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 111 to 112 in the following figure) Can be mentioned.
Examples include 5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to a phenyl group at the α-position of the hetero atom (formulas 113 to 119 in the following figure).
Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like as a hetero atom (formulas 120 to 125 in the following figure).

The divalent group having a metal complex structure in Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ is the remaining 2 obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand. Is a valent group.
The carbon number of the organic ligand is usually about 4 to 60. For example, 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof. Derivatives, 2-phenyl-benzoxazole and its derivatives, porphyrin and its derivatives and the like.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include the following (126 to 132).

  In the above formulas 1 to 132, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group. , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substitution A carboxyl group or a cyano group is shown. Moreover, the carbon atom which the group of Formula 1-132 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and the hydrogen atom may be substituted with the fluorine atom.

〔式中、Ｒ₁₄は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。nは０〜４の整数を示す。Ｒ₁₄が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₁₅およびＲ₁₆は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。oおよびpはそれぞれ独立に０〜３の整数を示す。Ｒ₁₅およびＲ₁₆がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₁₇およびＲ₂₀は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。qおよびrはそれぞれ独立に０〜４の整数を示す。Ｒ₁₈およびＲ₁₉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、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₁₇およびＲ₂₀が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₁は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。sは０〜２の整数を示す。Ａｒ₁₃およびＡｒ₁₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。ｓｓおよびｔｔはそれぞれ独立に０または１を示す。
Ｘ₄は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ，またはＴｅを示す。Ｒ₂₁が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₂およびＲ₂₅は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。tおよびuはそれぞれ独立に０〜４の整数を示す。Ｘ₅は、Ｏ、Ｓ、ＳＯ₂、Ｓｅ，Ｔｅ、Ｎ−Ｒ₂₄、またはＳｉＲ₂₅Ｒ₂₆を示す。Ｘ₆およびＸ₇は、それぞれ独立にＮまたはＣ−Ｒ₂₇を示す。Ｒ₂₄、Ｒ_25、Ｒ₂₆およびＲ₂₇はそれぞれ独立に水素原子、アルキル基、アリール基、アリールアルキル基または１価の複素環基を示す。Ｒ₂₂、Ｒ₂₃およびＲ₂₇が複数存在する場合、それらは同一でも異なっていてもよい。〕
式（１１）で示される繰り返し単位の中央の５員環の例としては、チアジアゾール、オキサジアゾール、トリアゾール、チオフェン、フラン、シロールなどが挙げられる。 Furthermore, among the repeating units represented by the above formulas (5), (6), (7) and (8), the following formula (9), formula (10), formula (11), formula (12), formula The repeating unit represented by (13) or formula (14) is preferred.

[Wherein, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, A substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group are shown. n represents an integer of 0 to 4. When a plurality of R ₁₄ are present, they may be the same or different. ]

Wherein R ₁₅ and R ₁₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. o and p each independently represent an integer of 0 to 3. When a plurality of R ₁₅ and R ₁₆ are present, they may be the same or different. ]

[Wherein, R ₁₇ and R ₂₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. q and r each independently represents an integer of 0 to 4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₁₇ and R ₂₀ are present, they may be the same or different. ]

[Wherein, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, A substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group are shown. s shows the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1.
X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₁ are present, they may be the same or different. ]

[Wherein R ₂₂ and R ₂₅ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. t and u each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₂₄ , or SiR ₂₅ R ₂₆ . X ₆ and X ₇ each independently represent N or C—R ₂₇ . R ₂₄ , R _25, R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When a plurality of R ₂₂ , R ₂₃ and R ₂₇ are present, they may be the same or different. ]
Examples of the central 5-membered ring of the repeating unit represented by the formula (11) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like.

〔式中、Ｒ₂₈およびＲ₃₃は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。vおよびwはそれぞれ独立に０〜４の整数を示す。Ｒ₂₉、Ｒ₃₀、Ｒ₃₁およびＲ₃₆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、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ａｒ₅はアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｒ₂₈およびＲ₃₃が複数存在する場合、それらは同一でも異なっていてもよい。〕

また上記式（６）で示される繰り返し単位の中で、下記式（１５）で示される繰り返し単位が、発光波長を変化させる観点、発光効率を高める観点、耐熱性を向上させる観点からも好ましい。

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈およびＡｒ₉はそれぞれ独立にアリーレン基または２価の複素環基を示す。Ａｒ₁₀、Ａｒ₁₁およびＡｒ₁₂はそれぞれ独立にアリール基、または１価の複素環基を示す。Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、およびＡｒ₁₀は置換基を有していてもよい。ｘおよびｙはそれぞれ独立に０または１を示し、０≦ｘ＋ｙ≦１である。〕

Wherein R ₂₈ and R ₃₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. v and w each independently represent an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. ]

Of the repeating units represented by the above formula (6), the repeating unit represented by the following formula (15) is preferable from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, and improving the heat resistance.

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ]

Specific examples of the repeating unit represented by the above formula (15) include those represented by the following (formulas 133 to 140).

In the above formula, R is the same as that in formulas 1-132.
In order to increase the solubility in a solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.

In the above-mentioned formula, in the substituent in which R contains alkyl, it is preferable that one or more alkyls having a cyclic or branched structure are contained in order to enhance the solubility of the polymer compound in the solvent.
Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

In the repeating unit represented by the above formula (15), Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ are each independently an arylene group from the viewpoints of adjusting the emission wavelength, device characteristics, etc., Ar ₁₀ , Ar It is preferable that ₁₁ and Ar ₁₂ each independently represent an aryl group.

Ar ₆ , Ar ₇ , and Ar ₈ are each independently preferably an unsubstituted phenylene group, an unsubstituted biphenyl group, an unsubstituted naphthylene group, or an unsubstituted anthracenediyl group.

The Ar _10, Ar ₁₁ and Ar _12, solubility, light emission efficiency, from the viewpoint of stability, independently, preferably has an aryl group having three or more substituents, Ar _10, Ar ₁₁ and Ar More preferably, ₁₂ is a phenyl group having 3 or more substituents, a naphthyl group having 3 or more substituents, or an anthranyl group having 3 or more substituents, and Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are substituted. What is a phenyl group which has 3 or more groups is more preferable.

〔式中、Ｒe、ＲfおよびＲgは、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、シリルオキシ基、置換シリルオキシ基、1価の複素環基またはハロゲン原子を表す。〕 Among them, it is preferable that Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are each independently the following formula (15-1).

[In the formula, Re, Rf and Rg are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. An alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group or a halogen atom is represented. ]

[ここで、(１５−２)、(１５−３)で示される構造に含まれるベンゼン環は、それぞれ独立に１個以上４個以下の置換基を有していてもよい。それら置換基は、互いに同一であっても、異なっていても良い。また、複数の置換基が連結して環を形成していても良い。さらに、該ベンゼン環に隣接して他の芳香族炭化水素環または複素環が結合していても良い。] In the repeating unit represented by the formula (15), Ar ₇ is preferably the following formula (15-2) or (15-3).

[Here, the benzene rings contained in the structures represented by (15-2) and (15-3) may each independently have 1 or more and 4 or less substituents. These substituents may be the same as or different from each other. A plurality of substituents may be connected to form a ring. Further, another aromatic hydrocarbon ring or heterocyclic ring may be bonded adjacent to the benzene ring. ]

〔式中、Ｒｅ〜Ｒｇは前述の通り。〕 As the repeating unit represented by the above formula (15), particularly preferred specific examples include those represented by the following (formulas 141 to 142).

[Wherein, Re to Rg are as described above. ]

In the above formula, Re to Rg are the same as those in the above formulas 1 to 132. In order to increase the solubility in a solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.
In the above formula, the substituent in which R includes an alkyl chain preferably includes one or more alkyl chains having a cyclic or branched structure in order to enhance the solubility of the polymer compound in the solvent.
Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

The polymer compound of the present invention has the above formulas (1-1), (1-2), (1-3) and formulas (5) to (15) as long as the light emission characteristics and the charge transport characteristics are not impaired. It may contain a repeating unit other than the repeating unit represented by In addition, these repeating units and other repeating units may be linked by non-conjugated units, or the repeating units may contain those non-conjugated parts. Examples of the binding structure include those shown below and combinations of two or more of the following. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

  Among the polymer compounds of the present invention, those comprising only the repeating unit represented by the above formula (1-1) and / or comprising only the repeating unit represented by (1-2) and / or (1 -3) consisting of only the repeating unit, substantially the above formulas (1-1) and / or (1-2) and / or (1-3) and the above formulas (5) to (15) Those consisting of one or more of the repeating units shown are preferred.

  The polymer compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, such as a random copolymer having a block property. Good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of fluorescence or phosphorescence, a random copolymer having a block property and a block or graft copolymer are 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.

  In addition, the terminal group of the polymer compound of the present invention may be protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and lifetime when the device is made will be reduced. . Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  In the polymer compound of the present invention, at least one of the molecular chain ends is composed of a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, and an aryl group. The aromatic end group selected is preferred. This aromatic terminal group may be one type or two or more types. It is preferable that terminal groups other than the aromatic terminal group are substantially absent from the viewpoints of fluorescence characteristics and device characteristics. Here, the molecular chain terminal means an aromatic terminal group present at the terminal of the polymer compound by the production method of the present invention, a leaving group of the monomer used for the polymerization, and the polymer is not detached at the time of polymerization. A leaving group existing at the end of a compound or a hydrogen atom bonded without a bonded aromatic end group without a leaving group derived from a monomer present at the end of a polymer compound. Of these molecular chain ends, the leaving group of the monomer used for the polymerization, and the leaving group present at the end of the polymer compound without being eliminated during the polymerization, for example, a monomer having a halogen atom as a raw material In the case of producing the polymer compound of the present invention using a polymer, since the fluorescence characteristics and the like tend to be reduced if halogen remains at the polymer compound terminal, the monomer leaving group is present at the terminal. It is preferable that no substantially remains.

In the polymer compound, at least one of the molecular chain ends is a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, or an aryl having a formula weight of 90 or more. By sealing with an aromatic end group selected from a group, it is expected to add various characteristics to the polymer compound. Specifically, the effect of increasing the time required to reduce the luminance of the device, the effect of increasing the charge injection property, the charge transport property, the light emission property, the effect of increasing the compatibility and interaction between the copolymers, the anchor effect Etc.

Examples of the monovalent aromatic amine group include a structure in which one of two bonds in the structure of the formula (15) is sealed with R.

Examples of the monovalent group derived from the heterocyclic coordination metal complex include a structure in which one of two bonds in the divalent group having the above metal complex structure is sealed with R. .

  Among the aromatic end groups of the polymer compound of the present invention, the aryl group having a formula weight of 90 or more usually has about 6 to 60 carbon atoms. Here, the formula weight of the aryl group means the sum of the number of atoms of each element multiplied by the atomic weight of each element in the chemical formula when the aryl group is represented by a chemical formula.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a group having a fluorene structure, and a condensed ring compound group.

があげられる。
Examples of the phenyl group for sealing the end include

Can be given.

があげられる。 As a naphthyl group for sealing the end, for example,

Can be given.

があげられる。 As an anthracenyl group, for example,

Can be given.

があげられる。 Examples of the group containing a fluorene structure include:

Can be given.

があげられる。 As the condensed ring compound group, for example,

Can be given.

As the terminal group for enhancing the charge injection property and the charge transport property, a monovalent heterocyclic group, a monovalent aromatic amine group, and a condensed ring compound group are preferable, and a monovalent heterocyclic group and a condensed ring compound group are more preferable. .

As the terminal group for enhancing the light emission characteristics, a monovalent group derived from a naphthyl group, an anthracenyl group, a condensed ring compound group or a heterocyclic coordination metal complex is preferable.

As the terminal group having an effect of prolonging the time required for reducing the luminance of the element, an aryl group having a substituent is preferable, and a phenyl group having 1 to 3 alkyl groups is preferable.

As an end group having an effect of enhancing compatibility and interaction between polymer compounds, an aryl group having a substituent is preferable. An anchor effect can be obtained by using a phenyl group substituted with an alkyl group having 6 or more carbon atoms. The anchor effect means an effect in which the end group plays an anchor role with respect to the polymer aggregate and enhances the interaction.

式中のＲは前述のＲが例示される。 As the group for enhancing the element characteristics, the following structure is preferable.

R in the formula is exemplified by the aforementioned R.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ . The weight average molecular weight in terms of polystyrene is 10 ³ to 10 ^8, preferably 10 ⁴ to 5 × 10 ^6.

Examples of the good solvent for the polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. 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.

The polymer compound of the present invention can emit light at a shorter wavelength than the corresponding polyfluorene derivative.

式（１６‐１） 式（１６‐２） 式（１６‐３）

〔式中、Ａ環、Ｂ環、Ｃ環、Ｚ₁〜Ｚ₅は前述の通り。Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄、Ｙ₅およびＹ₆はそれぞれ独立に重合に関与する置換基を表す。〕
で示される化合物を用いて重合させることで製造することができる。
Next, the method for producing the polymer compound of the present invention will be described.
Among the polymer compounds of the present invention, for example, those having a repeating unit represented by the formulas (1-1), (1-2), and (1-3) each include at least the following formula (16- 1), (16-2) and (16-3)

Formula (16-1) Formula (16-2) Formula (16-3)

[Wherein, A ring, B ring, C ring and Z _{1 to} Z ₅ are as described above. Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a substituent involved in polymerization. ]
It can manufacture by polymerizing using the compound shown by these.

式（１７‐１）

〔式中、Ｒ₁、Ｒ₂、ａ、ｂ、Ｄ環、Ｑ、ｚ、Ｙ₁およびＹ₂は前記と同じ意味を表す。〕 Of the compounds represented by the formula (16-1), the compound represented by the formula (17-1) is preferable.

Formula (17-1)

[Wherein R ₁ , R ₂ , a, b, D ring, Q, z, Y ₁ and Y ₂ represent the same meaning as described above. ]

式（１８−１） 式（１８−２）

式（１８−３） 式（１８−４）
Among the compounds represented by the formula (17-1), the structures represented by the formulas (18-1), (18-2), (18-3) and (18-4) are more preferable.

Formula (18-1) Formula (18-2)

Formula (18-3) Formula (18-4)

式（１７−２）
〔式中、Ｂ環、Ｃ環、Ｚ₂、Ｚ₃、Ｚ₄、Ｙ₃およびＹ₄は前記と同じ意味を表す。Ｚ₆、Ｚ₇およびＺ₈はそれぞれ独立にＣ−（Ｑ）ｚまたは窒素原子を示す。Ｚ_1a、Ｚ_5aおよびＺ₉はそれぞれ独立に炭素原子を示す。Ｑ、およびｚは前記と同じ意味を表す。Ｒ₄は置換基を示す。ｅは０〜２の整数を示す。Ｒ₄が複数ある場合、それらは同一でも異なっていてもよく、Ｒ₄同士が結合して環を形成していてもよい。〕
Of the compounds represented by formula (16-2), the compound represented by formula (17-2) is preferred.

Formula (17-2)
[Wherein, B ring, C ring, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y ₄ represent the same meaning as described above. Z ₆ , Z ₇ and Z ₈ each independently represent C— (Q) z or a nitrogen atom. Z _1a , Z _5a and Z ₉ each independently represent a carbon atom. Q and z have the same meaning as described above. R ₄ represents a substituent. e shows the integer of 0-2. When there are a plurality of R ₄ , they may be the same or different, and R ₄ may be bonded to form a ring. ]

式（１７−３）
〔式中、Ａ環、Ｂ環、Ｚ₁、Ｚ₄、Ｚ₅、Ｙ₅およびＹ₆は前記と同じ意味を表す。Ｚ₁₀、Ｚ₁₁、Ｚ₁₂およびＺ₁₃はそれぞれ独立に、Ｃ−（Ｑ）ｚまたは窒素原子を示す。Ｚ_2aおよびＺ_3aはそれぞれ独立に炭素原子を示す。Ｑ、およびｚは前記と同じ意味を表す。Ｒ₅は置換基を示す。ｆは０〜２の整数を示す。Ｒ₅が複数ある場合、それらは同一でも異なっていてもよく、Ｒ₅同士が結合して環を形成していてもよい。〕 Of the compounds represented by formula (16-3), the compound represented by formula (17-3) is preferred.

Formula (17-3)
[Wherein, A ring, B ring, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y ₆ represent the same meaning as described above. Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each independently represent C— (Q) z or a nitrogen atom. Z _2a and Z _3a each independently represent a carbon atom. Q and z have the same meaning as described above. R ₅ represents a substituent. f shows the integer of 0-2. When there are a plurality of R ₅ , they may be the same or different, and R ₅ may be bonded to each other to form a ring. ]

In the production method of the present invention, the substituents involved in the polymerization include halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, mono Examples thereof include a halogenated methyl group, —B (OH) ₂ , formyl group, cyano group, vinyl group and the like.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of improving the degree of polymerization, bromine atoms and iodine atoms are preferred.

  Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include benzyl. Examples include sulfonate groups.

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。 Examples of the borate group include groups represented by the following formula.

In the formula, Me represents a methyl group, and Et represents an ethyl group.

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
—CH ₂ PO (OR ′) ₂ (X represents a halogen atom, R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

  Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

A preferable substituent as a substituent involved in the polymerization varies depending on the type of polymerization reaction. For example, when a zerovalent nickel complex such as a Yamamoto coupling reaction is used, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group Is mentioned. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

  In particular, the polymer compound having a repeating unit of the formula (4-1) is a polymer compound having a repeating unit of the formulas (4-2) to (4-4), palladium, platinum, rhodium, ruthenium, or these. It can also be obtained by hydrogenating a noble metal mixed with a catalyst supported on activated carbon.

Conversely, the polymer compound having a repeating unit of formulas (4-2) to (4-4) is obtained by converting the polymer compound having a repeating unit of formula (4-1) to 2,3-dichloro-5,6- It can also be obtained by oxidation using dicyano-1,4-benzoquinone (DDQ) or brominated tetrabutylammonium under basic conditions.

  When the polymer compound of the present invention has a repeating unit other than formula (1-1), formula (1-2), or formula (1-3), formula (1-1) or formula (1) -2) or a compound having a substituent that participates in two polymerizations, which is a repeating unit other than formula (1-3), may be polymerized together.

式（２１）
Ｙ₁₁−Ａｒ₄−Ｘ₂−Ｙ₁₂

式（２２）
Ｙ₁₃−Ｘ₃−Ｙ₁₄
〔式中、Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄、ｆｆ、Ｘ₁、Ｘ₂およびＸ₃は前記と同じである。Ｙ₇、Ｙ₈、Ｙ₉、Ｙ₁₀、Ｙ₁₁、Ｙ₁₂、Ｙ₁₃、Ｙ₁₄はそれぞれ独立に重合可能な置換基を示す。〕
上記式(１−１)、（１−２）または（１−３）で示される単位に加えて、順に（５）、（６）、（７）または（８）の単位を１つ以上有する高分子化合物を製造することができる。 In addition to the compound represented by the above formula (16-1), (16-2) or (16-3), a compound represented by any of the following formulas (19) to (22) can be used as a raw material. .
Formula (19)
Y ₇ -Ar ₁ -Y ₈

Formula (20)

Formula (21)
Y ₁₁ -Ar ₄ -X ₂ -Y ₁₂

Formula (22)
Y ₁₃ -X ₃ -Y ₁₄
[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ ff, X ₁ , X ₂ and X ₃ are the same as described above. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a polymerizable substituent. ]
In addition to the unit represented by the above formula (1-1), (1-2) or (1-3), it has one or more units of (5), (6), (7) or (8) in order. A polymer compound can be produced.

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、Ａｒ₁₀、Ａｒ₁₁、Ａｒ₁₂、ｘおよびｙは前記と同じ。Ｙ₁₅およびＹ₁₆はそれぞれ独立に重合に関与する置換基を示す。〕
さらに好ましくは、式（１５−８）または式（１５−９）で示される化合物である。

式（１５−８） 式（１５−９）

〔式中、Ｒｅ〜Ｒｇは前述の通り。Ｙ₁₇、Ｙ₁₈、Ｙ₁₉、Ｙ₂₀はそれぞれ独立に重合に関与する置換基を示す。〕 Moreover, the substituent which participates in two superposition | polymerization corresponding to the said Formula (15) used as repeating units other than the repeating unit shown by said Formula (1-1), (1-2) or (1-3). Examples of the compound having a include a compound represented by the following formula (15-7).

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , x and y are the same as described above. Y ₁₅ and Y ₁₆ each independently represent a substituent involved in polymerization. ]
More preferred is a compound represented by formula (15-8) or formula (15-9).

Formula (15-8) Formula (15-9)

[Wherein, Re to Rg are as described above. Y ₁₇ , Y ₁₈ , Y ₁₉ and Y ₂₀ each independently represent a substituent involved in polymerization. ]

  Specifically, in the production method of the present invention, a compound having a plurality of substituents involved in condensation polymerization, which is a monomer, is dissolved in an organic solvent as necessary. For example, using an alkali or a suitable catalyst, Can be carried out at a melting point or higher and a boiling point or lower. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Vol. 6, (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Mac Molecular Symposium (Makromol., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

In the method for producing a polymer compound of the present invention, the method for polymerizing includes substituents involved in the polymerization of the compounds represented by the above formulas (16-1) to (16-3) and (22) to (25). Depending on the case, it can be produced by using a known polymerization reaction.
When the polymer compound of the present invention forms a double bond in polymerization, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by a Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or polymerization of a compound having a formyl group and a phosphonium methyl group, by a Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polymerization of a compound having two or more monohalogenated methyl groups by a dehydrohalogenation method, polymerization of a compound having two or more sulfonium methyl groups by a sulfonium salt decomposition method, and a compound having a formyl group Examples thereof include a method such as polymerization by a Knoevenagel reaction with a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the polymer compound of the present invention generates a triple bond in the main chain by polymerization, for example, Heck reaction and Sonogashira reaction can be used.

Further, when a double bond or triple bond is not generated, for example, 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) complex, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like.

  Among these, the structure is controlled by polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Knoevenagel reaction, polymerization by Suzuki coupling reaction, polymerization by Grignard reaction, and polymerization by nickel zero-valent complex. It is preferable because it is easy.

In the production method of the present invention, the compound represented by the formula (16-1), (16-2) or (16-3) is selected alone or from the compounds represented by the formulas (19) to (22). Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ , Y ₂₀ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group, and condensation polymerization in the presence of a nickel zero-valent complex The manufacturing method is preferred.

As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples thereof include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

In the production method of the present invention,
When polymerizing the compound represented by the formula (16-1), (16-2) or (16-3) alone or with at least one selected from the compounds represented by the formulas (19) to (22) Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ , and Y ₂₀ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, —B (OH) ₂ , or a borate group, and a halogen atom or an alkyl sulfonate The ratio of the total number of moles of the group arylsulfonate group and arylalkylsulfonate group to the total number of moles of —B (OH) ₂ and borate group is substantially 1 (usually K / J is 0.7-1) .2 range) and Nikke A production method in which condensation polymerization is performed using a palladium or palladium catalyst is preferred.

Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Further, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, aryl alkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. 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 the Suzuki coupling reaction.

  Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane and bromopentane. Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol Alcohols such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, tetra Ethers such as drofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N , N-diethylacetamide, amides such as N-methylmorpholine oxide, etc. are exemplified, and a single solvent or a mixed solvent thereof may be used. Of these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

  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.

  When the polymer compound of the present invention is used for a polymer LED or the like, its purity affects the performance of the device such as light emission characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, recrystallization, etc. It is preferable to polymerize. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

(16-1) to (16-3), (17-1) to (17-3) and (18-1) to (18-4) useful as raw materials for the polymer compound of the present invention are represented by the above formulae. Is obtained by brominating a compound having a structure in which Y ₁ to Y ₆ are replaced with hydrogen atoms.

  In particular, the compound having the structure of the formula (18-1) is obtained by replacing the compounds having the structures of the formulas (18-2) to (18-4) with palladium, platinum, rhodium, ruthenium, or a noble metal obtained by mixing these on activated carbon. It can also be obtained by hydrogenation with a catalyst supported on the catalyst.

Conversely, the compound having the structure of formulas (18-2) to (18-4) is obtained by converting the compound having the structure of formula (18-1) to 2,3-dichloro-5,6-dicyano-1,4- It can also be obtained by oxidation with benzoquinone (DDQ) or brominated tetrabutylammonium under basic conditions.

Next, the use of the polymer compound of the present invention will be described.
The polymer compound of the present invention usually emits fluorescence or phosphorescence in a solid state and can be used as a polymer light emitter (high molecular weight light emitting material).
Further, the polymer compound has an excellent charge transport ability, and can be suitably used as a polymer LED material or a charge transport material. The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency. Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display, a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display, and the like.
The polymer compound of the present invention can also be used as a material for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films.
Furthermore, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the polymer compound of the present invention.
The organic layer may be any of a light emitting layer, a hole transport layer, an electron transport layer, and the like, but the organic layer is preferably a light emitting layer.

  Here, the light emitting layer refers to a layer having a function of emitting light, the hole transport layer refers to a layer having a function of transporting holes, and the electron transport layer is a layer having a function of transporting electrons. Say. 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.

When the organic layer is a light emitting layer, the light emitting layer which is an organic layer may further contain a hole transport material, an electron transport material or a light emitting material. Here, the light-emitting material refers to a material that exhibits fluorescence and / or phosphorescence.
When the polymer compound of the present invention and the hole transport material are mixed, the mixing ratio of the hole transport material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. . When the polymer compound of the present invention and the electron transport material are mixed, the mixing ratio of the electron transport material to the entire mixture is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt%. Further, when the polymer compound of the present invention and the light emitting material are mixed, the mixing ratio of the light emitting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt%, with respect to the entire mixture. When the polymer compound of the present invention is mixed with a light emitting material, a hole transport material and / or an electron transport material, the mixing ratio of the light emitting material is 1 wt% to 50 wt%, preferably 5 wt% with respect to the entire mixture. The total amount of the hole transport material and the electron transport material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%, and the content of the polymer compound of the present invention is 99 wt% to 20 wt%.

As the hole transport material, the electron transport material, and the light-emitting material to be mixed, known low-molecular compounds, triplet light-emitting complexes, or polymer compounds can be used, but polymer compounds are preferably used. As the hole transport material, electron transport material, and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23434816, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636, WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07070720 WO95 / 07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-200065 136,379, JP-A 2000-104057, JP-A 2000-80167, JP-A 10-324870, JP-A 10-114891, JP-A 9-111233, JP-A 9-45478, etc. Examples include polymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.
Examples of low molecular weight fluorescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its derivatives of metals. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Examples of triplet light-emitting complexes include Ir (ppy) 3, Btp ₂ Ir (acac) with iridium as the central metal, PtOEP with platinum as the central metal, Eu (TTA) 3phen with europium as the central metal, etc. It is done.

三重項発光錯体として具体的には、例えばNature, (1998), 395, 151、Appl. Phys. Lett. (1999), 75(1), 4、Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105(Organic Light-Emitting Materials and DevicesＩＶ), 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 、Jpn.J.Appl.Phys.,34, 1883 (1995)などに記載されている。

Specific examples of triplet light-emitting complexes 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, Jpn. J. Appl. Phys., 34, 1883 (1995).

The composition of the present invention contains at least one material selected from a hole transport material, an electron transport material, and a light emitting material and the polymer compound of the present invention, and can be used as a light emitting material or a charge transport material.
The content ratio of at least one material selected from the hole transport material, electron transport material, and light emitting material and the polymer compound of the present invention may be determined according to the application.

  As another embodiment of the present invention, a polymer composition containing two or more polymer compounds of the present invention is exemplified.

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

Examples of the method for forming the light emitting layer include a method by film formation from a solution. When a polymer LED of the present invention is used to form a film from a solution during the production of a polymer LED, it is only necessary to remove the solvent by drying after coating the solution, and to mix a charge transport material and a light emitting material. In this case, the same technique can be applied, which is very advantageous in manufacturing.
As a film formation method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, A coating method such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

The ink composition of the present invention can be used as a solution used in a printing method or the like.
The ink composition of the present invention only needs to contain at least one polymer compound of the present invention and a solvent. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as stabilizers may be included.
The ink composition of the present invention is in a liquid state at the time of device preparation, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C.
Further, the ink composition of the present invention is not necessarily colored.

The ratio of the polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the ink composition excluding the solvent.
The proportion of the solvent in the ink composition is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.9 wt%, more preferably 90 wt% to 99.99 wt% with respect to the total weight of the ink composition. 8 wt%.
The viscosity of the ink composition (solution) varies depending on the printing method. However, when the solution passes through the discharge device, such as an ink jet printing method, the viscosity is 25 ° C. to prevent clogging and flight bending at the time of discharge. Is preferably in the range of 1 to 20 mPa · s.

  Examples of the solvent used in the ink composition of the present invention include chloroform solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, and ether solvents such as tetrahydrofuran and dioxane. Solvents, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane Solvents, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomer Polyethers such as ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and their derivatives, alcohols such as methanol, ethanol, propanol, isopropanol, cyclohexanol Examples include solvents, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination. Of the above solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring, a melting point of 0 ° C. or lower, and a boiling point of 100 ° C. or higher.

  Solvent types include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents from the viewpoints of solubility of the polymer compound of the present invention in organic solvents, uniformity during film formation, viscosity characteristics, and the like. Solvents and ketone solvents are preferable, and 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, 3-heptan Non, 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 in the ink composition is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics. .

  When the ink composition contains two types of solvents, 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 is a solvent having a boiling point of 180 ° C. or higher, and the other one type of solvent is preferably a solvent having a boiling point of 180 ° C. or lower. More preferably, the solvent is a solvent having a boiling point of 180 ° C. or lower. From the viewpoint of viscosity, it is preferable that 0.2 wt% or more of the polymer compound of the present invention dissolves at 60 ° C. in one of the two solvents. It is preferable that 0.2 wt% or more of the polymer compound of the present invention dissolves at a temperature of 0 ° C.

  When the ink composition contains three types of solvents, one or two of them 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 180 ° C. or lower. 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 180 ° C. or less. Further, from the viewpoint of viscosity, it is preferable that 0.2 wt% or more of the polymer compound of the present invention is dissolved in two of the three solvents at 60 ° C. Of the three solvents, It is preferable that 0.2 wt% or more of the polymer compound of the present invention is dissolved in one type of solvent at 25 ° C.

  When the ink composition contains two or more kinds of solvents, the solvent having the highest boiling point is preferably 40 to 90 wt% of the total solvent weight of the ink composition from the viewpoint of viscosity and film formability. More preferably, it is -90 wt%, and it is further more preferable that it is 65-85 wt%.

  The ink composition of the present invention includes, from the viewpoint of viscosity and film formability, a composition composed of anisole and bicyclohexyl, a composition composed of anisole and cyclohexylbenzene, a composition composed of xylene and bicyclohexyl, and xylene and cyclohexylbenzene. A composition consisting of mesitylene and methyl benzoate is preferred.

Among the additives that the ink composition of the present invention can contain,
As the hole transport material, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, a polyaniline or Examples thereof include a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof.
Electron transport materials include oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinodimethane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene Or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, or polyfluorene or a derivative thereof.
Examples of luminescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or metal complexes of its derivatives, aromatic amines, tetra Examples thereof include phenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof.

The ink composition (solution) of the present invention may contain an additive for adjusting viscosity and / or surface tension in addition to the polymer compound of the present invention. As the additive, a high molecular weight polymer compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. Use it.

The high molecular weight polymer compound may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a polymer compound of the present invention having a large molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, more preferably 1,000,000 or more.
A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and amount of the solvent may be selected as long as the solid content in the solution does not precipitate.

The ink composition (solution) of the present invention may contain an antioxidant in addition to the polymer compound of the present invention in order to improve storage stability. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  From the viewpoint of solubility of the polymer compound of the present invention in a solvent, the difference between the solubility parameter of the solvent and the solubility parameter of the polymer compound is preferably 10 or less, and more preferably 7 or less.

The solubility parameter of the solvent and the solubility parameter of the polymer compound of the present invention can be determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

  The polymer LED of the present invention includes a polymer LED provided with an electron transport layer between the cathode and the light emitting layer, a polymer LED provided with a hole transport layer between the anode and the light emitting layer, and a cathode. Examples include a polymer LED in which an electron transport layer is provided between the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

For example, the following structures a) to d) are specifically 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.)

The polymer LED of the present invention includes those in which the polymer compound of the present invention is contained in a hole transport layer and / or an electron transport layer.
When the polymer compound of the present invention is used for a hole transport layer, the polymer compound of the present invention is preferably a polymer compound containing a hole transporting group, and specific examples thereof include aromatic amines. And a copolymer with stilbene.
When the polymer compound of the present invention is used for an electron transport layer, the polymer compound of the present invention is preferably a polymer compound containing an electron transporting group, and specific examples thereof include oxadiazole. And a copolymer with triazole, a copolymer with quinoline, a copolymer with quinoxaline, a copolymer with benzothiadiazole, and the like.

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. , Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is 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-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain.

Examples of the hole transport material of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  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. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

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

  Since polysiloxane or a derivative thereof 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.

  Examples of film formation methods from solution include spin coating 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 Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  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 LED of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof. Derivatives, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or Examples thereof include polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, and for polymer electron transport materials, solution or Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, the above 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.

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

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving 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 a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly 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 an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, 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 laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

  The polymer compound of the present invention can also be used as a polymer field effect transistor as an organic semiconductor thin film. 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 supporting substrate is not particularly limited as long as the characteristics as a field effect transistor are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The field effect transistor can be manufactured 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. As a film forming method from a solution in which a polymer is dissolved in an organic solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, Coating methods such as spray coating, screen printing, flexographic printing, offset printing, and inkjet printing can be used.

A sealed polymer field effect transistor obtained by sealing a polymer field effect transistor after forming the polymer field effect transistor is preferable. Thereby, the polymer field effect transistor is shielded from the atmosphere, and the deterioration of the characteristics of the polymer field transistor can be suppressed.
Examples of the sealing method include a method of covering with a UV curable resin, a thermosetting resin or an inorganic SiONx film, and a method of bonding a glass plate or film with a UV curable resin or a thermosetting resin. In order to effectively shut off from the atmosphere, it is preferable to perform 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).

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
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 / electron 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 / electron 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 an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value 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 or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

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. 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 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 anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, 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 its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, 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 phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.
As the material of 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 a composite film 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. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material of the cathode used in the polymer LED of the present invention, 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 their Two or more of these alloys, or an alloy of 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 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. Further, 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 having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride 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 heat effect resin or a photo-curing 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 LED of the present invention can be used for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device (for example, a backlight of a liquid crystal display device).
In order to obtain planar light emission using the polymer LED 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 and 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 polymeric fluorescent substances 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 driven actively in combination with TFTs. 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 Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Number average molecular weight and weight average molecular weight)
Here, regarding the number average molecular weight and the weight average molecular weight, the polystyrene-equivalent number average molecular weight and weight average molecular weight were determined by GPC (manufactured by Shimadzu Corporation: LC-10Avp). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5 wt%, and 50 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A) was used as the detector.

(Fluorescence spectrum)
The fluorescence spectrum was measured by the following method. A polymer thin film was prepared by spin coating a 0.8 wt% polymer solution on quartz. This thin film was excited at a wavelength of 350 nm, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (Fluorolog manufactured by Horiba, Ltd.). In order to obtain the relative fluorescence intensity in the thin film, the intensity of the Raman line of water is used as a standard, the fluorescence spectrum plotted with wavenumber is integrated in the spectrum measurement range, and measured using a spectrophotometer (Varian Cary 5E). The value assigned by the absorbance at the excitation wavelength was determined.

(HPLC measurement)
Measuring instrument: Agilent 1100LC
Measurement conditions: L-Column ODS, 5 μm, 2.1 mm × 150 mm;
A liquid: acetonitrile, B liquid: THF
Gradient B liquid:
0% (60 min.) → 10% up / min → 100% (10 min),
Sample concentration: 5.0 mg / mL (THF solution),
Injection volume: 1 μL
Detection wavelength: 350 nm

不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、白色の固体３４．２ｇを得た。 Synthesis example 1
(Synthesis of 1-bromo-4-t-butyl-2,6-dimethylbenzene)

Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.

不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン３６ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．６３ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム ０．４１ｇ、１−ブロモ−４−ｔ−ブチル−２，６−ジメチルベンゼン９．６ｇ、ｔ−ブトキシナトリウム５．２ｇ、Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン４．７ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、約５０℃に温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン１００ｍｌを加えて、固体が溶解するまで加熱、放冷した後、沈殿をろ過し、白色の固体９．９ｇを得た。 <Synthesis of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 36 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of 1-bromo-4-t-butyl-2,6-dimethylbenzene, 5.2 g of sodium t-butoxy, N, N′-diphenyl-1 Then, 4.7 g of 4-phenylenediamine was added, followed by reaction at 100 ° C. for 3 hours.
The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After the solvent was distilled off, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved, and then the precipitate was filtered to obtain 9.9 g of a white solid.

不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン５．２ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド３．５ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し白色の固体４．４ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ(ｐｐｍ) ＝ １．３〔ｓ，１８Ｈ〕、２．０〔ｓ，１２Ｈ〕、６．６〜６．７〔ｄ，４Ｈ〕、６．８〜６．９〔ｂｒ，４Ｈ〕、７．１〔ｓ，４Ｈ〕、７．２〜７．３〔ｄ，４Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ７３８ <Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask, and N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) was added. After dissolving 5.2 g of -1,4-phenylenediamine, 3.5 g of N-bromosuccinimide / N, N-dimethylformamide solution was added dropwise in an ice bath and allowed to react all day and night.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

不活性雰囲気下で、３００ｍｌの３つ口フラスコに脱気した脱水トルエン１６６０ｍｌを入れ、Ｎ，Ｎ’−ジフェニルベンジジン２７５．０ｇ、４−ｔ−ブチル−２，６−ジメチルブロモベンゼン４４９．０ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム ７．４８ｇ、ｔ−ブトキシナトリウム１９６．４ｇ、を加えた後、トリ（ｔ−ブチル）ホスフィン５．０ｇを加えた。その後、１０５℃で７時間反応させた。

反応液にトルエン２０００ｍｌを加え、セライト濾過し、濾液を水１０００ｍｌで３回洗浄した後、７００ｍｌまで濃縮した。これにトルエン／メタノール（１：１）溶液１６００ｍｌを加え、析出した結晶を濾過し、メタノールで洗浄した。白色の固体４７９．４ｇを得た。


＜Ｎ，Ｎ’−ビス（４−ブロモフェニル）−Ｎ，Ｎ’−ビス（４−ｔ‐ブチル−２，６−ジメチルフェニル）−ベンジジンの合成＞

不活性雰囲気下で、クロロホルム４７３０ｇに、上記Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−ベンジジン４７２．８ｇを溶解した後、遮光および氷浴下でＮ−ブロモスクシンイミド２８１．８ｇを１２分割で１時間かけて仕込み、３時間反応させた。
クロロホルム１４３９ｍｌを反応液に加え、濾過し、濾液のクロロホルム溶液を５％チオ硫酸ナトリウム２１５９ｍｌで洗浄し、トルエンを溶媒留去して白色結晶を得た。得られた白色結晶をトルエン／エタノールで再結晶し、白色結晶６７８．７ｇを得た。
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ８１５．２ Synthesis example 2
<Synthesis of N, N'-diphenyl-N, N'-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine>

In an inert atmosphere, 1660 ml of degassed dehydrated toluene was placed in a 300 ml three-necked flask, and 275.0 g of N, N′-diphenylbenzidine and 449.0 g of 4-t-butyl-2,6-dimethylbromobenzene were added. added. Subsequently, after adding 7.48 g of tris (dibenzylideneacetone) dipalladium and 196.4 g of t-butoxy sodium, 5.0 g of tri (t-butyl) phosphine was added. Then, it was made to react at 105 degreeC for 7 hours.

Toluene (2000 ml) was added to the reaction mixture, and the mixture was filtered through Celite. The filtrate was washed with 1000 ml of water three times and concentrated to 700 ml. To this was added 1600 ml of a toluene / methanol (1: 1) solution, and the precipitated crystals were filtered and washed with methanol. 479.4 g of a white solid was obtained.


<Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine>

In an inert atmosphere, 472.8 g of the N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine was dissolved in 4730 g of chloroform, In an ice bath, 281.8 g of N-bromosuccinimide was charged in 12 portions over 1 hour and reacted for 3 hours.
Chloroform 1439 ml was added to the reaction solution, followed by filtration. The chloroform solution of the filtrate was washed with 2159 ml of 5% sodium thiosulfate, and toluene was distilled off to obtain white crystals. The obtained white crystals were recrystallized with toluene / ethanol to obtain 678.7 g of white crystals.
MS (APCI (+)): (M + H) ^<+ > 815.2

（化合物Ａ）

反応容器にイオン交換水３１ｍｌを入れ、撹拌しながら水酸化ナトリウム２９ｇを（７２７ｍｍｏｌ）を少しずつ加え、完全に溶かす。系内をアルゴン置換し、トルエン３０ｍｌと１、２、３、１０ｂ−テトラヒドロフルオランテン５.０ｇ（２４ｍｍｏｌ）を入れ、撹拌して溶かす。続いて臭化テトラブチルアンモニウム２.３ｇ（７.３ｍｍｏｌ）と臭化オクチル９．４ｇ（４８ｍｍｏｌ）を加えて４０℃で３時間反応させた。トルエンと水で分液、有機層を抽出後、硫酸ナトリウムで乾燥させた。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、淡黄色の結晶を６．４５ｇ得た。
ＭＳ（ＡＰＣＩ（＋）） ３１８（［Ｍ＋Ｈ］⁺）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）δ７．６９（１Ｈ，ｄ）、７．５０（１Ｈ，ｄ）、７．４０（１Ｈ，ｄ）、７．３４〜７．２２（３Ｈ，ｍ）、７．０３（１Ｈ，ｄ）、３．０７〜２．９６（１Ｈ，ｍ）、２．７７〜２．７０（１Ｈ，ｍ）、２．３７〜２．１８（２Ｈ，ｍ）、１．９５〜１．７４（３Ｈ，ｍ）、１．２７〜１．０４（１１Ｈ，ｍ）、０．８４〜０．６９（５Ｈ，ｍ） Example 1 <Synthesis of Compound B>
(Synthesis of Compound A)

(Compound A)

Add 31 ml of ion-exchanged water to the reaction vessel, add 29 g of sodium hydroxide (727 mmol) little by little with stirring, and dissolve completely. The system was purged with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added and dissolved by stirring. Subsequently, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of octyl bromide were added and reacted at 40 ° C. for 3 hours. After separating with toluene and water, the organic layer was extracted and dried over sodium sulfate. After distilling off the solvent, 6.45 g of pale yellow crystals were obtained by purification with a silica gel column using hexane as a developing solvent.
MS (APCI (+)) 318 ([M + H] ⁺ )
¹ H-NMR (300 MHz / CDCl ₃ ) δ 7.69 (1H, d), 7.50 (1H, d), 7.40 (1H, d), 7.34 to 7.22 (3H, m), 7.03 (1H, d), 3.07 to 2.96 (1H, m), 2.77 to 2.70 (1H, m), 2.37 to 2.18 (2H, m), 95 to 1.74 (3H, m), 1.27 to 1.04 (11H, m), 0.84 to 0.69 (5H, m)

（化合物Ｂ）

アルゴン置換した反応容器に化合物Ａ５．８ｇ（１８ｍｍｏｌ）と酢酸：ジクロロメタン＝１：１の混合溶媒１１５ｍｌを入れ、室温で撹拌し溶かした。続いて三臭化ベンジルトリメチルアンモニウム１４ｇ（３６ｍｍｏｌ）を入れ、撹拌しながら塩化亜鉛を三臭化ベンジルトリメチルアンモニウムが完全に解けるまで加えた。反応をＨＰＬＣで追跡しつつ、適宜三臭化ベンジルトリメチルアンモニウムと塩化亜鉛を加えた。反応終了後、クロロホルムと水で分液、有機層を抽出し、２回水洗後、炭酸カリウム水溶液で中和した。硫酸ナトリウムで乾燥後、溶媒を留去し、ヘキサンを展開溶媒とするシリカゲルカラムで精製後、エタノール：ヘキサン＝１０：１混合溶媒から再結晶し、化合物Ｂを白色の粉末として５．０８ｇ得た。
ＭＳ（ＡＰＰＩ（＋）） ４７６（Ｍ⁺）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）δ７．５３〜７．４３（４Ｈ，ｍ）、７．３３（１Ｈ，ｄ）、２．９０〜２．８４（２Ｈ，ｍ）、２．３３〜２．２２（２Ｈ，ｍ）、２．０５〜１．９６（１Ｈ，ｍ）、１．８３〜１．６４（２Ｈ，ｍ）、１．３２〜１．０５（１３Ｈ，ｍ）、０．８５〜０．８１（３Ｈ，ｍ） (Synthesis of Compound B)

(Compound B)

Into a reaction vessel purged with argon, 5.8 g (18 mmol) of Compound A and 115 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were added and stirred at room temperature for dissolution. Subsequently, 14 g (36 mmol) of benzyltrimethylammonium tribromide was added, and zinc chloride was added with stirring until the benzyltrimethylammonium tribromide was completely dissolved. While monitoring the reaction by HPLC, benzyltrimethylammonium tribromide and zinc chloride were added as appropriate. After completion of the reaction, the mixture was separated with chloroform and water, the organic layer was extracted, washed twice with water, and neutralized with an aqueous potassium carbonate solution. After drying with sodium sulfate, the solvent was distilled off. After purification with a silica gel column using hexane as a developing solvent, recrystallization from ethanol: hexane = 10: 1 mixed solvent gave 5.08 g of Compound B as a white powder. .
MS (APPI (+)) 476 (M ⁺ )
¹ H-NMR (300 MHz / CDCl ₃ ) δ 7.53 to 7.43 (4H, m), 7.33 (1H, d), 2.90 to 2.84 (2H, m), 2.33 to 2 .22 (2H, m), 2.05-1.96 (1H, m), 1.83 to 1.64 (2H, m), 1.32 to 1.05 (13H, m), 0.85 ~ 0.81 (3H, m)

Example 2
(Synthesis of polymer compound 1)
Compound B (0.1 g) and 2,2′-bipyridyl (0.089 g) were dissolved in 19 mL of dehydrated tetrahydrofuran, and then this solution was added to bis (1,5-cyclooctadiene) nickel (under nitrogen atmosphere). 0) {Ni (COD) ₂ } (0.156 g) was added, and the temperature was raised to 60 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 1 mL / methanol 19 mL / ion exchanged water 19 mL and stirred for 1 hour, and then the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 1) was 0.08 g. The number average molecular weight in terms of polystyrene was 2.9 × 10 ⁴ , and the weight average molecular weight was 6.1 × 10 ⁴ .

Example 3
<Synthesis of Polymer Compound 2>
Compound B (0.557 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine (0 0.096 g) and 2,2′-bipyridyl (0.548 g) were dissolved in 140 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with argon. After raising the temperature to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred for 3 hours. Reacted. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 5 mL / methanol 140 mL / ion exchanged water 140 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 40 ml of toluene. I let you. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column. Next, 80 mL of 5.2% aqueous hydrochloric acid was added and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, 80 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 80 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 2) was 0.33 g. The number average molecular weight and weight-average molecular weight in terms of polystyrene were respectively ^{Mn = 1.6x10 4, Mw = 8.7x10} 4.

Example 4
<Synthesis of Polymer Compound 3>
Compound B (0.433 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine (0.318 g), 2 , 2′-bipyridyl (0.548 g) was dissolved in 140 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with argon. After raising the temperature to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred for 3 hours. Reacted. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 5 mL / methanol 140 mL / ion exchanged water 140 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 40 ml of toluene. I let you. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column. Next, 80 mL of 5.2% aqueous hydrochloric acid was added and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, 80 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 80 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 3) was 0.46 g. The number average molecular weight and weight-average molecular weight in terms of polystyrene were respectively ^{Mn = 1.0x10 4, Mw = 6.1x10} 4.

Example 5
<Synthesis of Polymer Compound 4>
Compound B (0.588 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine (0.053 g), 2 , 2′-bipyridyl (0.548 g) was dissolved in 140 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with argon. After raising the temperature to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred for 3 hours. Reacted. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 5 mL / methanol 140 mL / ion exchanged water 140 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 40 ml of toluene. I let you. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column. Next, 80 mL of 5.2% aqueous hydrochloric acid was added and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, 80 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 80 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 0.31 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 2.5 × 10 ⁴ and Mw = 1.2 × 10 ⁵ , respectively.

Example 6 <Preparation and Performance of EL Element>
(Solution adjustment)
The polymer compound 2 obtained above was dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight.

(Production of EL element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is filtered through a 0.2 μm membrane filter on a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Using the solution, a thin film having a thickness of 70 nm was formed by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotational speed of 3400 rpm by spin coating using the toluene solution obtained above. The film thickness after film formation was about 95 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by 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.

(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 455 nm was obtained from this device. The EL emission color is changed to C.I. I. E. In terms of color coordinate values, x = 0.150 and y = 0.128, indicating a very good blue color. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 5.2V. The luminous efficiency increased monotonously in the measured applied voltage range (0 V to 12 V), but the value at 12 V showed a relatively high efficiency of 1.02 cd / m ² .

Example 7 <Production and Performance of EL Element>
(Solution adjustment)
90% by weight of the polymer compound 4 obtained above and 10% by weight of the polymer compound 3 were dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight.

(Production of EL element)
An EL device was prepared in exactly the same manner as in Example 6 except that the toluene solution obtained above was used. In addition, the rotation speed in the spin coat of the polymer solution was 3300 rpm, and the film thickness after film formation of the polymer film was 95 nm.

(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 425 nm was obtained from this device. The EL emission color is changed to C.I. I. E. In terms of color coordinate values, x = 0.155 and y = 0.072, indicating a very good blue color. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 5.5V. The luminous efficiency increased monotonously in the measured applied voltage range (0 V to 12 V), but the value at 12 V showed a relatively high efficiency of 0.22 cd / m ² .

Example 8 <Preparation and Performance of EL Element>
(Solution adjustment)
The polymer compound 4 obtained above was dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight.

(Creation of EL element)
An EL device was prepared in exactly the same manner as in Example 6 except that the toluene solution obtained above was used. In addition, the rotation speed in spin coating of the polymer solution was 2500 rpm, and the film thickness after film formation of the polymer film was 90 nm.

(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 425 nm was obtained from this device. The EL emission color is changed to C.I. I. E. In terms of color coordinate values, x = 0.155 and y = 0.074, indicating a very good blue color. The intensity of EL emission was almost proportional to the current density. In addition, the device started to emit light from 5.8V. The luminous efficiency increased monotonously in the measured applied voltage range (0 V to 12 V), but the value at 12 V showed a relatively high efficiency of 0.57 cd / m ² .

反応容器にイオン交換水３１ｍｌを入れ、撹拌しながら水酸化ナトリウム２９ｇを（７２７ｍｍｏｌ）を少しずつ加え、完全に溶かす。系内をアルゴン置換し、トルエン３０ｍｌと１、２、３、１０ｂ−テトラヒドロフルオランテン５.０ｇ（２４ｍｍｏｌ）を入れ、撹拌して溶かす。続いて臭化テトラブチルアンモニウム２.３ｇ（７.３ｍｍｏｌ）と２-エチルヘキシルブロミド９．４ｇ（４８ｍｍｏｌ）を加えて４０℃で３時間反応させた。トルエンと水で分液、有機層を抽出後、硫酸ナトリウムで乾燥させた。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、黄色のオイルを６.８８ｇ得た。
ＭＳ（ＡＰＰＩ（＋）） ３１８（［Ｍ＋Ｈ］⁺）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）δ７．６９（１Ｈ，ｄ）、７．５０（１Ｈ，ｄ）、７．４０（１Ｈ，ｄ）、７．３３〜７．２２（３Ｈ，ｍ）、７．０２（１Ｈ，ｄ）、３．０７〜２．９６（１Ｈ，ｍ）、２．７９〜２．７１（１Ｈ，ｍ）、２．３６〜２．２２（２Ｈ，ｍ）、２．１０〜１．９９（１Ｈ，ｍ）、１．９３〜１．７６（２Ｈ，ｍ）、１．２４〜１．１５（１Ｈ，ｍ）、０．８８〜０．３７（９Ｈ，ｍ） Example 9 <Synthesis of Compound D>
(Synthesis of Compound C)
(Compound C)

Add 31 ml of ion-exchanged water to the reaction vessel, add 29 g of sodium hydroxide (727 mmol) little by little with stirring, and dissolve completely. The system was purged with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added and dissolved by stirring. Subsequently, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of 2-ethylhexyl bromide were added and reacted at 40 ° C. for 3 hours. After separating with toluene and water, the organic layer was extracted and dried over sodium sulfate. After distilling off the solvent, 6.88 g of a yellow oil was obtained by purification with a silica gel column using hexane as a developing solvent.
MS (APPI (+)) 318 ([M + H] ⁺ )
¹ H-NMR (300 MHz / CDCl ₃ ) δ 7.69 (1H, d), 7.50 (1H, d), 7.40 (1H, d), 7.33 to 7.22 (3H, m), 7.02 (1H, d), 3.07-2.96 (1H, m), 2.79-2.71 (1H, m), 2.36-2.22 (2H, m), 2. 10-1.99 (1H, m), 1.93-1.76 (2H, m), 1.24-1.15 (1H, m), 0.88-0.37 (9H, m)

アルゴン置換した反応容器に化合物Ｃ６．８ｇ（２１ｍｍｏｌ）、塩化亜鉛６.７ｇ（４９ｍｍｏｌ）および酢酸：ジクロロメタン＝１：１の混合溶媒１３４ｍｌを入れ、室温で撹拌した。続いて三臭化ベンジルトリメチルアンモニウム１８ｇ（４７ｍｍｏｌ）をジクロロメタン１５０ｍｌに溶かして滴下した。滴下終了後、室温で２時間、続けて４０℃および５０℃で各３０分ずつ反応させた後、クロロホルムと５％亜硫酸水素ナトリウム水溶液を加えて反応を停止した。クロロホルムと水で分液、有機層を抽出し、２回水洗後、炭酸カリウム水溶液で中和した。硫酸ナトリウムで乾燥後、溶媒を留去し、ヘキサンを展開溶媒とするシリカゲルカラムで３回精製することにより、化合物Ｄを黄色のオイル（室温で放置するとゆっくり白色結晶化）として１．７３ｇ得た。
ＭＳ（ＡＰＰＩ（＋）） ４７６（Ｍ⁺）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）δ７．５２〜７．４２（４Ｈ，ｍ）、７．３３（１Ｈ，ｄ）、３．００〜２．８０（２Ｈ，ｍ）、２．４０〜２．２０（２Ｈ，ｍ）、２．０２〜１．８９（２Ｈ，ｍ）、１．７５〜１．７０（１Ｈ，ｍ）、１．３１〜１．１５（２Ｈ，ｍ）、０．９６〜０．３９（８Ｈ，ｍ） (Synthesis of Compound D)
(Compound D)

A reaction vessel purged with argon was charged with 6.8 g (21 mmol) of compound C, 6.7 g (49 mmol) of zinc chloride and 134 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1, and stirred at room temperature. Subsequently, 18 g (47 mmol) of benzyltrimethylammonium tribromide was dissolved in 150 ml of dichloromethane and added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours and subsequently at 40 ° C. and 50 ° C. for 30 minutes each, and then the reaction was stopped by adding chloroform and 5% aqueous sodium hydrogen sulfite solution. The mixture was separated with chloroform and water, and the organic layer was extracted, washed twice with water, and neutralized with an aqueous potassium carbonate solution. After drying with sodium sulfate, the solvent was distilled off, and purification was performed 3 times with a silica gel column using hexane as a developing solvent to obtain 1.73 g of Compound D as a yellow oil (slowly crystallized when left at room temperature). .
MS (APPI (+)) 476 (M ⁺ )
¹ H-NMR (300 MHz / CDCl ₃ ) δ 7.52 to 7.42 (4H, m), 7.33 (1H, d), 3.00 to 2.80 (2H, m), 2.40 to 2 .20 (2H, m), 2.02-1.89 (2H, m), 1.75-1.70 (1H, m), 1.31-1.15 (2H, m), 0.96 ~ 0.39 (8H, m)

Example 10 <Synthesis of Polymer Compound 5>
Under a nitrogen atmosphere, Compound D (0.476 g) and 2,2′-bipyridyl (0.422 g) were dissolved in 72 mL of dehydrated tetrahydrofuran and dissolved by stirring. Bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.743 g) was added to this solution, and the mixture was stirred and reacted at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 4 mL / methanol 72 mL / ion exchanged water 72 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 20 mL of toluene. I let you. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column. Next, 40 mL of 5.2% aqueous hydrochloric acid was added and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, 40 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 40 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 80 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 5) was 0.17 g. The number average molecular weight and weight-average molecular weight in terms of polystyrene were ^{Mn = 1.1x10 5, Mw = 3.2x10} 5 , respectively.

Comparative Example 1
<Synthesis of Polymer Compound 6>
2,7-Dibromo-9,9-dioctylfluorene 0.22 g (0.40 mmol) and N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6 -Dimethylphenyl) -1,4-phenylenediamine 0.20 g (0.27 mmol) and 2,2'-bipyridyl 0.24 g (1.5 mmol) were charged into a reaction vessel, and the reaction system was replaced with nitrogen gas. did. To this, 20 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 0.42 g (1.5 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled and then poured into a mixed solution of 25% aqueous ammonia 10 ml / methanol 120 ml / ion-exchanged water 50 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. The precipitate was washed with ethanol and dried under reduced pressure for 2 hours. Next, this precipitate was dissolved in 50 mL of toluene, 50 mL of 1N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, 50 mL of 4% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 1 hour. . The organic layer was dropped into 120 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 40 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 20g), and the collect | recovered toluene solution was dripped at methanol 120mL, it stirred for 1 hour, the depositing deposit was filtered, and it dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 6 was 0.094 g.
The polymer compound 6 had a polystyrene equivalent number average molecular weight of 2.0 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.1 × 10 ⁵ .

Comparative Example 2 <Production and Performance of EL Element>
(Solution adjustment)
The polymer compound 6 obtained above was dissolved in chloroform to prepare a chloroform solution having a polymer concentration of 1.8% by weight.

(Creation of EL element)
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotational speed of 2500 rpm by spin coating using the prepared chloroform solution. The film thickness was about 100 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 448 nm was obtained. The EL emission color is changed to C.I. I. E. In terms of color coordinate values, x = 0.155 and y = 0.133. The device showed the maximum luminous efficiency at about 10 V, and its value was 0.14 cd / A.

Claims (34)

A polymer compound comprising at least one residue of a compound represented by the following formula (1).

(Formula 1)

[Wherein, A ring, B ring and C ring each independently represents an aromatic ring or a non-aromatic ring optionally having a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ independently represents C- (Q) z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, and ring A and ring B constitute each ring. Atoms other than Z ₅ may be shared, and one or more of A ring, B ring and C ring are non-aromatic rings. ] The high molecular compound characterized by including the repeating unit shown by following formula (1-1), (1-2) or (1-3).

Formula (1-1) Formula (1-2) Formula (1-3)

[Wherein, A ring, B ring and C ring each independently represents an aromatic ring or a non-aromatic ring which may have a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ Each independently represents C- (Q) z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, and ring A and ring B share a ring atom other than Z ₅ In addition, substituents of each ring may be bonded to each other to form a ring, and one or more of the rings having no bond among A ring, B ring and C ring It is a non-aromatic ring. ] 3. The polymer compound according to claim 1, wherein all atoms constituting the A ring, B ring and C ring are carbon atoms. The polymer compound according to claim 2 or 3, wherein the repeating unit represented by the formula (1-1) is a repeating unit represented by the following formula (2-1).

Formula (2-1)
[Wherein, R ₁ and R ₂ each independently represents a substituent, the D ring represents a non-aromatic ring which may have a substituent, a represents an integer of 0 to 2, and b represents 0 Represents an integer of ˜3, and when there are a plurality of R ₁ and R ₂ , they may be the same or different, and R ₁ and R ₂ may be bonded to each other to form a ring. R ₁ and / or R ₂ may be bonded to the D ring to form a ring, and Q and z represent the same meaning as described above. ] The polymer compound according to claim 2 or 3, wherein the repeating unit represented by the formula (2-1) is a repeating unit represented by the following formula (3-1).

Formula (3-1)

[Wherein, R ₁ , R ₂ , D ring, Q, z, a and b represent the same meaning as described above. ] The repeating unit represented by the formula (3-1) is a repeating unit represented by the following formula (4-1), (4-2), (4-3) or (4-4). The polymer compound according to claim 5.

Formula (4-1) Formula (4-2)

Formula (4-3) Formula (4-4)

[Wherein, R _1a , R _1b , R _{2a to} R _2c and R _{3a to} R _3g each independently represents a hydrogen atom or a substituent. In formulas (4-1) to (4-3), R _2c and R _3g may be bonded to each other to form a ring. In formula (4-4), R _2c and R _3e may be bonded to each other to form a ring. ] The polymer compound according to any one of claims 1 to 6, further comprising a repeating unit represented by the following formula (5), formula (6), formula (7), or formula (8).
-Ar _1- (5)

—Ar ₄ —X ₂ — (7)
-X _3- (8)

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₉ ═CR ₁₀ —, —C≡C—, —N (R ₁₁ ) —, or — (SiR ₁₂ R ₁₃ ) _m —. R ₉ and R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents 1 or 2. m represents an integer of 1 to 12. When there are a plurality of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , they may be the same or different. ] Furthermore, the repeating unit shown by following formula (9), (10), (11), (12), (13) or (14) is included, The any one of Claims 1-6 characterized by the above-mentioned. High molecular compound.

[Wherein, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group Represents. n represents an integer of 0 to 4. When a plurality of R ₁₄ are present, they may be the same or different. ]

Wherein R ₁₅ and R ₁₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Represents a cyano group or a nitro group. o and p each independently represent an integer of 0 to 3. When a plurality of R ₁₅ and R ₁₆ are present, they may be the same or different. ]

[Wherein, R ₁₇ and R ₂₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Represents a cyano group or a nitro group. q and r each independently represents an integer of 0 to 4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₁₇ and R ₂₀ are present, they may be the same or different. ]

[Wherein, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group Represents. s represents the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₁ are present, they may be the same or different. ]

[Wherein R ₂₂ and R ₂₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Represents a cyano group or a nitro group. t and u each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₂₄ , or SiR ₂₅ R ₂₆ . X ₆ and X ₇ each independently represent N or C—R ₂₇ . R ₂₄ , R _25, R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When a plurality of R ₂₅ , R ₂₆ and R ₂₇ are present, they may be the same or different. ]

Wherein R ₂₈ and R ₃₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Represents a cyano group or a nitro group. v and w each independently represent an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. ] Furthermore, it has a repeating unit shown by following formula (15), The polymer compound in any one of Claims 1-6 characterized by the above-mentioned.

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ] As a raw material, at least the following formula (16-1), (16-2) or (16-3)

Formula (16-1) Formula (16-2) Formula (16-3)

[Wherein, A ring, B ring, C ring, and Z _{1 to} Z ₅ represent the same meaning as described above. Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a substituent involved in polymerization. ]
The method for producing a polymer compound according to claim 1, wherein polymerization is performed using a compound represented by the formula: The production method according to claim 10, wherein the compound represented by the following formula (16-1) is a compound represented by the following formula (17-1).

[Wherein R ₁ , R ₂ , a, b, D ring, Q, z, Y ₁ and Y ₂ represent the same meaning as described above. ] The compound represented by the following formula (17-1) is a compound represented by the following formula (18-1), (18-2), (18-3) or (18-4), 11. The production method according to 11.

Formula (18-1) Formula (18-2)

Formula (18-3) Formula (18-4)

[Wherein, R _1a , R _1b , R _{2a to} R _2c , R _{3a to} R _3g , Y ₁ and Y ₂ represent the same meaning as described above. ] The production method according to claim 10, wherein the compound represented by the formula (16-2) is a compound represented by the following formula (17-2).

Formula (17-2)
[Wherein, B ring, C ring, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y ₄ represent the same meaning as described above. Z ₆ , Z ₇ and Z ₈ each independently represent C— (Q) z or a nitrogen atom. Z _1a , Z _5a and Z ₉ each independently represent a carbon atom. Q and z have the same meaning as described above. R ₄ represents a substituent. e shows the integer of 0-2. When there are a plurality of R ₄ , they may be the same or different, and R ₄ may be bonded to form a ring. ] The method according to claim 10, wherein the compound represented by the formula (16-3) is a compound represented by the following formula (17-3).

Formula (17-3)

[Wherein, A ring, B ring, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y ₆ represent the same meaning as described above. Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each independently represent C— (Q) z or a nitrogen atom. Z _2a and Z _3a each independently represent a carbon atom. Q and z have the same meaning as described above. R ₅ represents a substituent. f shows the integer of 0-2. When there are a plurality of R ₅ , they may be the same or different, and R ₅ may be bonded to each other to form a ring. ] In addition to the compound represented by the above formula (16-1), (16-2) or (16-3), the compound represented by any one of the following formulas (19) to (22) is used as a raw material for polymerization. The manufacturing method according to any one of claims 10 to 14, wherein:

_{Y 7 -Ar 1 -Y 8 (19} )

_{Y 11 -Ar 4 -X 2 -Y 12} (21)
Y ₁₃ -X ₃ -Y ₁₄ (22)

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ ff, X ₁ , X ₂ and X ₃ represent the same meaning as described above. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a substituent involved in the polymerization. ] When polymerizing the compound represented by the formula (16-1), (16-2) or (16-3) alone or with at least one selected from the compounds represented by the formulas (19) to (22) Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ are each independently a halogen atom, alkyl The production method according to any one of claims 10 to 15, which is a sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group, and is subjected to condensation polymerization in the presence of a nickel zero-valent complex. When one kind selected from the formulas (16-1), (16-2) or (16-3) is polymerized alone or with at least one kind selected from the formulas (19) to (22), Y ₁ Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ are each independently a halogen atom, an alkyl sulfonate group, An aryl sulfonate group, an arylalkyl sulfonate group, —B (OH) ₂ , or a borate group, and the total number of moles of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an arylalkyl sulfonate group; and —B (OH) ratio of the total number of moles of ₂ and boric acid ester groups are substantially 1, claim 10 to 15, characterized in that the condensation polymerization using a nickel or palladium catalyst The method according. Compound represented by the above formula (17-1). A compound represented by the above formula (18-1), (18-2), (18-3) or (18-4). A compound represented by the above formula (16-2) or (16-3). A compound represented by the above formula (17-2) or (17-3).   A composition comprising at least one material selected from a hole transport material, an electron transport material, and a light-emitting material and the polymer compound according to claim 1.   An ink composition comprising the polymer compound according to claim 1 and a solvent.   The ink composition according to claim 23, wherein the viscosity is 1 to 20 mPa · s at 25 ° C.   The luminescent thin film containing the polymer compound in any one of Claims 1-9.   The electroconductive thin film containing the high molecular compound in any one of Claims 1-9.   The organic-semiconductor thin film containing the high molecular compound in any one of Claims 1-9.   A polymer light emitting device comprising an organic layer between electrodes composed of an anode and a cathode, wherein the organic layer contains the polymer compound according to any one of claims 1 to 9.   29. The polymer light emitting device according to claim 28, wherein the organic layer is a light emitting layer.   30. The polymer light emitting device according to claim 29, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material.   A planar light source comprising the polymer light-emitting device according to claim 28.   A segment display device comprising the polymer light-emitting device according to claim 28.   A dot matrix display device comprising the polymer light-emitting device according to claim 28. A liquid crystal display device comprising the polymer light-emitting device according to claim 28.