JP2010260879A - Polymer having residue of nitrogen-containing heterocyclic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer capable of giving organic electroluminescent elements exhibiting excellent element characteristics, when used for producing the organic electroluminescent elements. <P>SOLUTION: The polymer includes the residue of a compound represented by formula (1) (wherein, Ar is an aryl group or a monovalent heterocyclic group), and the residue of a compound represented by formula (2) [wherein, one of Z<SP>1</SP>to Z<SP>3</SP>is -N=, and two of Z<SP>1</SP>to Z<SP>3</SP>are -C(R')=; Z<SP>4</SP>and Z<SP>5</SP>are each -C(R')=; one of Z<SP>6</SP>to Z<SP>8</SP>is -N=; two of Z<SP>6</SP>to Z<SP>8</SP>are each -C(R')=; Z<SP>9</SP>to Z<SP>10</SP>are each -C(R')=; R' is H, alkyl or the like]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polymer compound having a residue of a nitrogen-containing heterocyclic compound.

  In recent years, organic electroluminescence displays using organic electroluminescence elements have attracted attention as next-generation displays. This organic electroluminescence device includes organic layers such as a light emitting layer and a charge transport layer. For the organic layer, an organic material excellent in electron injecting property is required. For example, a polymer compound having a triazine skeleton has been proposed (Patent Document 1).

JP-T-2004-532314

However, when this polymer compound is used in the production of an organic electroluminescence element, the light emission efficiency of the obtained organic electroluminescence element is insufficient.
Then, an object of this invention is to provide the high molecular compound which can give the organic electroluminescent element which shows the outstanding luminous efficiency, when it uses for manufacture of an organic electroluminescent element.

（式中、Ａｒは、置換基を有していてもよいアリール基、又は置換基を有していてもよい１価の複素環基を表す。３個存在するＡｒは、同一であっても異なっていてもよい。）
で表される化合物の残基、及び下記式（２）：

（式中、Ｚ¹、Ｚ²及びＺ³は、１個が−Ｎ＝を表し、２個が−Ｃ（Ｒ’）＝を表す。Ｚ⁴及びＺ⁵は、−Ｃ（Ｒ’）＝を表す。Ｚ⁶、Ｚ⁷及びＺ⁸は、１個が−Ｎ＝を表し、２個が−Ｃ（Ｒ’）＝を表す。Ｚ⁹及びＺ¹⁰は、−Ｃ（Ｒ’）＝を表す。Ｒ’は、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールチオ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアミノ基、置換基を有していてもよいシリル基、ハロゲン原子、置換基を有していてもよいアシル基、置換基を有していてもよいアシルオキシ基、置換基を有していてもよい１価の複素環基、置換基を有していてもよい複素環チオ基、イミン残基、置換基を有していてもよいアミド基、酸イミド基、カルボキシル基、ニトロ基、又はシアノ基を表す。８個存在する−Ｃ（Ｒ’）＝は、同一であっても異なっていてもよい。Ｚ²及びＺ³が−Ｃ（Ｒ’）＝である場合にはＺ²及びＺ³に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ³が−Ｃ（Ｒ’）＝である場合にはＺ³及びＺ⁴に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁴及びＺ⁵に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよいが、Ｚ²及びＺ³、Ｚ³及びＺ⁴、並びにＺ⁴及びＺ⁵の２個以上の組み合わせが同時にはベンゼン環を形成しない。Ｚ⁷及びＺ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁷及びＺ⁸に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁸及びＺ⁹に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁹及びＺ¹⁰に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよいが、Ｚ⁷及びＺ⁸、Ｚ⁸及びＺ⁹、並びにＺ⁹及びＺ¹⁰の２個以上の組み合わせが同時にはベンゼン環を形成しない。２個のＲ’が互いに結合して形成するベンゼン環は、置換基を有していてもよい。）
で表される化合物の残基を有する高分子化合物を提供する。
本発明は第二に、前記高分子化合物と、発光材料、正孔輸送材料、及び電子輸送材料からなる群から選ばれる少なくとも一種とを含む組成物を提供する。
本発明は第三に、前記高分子化合物を用いてなる有機エレクトロルミネッセンス素子、並びに該有機エレクトロルミネッセンス素子を備えた面状光源及び表示装置を提供する。 The present invention firstly has the following formula (1):

(In the formula, Ar represents an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. The three Ars may be the same. May be different.)
A residue of the compound represented by formula (2):

(In the formula, ^one of Z ¹ , Z ² and Z ³ represents —N═ and two represents —C (R ′) ═. Z ⁴ and Z ⁵ represent —C (R ′) = Z ⁶ , Z ⁷ and Z ⁸ each represent —N═, two represent —C (R ′) ═, and Z ⁹ and Z ¹⁰ represent —C (R ′) ═. R ′ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, and a substituent An optionally substituted acyloxy group, a monovalent heterocyclic group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue, and a substituent. Represents an amide group, an acid imide group, a carboxyl group, a nitro group, or a cyano group, and 8 —C (R ′) ═ may be the same or different, and Z ² and Z ³ are — When C (R ′) =, two R ′ contained in Z ² and Z ³ may be bonded to each other to form a benzene ring, and Z ³ is —C (R ′) =. In some cases, two R ′ contained in Z ³ and Z ⁴ may be bonded to each other to form a benzene ring, or two R ′ contained in Z ⁴ and Z ⁵ may be bonded to each other to form a benzene ring. may be formed but, Z ² and Z ^3, Z ³ and Z ^4, as well as two or more combinations of Z ⁴ and Z ⁵ are not simultaneously form a benzene ring. ⁷ and Z ⁸ is -C (R ') = a if two R contained in Z ⁷ and Z ^8' may form a benzene ring by bonding to each other, Z ⁸ is -C ( When R ′) =, two R ′ contained in Z ⁸ and Z ⁹ may be bonded to each other to form a benzene ring, and two R ′ contained in Z ⁹ and Z ¹⁰ may be Although they may be bonded to each other to form a benzene ring, two or more combinations of Z ⁷ and Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ do not form a benzene ring at the same time. The benzene ring formed by combining R ′ with each other may have a substituent.)
The high molecular compound which has the residue of the compound represented by these is provided.
Secondly, the present invention provides a composition comprising the polymer compound and at least one selected from the group consisting of a light emitting material, a hole transport material, and an electron transport material.
Thirdly, the present invention provides an organic electroluminescence element using the polymer compound, and a planar light source and a display device provided with the organic electroluminescence element.

  The polymer compound of the present invention can provide an organic electroluminescence device exhibiting excellent device characteristics (particularly, maximum light emission efficiency) when used in the production of an organic electroluminescence device. Furthermore, the polymer compound of the present invention is useful as a hole transport material and an electron transport material.

<Explanation of terms>
Hereinafter, terms commonly used in this specification will be described. In this specification, Me means a methyl group, t-Bu means a tert-butyl group, and Ph means a phenyl group.

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

The term “C _x -C _y ” (x, y is a positive integer satisfying x <y) indicates that the number of carbon atoms of the organic group described together with this term is x-y.

The alkyl group is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group. , A heterocyclic thio group, an imine residue, an amide group, an acid imide group, a carboxyl group, a nitro group, a cyano group and the like (hereinafter referred to as “substituent” have the same meaning unless otherwise specified. And is usually an unsubstituted alkyl group or an alkyl group substituted with a halogen atom or the like, and includes both a linear alkyl group and a cyclic alkyl group (cycloalkyl group). The alkyl group may have a branch. The number of carbon atoms of the alkyl group is usually 1-20, preferably 1-15, more preferably 1-10. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-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, dodecyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc. Is mentioned.
The C ₁ -C ₁₂ alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, s- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, cyclohexyl Group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and the like.

The alkoxy group may have a substituent, and is usually an unsubstituted alkoxy group and an alkoxy group substituted with a halogen atom, an alkoxy group, etc., and a linear alkoxy group and a cyclic alkoxy group (cycloalkoxy group). ) Both. The alkoxy group may have a branch. The number of carbon atoms of the alkoxy group is usually 1-20, preferably 1-15, more preferably 1-10. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl. Oxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl Examples thereof include an oxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.
The C ₁ -C ₁₂ alkoxy group include a methoxy group, an ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, s- butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, Examples include cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, and the like.

The alkylthio group may have a substituent, and is usually an unsubstituted alkylthio group and an alkylthio group substituted with a halogen atom, etc., both a linear alkylthio group and a cyclic alkylthio group (cycloalkylthio group). including. The alkylthio group may have a branch. The number of carbon atoms of the alkylthio group is usually 1-20, preferably 1-15, more preferably 1-10. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, Examples include octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group, trifluoromethylthio group and the like.
The C ₁ -C ₁₂ alkylthio group include a methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s- butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio Group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group and the like.

An aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, which may have a substituent, and is usually an unsubstituted aryl group And an aryl group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. Aryl groups include those having a condensed ring and those in which two or more independent benzene rings or condensed rings are bonded via a single bond or a divalent organic group, for example, an alkenylene group such as a vinylene group. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 48, and more preferably 6 to 30. Examples of the aryl group include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9- anthracenyl group, pentafluorophenyl group, biphenyl group, C ₁ -C ₁₂ alkoxybiphenyl group, C ₁ -C ₁₂ alkyl biphenyl group, and among these, a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ ~ C ₁₂ alkylphenyl group, biphenyl group, C ₁ -C ₁₂ alkoxybiphenyl group, C ₁ -C ₁₂ alkyl biphenyl groups are preferred.
The C ₁ -C ₁₂ alkoxyphenyl group, for example, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butyloxyphenyl group, isobutyloxyphenyl group, t- butyl oxyphenyl group, pentyloxy A phenyl group, a hexyloxyphenyl group, an octyloxyphenyl group, etc. are mentioned.
The C ₁ -C ₁₂ alkylphenyl group, for example, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t -A butylphenyl group, a pentylphenyl group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, a dodecylphenyl group, and the like.

The aryloxy group may have a substituent, and is usually an unsubstituted aryloxy group and an aryloxy group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the aryloxy group is usually 6 to 60, preferably 6 to 48, and more preferably 6 to 30. The aryloxy group include a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and a pentafluorophenyl group and the like, Of these C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.
The C ₁ -C ₁₂ alkoxy phenoxy group, for example, methoxyphenoxy group, ethoxyphenoxy group, propyloxy phenoxy group, isopropyloxy phenoxy group, butyloxy phenoxy group, iso-butyloxy phenoxy group, t- butyl oxy phenoxy group, pentyloxy A phenoxy group, a hexyloxyphenoxy group, an octyloxyphenoxy group, etc. are mentioned.
Examples of the C _{1 to} C ₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, and a butylphenoxy group. Group, isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc. Is mentioned.

The arylthio group may have a substituent, and generally means an unsubstituted arylthio group and an arylthio group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylthio group is usually 6 to 60, preferably 6 to 48, and more preferably 6 to 30. The arylthio group, for example, 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.

The arylalkyl group may have a substituent, and is usually an unsubstituted arylalkyl group and an arylalkyl group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylalkyl group is usually 7 to 60, preferably 7 to 48, and more preferably 7 to 30. The aryl alkyl group, e.g., 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, Examples include ₁ -naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, and the like.

The arylalkoxy group may have a substituent, and is usually an unsubstituted arylalkoxy group and an arylalkoxy group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylalkoxy group is usually 7 to 60, preferably 7 to 48, more preferably 7 to 30. The arylalkoxy group, for example, phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group, Examples include ₁ -naphthyl-C ₁ -C ₁₂ alkoxy group and 2-naphthyl-C ₁ -C ₁₂ alkoxy group.

The arylalkylthio group may have a substituent, and is usually an unsubstituted arylalkylthio group and an arylalkylthio group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylalkylthio group is usually 7 to 60, preferably 7 to 48, and more preferably 7 to 30. Arylalkylthio group, for example, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, Examples include ₁ -naphthyl-C ₁ -C ₁₂ alkylthio group, 2-naphthyl-C ₁ -C ₁₂ alkylthio group, and the like.

  The alkenyl group may have a substituent, and includes a linear alkenyl group, a branched alkenyl group, and a cyclic alkenyl group. The number of carbon atoms of the alkenyl group is usually 2-20, preferably 2-15, more preferably 2-10. Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1 -An octenyl group etc. are mentioned.

The arylalkenyl group may have a substituent, and is usually an unsubstituted arylalkenyl group and an arylalkenyl group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylalkenyl group is usually 8 to 60, preferably 8 to 48, and more preferably 8 to 30. Arylalkenyl group, for example, phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, Examples include 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group, etc. Among them, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.
The C ₂ -C ₁₂ alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group and the like can be mentioned.

  The alkynyl group may have a substituent, and includes a linear alkynyl group and a branched alkynyl group. The number of carbon atoms in the alkynyl group is usually 2-20, preferably 2-15, more preferably 2-10. Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, 2-hexynyl group, 1 -An octynyl group etc. are mentioned.

The arylalkynyl group may have a substituent, and is usually an unsubstituted arylalkynyl group and an arylalkynyl group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylalkynyl group is usually 8 to 60, preferably 8 to 48, more preferably 8 to 30. The arylalkynyl group, e.g., 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, Examples include 1-naphthyl-C ₂ -C ₁₂ alkynyl group, 2-naphthyl-C ₂ -C ₁₂ alkynyl group, etc. Among them, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.
The C ₂ -C ₁₂ alkynyl group include an ethynyl group, 1-propynyl, 2-propynyl, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, A 2-hexynyl group, a 1-octynyl group, etc. are mentioned.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound (particularly an aromatic heterocyclic compound), and may have a substituent. An unsubstituted monovalent heterocyclic group and a monovalent heterocyclic group substituted with a substituent such as an alkyl group. The number of carbon atoms of the monovalent heterocyclic group is usually 4 to 60, preferably 4 to 30, and more preferably 4 to 20 without including the number of carbon atoms of the substituent. Heterocyclic compounds are not only carbon atoms but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms as elements constituting the ring among organic compounds having a cyclic structure. , And those containing heteroatoms such as tellurium atoms and arsenic atoms. Examples of the monovalent heterocyclic group, for example, 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, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, among which thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.

  The heterocyclic thio group is a group in which a hydrogen atom of a mercapto group is substituted with a monovalent heterocyclic group, and may have a substituent. Examples of the heterocyclic thio group include heteroarylthio groups such as a pyridylthio group, a pyridazinylthio group, a pyrimidylthio group, a pyrazinylthio group, and a triazinylthio group.

The amino group may have a substituent and is usually substituted with an unsubstituted amino group and 1 or 2 substituents selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Amino group (hereinafter referred to as “substituted amino group”). The substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). The carbon atom number of a substituted amino group is 1-60 normally without including the carbon atom number of a secondary substituent, Preferably it is 2-48, More preferably, it is 2-40. Examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s- Butylamino group, t-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group , cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ al Kishifeniru) amino group, C ₁ -C ₁₂ alkylphenyl group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dajiniruamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups and the like.

The silyl group may have a substituent, and is usually an unsubstituted silyl group and 1, 2 or 3 substituents selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. A silyl group substituted with (hereinafter referred to as “substituted silyl group”). The substituent may have a secondary substituent. The number of carbon atoms of the substituted silyl group is usually 1 to 60, preferably 3 to 48, more preferably 3 to 40, not including the number of carbon atoms of the secondary substituent. Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, 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, - 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 A silyl group, a dimethylphenylsilyl group, etc. are mentioned.

  The acyl group may have a substituent, and is usually an unsubstituted acyl group and an acyl group substituted with a halogen atom or the like. The number of carbon atoms of the acyl group is usually 2 to 20, preferably 2 to 18, and more preferably 2 to 16. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group may have a substituent, and is usually an unsubstituted acyloxy group and an acyloxy group substituted with a halogen atom or the like. The number of carbon atoms of the acyloxy group is usually 2 to 20, preferably 2 to 18, and more preferably 2 to 16. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The imine residue means a residue obtained by removing one hydrogen atom in this structure from an imine compound having a structure represented by at least one of the formula: HN═C <and the formula: —N═CH—. To do. Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like. It is done. The number of carbon atoms in the imine residue is usually 2-20, preferably 2-18, more preferably 2-16. Examples of the imine residue include a general formula: —CR ^X = N—R ^Y or a general formula: —N═C (R ^Y ) ₂ (wherein R ^X is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl) Group, arylalkenyl group, arylalkynyl group, R ^Y represents an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, provided that when two R ^Y are present, they are the same Or two R ^Y may be bonded to each other to form a divalent group such as an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group. A group may be formed as an alkylene group having 2 to 18 carbon atoms, and the like. Specific examples of the imine residue include groups represented by the following structural formulas.

  The amide group may have a substituent, and is usually an unsubstituted amide group or an amide group substituted with a halogen atom or the like. The number of carbon atoms in the amide group is usually 2 to 20, preferably 2 to 18, and more preferably 2 to 16. Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, Examples include a ditrifluoroacetamide group and a dipentafluorobenzamide group.

  The acid imide group means a residue obtained by removing one hydrogen atom bonded to the nitrogen atom from the acid imide. The number of carbon atoms of the acid imide group is usually 4 to 20, preferably 4 to 18, and more preferably 4 to 16. Examples of the acid imide group include the following groups.

  An arylene group means an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and includes those having an independent benzene ring or condensed ring. The arylene group usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, more preferably 6 to 30 carbon atoms, and still more preferably 6 to 18 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include unsubstituted or substituted phenylene groups such as 1,4-phenylene group, 1,3-phenylene group, and 1,2-phenylene group; 1,4-naphthalenediyl group and 1,5-naphthalenediyl group. 1,6-naphthalenediyl group such as 2,6-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group Unsubstituted or substituted anthracenediyl group such as 2,7-phenanthrenediyl group and the like; 1,7-naphthacenediyl group, 2,8-naphthacenediyl group, 5,12-naphthacenediyl group and the like An unsubstituted or substituted naphthacenediyl group; an unsubstituted 2,7-fluorenediyl group, 3,6-fluorenediyl group, etc. Is a substituted fluorenediyl group; an unsubstituted or substituted pyrenediyl group such as 1,6-pyrenediyl group, 1,8-pyrenediyl group, 2,7-pyrenediyl group, 4,9-pyrenediyl group; 3,9-perylenediyl And an unsubstituted or substituted perylenediyl group such as a 3,10-perylenediyl group, and the like, preferably an unsubstituted or substituted phenylene group and an unsubstituted or substituted fluorenediyl group.

  The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound (particularly an aromatic heterocyclic compound), an unsubstituted divalent heterocyclic group and an alkyl group. It means a divalent heterocyclic group substituted with a substituent such as. The carbon atom number of a bivalent heterocyclic group is 4-60 normally without including the carbon atom number of a substituent, Preferably it is 4-30, Most preferably, it is 6-12. Specific examples of the divalent heterocyclic group include unsubstituted or substituted pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; and unsubstituted groups such as 2,5-thiophenediyl group. Or a substituted thiophenediyl group; an unsubstituted or substituted furandyl group such as a 2,5-furandiyl group; an unsubstituted or substituted quinoline diyl group such as a 2,6-quinolinediyl group; a 1,4-isoquinolinediyl group; Unsubstituted or substituted isoquinolinediyl group such as 1,5-isoquinolinediyl group; Unsubstituted or substituted quinoxalinediyl group such as 5,8-quinoxalinediyl group; 4,7-benzo [1,2,5] thiadiazolediyl group An unsubstituted or substituted benzo [1,2,5] thiadiazolediyl group such as; an unsubstituted or substituted benzothiazolediyl group such as a 4,7-benzothiazolediyl group; Unsubstituted or substituted carbazolediyl group such as 2,7-carbazolediyl group, 3,6-carbazolediyl group; unsubstituted or substituted phenoxazinediyl group such as 3,7-phenoxazinediyl group; An unsubstituted or substituted phenothiazinediyl group such as a phenothiazinediyl group; an unsubstituted or substituted dibenzosiloldiyl group such as a 2,7-dibenzosiloldiyl group and the like, preferably an unsubstituted or substituted benzo [1, 2,5] thiadiazolediyl group, unsubstituted or substituted phenoxazinediyl group, unsubstituted or substituted phenothiazinediyl group. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

  The divalent group having a metal complex structure means a remaining atomic group formed by removing two hydrogen atoms from the organic ligand of a metal complex having an organic ligand and a central metal. The number of carbon atoms of the organic ligand is usually 4 to 60. Examples of the organic ligand include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, and 2-phenyl-benzoxazole and derivatives thereof. , Porphyrin and derivatives thereof.

  Examples of the central metal of the metal complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.

  Examples of the metal complex include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

<Polymer compound>
-Residue of compound represented by formula (1)-
The residue of the compound represented by the formula (1) is the remaining atomic group obtained by removing some or all (usually one or two) of the hydrogen atoms in the compound represented by the formula (1). Means. The residue of the compound represented by the formula (1) is included in the polymer compound as a repeating unit (for example, a divalent group), and is a molecular chain (for example, a monovalent group). It is preferably present at the terminal and contained in the repeating unit, and more preferably contained in the polymer compound as a repeating unit.

  In the formula (1), when the aryl group which may have a substituent represented by Ar or the monovalent heterocyclic group which may have a substituent has a substituent, the substituent As, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, alkenyl group, alkynyl group, amino group, substituted amino group Silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, heterocyclic thio group, imine residue, amide group, acid imide group, carboxyl group, nitro group, cyano group and the like. Some or all of the hydrogen atoms contained in these substituents may be substituted with fluorine atoms.

In the formula (1), Ar is preferably a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, biphenyl group, C ₁ -C ₁₂ alkoxybiphenyl group, C ₁ -C ₁₂ alkyl biphenyl group, pyridyl phenyl group, a phenyl pyridyl group, more preferably a phenyl group, at C ₁ -C ₁₂ alkyl biphenyl group (e.g., a biphenyl group substituted with an alkyl group having 1 to 12 carbon atoms) is there. These groups may have a substituent.

（式中、Ａｒは前記と同じ意味を有する。Ａｒ’は置換基を有していてもよいアリーレン基、又は置換基を有していてもよい２価の複素環基を表す。２個存在するＡｒ’は、同一であっても異なっていてもよい。）
で表される繰り返し単位であることが好ましく、この式（３）において、Ａｒが置換基を有していてもよいフェニル基であり、Ａｒ’が置換基を有していてもよい１,４−フェニレン基である繰り返し単位であることがより好ましい。 The repeating unit composed of the residue of the compound represented by the formula (1) is represented by the following formula (3) from the viewpoint of charge injection / transport:

(In the formula, Ar has the same meaning as described above. Ar ′ represents an arylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent. Ar ′ may be the same or different.)
In the formula (3), Ar is a phenyl group which may have a substituent, and Ar ′ may have a substituent. -It is more preferable that it is a repeating unit which is a phenylene group.

  In the formula (3), when the arylene group which may have a substituent represented by Ar ′ and the divalent heterocyclic group which may have a substituent have a substituent, Groups include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkenyl groups, arylalkynyl groups, alkenyl groups, alkynyl groups, amino groups, substituted amino groups. Group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, heterocyclic thio group, imine residue, amide group, acid imide group, carboxyl group, nitro group, cyano group and the like. . Some or all of the hydrogen atoms contained in these substituents may be substituted with fluorine atoms.

Ar ′ is, for example, a phenylene group, a C ₁ -C ₁₂ alkoxyphenylene group, a C ₁ -C ₁₂ alkylphenylene group, a biphenylene group, a C ₁ -C ₁₂ alkoxy biphenylene group, a C ₁ -C ₁₂ alkyl biphenylene group, a pyridinediyl group, a C ₁ -C ₁₂ alkoxypyridin-diyl group, C ₁ -C ₁₂ alkyl pyridinediyl group, preferably a 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene, 1, 4-pyridinediyl group, 1,3-pyridinediyl group, 1,2-pyridinediyl group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 1,4-anthracenediyl group, 1,5- Anthracenediyl group, 2,6-anthracenediyl group, and 9,10-anthracenediyl group, more preferably 1,4-phenylene group, 1,3-phenylene group, 1,2 -Phenylene group, 1,4-pyridinediyl group, 1,3-pyridinediyl group, 1,2-pyridinediyl group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, more preferably 1 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalenediyl group, 1,4-pyridinediyl group, 1,3-pyridinediyl group, 1,2-pyridinediyl group, particularly preferably 1,4-phenylene group and 1,4-pyridinediyl group.

（式中、Ｘは、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、アリールアルケニル基、アリールアルキニル基、アルケニル基、アルキニル基、アミノ基、置換アミノ基、シリル基、ハロゲン原子、アシル基、アシルオキシ基、１価の複素環基、複素環チオ基、イミン残基、アミド基、酸イミド基、カルボキシル基、ニトロ基、又はシアノ基を表す。Ｘで表される基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。） Examples of the repeating unit represented by the formula (3) include repeating units represented by the following formulas (3) ′ and (3) ″.

Wherein X is a hydrogen atom, 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 arylalkenyl group, an arylalkynyl group, an alkenyl group, an alkynyl group , Amino group, substituted amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, heterocyclic thio group, imine residue, amide group, acid imide group, carboxyl group, nitro group, or Represents a cyano group, part or all of the hydrogen atoms contained in the group represented by X may be substituted with fluorine atoms.)

Examples of the repeating unit represented by the formula (3) include repeating units represented by the following formula.

  In addition, the residue of the compound represented by the formula (1) may be contained alone or in combination of two or more in the polymer compound.

-Residue of compound represented by formula (2)-
The residue of the compound represented by the formula (2) is the remaining atomic group obtained by removing some or all (usually one or two) of the hydrogen atoms in the compound represented by the formula (2). Means. The residue of the compound represented by the formula (2) is included in the polymer compound as a repeating unit (for example, a divalent group), and is a molecular chain (for example, a monovalent group). It is preferably present at the end, contained in the repeating unit, more preferably contained in the polymer compound as a repeating unit, and more preferably present at the end of the molecular chain.

In the formula (2), —C (R ′) represented by 8 of Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ and Z ^10. ) =, R ′ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, and a substituent. An acyloxy group which may have, a monovalent heterocyclic group which may have a substituent, and a compound which may have a substituent. Represents an thio group, an imine residue, an amide group, an acid imide group, a carboxyl group, a nitro group, or a cyano group, which may have a substituent, preferably substituted with a hydrogen atom or a fluorine atom May be an alkyl group which may be substituted with a fluorine atom, an aryl group which may be substituted with a fluorine atom, an aryloxy group which may be substituted with a fluorine atom, or a fluorine atom A good arylalkyl group, an arylalkoxy group optionally substituted with a fluorine atom, an arylalkenyl group optionally substituted with a fluorine atom, an arylalkynyl group optionally substituted with a fluorine atom, or a fluorine atom substituted An optionally substituted amino group, a substituted amino group optionally substituted with a fluorine atom, a halogen atom, or a fluorine atom An acyl group optionally substituted with a fluorine atom, a monovalent heterocyclic group optionally substituted with a fluorine atom, a carboxyl group, a nitro group, or a cyano group, more preferably a hydrogen atom, An alkyl group optionally substituted by a fluorine atom, an alkoxy group optionally substituted by a fluorine atom, an aryl group optionally substituted by a fluorine atom, an aryloxy group optionally substituted by a fluorine atom, fluorine An arylalkyl group optionally substituted with an atom, an arylalkoxy group optionally substituted with a fluorine atom, a halogen atom, and a monovalent heterocyclic group optionally substituted with a fluorine atom, more preferably Hydrogen atom, alkyl group optionally substituted with fluorine atom, aryl group optionally substituted with fluorine atom, fluorine atom An arylalkyl group which may be substituted, a monovalent heterocyclic group which may be substituted with a halogen atom or a fluorine atom, particularly preferably a hydrogen atom or an alkyl group which may be substituted with a fluorine atom, fluorine An aryl group which may be substituted with an atom, particularly preferably an alkyl group which may be substituted with a hydrogen atom or a fluorine atom.

In the formula (2), represented by one of Z ¹ , Z ² and Z ³ , and represented by one of N ⁶ , Z ⁷ and Z ^8. The position of N = is preferably symmetric. For example, Z ¹ and Z ⁶ are -N =, Z ² , Z ³ , Z ⁷ and Z ⁸ are -C (R ') =, Z ² and Z ⁷ are -N =, Z ¹ , Z ³ , Z ⁶ and Z ⁸ are —C (R ′) ═, Z ³ and Z ⁸ are —N═, and Z ¹ , Z ² , Z ⁶ and Z ⁷ are —C ( R ′) = is preferred, Z ¹ and Z ⁶ are —N═, and Z ² , Z ³ , Z ⁷ and Z ⁸ are more preferably —C (R ′) ═.

（式中、Ｚ^1*、Ｚ^2*及びＺ^3*は、１個が−Ｎ＝を表し、２個が−Ｃ（Ｒ''）＝を表す。Ｚ^4*及びＺ^5*は、−Ｃ（Ｒ''）＝を表す。Ｚ^6*、Ｚ^7*及びＺ^8*は、１個が−Ｎ＝を表し、２個が−Ｃ（Ｒ''）＝を表す。Ｚ^9*及びＺ^10*は、−Ｃ（Ｒ''）＝を表す。Ｒ''は、水素原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、ハロゲン原子、アシル基、アシルオキシ基、１価の複素環基、カルボキシル基、ニトロ基、又はシアノ基を表すが、Ｚ^1*、Ｚ^2*、Ｚ^3*、Ｚ^4*及びＺ^5*に含まれるＲ''の１個は結合手を表し、Ｚ^6*、Ｚ^7*、Ｚ^8*、Ｚ^9*及びＺ^10*に含まれるＲ''の１個は結合手を表す。Ｒ''で表される基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。８個存在する−Ｃ（Ｒ''）＝は、同一であっても異なっていてもよい。Ｚ^2*及びＺ^3*が−Ｃ（Ｒ''）＝である場合にはＺ^2*及びＺ^3*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^3*が−Ｃ（Ｒ''）＝である場合にはＺ^3*及びＺ^4*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^4*及びＺ^5*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよいが、Ｚ^2*及びＺ^3*、Ｚ^3*及びＺ^4*、並びにＺ^4*及びＺ^5*の２個以上の組み合わせが同時にはベンゼン環を形成しない。Ｚ^7*及びＺ^8*が−Ｃ（Ｒ''）＝である場合にはＺ^7*及びＺ^8*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^8*が−Ｃ（Ｒ''）＝である場合にはＺ^8*及びＺ^9*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^9*及びＺ^10*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよいが、Ｚ^7*及びＺ^8*、Ｚ^8*及びＺ^9*、並びにＺ^9*及びＺ^10*の２個以上の組み合わせが同時にはベンゼン環を形成しない。２個のＲ''が互いに結合して形成するベンゼン環は、置換基を有していてもよい。）
で表される繰り返し単位、又は下記式（５）：

（式中、Ｚ^1**、Ｚ^2**及びＺ^3**は、１個が−Ｎ＝を表し、２個が−Ｃ（Ｒ'''）＝を表す。Ｚ^4**及びＺ^5**は、−Ｃ（Ｒ'''）＝を表す。Ｒ'''は、水素原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、ハロゲン原子、アシル基、アシルオキシ基、１価の複素環基、カルボキシル基、ニトロ基、又はシアノ基を表すが、Ｚ^1**、Ｚ^2**、Ｚ^3**、Ｚ^4**及びＺ^5**に含まれるＲ'''の２個は結合手を表す。Ｚ⁶、Ｚ⁷、Ｚ⁸、Ｚ⁹及びＺ¹⁰は、前記と同じ意味を有する。Ｒ’、Ｒ'''で表される基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。４個存在する−Ｃ（Ｒ’）＝は、同一であっても異なっていてもよい。４個存在する−Ｃ（Ｒ'''）＝は、同一であっても異なっていてもよい。Ｚ^2**及びＺ^3**が−Ｃ（Ｒ'''）＝である場合にはＺ^2**及びＺ^3**に含まれる２個のＲ'''が互いに結合してベンゼン環を形成してもよく、Ｚ^3**が−Ｃ（Ｒ'''）＝である場合にはＺ^3**及びＺ^4**に含まれる２個のＲ'''が互いに結合してベンゼン環を形成してもよく、Ｚ^4**及びＺ^5**に含まれる２個のＲ'''が互いに結合してベンゼン環を形成してもよいが、Ｚ^2**及びＺ^3**、Ｚ^3**及びＺ^4**、並びにＺ^4**及びＺ^5**の２個以上の組み合わせが同時にはベンゼン環を形成しない。Ｚ⁷及びＺ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁷及びＺ⁸に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁸及びＺ⁹に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁹及びＺ¹⁰に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよいが、Ｚ⁷及びＺ⁸、Ｚ⁸及びＺ⁹、並びにＺ⁹及びＺ¹⁰の２個以上の組み合わせが同時にはベンゼン環を形成しない。２個のＲ’が互いに結合して形成するベンゼン環は、置換基を有していてもよく、２個のＲ'''が互いに結合して形成するベンゼン環は、置換基を有していてもよい。）
で表される繰り返し単位であることが好ましく、これらの式において、結合手ではないＲ''が、水素原子又はアルキル基である繰り返し単位であること、結合手ではないＲ'''が、水素原子又はアルキル基である繰り返し単位であること、結合手ではないＲ''が、水素原子又はアルキル基である繰り返し単位であり、かつ、結合手ではないＲ'''が、水素原子又はアルキル基である繰り返し単位であることがより好ましい。 The repeating unit consisting of the residue of the compound represented by the formula (2) is represented by the following formula (4):

(In the formula, ^one of Z ^{1 *} , Z ^{2 *} and Z ^{3 *} represents -N = and two represents -C (R '') =. Z ^{4 *} and Z ^{5 *} are- ^{C (R '') .Z 6} * represents a =, Z ^{7 *} and Z ^{8 *} are one represents -N =, 2 pieces is -C (R '') = represented .Z ^{9 *} and Z ^{10 *} represents —C (R ″) ═. R ″ represents a hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, aryl. An alkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group, or a cyano group, Z ^{1 *} , Z ^{2 *} , Z ^{3 *} , Z ^{4 *} and Z ^{5 *} , one of R ″ represents a bond, and one of R ″ included in Z ^{6 *} , Z ^{7 *} , Z ^{8 *} , Z ^{9 *} and Z ^{10 *.} Each represents a bond, and is contained in the group represented by R ″. Some or all of the hydrogen atoms, -C present .8 amino which may optionally be substituted with a fluorine atom (R '') = is optionally be the same or different .Z 2 ^* and Z ^{3 *} is -C (R '') when a = two R contained in Z ^{2 *} and Z ^{3 *} 'may form a benzene ring bonded' to each other, Z 3 ^* is When —C (R ″) =, two R ″ contained in Z ^{3 *} and Z ^{4 *} may be bonded to each other to form a benzene ring, and Z ^{4 *} and Z ^{5 * May} be bonded to each other to form a benzene ring, Z ^{2 *} and Z ^{3 *} , Z ^{3 *} and Z ^{4 *} , and Z ^{4 *} and Z ^{5 *} 2 .Z 7 ^* and Z ^{8 *} represents -C a combination of more pieces do not form a benzene ring at the same time (R '') of the two contained in Z ^{7 *} and Z ^{8 *} if a = R '' There may form a benzene ring bonded to each other, is Z 8 ^* -C (R '' = If it is may form a benzene ring bonded two R '' each other contained in Z ^{8 *} and Z ^{9 *,} two R's contained in Z 9 ^* and Z ^{10 *} '' May combine with each other to form a benzene ring, but two or more combinations of Z ^{7 *} and Z ^{8 *} , Z ^{8 *} and Z ^{9 *} , and Z ^{9 *} and Z ^{10 *} A benzene ring is not formed. The benzene ring formed by bonding two R ″ to each other may have a substituent.)
Or a repeating unit represented by the following formula (5):

(In the formula, ^one of Z ^{1 **} , Z ^{2 **} and Z ^{3 **} represents -N = and two represents -C (R ''') =. Z ^{4 **} and Z ^{3 ** 5 **} represents -C (R ''') =. R''' represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group. Represents an arylalkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group, or a cyano group, Z ^{1 **} , Z ^{2 **} , Z ^{3 **} , Z ^{4 **} and Z ^{5 **} represent two bonds. Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰ are the same as above. The hydrogen atom contained in the group represented by R ′ or R ″ ′ may be partially or entirely substituted with a fluorine atom. Four —C (R ′) ═ The same -C also present .4 pieces which may be different from (R ''') = is optionally be the same or different .Z 2 ^** and Z ^{3 **} is -C (R''' ) =, Two R ′ ″ contained in Z ^{2 **} and Z ^{3 **} may be bonded to each other to form a benzene ring, and Z ^{3 **} is —C (R ′ '') = in the case of two R contained in Z ^{3 **} and Z ^{4 **} 'may form a benzene ring bonded''to each other, Z 4 ^** and Z ^{5 *} Two R ′ ″ contained in ^* may be bonded to each other to form a benzene ring, but Z ^{2 **} and Z ^{3 **} , Z ^{3 **} and Z ^{4 **} , and Z ^{4 *} The combination of two or more of ^* and Z ^{5 **} does not form a benzene ring at the same time.When Z ⁷ and Z ⁸ are —C (R ′) ═, two of Z ⁷ and Z ⁸ R 'and are bonded together, may form a benzene ring, Z ⁸ is -C (R' including the Z ⁸ and Z ⁹ when a) = The two instances of R 'may be bonded to form a benzene ring together, two R contained in Z ⁹ and Z ^10' may form a benzene ring are bonded to each other but, Z ⁷ And a combination of two or more of Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ do not form a benzene ring at the same time. The benzene ring formed by bonding two R ′ ″ to each other may have a substituent.
In these formulas, R ″ that is not a bond is a hydrogen atom or a repeating unit that is an alkyl group, and R ′ ″ that is not a bond is hydrogen. It is a repeating unit that is an atom or an alkyl group, R ″ that is not a bond is a hydrogen atom or an alkyl group, and R ′ ″ that is not a bond is a hydrogen atom or an alkyl group It is more preferable that it is a repeating unit.

In the formula (4), 8 out of Z ^{1 *} , Z ^{2 *} , Z ^{3 *} , Z ^{4 *} , Z ^{5 *} , Z ^{6 *} , Z ^{7 *} , Z ^{8 *} , Z ^{9 *} and Z ^{10 *} In —C (R ″) ═, one represents a bond, but the remaining R ″ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, An arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, or cyano group have the same meaning as described above. And preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom or a monovalent heterocyclic group, more preferably a hydrogen atom, Alkyl group, aryl group, aryl A rualkyl group, a halogen atom, and a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, and an aryl group, and particularly preferably a hydrogen atom and an alkyl group.

In the formula (4), a position of -N = represented by one of Z ^{1 *} , Z ^{2 *} and Z ^{3 *} , and one of Z ^{6 *} , Z ^{7 *} and Z ^{8 *} It is preferable that the position of -N = represented by Specifically, Z1 ^* and Z6 ^* are -N =, Z2 ^* , Z3 ^* , Z7 ^* and Z8 ^* are -C (R '') =, Z2 ^* And Z ^{7 *} is -N =, Z ^{1 *} , Z ^{3 *} , Z ^{6 *} and Z ^{8 *} are -C (R '') =, Z ^{3 *} and Z ^{8 *} are -N = Z ^{1 *} , Z ^{2 *} , Z ^{6 *} and Z ^{7 *} are preferably —C (R ″) ═, Z ^{1 *} and Z ^{6 *} are —N═, and Z ^{2 *} , Z ^{3 *} , Z ^{7 *} and Z ^{8 *} are more preferably —C (R ″) ═.

In the polymer compound having a repeating unit represented by the above formula (4), the two bonds are preferably formed by removing R ″ contained in Z ^{3 *} and Z ^{8 *} .

Examples of the repeating unit represented by the formula (4) include repeating units represented by the following formula.

In the formula (5), in —C (R ′ ″) = represented by four of Z ^{1 **} , Z ^{2 **} , Z ^{3 **} , Z ^{4 **} and Z ^{5 **} 2 represents a bond, but the remaining alkyl group represented by R ′ ″, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group Group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, or cyano group have the same meaning as described above, preferably a hydrogen atom, an alkyl group, An alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom, and a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a halogen atom, The valence of the heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, particularly preferably a hydrogen atom, an alkyl group.

In the above formula (5), the position of -N = in Z ^{1 **} , Z ^{2 **} and Z ^{3 **} and the position of -N = in Z ⁶ , Z ⁷ and Z ⁸ are symmetrical. Is preferred. Specifically, Z ^{1 **} and Z ⁶ are —N═, Z ^{2 **} and Z ^{3 **} are —C (R ′ ″), and Z ⁷ and Z ⁸ are —C (R ′). Z, Z ^{2 **} and Z ⁷ are —N═, Z ^{1 **} and Z ^{3 **} are —C (R ′ ″) =, Z ⁶ and Z ⁸ are —C (R ′ '') =, Z ^{3 **} and Z ⁸ are -N =, Z ^{1 **} and Z ^{2 **} are -C (R ''') =, and Z ⁶ and Z ⁷ are -C. (R ′ ″) = is preferred, Z ^{1 **} and Z ⁶ are —N═, Z ^{2 **} and Z ^{3 **} are —C (R ′ ″), Z ⁷ and Z More preferably, ⁸ is -C (R ') =.

In the polymer compound having a repeating unit represented by the formula (5), two bonds are R ² contained in Z ^{2 **} and Z ^{5 **} , or Z ^{2 **} and Z ^{4 **.} It is preferable that '' is removed.

As the repeating unit represented by the formula (5), a repeating unit composed of a 2,2′-bipyridine-5,5′-diyl group which may have a substituent, and a repeating unit represented by the following formula: Examples include units.

（式中、Ｚ^1*、Ｚ^2*、Ｚ^3*、Ｚ^4*、Ｚ^5*、Ｚ⁶、Ｚ⁷、Ｚ⁸、Ｚ⁹及びＺ¹⁰は、前記と同じ意味を有する。Ｒ’、Ｒ''で表される基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。４個存在する−Ｃ（Ｒ’）＝は、同一であっても異なっていてもよい。４個存在する−Ｃ（Ｒ''）＝は、同一であっても異なっていてもよい。Ｚ^2*及びＺ^3*が−Ｃ（Ｒ''）＝である場合にはＺ^2*及びＺ^3*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^3*が−Ｃ（Ｒ''）＝である場合にはＺ^3*及びＺ^4*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよく、Ｚ^4*及びＺ^5*に含まれる２個のＲ''が互いに結合してベンゼン環を形成してもよいが、Ｚ^2*及びＺ^3*、Ｚ^3*及びＺ^4*、並びにＺ^4*及びＺ^5*の２個以上の組み合わせが同時にはベンゼン環を形成しない。Ｚ⁷及びＺ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁷及びＺ⁸に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁸が−Ｃ（Ｒ’）＝である場合にはＺ⁸及びＺ⁹に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよく、Ｚ⁹及びＺ¹⁰に含まれる２個のＲ’が互いに結合してベンゼン環を形成してもよいが、Ｚ⁷及びＺ⁸、Ｚ⁸及びＺ⁹、並びにＺ⁹及びＺ¹⁰の２個以上の組み合わせが同時にはベンゼン環を形成しない。２個のＲ’が互いに結合して形成するベンゼン環は、置換基を有していてもよく、２個のＲ''が互いに結合して形成するベンゼン環は、置換基を有していてもよい。）
で表される基として存在することが好ましい。 When the residue of the compound represented by the formula (2) is present at the molecular chain end, the following formula (6):

(In the formula, Z ^{1 *} , Z ^{2 *} , Z ^{3 *} , Z ^{4 *} , Z ^{5 *} , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰ have the same meaning as described above. R ′, Some or all of the hydrogen atoms contained in the group represented by R ″ may be substituted with fluorine atoms. The four —C (R ′) ═ may be the same or different. The four —C (R ″) ═ may be the same or different. When Z ^{2 *} and Z ^{3 *} are —C (R ″) ═, ^Two R ″ contained in Z ^{2 *} and Z ^{3 *} may be bonded to each other to form a benzene ring. When Z ^{3 *} is —C (R ″) ═, Z ^{3 *} And two R ″ contained in Z ^{4 *} may be bonded to each other to form a benzene ring, and two R ″ contained in Z ^{4 *} and Z ^{5 *} may be bonded to each other to form a benzene ring. Z ^{2 *} and Z ^{3 *} , Z ^{3 *} and Z ^{4 *} , and Z ^{4 *} and Z ^{5 *} Two or more combinations do not form a benzene ring at the same time.When Z ⁷ and Z ⁸ are —C (R ′) ═, two R ′ contained in Z ⁷ and Z ⁸ are bonded to each other. A benzene ring may be formed, and when Z ⁸ is —C (R ′) ═, two R ′ contained in Z ⁸ and Z ⁹ may be bonded to each other to form a benzene ring. , Z ⁹ and Z ¹⁰ may be bonded to each other to form a benzene ring, but two of Z ⁷ and Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ The above combination does not form a benzene ring at the same time.The benzene ring formed by bonding two R's to each other may have a substituent and formed by bonding two R '' to each other. (The benzene ring to be bonded may have a substituent.)
It is preferable that it exists as group represented by these.

In the formula (6), it is preferable that the position of -N = in Z ^{1 *} , Z ^{2 *} and Z ^{3 *} and the position of -N = in Z ⁶ , Z ⁷ and Z ⁸ are symmetric. Specifically, Z ^{1 *} and Z ⁶ are —N═, Z ^{2 *} and Z ^{3 *} are —C (R ″) =, and Z ⁷ and Z ⁸ are —C (R ′) =. Z ^{2 *} and Z ⁷ are -N =, Z ^{1 *} and Z ^{3 *} are -C (R '') =, Z ⁶ and Z ⁸ are -C (R ') =, Z ^{3 *} and Z ⁸ are —N═, Z ^{1 *} and Z ^{2 *} are preferably —C (R ″) ═, and Z ⁶ and Z ⁷ are preferably —C (R ′) ═, and Z ¹ More preferably, ^* and Z ⁶ are -N =, Z ^{2 *} and Z ^{3 *} are -C (R '') =, and Z ⁷ and Z ⁸ are -C (R ') =.

In the formula (6), it is preferable that one bond is formed by removing R ″ contained in Z ^{3 *} .

  When the group represented by the formula (6) is present at the molecular chain end, the ratio (number of groups represented by the formula (6) present at the molecular chain terminal out of the total molecular chain terminals of the polymer compound The standard) is preferably 10 to 100%, more preferably 25 to 100%, and particularly preferably 40 to 100%.

Examples of the group represented by the formula (6) include a 2,2′-bipyridin-5-yl group which may have a substituent, a group represented by the following formula, and the like.

  In addition, the residue of the compound represented by the formula (2) may be included alone or in a combination of two or more in the polymer compound.

-Ratio of residue of compound represented by formula (1) and residue of compound represented by formula (2)-
The polymer compound of the present invention is preferably a conjugated polymer from the viewpoint of charge injection / transport. The conjugated polymer means a polymer compound in which 50 to 100%, particularly 70 to 100%, particularly 80 to 100% of all bonds in the main chain are conjugated.

  The polymer compound of the present invention includes a residue of the compound represented by the formula (1) (a repeating unit represented by the formula (3). Hereinafter, the compound represented by the formula (1) And a residue of the compound represented by the formula (2) (a repeating unit represented by the formula (4), a repeating unit represented by the formula (5), 6) including the group represented by 6) is usually 1: 0.001 to 1: 5, preferably 1: 0.005 to 1: 3, and more Preferably, it is 1: 0.01-1: 1.

From the viewpoint of luminous efficiency and durability of the device, the polymer compound of the present invention is
A repeating unit represented by the formula (3);
At least one selected from the group consisting of the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5), and / or a group represented by the formula (6),
It is preferable that it is a high molecular compound which has these.

（式中、Ａｒ³及びＡｒ⁷はそれぞれ独立に、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、又は置換基を有していてもよい金属錯体構造を有する２価の基を表す。Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、又は置換基を有していてもよい２個の芳香環が単結合で連結した２価の基を表す。Ｒ¹及びＲ²はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はアリールアルキル基を表す。Ｘ¹は−ＣＲ³＝ＣＲ⁴−又は−Ｃ≡Ｃ−を表す。Ｒ³及びＲ⁴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、又はシアノ基を表す。ａは０又は１である。） -Other repeating units-
From the viewpoint of charge transport / injection and luminance half life, the polymer compound of the present invention is further represented by the following repeating unit represented by the following formula (A), repeating unit represented by the following formula (B), and the following formula ( It is preferable to have at least one repeating unit selected from the group consisting of repeating units represented by C).

(In the formula, Ar ³ and Ar ⁷ each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. Represents a divalent group having a metal complex structure, and Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an arylene group which may have a substituent or a divalent which may have a substituent. Or a divalent group in which two aromatic rings optionally having a substituent are connected by a single bond, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl A monovalent heterocyclic group or an arylalkyl group, X ¹ represents —CR ³ ═CR ⁴ — or —C≡C—, R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, Represents an aryl group, a monovalent heterocyclic group, a carboxyl group, or a cyano group, and a is 0 or 1.)

-Repeating unit represented by formula (A)-
In the formula (A), when the group represented by Ar ³ has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and an arylalkenyl group. Group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, etc., preferably alkyl group, alkoxy group , An aryl group, an aryloxy group, a substituted amino group, and a monovalent heterocyclic group, more preferably an alkyl group, an alkoxy group, and an aryl group.

In the formula (A), the arylene group in the arylene group which may have a substituent represented by Ar ³ means an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and is independent. Including those having a benzene ring or condensed ring. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18. In the formula (A), as the arylene group in the arylene group which may have a substituent represented by Ar ³ , 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalenediyl Group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-phenanthrylene group, 5,12-naphthacenylene group, 2,7-fluorenediyl group, 3 , 6-fluorenediyl group, 1,6-pyrene diyl group, 1,8-pyrene diyl group, 3,9-perylene diyl group, 3,10-perylene diyl group, 2,6-quinoline diyl group, 1,4-isoquinoline diyl group 1,5-isoquinolinediyl group, 5,8-quinoxalinediyl group, etc., preferably 1,4-phenylene group, 1,4-naphthalenediyl group, 1, -Naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-fluorenediyl group, 1,6-pyrenediyl group, 3,9-perylenediyl group, 3,10-perylenediyl group 2,6-quinolinediyl group, 1,4-isoquinolinediyl group, 5,8-quinoxalinediyl group, more preferably 1,4-phenylene group, 1,4-naphthalenediyl group, 1,5-naphthalene A diyl group, a 2,6-naphthalenediyl group, a 9,10-anthracenediyl group, a 2,7-fluorenediyl group, and a 5,8-quinoxalinediyl group, particularly preferably a 1,4-phenylene group, , 7-fluorenediyl group.

In the formula (A), the divalent heterocyclic group in the divalent heterocyclic group which may have a substituent represented by Ar ³ is 4,7-benzo [1,2,5]. And thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,7-phenothiazinediyl group and the like, and preferably 4,7-benzo [1,2,5] thiadiazolediyl group, 3,7-phenoxazine Diyl group, 3,7-phenothiazinediyl group, 4,7-benzo [1,2,5] thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,7-phenothiazinediyl group, particularly preferred Are 4,7-benzo [1,2,5] thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,7-phenothiazinediyl group.

In the formula (A), examples of the divalent group having a metal complex structure which may have a substituent represented by Ar ³ include groups represented by the following formulas M-1 to M-7. Can be mentioned.

（式中、Ｒ¹⁰は、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、ハロゲン原子、アシル基、アシルオキシ基、１価の複素環基、カルボキシル基、ニトロ基又はシアノ基である。これらの基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。ｆは０〜４の整数を表す。Ｒ¹⁰が複数存在する場合には、それらは同一であっても異なっていてもよい。）

（式中、Ｒ¹¹及びＲ¹²はそれぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基又は１価の複素環基を表す。）

（式中、Ｒ¹³及びＲ¹⁴はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、ハロゲン原子、アシル基、アシルオキシ基、１価の複素環基、カルボキシル基、ニトロ基又はシアノ基である。これらの基に含まれる水素原子の一部又は全部は、フッ素原子で置換されていてもよい。）

（式中、Ｒ¹⁵は、水素原子、アルキル基、アリール基、１価の複素環基又はアリールアルキル基を表す。）

（式中、Ｒ¹⁶は、水素原子、アルキル基、アリール基、１価の複素環基又はアリールアルキル基を表す。） Among these, the group represented by Ar ³ is preferably at least one of the following formulas (D), (E), (F), (G), and (H).

(Wherein R ¹⁰ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl group, An acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group, or a cyano group, wherein some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms. Represents an integer of 4. When a plurality of R ¹⁰ are present, they may be the same or different.

(Wherein R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group.)

Wherein R ¹³ and R ¹⁴ are each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted An amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group, or a cyano group, wherein some or all of the hydrogen atoms contained in these groups are substituted with fluorine atoms. May be.)

(Wherein R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group.)

(Wherein R ¹⁶ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group.)

In the formula (D), R ¹⁰ is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, a substituted amino group, an acyl group, A monovalent heterocyclic group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a substituted amino group, an acyl group, and a monovalent heterocyclic group, still more preferably an alkyl group, an alkoxy group. A group, an aryl group, and a monovalent heterocyclic group, particularly preferably an alkyl group, an alkoxy group, and an aryl group.

  In the formula (D), f is preferably an integer of 0 to 2.

In the formula (E), R ¹¹ and R ¹² are preferably an alkyl group, an aryl group, and a monovalent heterocyclic group, and more preferably an alkyl group and an aryl group.

In the formula (F), R ¹³ and R ¹⁴ are preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group, and a monovalent group. More preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, still more preferably a hydrogen atom or an alkyl group, particularly preferably. Is a hydrogen atom.

In the formula (G), R ¹⁵ is preferably an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

In the formula (H), R ¹⁶ is preferably an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

  As the repeating unit represented by the formula (A), a fluorenediyl group which may have a substituent, a phenylene group which may have a substituent, and a combination thereof are preferable.

-Repeating unit represented by formula (B) In the formula (B), when the group represented by Ar ⁴ , Ar ⁵ , Ar ⁶ has a substituent, the substituent includes an alkyl group, an alkoxy group, Aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group Group, cyano group, preferably alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group, cyano group, more preferably alkyl group An alkoxy group and an aryl group.

In the formula (B), the arylene group in the arylene group which may have a substituent represented by Ar ⁴ , Ar ⁵ or Ar ⁶ is an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon. And includes those having an independent benzene ring or condensed ring. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.

In the formula (B), as the arylene group in the arylene group which may have a substituent represented by Ar ⁴ , Ar ⁵ , Ar ⁶ , a 1,3-phenylene group, a 1,4-phenylene group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12-naphthacenediyl group, 2,7-fluorenediyl group, 3, An 8-perylenediyl group and the like can be mentioned.

In the formula (B), the divalent heterocyclic group in the divalent heterocyclic group which may have a substituent represented by Ar ⁴ , Ar ⁵ , Ar ⁶ has usually a carbon atom number of It is 4-60, Preferably it is 4-20, More preferably, it is 4-9. In the formula (B), the divalent heterocyclic group in the divalent heterocyclic group which may have a substituent represented by Ar ⁴ , Ar ⁵ or Ar ⁶ is 2,5-thiophenediyl. Group, N-methyl-2,5-pyrrolediyl group, 2,5-furandiyl group, 4,7-benzo [1,2,5] thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,6- Examples thereof include a carbazole diyl group.

In the formula (A), two aromatic rings in a divalent group in which two aromatic rings optionally having a substituent represented by Ar ⁴ , Ar ⁵ , Ar ⁶ are connected by a single bond are Examples of the divalent group linked by a single bond include groups represented by the following formulas (3A-1) to (3A-4).

In the formula (B), Ar ⁴ and Ar ⁶ are preferably each independently an arylene group which may have a substituent, more preferably 1, 3 which may have a substituent. -A phenylene group, an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthalenediyl group, an optionally substituted 2,6- A naphthalenediyl group, a group represented by the above formula (3A-1), more preferably a 1,4-phenylene group which may have a substituent, A 4-naphthalenediyl group, particularly preferably a 1,4-phenylene group which may have a substituent.

In the formula (B), Ar ⁵ preferably has a 1,3-phenylene group which may have a substituent, a 1,4-phenylene group which may have a substituent, or a substituent. 1,4-naphthalenediyl group which may be substituted, 2,7-fluorenediyl group which may be substituted, 4,7-benzo [1,2, which may be substituted 5] a thiadiazolediyl group, an optionally substituted 3,7-phenoxazinediyl group, a group represented by the formula (3A-1), a group represented by the formula (3A-4) Yes, preferably 1,4-phenylene group which may have a substituent, 1,4-naphthalenediyl group which may have a substituent, 2,7 which may have a substituent A fluorenediyl group, a group represented by the formula (3A-1), more preferably a substituent. It is a group represented by the formula (3A-1) which may have a good 1,4-phenylene group and a substituent.

In the formula (B), R ¹ and R ² are each independently preferably an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, still more preferably. , An aryl group.

Examples of the repeating unit represented by the formula (B) include repeating units represented by the following formulas (3B-1) to (3B-4). In the formula, R ^a represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, or a halogen atom. , An acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group, or a cyano group. A plurality of R ^a may be the same or different.

- type repeating units the formula represented by (C) in (C), an arylene group optionally having a substituent represented by Ar ^7, divalent or substituted heterocyclic ring The divalent group having a metal complex structure which may have a group or a substituent is the same as that described and exemplified in the above Ar ³ section.

In the formula (C), R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an aryl group.

Examples of the repeating unit represented by the formula (C) include repeating units represented by the following formulas (4A-1) to (4A-11).

  The polymer compound of the present invention is selected from the group consisting of the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (C). When having at least one repeating unit, the residue of the compound represented by the formula (1), the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the above The ratio (molar ratio) with at least one repeating unit selected from the group consisting of repeating units represented by formula (C) is usually from 1: 0.01 to 1: 100, preferably 1: 0. 0.05 to 1:50, more preferably 1: 0.1 to 1:20.

  In addition, the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (C) are each included in the polymer compound only one kind. Or two or more of them may be contained.

The polymer compound of the present invention has a polystyrene-equivalent number average molecular weight of usually 1 × 10 ³ to 1 × 10 ⁷ , preferably 1 × 10 ^{4 to} 5 × 10 ⁶ , and a polystyrene-equivalent weight average molecular weight. Is usually 1 × 10 ^{4 to} 5 × 10 ⁷ , preferably 5 × 10 ⁴ to 1 × 10 ⁷ .

  Examples of the polymer compound of the present invention include polymer compounds 1 to 4 represented by the following formula.

（式中、ｘ、ｙ、ｍ、ｎは、高分子化合物１中の各繰り返し単位の組成比（モル％）を表し、ｘは30≦ｘ≦60を満たす正の数であり、ｙは20≦ｙ≦40を満たす正の数であり、ｍは５≦ｍ≦30を満たす正の数であり、ｎは３≦ｎ≦20を満たす正の数である。但し、ｘ＋ｙ＋ｍ＋ｎ＝100である。高分子化合物１のポリスチレン換算の重量平均分子量は１×10⁴〜１×10⁶である。） ・ Polymer compound 1

(Wherein, x, y, m and n represent the composition ratio (mol%) of each repeating unit in the polymer compound 1, x is a positive number satisfying 30 ≦ x ≦ 60, and y is 20 ≦ y ≦ 40, m is a positive number satisfying 5 ≦ m ≦ 30, and n is a positive number satisfying 3 ≦ n ≦ 20, where x + y + m + n = 100. The polymer compound 1 has a polystyrene-equivalent weight average molecular weight of 1 × 10 ⁴ to 1 × 10 ^6. )

（式中、ｘ'、ｙ'、ｍ'、ｎ'は、高分子化合物２中の各繰り返し単位の組成比（モル％）を表し、ｘ'は30≦ｘ'≦60を満たす正の数であり、ｙ'は20≦ｙ'≦40を満たす正の数であり、ｍ'は５≦ｍ'≦30を満たす正の数であり、ｎ'は３≦ｎ'≦20を満たす正の数である。但し、ｘ'＋ｙ'＋ｍ'＋ｎ'＝100である。高分子化合物２のポリスチレン換算の重量平均分子量は１×10⁴〜１×10⁶である。） ・ High molecular compound 2

(Wherein x ′, y ′, m ′, n ′ represent the composition ratio (mol%) of each repeating unit in the polymer compound 2, and x ′ is a positive number satisfying 30 ≦ x ′ ≦ 60. Y ′ is a positive number satisfying 20 ≦ y ′ ≦ 40, m ′ is a positive number satisfying 5 ≦ m ′ ≦ 30, and n ′ is a positive number satisfying 3 ≦ n ′ ≦ 20. (However, x ′ + y ′ + m ′ + n ′ = 100. The polystyrene equivalent weight average molecular weight of the polymer compound 2 is 1 × 10 ⁴ to 1 × 10 ⁶ )

（式中、ｘ''、ｙ''、ｍ''、ｎ''は、高分子化合物３中の各繰り返し単位の組成比（モル％）を表し、ｘ''は30≦ｘ''≦60を満たす正の数であり、ｙ''は20≦ｙ''≦40を満たす正の数であり、ｍ''は５≦ｍ''≦30を満たす正の数であり、ｎ''は３≦ｎ''≦20を満たす正の数である。但し、ｘ''＋ｙ''＋ｍ''＋ｎ''＝100ある。高分子化合物３のポリスチレン換算の重量平均分子量は１×10⁴〜１×10⁶である。） ・ Polymer compound 3

(In the formula, x ″, y ″, m ″, n ″ represent the composition ratio (mol%) of each repeating unit in the polymer compound 3, and x ″ is 30 ≦ x ″ ≦. Y ″ is a positive number satisfying 20 ≦ y ″ ≦ 40, m ″ is a positive number satisfying 5 ≦ m ″ ≦ 30, and n ″. Is a positive number satisfying 3 ≦ n ″ ≦ 20, where x ″ + y ″ + m ″ + n ″ = 100.The polystyrene equivalent weight average molecular weight of the polymer compound 3 is 1 × 10 ^4. ˜1 × 10 ⁶ )

（式中、ｘ'''、ｙ'''、ｍ'''、ｎ'''は、高分子化合物４中の各繰り返し単位の組成比（モル％）を表し、ｘ'''は30≦ｘ'''≦60を満たす正の数であり、ｙ'''は10≦ｙ'''≦30を満たす正の数であり、ｚは５≦ｚ≦20を満たす正の数であり、ｍ'''は5≦ｍ'''≦30を満たす正の数であり、ｎ'''は3≦ｎ'''≦20を満たす正の数である。但し、ｘ'''＋ｙ'''＋ｚ＋ｍ'''＋ｎ'''＝100である。高分子化合物４のポリスチレン換算の重量平均分子量は１×10⁴〜１×10⁶である。） ・ Polymer compound 4

(Wherein x ′ ″, y ′ ″, m ′ ″, n ′ ″ represent the composition ratio (mol%) of each repeating unit in the polymer compound 4, and x ′ ″ is 30 ≦ x ′ ″ ≦ 60 is a positive number, y ′ ″ is a positive number that satisfies 10 ≦ y ′ ″ ≦ 30, and z is a positive number that satisfies 5 ≦ z ≦ 20 , M ′ ″ is a positive number satisfying 5 ≦ m ′ ″ ≦ 30, and n ′ ″ is a positive number satisfying 3 ≦ n ′ ″ ≦ 20, provided that x ′ ″ + y '''+ Z + m''' + n '''= 100. The weight average molecular weight in terms of polystyrene of the polymer compound 4 is 1 × 10 ⁴ to 1 × 10 ^6. )

<Composition>
The polymer compound of the present invention can be used in combination with at least one selected from the group consisting of a light-emitting material, a hole transport material, and an electron transport material.

  Examples of the light emitting material include low molecular fluorescent light emitting materials and phosphorescent light emitting materials. Specific examples thereof include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine dyes, xanthene dyes, and coumarin dyes. , Dyes such as cyanine dyes, metal complexes having 8-hydroxyquinoline as a ligand, metal complexes having 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, aromatic amines, tetraphenylcyclo Pentadiene and its derivatives, tetraphenylbutadiene and its derivatives, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, acetylene, etc. Low molecular weight fluorescent material, Rijiumu complexes, metal complexes such as platinum complexes, triplet light emitting complexes, and the like. Other examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  The proportion of the light emitting material is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, from the viewpoint of the chromaticity of the organic electroluminescence device, with respect to 100 parts by weight of the polymer compound of the present invention. It is particularly preferably 3 to 30 parts by weight.

  Examples of the hole transport material include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline And derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like. In addition, JP-A-63-70257, 63-175860, JP-A-2-135359, 2-135361, 2-209988, 3-37992, The thing described in 3-152184 gazette is also mentioned.

  The ratio of the hole transport material is preferably 3 to 30 parts by weight, more preferably 3 to 20 parts by weight, in view of charge balance, with respect to 100 parts by weight of the polymer compound of the present invention. Preferably it is 3-10 weight part.

  Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyano Examples include ethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, and the like. In addition, JP-A-63-70257, 63-175860, JP-A-2-135359, 2-135361, 2-209988, 3-37992, The thing described in 3-152184 gazette is also mentioned.

  The proportion of the electron transport material is preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, particularly preferably 100 parts by weight of the polymer compound of the present invention, from the viewpoint of charge balance. Is 5 to 20 parts by weight.

  The composition of the present invention includes a compound represented by the formula (1), a compound having a residue of the compound represented by the formula (1), and the formula (2) from the viewpoint of luminous efficiency and device durability. Or a compound having a residue of the compound represented by the formula (2).

  The composition of the present invention can be made into a solution or dispersion (hereinafter simply referred to as “solution”) by containing an organic solvent. By doing so, film formation by a coating method can be performed. This solution is generally called an ink, a liquid composition or the like.

  Examples of the organic solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and other chlorine solvents, tetrahydrofuran, dioxane and other ether solvents, toluene, xylene, Aromatic hydrocarbon solvents such as trimethylbenzene and mesitylene, and aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane , Ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Ter, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and other polyhydric alcohols and derivatives thereof, methanol, ethanol, propanol, isopropanol, cyclo Examples thereof include alcohol solvents such as hexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. In addition, the said solvent may be used individually by 1 type, or may use 2 or more types together. Among the solvents, it is preferable from the viewpoint of viscosity, film formability, and the like to include an organic solvent having a structure containing a benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher.

When the composition of the present invention contains the organic solvent, in order to laminate and form a film from the composition of the present invention, it is only necessary to remove the organic solvent by drying after applying the composition of the present invention. Very advantageous. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried by reducing pressure to about 10 ^<-3 > Pa.

  For the lamination and film formation, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spraying Coating methods such as a coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, and a nozzle coating method can be used.

  When the composition of the present invention contains the organic solvent, the preferred viscosity of the solution varies depending on the printing method, but is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. In the case of passing through, it is preferable that the viscosity is in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent clogging and flight bending at the time of discharge.

<Organic electroluminescence device>
The organic electroluminescence device of the present invention is formed by using the polymer compound of the present invention, and is usually formed by using the polymer compound of the present invention between an anode, a cathode, and the anode and the cathode. It is preferable that the layer using the polymer compound is a light emitting layer. Hereinafter, the case where the layer using the polymer compound of the present invention is a light emitting layer will be described as an example.

The structure of the organic electroluminescent element of the present invention includes the following structures a) to d).
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 applies hereinafter.)

  Note that the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. is there. The hole transport layer and the electron transport layer are collectively referred to as a charge transport layer. In addition, the hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.

  Lamination and film formation of each layer can be performed from a solution. For lamination and film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, inkjet printing, and nozzle coating can be used.

  The film thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency are moderate values, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. .

  When the organic electroluminescent device of the present invention has a hole transport layer, the hole transport material used is as described above. The hole transport layer may be formed by any method, but when the hole transport material is a low molecular compound, it is preferably formed from a mixed solution with a polymer binder. When the hole transport material is a polymer compound, it is preferable to form a film from a solution. For film formation from a solution, the method exemplified as the coating method can be used.

  The polymer binder to be mixed is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

  The film thickness of the hole transport layer may be selected so that the drive voltage and the light emission efficiency are appropriate values, but at least a thickness that does not cause pinholes is required. Is undesirably high. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the organic electroluminescent element of the present invention has an electron transport layer, the electron transport material used is as described above. The electron transport layer may be formed by any method, but when the electron transport material is a low-molecular compound, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is preferable. When the electron transport material is a polymer compound, a method of forming a film from a solution or a molten state is preferable. For film formation from a solution or a molten state, a polymer binder may be used in combination. For film formation from a solution, the method exemplified as the coating method can be used.

  The polymer binder to be mixed is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. As the polymer binder, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the electron transport layer may be selected so that the drive voltage and the light emission efficiency have appropriate values, but at least a thickness that does not cause pinholes is necessary. It becomes high and is not preferable. Therefore, the film thickness of the electron transport layer is usually 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). , Sometimes referred to as an electron injection layer). Further, in order to improve the adhesion with the electrode and the charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode. Therefore, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. Note that the order and number of layers to be stacked, and the thickness of each layer may be appropriately selected in consideration of light emission efficiency and element lifetime.

Examples of the organic electroluminescence element provided with the charge injection layer include those having the following structures e) to p).
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / charge transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

  The charge injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and has an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer. Examples thereof include a layer including a material having a material, a layer including a material provided between the cathode and the electron transport layer, and having a material having an intermediate electron affinity between the cathode material and the electron transport material included in the electron transport layer.

When the charge injection layer is a layer containing a conductive polymer, the electric conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm to 10 ³ S / cm, and the leakage current between the light emitting pixels is reduced. For this purpose, 10 ⁻⁵ S / cm to 10 ² S / cm is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ S / cm is particularly preferable. In order to satisfy this range, the conductive polymer may be doped with an appropriate amount of ions.
The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like. Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

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

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

The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm.
Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the organic electroluminescence device provided with an insulating layer include those having the following structures q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode
ab) Anode / insulating layer / hole transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode

  The substrate for forming the organic electroluminescence element of the present invention may be any substrate that does not change when the electrode and the organic layer are formed, and examples thereof include substrates such as glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the electrode on the opposite side to the electrode closer to the substrate is preferably transparent or translucent.

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

  As the material 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 thereof, indium tin oxide. A film (NESA or the like) manufactured using a conductive inorganic compound made of (ITO), indium, zinc, oxide or the like, gold, platinum, silver, copper, or the like is used. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode. In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. .

  Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

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

  As a material of the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Metals such as europium, terbium, ytterbium, and two or more of them, or one or more of them, and one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with a seed or more, graphite, or a graphite intercalation compound is used.

  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.

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

  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 may be provided between the cathode and the light emitting layer or between the cathode and the electron transport layer. A protective layer for protecting the organic electroluminescence element may be attached. In order to use the organic electroluminescence element stably 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, resins, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used, and a method of sealing the protective cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is used. Preferably used. 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, oxidation of the cathode can be prevented, and further, moisture adsorbed in the manufacturing process can be obtained by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element.

  The polymer compound, composition, and organic electroluminescence device of the present invention are a planar light source such as a curved light source or a planar light source (for example, illumination); a segment display device (for example, a segment type display device), dot It is useful for display devices such as a matrix display device (for example, a dot matrix flat display) and a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display). Moreover, the polymer compound of the present invention is suitable as a material used for the production thereof, and is also suitable for laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, organic semiconductor thin films, etc. It is also useful as a material for conductive thin films, a light emitting thin film material that emits fluorescence, a material for polymer field effect transistors, and the like.

  In order to obtain planar light emission using the organic electroluminescence element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. Further, in order to obtain pattern-like light emission, a method in which a mask provided with a pattern-like window is provided on the surface of the planar light-emitting element, either the anode or the cathode, or both electrodes in a pattern shape. There is a method of forming. 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. Furthermore, in order to obtain a dot matrix element, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  The present invention will be specifically described with reference to examples. Hereinafter, “F8” means 9,9-dioctylfluorene, and “F8Br2” means 2,7-dibromo-9,9-dioctylfluorene.

(Number average molecular weight and weight average molecular weight)
In the examples, the polystyrene-equivalent number average molecular weight and weight average molecular weight were determined by gel permeation chromatography (GPC, Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran (hereinafter referred to as “THF”) to a concentration of about 0.5% by weight, and 30 μL was injected into GPC. THF 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, trade name: RID-10A) was used as the detector.

(NMR measurement)
In Examples, NMR measurement of monomers was performed under the following conditions.
Apparatus: Nuclear magnetic resonance apparatus, INOVA300 (trade name), manufactured by Varian Inc. Measurement solvent: Deuterated chloroform Sample concentration: Approximately 1% by weight
Measurement temperature: 25 ° C

(High performance liquid chromatography)
In the Examples, monomer high performance liquid chromatography (hereinafter referred to as “HPLC”) was performed under the following conditions.
Apparatus: LC-20A (trade name), manufactured by Shimadzu Corporation Column: Kaseisorb LC ODS-AM 4.6 mm I.D. × 100 mm, manufactured by Tokyo Chemical Industry Mobile phase: water containing 0.1 wt% acetic acid / 0.1 wt% acetic acid Acetonitrile detector: UV detector, detection wavelength 254 nm

(Gas chromatography)
In Examples, monomer gas chromatography (hereinafter referred to as “GC”) was performed under the following conditions.
Equipment: Agilent Technology 6890N Network GC
Column: BPX5 0.25mmI.D. × 30m, manufactured by SGE Analytical Science Mobile phase: Helium Detector: Flame ionization detector (FID)

窒素雰囲気下、１，４−ジブロモベンゼン２７．１ｇ（１１４．９７mmol）に脱水ジエチルエーテル（２１７ｍｌ）を加えて調製した溶液を−６６℃まで冷却した。得られた懸濁液に２．７７Ｍのｎ−ブチルリチウムのヘキサン溶液３７．２ｍｌ（ｎ−ブチルリチウム純分：１０３．０４mmol）を−６６℃以下で２時間かけて滴下した後、同じ温度で１時間攪拌し、リチウム試薬を調製した。
窒素雰囲気下、塩化シアヌル１０．０ｇ（５４．２３mmol）に脱水ジエチルエーテル６８ｍｌを加えて調製した懸濁液を−５０℃に冷却し、前記リチウム試薬を、−３５℃以下で４５分かけてゆっくり加えた後に室温まで昇温し、室温で反応させた。得られた生成物を濾過し、減圧して乾燥させた。得られた固体１６．５ｇを精製し、１３．２ｇの針状結晶を得た。

窒素雰囲気下、マグネシウム１．３７ｇ（５６．４mmol）に脱水ＴＨＦ６５ｍｌを加えた懸濁液に、４−ヘキシルブロモベンゼン１４．２ｇ（５９．２mmol）の脱水ＴＨＦ１５ｍｌ溶液を少量ずつ加え、加熱して、還流下で攪拌した。得られた反応液に、放冷後、マグネシウム０．３９ｇ（１６．３mmol）を追加し、再び加熱して、還流下で反応させ、グリニヤール試薬を調製した。
窒素雰囲気下、前記針状結晶１２．０ｇ（２８．２mmol）の脱水ＴＨＦ１００ｍｌ懸濁液に前記グリニヤール試薬を加え、加熱して、還流下で攪拌した。得られた反応液に、放冷後、希塩酸水溶液で洗浄し、分液し、水相をジエチルエーテルで抽出した。得られた有機相を合わせて、水で洗浄後、分液し、有機相を無水硫酸マグネシウムで乾燥させ、濾過し、濃縮した。得られた白色固体をシリカゲルカラムで精製し、更に再結晶することによって、白色固体（以下、「低分子化合物Ａ」と言う。）６．５ｇを得た。
¹Ｈ−ＮＭＲ（４００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．３１〜１．３４（ｍ、６Ｈ）、１．６９（ｍ、２Ｈ）、２．７３（ｔ、２Ｈ）、７．３７（ｄ、２Ｈ）、７．６９（ｄ、４Ｈ）、８．５９〜８．６４（ｍ、６Ｈ）
LC/MS（APCI posi）：[M+H]⁺ 566 <Synthesis Example 1> (Synthesis of Low Molecular Compound A)

Under a nitrogen atmosphere, a solution prepared by adding dehydrated diethyl ether (217 ml) to 27.1 g (114.97 mmol) of 1,4-dibromobenzene was cooled to −66 ° C. To the obtained suspension, 37.2 ml of n-butyllithium hexane solution of 2.77 M (pure n-butyllithium: 103.04 mmol) was added dropwise at −66 ° C. or less over 2 hours, and then at the same temperature. The mixture was stirred for 1 hour to prepare a lithium reagent.
Under a nitrogen atmosphere, a suspension prepared by adding 68 ml of dehydrated diethyl ether to 10.0 g (54.23 mmol) of cyanuric chloride was cooled to −50 ° C., and the lithium reagent was slowly added at −35 ° C. or lower over 45 minutes. After the addition, the temperature was raised to room temperature and reacted at room temperature. The resulting product was filtered and dried under reduced pressure. 16.5 g of the obtained solid was purified to obtain 13.2 g of acicular crystals.

Under a nitrogen atmosphere, to a suspension obtained by adding 65 ml of dehydrated THF to 1.37 g (56.4 mmol) of magnesium, a solution of 14.2 g (59.2 mmol) of 4-hexylbromobenzene in 15 ml of dehydrated THF was added little by little and heated. Stir under reflux. To the obtained reaction solution, 0.39 g (16.3 mmol) of magnesium was added after being allowed to cool, heated again and reacted under reflux to prepare a Grignard reagent.
Under a nitrogen atmosphere, the Grignard reagent was added to a suspension of 12.0 g (28.2 mmol) of the needle-like crystals in 100 ml of dehydrated THF, heated, and stirred under reflux. The resulting reaction solution was allowed to cool, then washed with dilute hydrochloric acid aqueous solution, and separated, and the aqueous phase was extracted with diethyl ether. The obtained organic phases were combined, washed with water, and separated, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated. The obtained white solid was purified with a silica gel column and recrystallized to obtain 6.5 g of a white solid (hereinafter referred to as “low molecular compound A”).
¹ H-NMR (400 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.31-1.34 (m, 6H), 1.69 (m, 2H), 2.73 (t, 2H), 7.37 (d, 2H), 7 .69 (d, 4H), 8.59 to 8.64 (m, 6H)
LC / MS (APCI posi): [M + H] ⁺ 566

で表される５，５’−ジブロモ−２，２’−ビピリジル（以下、「低分子化合物Ｂ」と言う。）を１．１７ｇ得た（収率３％、ＨＰＬＣ面積百分率９９．５％、ＧＣ面積百分率９９．２％）。¹Ｈ−ＮＭＲにおいて不純物に由来するピークは観測されなかった。
¹Ｈ−ＮＭＲ (２９９．４ ＭＨｚ、ＣＤＣｌ₃) ： ７．９４ (ｄ、２H)、 ８．２９ (ｄ、２Ｈ)、 ８．７１ (ｓ, ２Ｈ)
ＬＣ−ＭＳ（ＡＰＰＩ−ＭＳ（ｐｏｓｉ）） ： ３１３ [Ｍ＋Ｈ]⁺ <Synthesis Example 2> (Synthesis of Low Molecular Compound B)
Under a nitrogen atmosphere, 37.0 g of bis (pinacolato) diboron (CAS number: 73183-34-3), 103.5 g of 2,5-dibromopyridine, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium ( 7.14 g of a compound complexed with CH ₂ Cl ₂ (manufactured by Aldrich), 4.85 g of 1,1′-bis (diphenylphosphino) ferrocene, 35.0 g of sodium hydroxide, and 568 mL of 1,4-dioxane, The mixture was stirred at 100 to 105 ° C. for 95 hours. After cooling the obtained solution to room temperature, 460 mL of toluene was added and stirred at room temperature for 20 minutes. The obtained solution was filtered through a filter packed with silica gel, and the filtrate was concentrated to dryness to obtain a solid. Then, the solid was recrystallized twice with acetonitrile, recrystallized once with ethyl acetate, and recrystallized twice with chloroform to obtain 2.2 g of a solid. Next, acetonitrile (650 mL) was added to the solid, stirred at a temperature at which refluxing occurred, filtered at the same temperature, and the obtained filtrate was concentrated to dryness. Subsequently, when the obtained solid was recrystallized with chloroform, the following formula:

1.17 g of 5,5′-dibromo-2,2′-bipyridyl (hereinafter referred to as “low molecular compound B”) represented by the following formula (yield: 3%, HPLC area percentage: 99.5%, GC area percentage 99.2%). ^{In 1} H-NMR, no peak derived from impurities was observed.
¹ H-NMR (299.4 MHz, CDCl ₃ ): 7.94 (d, 2H), 8.29 (d, 2H), 8.71 (s, 2H)
LC-MS (APPI-MS (posi)): 313 [M + H] ⁺

で表される4.23gの白色針状結晶（以下、「低分子化合物Ｃ」と言う。）を42.4％の収率で得た。
¹Ｈ−ＮＭＲ（２９９．４ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３９〜１．４２（ｂｄ、３６Ｈ）、１．６２（ｍ、４Ｈ）、２．８８（ｔ、４Ｈ）、７．５９（ｂｄ、２Ｈ）
LC/MS（ESI posi KCl添加）：[M+K]⁺ 573 <Synthesis Example 3> (Synthesis of Low Molecular Compound C)
In a 300 ml four-necked flask, 8.08 g (20.0 mmol) of 1,4-dihexyl-2,5-dibromobenzene, 12.19 g (48.0 mmol) of bis (pinacolato) diboron (CAS number: 73183-34-3), and acetic acid 11.78 g (120.0 mmol) of potassium was charged and replaced with argon. 100 ml of dehydrated 1,4-dioxane was charged and degassed with argon. Thereto was charged 0.98 g (1.2 mmol) of [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex, followed by deaeration with argon. When heated to reflux for 6 hours, a dark brown slurry was obtained. Toluene and ion-exchanged water were added thereto for liquid separation, and the obtained organic layer was washed with ion-exchanged water. To the obtained organic layer, anhydrous sodium sulfate and activated carbon were added, and the mixture was filtered through a funnel pre-coated with Celite. The filtrate was concentrated to obtain 11.94 g of dark brown crystals. The crystals were recrystallized from n-hexane and washed with methanol. When the obtained crystals were dried under reduced pressure, the following formula:

4.23 g of white needle crystals (hereinafter referred to as “low molecular compound C”) represented by the formula (42.4%) was obtained.
¹ H-NMR (299.4 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.39 to 1.42 (bd, 36H), 1.62 (m, 4H), 2.88 (t, 4H), 7.59 (bd, 2H)
LC / MS (ESI posi KCl added): [M + K] ⁺ 573

で表される５−ブロモ−２,２'−ビピリジル（以下、「低分子化合物Ｄ」と言う。）を白色板状結晶として８．６９ｇ得た（収率２２％、ＬＣ面積百分率９９．９％）。
¹Ｈ−ＮＭＲ (２９９．４ ＭＨｚ、ＣＤＣｌ₃) ：７．３２(ｄｄｄ、１Ｈ)、７．８２(ｔｄ、１Ｈ)、７．９４(ｄｄ、１Ｈ)、８．３２(ｄ、１Ｈ)、８．３８(ｄ、１Ｈ)、８．６７(ｄｔ、１Ｈ)、８．７３(ｄ、１Ｈ) <Synthesis Example 4> (Synthesis of Low Molecular Compound D)
Under a nitrogen atmosphere, 500 mL of a 0.5M THF solution of 2-pyridylzinc bromide was added to 47.5 g of 5-bromo-2-iodopyridine and 5.73 g of tetrakis (triphenylphosphine) palladium at 20 to 23 ° C. Stir. Thereto, 23 mL of water was added and stirred for 10 minutes. Next, 10 g of Celite (trade name: Celite 545, manufactured by Aldrich) and 250 mL of THF were added and stirred for 15 minutes, and then the filtrate obtained by filtration was concentrated to dryness. The obtained crude product was dissolved in 600 ml of THF, 12 g of ethylenediamine, 700 ml of water, and 1200 ml of toluene were added, stirred, allowed to stand, and then separated. The obtained aqueous layer was extracted with 200 ml of toluene, and the obtained organic layers were combined. Then, 8 g of ethylenediamine and 400 ml of water were added, washed, allowed to stand, and separated. Since a solid precipitated, it was removed by filtration, and the filtrate was further washed twice with 400 ml of water and once with 100 ml of 15 wt% brine. The obtained organic layer was dried over 50 g of anhydrous sodium sulfate and concentrated to obtain 21 g of a brown oil. The obtained oil was purified by silica gel column chromatography, concentrated and dried to obtain 10.8 g of yellowish white crystals. The obtained crystals were dissolved by heating in 22 g of hexane, cooled and crystallized, and dried under reduced pressure.

8.69 g of 5-bromo-2,2′-bipyridyl (hereinafter referred to as “low molecular compound D”) represented by the following formula was obtained as a white plate crystal (yield 22%, LC area percentage 99.9). %).
¹ H-NMR (299.4 MHz, CDCl ₃ ): 7.32 (ddd, 1H), 7.82 (td, 1H), 7.94 (dd, 1H), 8.32 (d, 1H), 8.38 (d, 1H), 8.67 (dt, 1H), 8.73 (d, 1H)

で表される２−（３'−ブロモフェニル）ピリジンを得た。
次に、窒素雰囲気下、トリブロモベンゼンと、２．２当量の４−ｔｅｒｔ−ブチルフェニルホウ酸との鈴木カップリング（触媒：テトラキス（トリフェニルホスフィン）パラジウム（０）、塩基：２Ｍ炭酸ナトリウム水溶液、溶媒：エタノール、トルエン）により、下記式：

で表されるブロモ化合物を得た。
窒素雰囲気下、このブロモ化合物を無水ＴＨＦに溶解後、−７８℃に冷却し、小過剰のｔｅｒｔ−ブチルリチウムを滴下した。冷却下、更に、Ｂ（ＯＣ₄Ｈ₉）₃を滴下し、室温で反応させた。得られた反応液を３Ｍ塩酸水で後処理したところ、下記式：

で表されるホウ酸化合物を得た。
１．２当量のこの前記ホウ酸化合物と、２−（３'−ブロモフェニル）ピリジンとの鈴木カップリング（触媒：テトラキス（トリフェニルホスフィン）パラジウム（０）、塩基：２Ｍ炭酸ナトリウム水溶液、溶媒：エタノール、トルエン）により、下記式：

で表される配位子（即ち、配位子となる化合物）を得た。
アルゴン雰囲気下、前記配位子、４当量のＩｒＣｌ₃・３Ｈ₂Ｏ、２−ＥｔＯＥｔＯＨ、及びイオン交換水を仕込み、還流させた。析出した固体を吸引濾過した。得られた固体をエタノール、イオン交換水で洗浄後、乾燥させたところ、下記式：

で表される黄色粉体を得た。
アルゴン雰囲気下、前記黄色粉体に２当量の前記配位子を加え、グリコール系溶媒中で加熱したところ、下記式：

で表されるイリジウム錯体（以下、「発光材料Ａ」と言う。）を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ１．３７（ｓ、５４Ｈ）、６．９０（ｔ、３Ｈ）、７．３５（ｄ、３Ｈ）、７．４８（ｄ、１２Ｈ）、７．５７（ｄ、６Ｈ）、７．６４（ｄ、１２Ｈ）、７．５５〜７．７０（ｍ、６Ｈ）、７．７８（ｓ、６Ｈ）、８．００（ｄ、３Ｈ）、８．０５（ｓ、３Ｈ）
LC/MS（APCI posi）：[M+H]⁺ 1677 <Synthesis Example 5> (Synthesis of Luminescent Material A)
Synthesized according to the synthesis method described in WO02 / 066552. That is, Suzuki coupling of 2-bromopyridine and 1.2 equivalent of 3-bromophenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution, solvent : Ethanol, toluene), the following formula:

2- (3′-bromophenyl) pyridine represented by the formula:
Next, Suzuki coupling of tribromobenzene and 2.2 equivalents of 4-tert-butylphenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution , Solvent: ethanol, toluene), the following formula:

The bromo compound represented by this was obtained.
Under a nitrogen atmosphere, this bromo compound was dissolved in anhydrous THF, cooled to −78 ° C., and a small excess of tert-butyllithium was added dropwise. Under cooling, B (OC ₄ H ₉ ) ₃ was further added dropwise and reacted at room temperature. The resulting reaction solution was post-treated with 3M aqueous hydrochloric acid to give the following formula:

The boric acid compound represented by this was obtained.
Suzuki coupling of 1.2 equivalents of this boric acid compound with 2- (3′-bromophenyl) pyridine (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution, solvent: Ethanol, toluene), the following formula:

Was obtained (that is, a compound to be a ligand).
Under an argon atmosphere, the ligand, 4 equivalents of IrCl ₃ .3H ₂ O, 2-EtOEtOH, and ion-exchanged water were charged and refluxed. The precipitated solid was suction filtered. When the obtained solid was washed with ethanol and ion-exchanged water and dried, the following formula:

A yellow powder represented by
Under an argon atmosphere, 2 equivalents of the ligand was added to the yellow powder and heated in a glycol solvent.

Was obtained (hereinafter referred to as “light-emitting material A”).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 1.37 (s, 54H), 6.90 (t, 3H), 7.35 (d, 3H), 7.48 (d, 12H), 7.57 (d, 6H), 7.64 (d 12H), 7.55 to 7.70 (m, 6H), 7.78 (s, 6H), 8.00 (d, 3H), 8.05 (s, 3H)
LC / MS (APCI posi): [M + H] ⁺ 1677

で表される化合物Ｅ−１を１３３．４８ｇ得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ ３．６８（ｓ，３Ｈ）、７．１５（ｄ，２Ｈ）、７．２０（ｄ，１Ｈ）、７．５２（ｄ，２Ｈ）、７．６５（ｄ，１Ｈ）、８．００（ｂｒｓ，１Ｈ）
¹³Ｃ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ ５２．６、１２１．８、１２２．２、１３０．１、１３１．６、１３２．３、１３２．４、１３３．２、１３４．７、１３９．４、１４０．６、１６７．８
・化合物Ｅ−２の合成
（Ｅ−２）
２Ｌの３口丸底フラスコに、1-ブロモ-4-n-ヘキシルベンゼン75g及び無水ＴＨＦ 847mlを仕込み、−78℃に冷却した。そこに、ゆっくりとｎ-BuLi（1.6Mヘキサン溶液）を198ml仕込み、−78℃で2時間攪拌して、反応液を得た。化合物Ｅ−１ 49.53gを無水THF 141mlに溶かした溶液を滴下ロートに仕込み、反応液の温度が−７０℃以下を超えないような滴下速度で滴下した。滴下終了後、2時間同温で攪拌し、ゆっくり室温まで昇温した。その後、そこに、塩化アンモニウム飽和水溶液を500ml加えて攪拌し、分液ロートに移して水層を除去した。得られた有機層を水500mlで2回洗浄し、得られた有機層に無水硫酸ナトリウムを加えて乾燥させた。グラスフィルターにシリカゲルの層を7cmの厚さで敷き、THF溶液を通じてろ過した後、THF１Lで洗浄した。得られた溶液を濃縮し乾燥させた。ヘキサン300mlでリパルプ洗浄し、下記式：

で表される化合物Ｅ−２を60g得た。
・化合物Ｅの合成
１Ｌの３口フラスコに化合物Ｅ−２ 60.0g及びジクロロメタン202mlを仕込み、氷浴を用いて０℃に冷却した。三フッ化ホウ素ジエチルエーテル錯体 234mlを滴下ロートに仕込み、そこに、滴下した。得られた反応溶液を２時間０℃で攪拌した後、水500mlと氷500gを仕込んだビーカーに注加して反応を停止させた。得られた反応溶液を分液ロートへ移して分液し、ジクロロメタン200mlで抽出した後、有機層を合わせて水500mlで２回洗浄し、無水硫酸ナトリウムで乾燥させた。グラスフィルターにシリカゲルの層を７cmの厚さで敷き、THF溶液を通じて硫酸ナトリウムをろ過し、濃縮した。得られた油状物にトルエン100mlを加え、加熱して還流させた。次いで、70℃まで冷却した後、イソプロピルアルコールを700ml加えて攪拌し、室温まで放置したところ、結晶が生じた。この結晶をろ過し、乾燥させた後、ナスフラスコに仕込み、ヘキサン800ml、活性炭50gを加えて加熱し、還流を2時間行って混合物を得た。グラスフィルターにラジオライト（2cm）を敷き、その上にセライト（3cm）を敷き、オーブンで70℃に加熱しておき、これを用いて前記混合物を濾過した。得られた溶液を半量濃縮し、濃縮物を加熱し還流させた後、室温で１時間攪拌した。さらに氷浴を用いて冷やしながら2時間攪拌し、生じた結晶を濾過して集めたところ、下記式：

で表される化合物Ｅを53.9g得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．８７（ｔ，６Ｈ）、１．２８〜１．３７（ｍ，１２Ｈ）、１．５０〜１．６２（ｍ，４Ｈ）、２．５４（ｔ，４Ｈ）、７．０４（ｓ，８Ｈ）、７．４５（ｄ，２Ｈ）、７．４９（ｓ，２Ｈ）、７．５５（ｄ，２Ｈ）
¹³Ｃ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ１４．４、２２．９、２９．４、３１．６、３２．０、３５．８、６５．４、１２１．８、１２２．１、１２８．１、１２８．７、１２９．７、１３１．１、１３８．３、１４１．９、１４２．１、１５３．７ <Synthesis Example 6> (Synthesis of Low Molecular Compound E)
Synthesis of Compound E-1 A 3 L 4-neck flask was purged with nitrogen, and 165 g of 2,7-dibromofluorenone was added and suspended in 2.4 L of diphenyl ether. The obtained suspension was heated to 120 ° C. to dissolve 2,7-dibromofluorenone, 155 g of potassium hydroxide was added thereto, the temperature was raised to 160 ° C., and the mixture was stirred for 2.5 hours. After allowing to cool to room temperature, 1.5 L of hexane was added, filtered, and washed with hexane to obtain a crude product. A 3 L four-necked flask was purged with nitrogen, and the resulting crude product was added and dissolved in 1.5 L of dehydrated DMF. The resulting solution was heated to 90 ° C., and 530 g of methyl iodide was gradually added. Then, it was made to react for 10 hours. The resulting reaction solution was allowed to cool to room temperature, then dropped into 3 L of water cooled to 0 ° C., and extracted twice with 3 L of hexane. The obtained extract was filtered through a glass filter laid with silica gel, and the obtained organic layer was concentrated. This was purified by silica gel column chromatography, and the following formula:

133.48g of compound E-1 represented by these was obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 3.68 (s, 3H), 7.15 (d, 2H), 7.20 (d, 1H), 7.52 (d, 2H), 7.65 (d, 1H), 8.00 ( brs, 1H)
¹³ C-NMR (300 MHz / CDCl ₃ ):
δ 52.6, 121.8, 122.2, 130.1, 131.6, 132.3, 132.4, 133.2, 134.7, 139.4, 140.6, 167.8
Synthesis of compound E-2 (E-2)
A 2 L 3-neck round bottom flask was charged with 75 g of 1-bromo-4-n-hexylbenzene and 847 ml of anhydrous THF, and cooled to -78 ° C. Thereto, 198 ml of n-BuLi (1.6M hexane solution) was slowly added and stirred at −78 ° C. for 2 hours to obtain a reaction solution. A solution prepared by dissolving 49.53 g of compound E-1 in 141 ml of anhydrous THF was charged into a dropping funnel and added dropwise at a dropping rate such that the temperature of the reaction solution did not exceed −70 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours and slowly warmed to room temperature. Thereafter, 500 ml of a saturated aqueous solution of ammonium chloride was added thereto and stirred, and transferred to a separatory funnel to remove the aqueous layer. The obtained organic layer was washed twice with 500 ml of water, and anhydrous sodium sulfate was added to the obtained organic layer for drying. A layer of silica gel was spread on a glass filter to a thickness of 7 cm, filtered through a THF solution, and then washed with 1 L of THF. The resulting solution was concentrated and dried. Repulp washed with 300 ml of hexane, the following formula:

60 g of the compound E-2 represented by the formula:
-Synthesis | combination of compound E The compound E-2 60.0g and the dichloromethane 202ml were prepared to the 1 L 3 necked flask, and it cooled to 0 degreeC using the ice bath. 234 ml of boron trifluoride diethyl ether complex was charged into a dropping funnel and dropped therein. The resulting reaction solution was stirred at 0 ° C. for 2 hours, and then poured into a beaker charged with 500 ml of water and 500 g of ice to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and separated, and extracted with 200 ml of dichloromethane. The organic layers were combined, washed twice with 500 ml of water, and dried over anhydrous sodium sulfate. A silica gel layer was spread on a glass filter to a thickness of 7 cm, and sodium sulfate was filtered through a THF solution and concentrated. To the obtained oily substance, 100 ml of toluene was added and heated to reflux. Next, after cooling to 70 ° C., 700 ml of isopropyl alcohol was added and stirred, and allowed to stand at room temperature, crystals were formed. The crystals were filtered and dried, charged into an eggplant flask, heated with 800 ml of hexane and 50 g of activated carbon, and refluxed for 2 hours to obtain a mixture. Radiolite (2 cm) was laid on a glass filter, celite (3 cm) was laid on the glass filter, and the mixture was heated to 70 ° C. in an oven, and the mixture was filtered using this. The obtained solution was concentrated in half, and the concentrate was heated to reflux and then stirred at room temperature for 1 hour. The mixture was further stirred for 2 hours while cooling in an ice bath, and the resulting crystals were collected by filtration.

53.9 g of the compound E represented by the formula:
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.87 (t, 6H), 1.28 to 1.37 (m, 12H), 1.50 to 1.62 (m, 4H), 2.54 (t, 4H), 7.04 (s, 8H), 7.45 (d, 2H), 7.49 (s, 2H), 7.55 (d, 2H)
¹³ C-NMR (300 MHz / CDCl ₃ ):
δ14.4, 22.9, 29.4, 31.6, 32.0, 35.8, 65.4, 121.8, 122.1, 128.1, 128.7, 129.7, 131. 1, 138.3, 141.9, 142.1, 153.7

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位とを、５０：３０：１０：１０のモル比で有するランダム共重合体である。 <Example 1> (Synthesis of polymer compound A)
Under a nitrogen atmosphere, low molecular compound C 0.997 g (2.0 mmol), F8Br2 0.658 g (1.20 mmol), low molecular compound A 0.221 g (0.40 mmol), low molecular compound B 0.126 g (0. 40 mmol), 0.7 mg of palladium acetate, 4.2 mg of tris (2-methoxyphenyl) phosphine, and 30 ml of toluene were mixed and heated to 105 ° C. To the obtained solution, 6.6 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 26 hours. Thereafter, 0.24 g of phenylboric acid was added, and the mixture was further refluxed for 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed twice with 27 ml of water, twice with 27 ml of 3% by weight acetic acid aqueous solution and twice with 27 ml of water, and the obtained solution was dropped into 310 mL of methanol and collected by filtration to obtain a precipitate. This precipitate was dissolved in 63 mL of toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained toluene solution was dropped into 310 ml of methanol and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of this precipitate (hereinafter referred to as “polymer compound A”) was 0.85 g.
The number average molecular weight in terms of polystyrene of the polymer compound A was 8.9 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 2.1 × 10 ⁵ .
The polymer compound A has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer having a molar ratio of 50: 30: 10: 10.

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位とを、５０：４０：１０のモル比で有し、下記式：

で表される基を分子鎖末端に持つランダム共重合体である。 <Example 2> (Synthesis of polymer compound B)
Under a nitrogen atmosphere, low molecular compound C 2.118 g (4.25 mmol), F8Br2 1.865 g (3.40 mmol), low molecular compound A 0.469 g (0.85 mmol), low molecular compound D 0.008 g (0. 03 mmol), 1.4 mg of palladium acetate, 9.0 mg of tris (2-methoxyphenyl) phosphine, and 43 ml of toluene were mixed and heated to 105 ° C. To the resulting solution, 14.2 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 4 hours. After the reaction, 0.52 g of phenylboric acid was added, and the mixture was further refluxed for 16 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, it was washed twice with 57 ml of water, twice with 57 ml of 3% by weight acetic acid aqueous solution and twice with 57 ml of water, and the resulting solution was dropped into 663 mL of methanol and filtered to obtain a precipitate. This precipitate was dissolved in 134 mL of toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained toluene solution was added dropwise to 663 ml of methanol and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of this precipitate (hereinafter referred to as “polymer compound B”) was 1.97 g.
The number average molecular weight in terms of polystyrene of the polymer compound B was 1.1 × 10 ⁵ , and the weight average molecular weight in terms of polystyrene was 2.4 × 10 ⁵ .
The polymer compound B has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Having a molar ratio of 50:40:10, and having the following formula:

A random copolymer having a group represented by

で表される繰り返し単位を５０：５０（仕込み量からの理論値（モル比））で有する高分子化合物（交互共重合体）（以下、「高分子化合物Ｃ」と言う。）の収量は５．２５ｇであった。高分子化合物Ｃのポリスチレン換算の数平均分子量は１．２×１０⁵であり、ポリスチレン換算の重量平均分子量は２．６×１０⁵であった。 <Synthesis Example 7> (Synthesis of Polymer Compound C)
Under a nitrogen atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene 5.20 g, bis (4-bromophenyl)-(4-s-butylphenyl)- 4.50 g of amine, 2.2 mg of palladium acetate, 15.1 mg of tri (2-methylphenyl) phosphine, 0.91 g of trioctylmethylammonium chloride (trade name: Aliquat (registered trademark) 336, manufactured by Aldrich), and 70 ml of toluene Mix and heat to 105 ° C. To the resulting solution, 19 ml of 2M aqueous sodium carbonate solution was added dropwise and refluxed for 4 hours. Thereafter, 121 mg of phenylboric acid was added thereto, and the mixture was further refluxed for 3 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the mixture was washed 3 times with 60 ml of water, 3 times with 60 ml of 3% by weight acetic acid aqueous solution and 3 times with 60 ml of water, and purified by passing through an alumina column and a silica gel column in this order. The obtained toluene solution was dropped into 3 L of methanol and stirred for 3 hours, and then the obtained solid was taken out and dried. The following formula thus obtained:

The yield of the polymer compound (alternate copolymer) (hereinafter referred to as “polymer compound C”) having 50:50 (theoretical value (molar ratio) from the charged amount) represented by .25 g. The polymer compound C had a polystyrene-equivalent number average molecular weight of 1.2 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 2.6 × 10 ⁵ .

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位とを、５０：３７：１０：３のモル比で有するランダム共重合体である。 <Example 4> (Synthesis of polymer compound E)
Low molecular compound C (1.495 g, 3.0 mmol), low molecular compound E (1.431 g, 2.22 mmol), low molecular compound A (0.331 g, 0.60 mmol), low molecular compound B under nitrogen atmosphere (0.0566 g, 0.18 mmol), palladium acetate 1.0 mg, tris (2-methoxyphenyl) phosphine 6.3 mg, and toluene 33 ml were mixed and heated to 105 ° C. To the resulting solution, 10 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 19 hours. Thereafter, 0.37 g of phenylboric acid was added, and the mixture was further refluxed for 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed twice with 40 ml of water, twice with 40 ml of 3% by weight acetic acid aqueous solution and twice with 40 ml of water. The obtained solution was dropped into 500 mL of methanol and collected by filtration to obtain a precipitate. The precipitate was dissolved in 94 mL of toluene and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to 600 ml of methanol and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of this precipitate (hereinafter referred to as “polymer compound E”) was 1.53 g.
The polymer compound E had a polystyrene equivalent number average molecular weight of 1.3 × 10 ⁵ and a polystyrene equivalent weight average molecular weight of 3.3 × 10 ⁵ .
The polymer compound E has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer having a molar ratio of 50: 37: 10: 3.

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位とを、５０：３０：１０：１０のモル比で有するランダム共重合体である。 <Example 5> (Synthesis of polymer compound F)
Low molecular compound C (1.495 g, 3.0 mmol), low molecular compound E (1.160 g, 1.80 mmol), low molecular compound A (0.331 g, 0.60 mmol), low molecular compound B under nitrogen atmosphere (0.188 g, 0.60 mmol), palladium acetate 1.0 mg, tris (2-methoxyphenyl) phosphine 6.3 mg, and toluene 33 ml were mixed and heated to 105 ° C. To the resulting solution, 10 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 19 hours. Thereafter, 0.37 g of phenylboric acid was added, and the mixture was further refluxed for 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed twice with 40 ml of water, twice with 40 ml of 3% by weight acetic acid aqueous solution and twice with 40 ml of water. The obtained solution was dropped into 500 mL of methanol and collected by filtration to obtain a precipitate. The precipitate was dissolved in 94 mL of toluene and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was dropped into 800 ml of methanol and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of this precipitate (hereinafter referred to as “polymer compound F”) was 1.39 g.
The polystyrene reduced number average molecular weight of the polymer compound F is 1.3 × 10 ^5, a polystyrene-reduced weight average molecular weight was 3.8 × 10 ^5.
The polymer compound F has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer having a molar ratio of 50: 30: 10: 10.

で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

で表される繰り返し単位とを、５０：４０：１０のモル比で有するランダム共重合体である。 <Comparative Example 1> (Synthesis of Polymer Compound D)
Under a nitrogen atmosphere, low molecular compound C 0.987 g (2.0 mmol), F8Br2 0.878 g (1.6 mmol), low molecular compound A 0.221 g (0.40 mmol), palladium acetate 0.7 mg, tris (2- Methoxyphenyl) phosphine (4.2 mg) and toluene (30 ml) were mixed and heated to 105 ° C. To the obtained solution, 6.6 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 23 hours. Thereafter, 0.24 g of phenylboric acid was added, and the mixture was further refluxed for 8 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed twice with 27 ml of water, twice with 27 ml of a 3% by weight acetic acid aqueous solution and twice with 27 ml of water, and the obtained solution was dropped into 310 mL of methanol and collected by filtration to obtain a precipitate. The precipitate was dissolved in 63 mL of toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained toluene solution was dropped into 310 ml of methanol and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of this precipitate (hereinafter referred to as “polymer compound D”) was 1.1 g.
The polymer compound D had a polystyrene-equivalent number average molecular weight of 1.2 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 3.2 × 10 ⁵ .
The polymer compound D has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer having a molar ratio of 50:40:10.

<Example 6>
Poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by HC Starck, trade name: BaytronP) (hereinafter referred to as “BaytronP”) on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering. The suspension was put on, formed into a film having a thickness of about 65 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound C was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd., for electronics industry (EL grade)) at a concentration of 0.5% by weight, and the resulting xylene solution was placed on the BaytronP film, After film formation by the coating method, the film was dried at 180 ° C. for 15 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound A and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5% by weight (polymer compound A / light emitting material A = 70/30 in weight ratio). Was dissolved at a concentration of The obtained xylene solution was placed on the polymer compound C film, and a light emitting layer A was formed to a thickness of about 90 nm by spin coating. And it dried at 90 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was deposited on the luminescent layer A film at about 5 nm as a cathode, and then aluminum was deposited on the barium layer at about 100 nm. After vapor deposition, the organic electroluminescent element was produced by sealing using a glass substrate. The element configuration is as follows.
ITO / BaytronP (about 65 nm) / polymer compound C (about 10 nm) / light emitting layer A (90 nm) / barium / aluminum When a voltage of 4.8 V is applied to the obtained organic electroluminescence device, the maximum luminous efficiency is It was 35.0 cd / A.

<Example 7>
A BaytronP suspension is placed on a glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering, and is formed to a thickness of about 65 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. I let you. Next, the polymer compound C was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.5% by weight, and the resulting xylene solution was placed on the BaytronP film, After film formation by the coating method, the film was dried at 180 ° C. for 15 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound E and the luminescent material A were added to xylene (manufactured by Kanto Chemical Co., Ltd., for the electronics industry (EL grade)) at 1.5% by weight (polymer compound E / luminescent material A = 70/30 by weight). Was dissolved at a concentration of The obtained xylene solution was placed on the polymer compound C film, and a light emitting layer E was formed to a thickness of about 90 nm by spin coating. And it dried at 90 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was deposited on the light emitting layer E film at about 5 nm as a cathode, and then aluminum was deposited on the barium layer at about 100 nm. After vapor deposition, the organic electroluminescent element was produced by sealing using a glass substrate. The element configuration is as follows.
ITO / BaytronP (about 65 nm) / polymer compound C (about 10 nm) / light emitting layer E (90 nm) / barium / aluminum When a voltage of 8.4 V is applied to the obtained organic electroluminescence device, the maximum luminous efficiency is It showed 35.2 cd / A.

<Example 8>
A BaytronP suspension is placed on a glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering, and is formed to a thickness of about 65 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. I let you. Next, the polymer compound C was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.5% by weight, and the resulting xylene solution was placed on the BaytronP film, After film formation by the coating method, the film was dried at 180 ° C. for 15 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound F and the light-emitting material A were 1.4% by weight (polymer compound F / light-emitting material A = 70/30 in weight ratio) in xylene (manufactured by Kanto Chemical Co., Inc., for electronics industry (EL grade)). Was dissolved at a concentration of The obtained xylene solution was placed on the polymer compound C film, and a light emitting layer F was formed to a thickness of about 90 nm by spin coating. And it dried at 90 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer F film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 100 nm. After vapor deposition, the organic electroluminescent element was produced by sealing using a glass substrate. The element configuration is as follows.
ITO / BaytronP (about 65 nm) / polymer compound C (about 10 nm) / light emitting layer F (90 nm) / barium / aluminum When a voltage of 7.8 V is applied to the obtained organic electroluminescence device, the maximum luminous efficiency is It showed 32.6 cd / A.

<Comparative example 2>
A BaytronP suspension is placed on a glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering, and is formed to a thickness of about 65 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. I let you. Next, the polymer compound C was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.5% by weight, and the resulting xylene solution was placed on the BaytronP film, After film formation by the coating method, the film was dried at 180 ° C. for 15 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound D and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.3 wt% (weight ratio of polymer compound D / light emitting material A = 70/30). Was dissolved at a concentration of The obtained xylene solution was placed on the polymer compound C film, and a light emitting layer D was formed by spin coating so as to have a thickness of about 90 nm. And it dried at 90 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer D film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 100 nm. After vapor deposition, the organic electroluminescent element was produced by sealing using a glass substrate. The element configuration is as follows.
ITO / BaytronP (about 65 nm) / polymer compound C (about 10 nm) / light emitting layer D (90 nm) / barium / aluminum When a voltage of 5.2 V is applied to the obtained organic electroluminescence device, the maximum luminous efficiency is It showed 27.1 cd / A.

Claims (21)

Following formula (1):

(In the formula, Ar represents an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. The three Ars may be the same. May be different.)
A residue of the compound represented by formula (2):

(In the formula, ^one of Z ¹ , Z ² and Z ³ represents —N═ and two represents —C (R ′) ═. Z ⁴ and Z ⁵ represent —C (R ′) = Z ⁶ , Z ⁷ and Z ⁸ each represent —N═, two represent —C (R ′) ═, and Z ⁹ and Z ¹⁰ represent —C (R ′) ═. R ′ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, and a substituent An optionally substituted acyloxy group, a monovalent heterocyclic group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue, and a substituent. Represents an amide group, an acid imide group, a carboxyl group, a nitro group, or a cyano group, and 8 —C (R ′) ═ may be the same or different, and Z ² and Z ³ are — When C (R ′) =, two R ′ contained in Z ² and Z ³ may be bonded to each other to form a benzene ring, and Z ³ is —C (R ′) =. In some cases, two R ′ contained in Z ³ and Z ⁴ may be bonded to each other to form a benzene ring, or two R ′ contained in Z ⁴ and Z ⁵ may be bonded to each other to form a benzene ring. may be formed but, Z ² and Z ^3, Z ³ and Z ^4, as well as two or more combinations of Z ⁴ and Z ⁵ are not simultaneously form a benzene ring. ⁷ and Z ⁸ is -C (R ') = a if two R contained in Z ⁷ and Z ^8' may form a benzene ring by bonding to each other, Z ⁸ is -C ( When R ′) =, two R ′ contained in Z ⁸ and Z ⁹ may be bonded to each other to form a benzene ring, and two R ′ contained in Z ⁹ and Z ¹⁰ may be Although they may be bonded to each other to form a benzene ring, two or more combinations of Z ⁷ and Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ do not form a benzene ring at the same time. The benzene ring formed by combining R ′ with each other may have a substituent.)
The high molecular compound which has the residue of the compound represented by these.   R ′ in the formula (2) is a hydrogen atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, an aryl group optionally substituted with a fluorine atom, fluorine An aryloxy group optionally substituted with an atom, an arylalkyl group optionally substituted with a fluorine atom, an arylalkoxy group optionally substituted with a fluorine atom, an arylalkenyl group optionally substituted with a fluorine atom An arylalkynyl group optionally substituted with a fluorine atom, an amino group optionally substituted with a fluorine atom, a substituted amino group optionally substituted with a fluorine atom, a halogen atom, or a fluorine atom A good acyl group, an acyloxy group optionally substituted with a fluorine atom, a monovalent heterocyclic ring optionally substituted with a fluorine atom , Carboxyl group, a nitro group, or a cyano group, a polymer compound according to claim 1.   The polymer compound according to claim 1, wherein R ′ is a hydrogen atom or an alkyl group.   The polymer compound according to any one of claims 1 to 3, wherein a residue of the compound represented by the formula (1) is contained as a repeating unit. The repeating unit consisting of the residue of the compound represented by the formula (1) is represented by the following formula (3):

(In the formula, Ar has the same meaning as described above. Ar ′ represents an arylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent. Ar ′ may be the same or different.)
The polymer compound according to claim 4, which is a repeating unit represented by:   The polymer compound according to claim 5, wherein Ar is a phenyl group which may have a substituent, and Ar ′ is a 1,4-phenylene group which may have a substituent.   The high molecular compound as described in any one of Claims 1-6 in which the residue of the compound represented by said Formula (2) is contained as a repeating unit. The repeating unit consisting of the residue of the compound represented by the formula (2) is represented by the following formula (4):

(In the formula, ^one of Z ^{1 *} , Z ^{2 *} and Z ^{3 *} represents -N = and two represents -C (R '') =. Z ^{4 *} and Z ^{5 *} are- ^{C (R '') .Z 6} * represents a =, Z ^{7 *} and Z ^{8 *} are one represents -N =, 2 pieces is -C (R '') = represented .Z ^{9 *} and Z ^{10 *} represents —C (R ″) ═. R ″ represents a hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, aryl. An alkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group, or a cyano group, Z ^{1 *} , Z ^{2 *} , Z ^{3 *} , Z ^{4 *} and Z ^{5 *} represent one bond, and R 6 contained in Z ^{6 *} , Z ^{7 *} , Z ^{8 *} , Z ^{9 *} and Z ^{10 *.} One of '' represents a bond. Some or all of the hydrogen atoms contained in the group represented by ″ may be substituted with fluorine atoms. Eight —C (R ″) ═ may be the same or different. form a benzene ring ^* good .Z 2 ^* and Z ³ even if -C (R '') = a when it Z ^{2 *} and Z ^{3 *} to two R included '' are combined with each other If Z ^{3 *} is —C (R ″) =, two R ″ contained in Z ^{3 *} and Z ^{4 *} may be bonded to each other to form a benzene ring. Well, two R ″ contained in Z ^{4 *} and Z ^{5 *} may be bonded to each other to form a benzene ring, but Z ^{2 *} and Z ^{3 *} , Z ^{3 *} and Z ^{4 *} , and Two or more combinations of Z ^{4 *} and Z ^{5 *} do not form a benzene ring at the same time.When Z ^{7 *} and Z ^{8 *} are —C (R ″) ═, Z ^{7 *} and Z ^{8 *} Two R ″ contained in may combine with each other to form a benzene ring. When Z ^{8 *} is —C (R ″) ═, two R ″ contained in Z ^{8 *} and Z ^{9 *} may be bonded to each other to form a benzene ring. Two R ″ contained in ^{9 *} and Z ^{10 *} may be bonded to each other to form a benzene ring, but Z ^{7 *} and Z ^{8 *} , Z ^{8 *} and Z ^{9 *} , and Z ^{9 *} And two or more combinations of Z ^{10 *} do not simultaneously form a benzene ring. The benzene ring formed by bonding two R ″ to each other may have a substituent.)
Or a repeating unit represented by the following formula (5):

(In the formula, ^one of Z ^{1 **} , Z ^{2 **} and Z ^{3 **} represents -N = and two represents -C (R ''') =. Z ^{4 **} and Z ^{3 ** 5 **} represents -C (R ''') =. R''' represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group. , arylalkynyl group, amino group, substituted amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, carboxyl group, substituted carboxyl group, represents a nitro group, or cyano group, Z 1 ^{**, Z 2 **, Z 3 **,} Z 4 2 amino ^** and Z ⁵ R contained in the ^** '''represents a bond ^{.Z 6, Z 7, Z 8} , Z 9 and Z ¹⁰ is , Having the same meaning as described above, part or all of the hydrogen atoms contained in the group represented by R ′ and R ′ ″ may be substituted with a fluorine atom. ') = Is, -C present .4 pieces which may be different from be the same (R''') = is optionally be the same or different .Z 2 ^** and Z ^{3 * When *} is —C (R ′ ″) =, two R ′ ″ contained in Z ^{2 **} and Z ^{3 **} may be bonded to each other to form a benzene ring. ^{When 3 **} is —C (R ′ ″) =, two R ′ ″ contained in Z ^{3 **} and Z ^{4 **} may be bonded to each other to form a benzene ring. , Z ^{4 **} and Z ^{5 **} may be bonded to each other to form a benzene ring, but Z ^{2 **} and Z ^{3 **} , Z ^{3 **} and Z 4 ^**, and Z ^{4 **} and Z ^{5 **} in two or more combinations .Z ⁷ and Z ⁸ which do not form a benzene ring is -C simultaneously (R ') in the case of = Z ⁷ and 'may form a benzene ring bonded to each other, Z ⁸ is -C (R' 2 pieces of R contained in Z ⁸⁾ = a is situ Two instances of R 'may be bonded to form a benzene ring together, two R contained in Z ⁹ and Z ^10' benzene ring by bonding to each other contained in Z ⁸ and Z ⁹ to May be formed, but two or more combinations of Z ⁷ and Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ do not form a benzene ring at the same time. The benzene ring to be formed may have a substituent, and the benzene ring formed by bonding two R ′ ″ to each other may have a substituent.
The polymer compound according to claim 7, which is a repeating unit represented by:   The repeating unit composed of a residue of the compound represented by the formula (2) is a repeating unit composed of a 2,2′-bipyridine-5,5′-diyl group which may have a substituent. 9. The polymer compound according to 8. The residue of the compound represented by the formula (2) is represented by the following formula (6):

(In the formula, Z ^{1 *} , Z ^{2 *} , Z ^{3 *} , Z ^{4 *} , Z ^{5 *} , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰ have the same meaning as described above. R ′, Some or all of the hydrogen atoms contained in the group represented by R ″ may be substituted with fluorine atoms. The four —C (R ′) ═ may be the same or different. The four —C (R ″) ═ may be the same or different. When Z ^{2 *} and Z ^{3 *} are —C (R ″) ═, ^Two R ″ contained in Z ^{2 *} and Z ^{3 *} may be bonded to each other to form a benzene ring. When Z ^{3 *} is —C (R ″) ═, Z ^{3 *} And two R ″ contained in Z ^{4 *} may be bonded to each other to form a benzene ring, and two R ″ contained in Z ^{4 *} and Z ^{5 *} may be bonded to each other to form a benzene ring. Z ^{2 *} and Z ^{3 *} , Z ^{3 *} and Z ^{4 *} , and Z ^{4 *} and Z ^{5 *} Two or more combinations do not form a benzene ring at the same time.When Z ⁷ and Z ⁸ are —C (R ′) ═, two R ′ contained in Z ⁷ and Z ⁸ are bonded to each other. A benzene ring may be formed, and when Z ⁸ is —C (R ′) ═, two R ′ contained in Z ⁸ and Z ⁹ may be bonded to each other to form a benzene ring. , Z ⁹ and Z ¹⁰ may be bonded to each other to form a benzene ring, but two of Z ⁷ and Z ⁸ , Z ⁸ and Z ⁹ , and Z ⁹ and Z ¹⁰ The above combination does not form a benzene ring at the same time.The benzene ring formed by bonding two R's to each other may have a substituent and formed by bonding two R '' to each other. (The benzene ring to be bonded may have a substituent.)
The polymer compound according to any one of claims 1 to 6, which is a group represented by   The residue of the compound represented by the formula (2) is a 2,2′-bipyridin-5-yl group which may have a substituent, and is present at the end of the molecular chain. The polymer compound described.   The polymer compound according to claim 8 or 10, wherein R '' which is not a bond is a hydrogen atom or an alkyl group.   9. The polymer compound according to claim 8, wherein R ′ ″ that is not a bond is a hydrogen atom or an alkyl group. A repeating unit represented by the formula (3);
At least one selected from the group consisting of the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5), and / or a group represented by the formula (6),
The polymer compound according to any one of claims 10 to 13, which comprises Furthermore, at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (A), a repeating unit represented by the following formula (B), and a repeating unit represented by the following formula (C): The polymer compound according to any one of claims 1 to 14.

(In the formula, Ar ³ and Ar ⁷ each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. Represents a divalent group having a metal complex structure, and Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an arylene group which may have a substituent, or a divalent which may have a substituent. Or a divalent group in which two aromatic rings optionally having a substituent are connected by a single bond, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl A monovalent heterocyclic group or an arylalkyl group, X ¹ represents —CR ³ ═CR ⁴ — or —C≡C—, R ³ and R ⁴ 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, where a is 0. It is one.)   The repeating unit represented by the formula (A) is a fluorenediyl group which may have a substituent, a phenylene group which may have a substituent, or a combination thereof. High molecular compound.   A composition comprising the polymer compound according to any one of claims 1 to 16, and at least one selected from the group consisting of a light emitting material, a hole transport material, and an electron transport material.   The composition according to claim 17, further comprising an organic solvent.   The organic electroluminescent element formed using the high molecular compound as described in any one of Claims 1-16.   A planar light source comprising the organic electroluminescence device according to claim 19.   A display device comprising the organic electroluminescence element according to claim 19.