JP4904752B2 - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound useful as a light-emitting material, a charge transporting material or the like and excellent in heat resistance. <P>SOLUTION: The polymer compound has as a recurring unit a structure obtained by fusing a tetralin ring with an indene ring, the five-membered ring of the indene ring and the benzene ring in the tetralin ring holding two adjacent carbon atoms in the five-membered ring in common in the structure, and has a number-average molecular weight of 10<SP>3</SP>-10<SP>8</SP>in terms of polystyrene. The polymer light-emitting element has an organic layer between electrodes comprising an anode and a cathode, where the organic layer comprises the polymer compound. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a polymer compound and a polymer light emitting device (polymer LED) using the polymer compound.

High-molecular-weight light-emitting materials and charge transport materials have been studied in various ways because they are soluble in solvents and can form an organic layer in a light-emitting element by a coating method. A polymer compound having the following structure is known (for example, Non-Patent Document 1 and Patent Document 1).

Advanced Materials 1997, Vol. 9, No. 10, 798 International Publication No. 99/54385 Pamphlet

However, the polymer compound has a problem that its heat resistance is not always sufficient.
An object of the present invention is to provide a polymer compound that is useful as a light-emitting material, a charge transport material, and the like and has excellent heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer compound having a structure in which a tetralin ring is condensed with an indene ring as a repeating unit is useful as a light-emitting material or a charge transport material and has excellent heat resistance. As a result, the present invention has been completed.

That is, the present invention has a structure in which a tetralin ring is condensed to an indene ring as a repeating unit, and in this structure, the 5-membered ring of the indene ring and the benzene ring of the tetralin ring are The present invention provides a polymer compound that shares two adjacent carbon atoms and has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

  The polymer compound of the present invention is useful as a light emitting material, a charge transporting material and the like, and has excellent heat resistance. Therefore, the polymer LED containing the polymer compound of the present invention can be used for a curved or flat light source, a segment type display element, a dot matrix flat panel display, etc. for backlight or illumination of a liquid crystal display.

〔式中、Ｒ₁およびＲ₂はそれぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を表す。ａは０〜３の整数を表し、ｂは０〜５の整数を表す。Ｒ₁およびＲ₂が複数個存在する場合、それらは同一でも異なっていてもよい。Ｒ₃およびＲ₄はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を表し、Ｒ₃とＲ₄は互いに結合して環を形成していてもよい。〕 The polymer compound of the present invention has a structure in which a tetralin ring is condensed to an indene ring as a repeating unit, in which the 5-membered ring of the indene ring and the benzene ring of the tetralin ring are the 5-membered Although it is a polymer compound that shares two adjacent carbon atoms in the ring,
As this repeating unit (hereinafter sometimes referred to as a repeating unit (A)), a repeating unit represented by the following formula (1) is preferred.

Wherein R ₁ and R ₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or Represents a cyano group. a represents an integer of 0 to 3, and b represents an integer of 0 to 5. When a plurality of R ₁ and R ₂ are present, they may be the same or different. R ₃ and R ₄ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Represents a group, and R ₃ and R ₄ may be bonded to each other to form a ring. ]

In the above formula (1), R ₃ and R ₄ are alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, substituted amino group, substituted Silyl group, fluorine atom, acyl group, acyloxy group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group are preferred, alkyl group, alkoxy group, aryl group, aryloxy group More preferred are an arylalkyl group, an arylalkoxy group and an arylalkylthio group.

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

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

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

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

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

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

Arylalkyl group is usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

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

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

Arylalkenyl group has a carbon number of usually about 8 to 60, and examples thereof include 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, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

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

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. The carbon number of the substituted amino group is usually about 1 to 60 without including the carbon number of the substituent, and preferably has 2 to 48 carbon atoms.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

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

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

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

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

The imine residue has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include groups represented by the following structural formulas.

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

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

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  The substituted carboxyl group means a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group. , Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. Can be mentioned. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

In the above formula (1), when R ₃ and R ₄ are each bonded to form a ring, the ring may be a C _{4 to} C ₁₀ cycloalkyl ring optionally having a substituent, C ₄ -C. ₁₀ cycloalkenyl ring, C6～C ₁₀ aromatic hydrocarbon ring, C ₄ -C ₁₀ heterocyclic are exemplified.

  Examples of the cycloalkyl ring include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and the like.

  Examples of the cycloalkenyl ring include a cyclohexadiene ring and a cyclooctatriene ring.

Examples of the aromatic hydrocarbon ring include a cyclopentatriene ring.

Examples of the heterocyclic ring include a tetrahydrofuran ring, a tetrahydrothiophene ring, a tetrahydroindole ring, a tetrahydroquinoline ring, a hexahydropyridine ring, a tetrahydroisoquinoline ring, and a julolidin ring.

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

が挙げられる。

Is mentioned.

  In the above formula (1), a = b = 0 is preferable from the viewpoint of increasing the molecular weight and improving the heat resistance.

  The total amount of the repeating unit (A) possessed by the polymer compound of the present invention is usually 1 mol% or more and 100 mol% or less, and 20 mol% or more of the total of all repeating units possessed by the polymer compound of the present invention. It is preferable that it is 30 mol% or more and 100 mol% or less.

−Ａｒ₄−Ｘ₂− （５）
−Ｘ₃− （６）

式中、Ａｒ₁、Ａｒ₂、Ａｒ₃およびＡｒ₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｘ₁、Ｘ₂およびＸ₃はそれぞれ独立に−ＣＲ₉＝ＣＲ₁₀−、−Ｃ≡Ｃ−、−Ｎ（Ｒ₁₁）−、または−（ＳｉＲ₁₂Ｒ₁₃）_m−を示す。Ｒ₉およびＲ₁₀は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₁₁、Ｒ₁₂およびＲ₁₃は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、アリールアルキル基または置換アミノ基を示す。ｆｆは０〜２の整数を示す。mは１〜１２の整数を示す。Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂およびＲ₁₂がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。 The polymer compound of the present invention is not limited to the repeating unit (A) of the polymer compound of the present invention, from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, improving the heat resistance, etc. A copolymer containing one or more types of units is preferred. The repeating unit other than the repeating unit (A) is preferably a repeating unit represented by the following formula (3), formula (4), formula (5) or formula (6).
-Ar _1- (3)

—Ar ₄ —X ₂ — (5)
-X _3- (6)

In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₉ ═CR ₁₀ —, —C≡C—, —N (R ₁₁ ) —, or — (SiR ₁₂ R ₁₃ ) _m —. R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents an integer of 0 to 2. m represents an integer of 1 to 12. When a plurality of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₂ are present, they may be the same or different.

Here, an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or via a group such as vinylene. Are combined. The arylene group may have a substituent.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and cyano group.

Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.

Examples of the arylene group include a phenylene group (for example, Formulas 1 to 3 in the following figure), a naphthalenediyl group (Formulas 4 to 13 in the following figure), an anthracene-diyl group (Formulas 14 to 19 in the following figure), and a biphenyl-diyl group ( Formulas 20 to 25), fluorene-diyl groups (formulas 36 to 38 in the following diagram), terphenyl-diyl groups (formulas 26 to 28 in the diagram below), condensed ring compound groups (formulas 29 to 35 in the diagram below), stilbene-diyl ( Examples are formulas A to D) and distilben-diyl (formulas E and F below). Of these, a phenylene group, a biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferable.

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

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups containing silicon, nitrogen, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure)
5-membered ring condensed hetero groups containing silicon, nitrogen, selenium and the like as a hetero atom: (Formulas 99 to 108 in the following figure)
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 109 to 113 in the figure below) Can be mentioned.
Examples include 5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to a phenyl group at the α-position of the hetero atom (formulas 113 to 119 in the following figure).
Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like as a hetero atom (formulas 120 to 125 in the following figure).

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

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

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

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

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

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

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

〔式中、Ｒ₂₂およびＲ₂₅は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。tおよびuはそれぞれ独立に０〜４の整数を示す。Ｘ₅は、Ｏ、Ｓ、ＳＯ₂、Ｓｅ，Ｔｅ、Ｎ−Ｒ₂₄、またはＳｉＲ₂₅Ｒ₂₆を示す。Ｘ₆およびＸ₇は、それぞれ独立にＮまたはＣ−Ｒ₂₇を示す。Ｒ₂₄、Ｒ_25、Ｒ₂₆およびＲ₂₇はそれぞれ独立に水素原子、アルキル基、アリール基、アリールアルキル基または１価の複素環基を示す。Ｒ₂₂、Ｒ₂₃およびＲ₂₇が複数存在する場合、それらは同一でも異なっていてもよい。〕
式（１１）で示される繰り返し単位の中央の５員環の例としては、チアジアゾール、オキサジアゾール、トリアゾール、チオフェン、フラン、シロールなどが挙げられる。 Among the repeating units represented by the above formula (3), the repeating units represented by the following formula (7), formula (8), formula (9), formula (10), formula (11), or formula (12) Is preferred.

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

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

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

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

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

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

また上記式（４）で示される繰り返し単位の中で、下記式（１３）で示される繰り返し単位が、発光波長を変化させる観点、発光効率を高める観点、耐熱性を向上させる観点からも好ましい。

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

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

Of the repeating units represented by the above formula (4), the repeating unit represented by the following formula (13) is also preferable from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, and improving the heat resistance.

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

Specific examples of the repeating unit represented by the above formula (13) include those represented by the following (formulas 133 to 140).

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

〔式中、Ｒ₄₂、Ｒ₄₃およびＲ₄₄は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｈｈ、ｉｉおよびｊｊはそれぞれ独立に０〜４の整数を示す。ｚは１〜２の整数を示す。Ｒ₄₂、Ｒ₄₃およびＲ₄₄が複数ある場合、それらは同一でも異なっていてもよい。〕 In the following formula (13), a repeating unit represented by the following formula (13-2) is preferable.

Wherein R ₄₂ , R ₄₃ and R ₄₄ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group Group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, A substituted carboxyl group or a cyano group is shown. hh, ii and jj each independently represent an integer of 0 to 4. z shows the integer of 1-2. When there are a plurality of R ₄₂ , R ₄₃ and R ₄₄ , they may be the same or different. ]

In addition, the polymer compound of the present invention includes a repeating unit other than the repeating units represented by the above formulas (1) and (3) to (13) as long as the light emission characteristics and the charge transport characteristics are not impaired. Also good. In addition, these repeating units and other repeating units may be linked by non-conjugated units, or the repeating units may contain those non-conjugated parts. Examples of the binding structure include those shown below and combinations of two or more of the following. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

  Among the polymer compounds of the present invention, those comprising only the repeating unit represented by the above formula (1-1) and / or comprising only the repeating unit represented by (1-2), substantially the above formula Those consisting of (1-1) and / or (1-2) and one or more repeating units represented by the above formulas (3) to (13) are preferred.

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

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

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

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

〔式中、Ｒ₃₄、Ｒ₃₅はそれぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基およびシアノ基からなる群から選ばれる置換基を示す。ａは０〜３の整数を表し、ｂは０〜５の整数を表す。Ｒ₃₄、Ｒ₃₅が複数存在する場合、それらは同一でも異なっていてもよい。Ｒ₃₆、Ｒ₃₇はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を表す。Ｒ₃₆とＲ₃₇、Ｒ₄₀とＲ₄₁はそれぞれ互いに結合して環を形成していてもよい。Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄はそれぞれ独立に縮合重合に関与する置換基を表す。〕
で示される化合物を原料の一つとして用いて縮合重合させることにより製造することができる。 Next, the manufacturing method of the high molecular compound of this invention is demonstrated.
Among the polymer compounds of the present invention, for example, those having a repeating unit represented by the formula (1)
Formula (14)

[Wherein, R ₃₄ and R ₃₅ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and A substituent selected from the group consisting of a cyano group is shown. a represents an integer of 0 to 3, and b represents an integer of 0 to 5. When a plurality of R ₃₄ and R ₃₅ are present, they may be the same or different. R ₃₆ and R ₃₇ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Represents a group. R ₃₆ and R ₃₇ , R ₄₀ and R ₄₁ may be bonded to each other to form a ring. Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a substituent involved in condensation polymerization. ]
It can manufacture by carrying out condensation polymerization using the compound shown by one as a raw material.

In the production method of the present invention, the substituent involved in the condensation polymerization includes a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, Examples thereof include a monohalogenated methyl group, —B (OH) ₂ , formyl group, cyano group, vinyl group and the like.

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

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

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

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

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

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

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

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

The preferred substituents involved in the condensation polymerization vary depending on the type of polymerization reaction. For example, when using a zerovalent nickel complex such as a Yamamoto coupling reaction, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate. Groups. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

  In addition, when the polymer compound of the present invention has a repeating unit other than the formula (1), the compound having two substituents involved in the condensation polymerization, which becomes a repeating unit other than the formula (1), coexists. And may be subjected to condensation polymerization.

式（１７）
Ｙ₉−Ａｒ₄−Ｘ₂−Ｙ₁₀

式（１８）
Ｙ₁₁−Ｘ₃−Ｙ₁₂
〔式中、Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄、ｆｆ、Ｘ₁、Ｘ₂およびＸ₃は前記と同じである。Ｙ₅、Ｙ₆、Ｙ₇、Ｙ₈、Ｙ₉、Ｙ₁₀、Ｙ₁₁、およびＹ₁₂はそれぞれ独立に縮合重合可能な置換基を示す。〕
上記式(１）で示される単位に加えて、順に（３）、（４）、（５）または（６）の単位を１つ以上有する高分子化合物を製造することができる。 Examples of the compound having two condensation-polymerizable substituents that are repeating units other than the repeating unit represented by the formula (1) include compounds represented by the following formulas (15) to (18).
In addition to the compound represented by the above formula (14), a compound represented by any one of the following formulas (15) to (18) is subjected to condensation polymerization to thereby formula (15)
Y ₅ —Ar ₁ —Y ₆

Formula (16)

Formula (17)
Y ₉ -Ar ₄ -X ₂ -Y ₁₀

Formula (18)
Y ₁₁ -X ₃ -Y ₁₂
[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ ff, X ₁ , X ₂ and X ₃ are the same as described above. Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , and Y ₁₂ each independently represent a substituent capable of condensation polymerization. ]
In addition to the unit represented by the above formula (1), a polymer compound having one or more units of (3), (4), (5) or (6) in order can be produced.

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、Ａｒ₁₀、Ａｒ₁₁、Ａｒ₁₂、ｘおよびｙは前記と同じ。Ｙ₁₃およびＹ₁₄はそれぞれ独立に縮合重合に関与する置換基を示す。〕
さらに好ましくは、式（１５−２）で示される化合物である。

〔式中、Ｒ₄₂、Ｒ₄₃、Ｒ₄₄、ｈｈ、ｉｉ、ｊｊ、およびｚは前記と同じ。Ｙ₁₅およびＹ₁₆はそれぞれ独立に縮合重合に関与する置換基を示す。〕 Moreover, as a compound which has a substituent which participates in two condensation corresponding to the said Formula (13) which becomes repeating units other than the repeating unit shown by the said Formula (1), following formula (15-1) is shown. And the compounds shown.

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , x and y are the same as described above. Y ₁₃ and Y ₁₄ each independently represent a substituent involved in condensation polymerization. ]
More preferably, it is a compound shown by Formula (15-2).

[Wherein, R ₄₂ , R ₄₃ , R ₄₄ , hh, ii, jj, and z are the same as described above. Y ₁₅ and Y ₁₆ each independently represent a substituent involved in condensation polymerization. ]

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

In the method for producing a polymer compound of the present invention, a condensation polymerization method is a known condensation reaction depending on the substituents involved in the condensation polymerization of the compounds represented by the above formulas (14) to (15-2). It can manufacture by using.
When the polymer compound of the present invention forms a double bond in condensation polymerization, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group, by Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polycondensation of compounds having two or more monohalogenated methyl groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium methyl groups by decomposing sulfonium salt, having a formyl group Examples include a method such as polymerization by a Knoevenagel reaction between a compound and a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the polymer compound of the present invention forms a triple bond in the main chain by condensation polymerization, for example, Heck reaction and Sonogashira reaction can be used.

Further, when a double bond or triple bond is not generated, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like.

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

In the production method of the present invention, Y ₁ , Y ₂ , Y _3, Y _4, Y _5, Y _6, Y _7, Y _8, Y _9, Y _10, Y _11, and Y ₁₂ are each independently halogen. The production method is preferably an atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, in which condensation polymerization is performed in the presence of a nickel zero-valent complex.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

Further, in the manufacturing method of the present _{invention, Y 1, Y 2, Y} 3, Y 4, Y 5, Y 6, Y 7, Y 8, Y 9, Y 10, Y 11, and Y ₁₂ are each independently Are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid group, or a boric acid ester group, and the total number of moles of the halogen atom, the alkyl sulfonate group, the aryl sulfonate group, and the arylalkyl sulfonate group ( J) and the total number of moles of boric acid groups and boric acid ester groups (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2) and nickel catalyst or palladium A production method in which condensation polymerization is performed using a catalyst is preferred.
Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

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

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

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

(14) useful as a starting material for the polymer compound of the present invention can be obtained by brominating a compound having a structure in which Y ₁ and Y ₂ in (14) are replaced with hydrogen atoms.

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

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

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

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

As the hole-transporting material, electron-transporting material, and light-emitting material to be mixed, a known low-molecular compound, triplet light-emitting complex, or polymer compound can be used, but a polymer compound is preferably used. As the hole transporting material, electron transporting material and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636 , WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP0707. 20, WO 95/07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, (co) polymers of aromatic amines and derivatives thereof.
Examples of low molecular weight fluorescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its derivatives of metals. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

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

三重項発光錯体として具体的には、例えばNature, (1998), 395, 151、Appl. Phys. Lett. (1999), 75(1), 4、Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105(Organic Light-Emitting Materials and DevicesＩＶ), 119、J. Am. Chem. Soc., (2001), 123, 4304、Appl. Phys. Lett., (1997), 71(18), 2596、Syn. Met., (1998), 94(1), 103、Syn. Met., (1999), 99(2), 1361、Adv. Mater., (1999), 11(10), 852 、Jpn.J.Appl.Phys.,34, 1883 (1995)などに記載されている。

Specific examples of triplet light emitting complexes include Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn. J. Appl. Phys., 34, 1883 (1995).

When a triplet light emitting complex is used as a light emitting material, it is usually used by mixing with a host material. In this case, the host material preferably has a high excited triplet energy.
[Organic EL handbook (Realize Science and Technology Center, issued on June 30, 2004), 198 pages]
Since the polymer compound of the present invention has high excited triplet energy, it is excellent as a host material for a triplet light-emitting complex.

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

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

  Examples of the method for forming the light emitting layer include a method by film formation from a solution. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

The ink composition used in the printing method or the like only needs to contain at least one polymer compound of the present invention. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as solvents and stabilizers may be included.
The ratio of the polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
When the ink composition contains a solvent, the ratio of the solvent is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.5 wt%, and more preferably 80 wt% with respect to the total weight of the composition. % To 99.0 wt%.
The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device such as an ink jet printing method, the viscosity is 1 at 25 ° C. in order to prevent clogging at the time of discharge and flight bending. It is preferably in the range of ˜20 mPa · s.

  Although there is no restriction | limiting in particular as a solvent used as an ink composition, The thing which can melt | dissolve or disperse | distribute materials other than the solvent which comprises this ink composition is preferable. When the material constituting the ink composition is soluble in a nonpolar solvent, the solvent is a chlorinated solvent such as chloroform, methylene chloride or dichloroethane, an ether solvent such as tetrahydrofuran, or an aromatic such as toluene or xylene. Examples include aromatic hydrocarbon solvents, ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

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

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, polysiloxane having an aromatic amine in a side chain or a main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5- Thienylene vinylene) or a derivative thereof.

  Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

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

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

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

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

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

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

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

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

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

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

  When the polymer LED of the present invention has an electron transport layer, known materials can be used as the electron transport material used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline Alternatively, derivatives thereof, polyfluorene or derivatives thereof, and the like are exemplified.

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

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

  There are no particular restrictions on the method of forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, solution for polymer electron transport materials is possible. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

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

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

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

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

Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

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

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

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

The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.
The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

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

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

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

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

Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.
As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.
The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to use the polymer LED stably for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

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

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

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

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, for the number average molecular weight, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

化合物Ａ
不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、白色の固体３４．２ｇを得た。
１Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ３）：
δ（ｐｐｍ） ＝ １．３〔ｓ，９Ｈ〕、２．４〔ｓ，６Ｈ〕、７．１〔ｓ，２Ｈ〕
ＭＳ（ＦＤ＋）Ｍ＋ ２４１ Synthesis example 1
(Synthesis of Compound A)

Compound A
Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.
1H-NMR (300 MHz / CDCl3):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD +) M + 241

化合物Ｂ

不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン３６ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．６３ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム０．４１ｇ、化合物Ａ９．６ｇ、ｔ−ブトキシナトリウム５．２ｇ、Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン４．７ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、約５０℃に温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン１００ｍｌを加えて、固体が溶解するまで加熱、放冷した後、沈殿をろ過し、白色の固体９．９ｇを得た。 (Synthesis of Compound B)

Compound B

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

化合物Ｃ

不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、化合物Ｂ５．２ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド３．５ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し白色の固体４．４ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ(ｐｐｍ) ＝ １．３〔ｓ，１８Ｈ〕、２．０〔ｓ，１２Ｈ〕、６．６〜６．７〔ｄ，４Ｈ〕、６．８〜６．９〔ｂｒ，４Ｈ〕、７．１〔ｓ，４Ｈ〕、７．２〜７．３〔ｄ，４Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ７３８
(Synthesis of Compound C)

Compound C

Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask to dissolve 5.2 g of Compound B, and then 3.5 g of N-bromosuccinimide / N, N-dimethyl under an ice bath. A formamide solution was added dropwise to react overnight.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

化合物Ｄ
不活性雰囲気下、３００ｍｌ三つ口フラスコに１‐ナフタレンボロン酸５．００ｇ（２９ｍｍｏｌ）、２−ブロモベンズアルデヒド６．４６ｇ（３５ｍｍｏｌ）、炭酸カリウム１０.０ｇ（７３ｍｍｏｌ）、トルエン３６ｍｌ、イオン交換水３６ｍｌを入れ、室温で撹拌しつつ２０分間アルゴンバブリングした。続いてテトラキス（トリフェニルホスフィン）パラジウム１６．８ｍｇ（０.１５ｍｍｏｌ）を入れ、さらに室温で撹拌しつつ１０分間アルゴンバブリングした。１００℃に昇温し、２５時間反応させた。室温まで冷却後、トルエンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。トルエン：シクロヘキサン＝１：２混合溶媒を展開溶媒としたシリカゲルカラムで生成することにより、化合物Ｄ５.１８ｇ（収率８６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．３９〜７．６２（ｍ、５Ｈ）、７．７０（ｍ、２Ｈ）、７．９４（ｄ、２Ｈ）、８．１２（ｄｄ、２Ｈ）、９．６３（ｓ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ２３３ Synthesis example 2
(Synthesis of Compound D)

Compound D
Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes with stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing with a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent, 5.18 g (yield 86%) of Compound D was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

（化合物Ｅの合成）
化合物Ｅ
不活性雰囲気下で３００ｍｌの三つ口フラスコに化合物Ｄ ８．００ｇ（３４.４ｍｍｏｌ）と脱水ＴＨＦ４６ｍｌを入れ、−７８℃まで冷却した。続いてｎ−オクチルマグネシウムブロミド（１.０ｍｏｌ／ｌＴＨＦ溶液）５２ｍｌを３０分かけて滴下した。滴下終了後０℃まで昇温し、１時間撹拌後、室温まで昇温して４５分間撹拌した。氷浴して１Ｎ塩酸２０ｍｌを加えて反応を終了させ、酢酸エチルで有機層を抽出、硫酸ナトリウムで乾燥した。溶媒を留去した後トルエン：ヘキサン＝１０：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｅ７．６４ｇ（収率６４％）を淡黄色のオイルとして得た。ＨＰＬＣ測定では２本のピークが見られたが、ＬＣ−ＭＳ測定では同一の質量数であることから、異性体の混合物であると判断した。

(Synthesis of Compound E)
Compound E
Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound D and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After the solvent was distilled off, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound E as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were determined to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

化合物Ｆ
不活性雰囲気下、５００ｍｌ三つ口フラスコに化合物Ｅ（異性体の混合物）５.００ｇ（１４.４ｍｍｏｌ）と脱水ジクロロメタン７４ｍｌを入れ、室温で撹拌、溶解させた。続いて、三フッ化ホウ素のエーテラート錯体を室温で１時間かけて滴下し、的か終了後室温で４時間撹拌した。撹拌しながらエタノール１２５ｍｌをゆっくりと加え、発熱がおさまったらクロロホルムで有機層を抽出、２回水洗し、硫酸マグネシウムで乾燥した。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｆ３．２２ｇ（収率６８％）を無色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．０３〜１．２６（ｍ、１４Ｈ）、２．１３（ｍ、２Ｈ）、４．０５（ｔ、１Ｈ）、７．３５（ｄｄ、１Ｈ）、７．４６〜７．５０（ｍ、２Ｈ）、７．５９〜７．６５（ｍ、３Ｈ）、７．８２（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３５（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ３２９ (Synthesis of Compound F)

Compound F
Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound E (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask, and stirred and dissolved at room temperature. Subsequently, boron ether trifluoride etherate complex was added dropwise at room temperature over 1 hour, and after completion, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound F as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

化合物Ｇ
不活性雰囲気下２００ｍｌ三つ口フラスコにイオン交換水２０ｍｌをいれ、撹拌しながら水酸化ナトリウム１８．９ｇ（０.４７ｍｏｌ）を少量ずつ加え、溶解させた。水溶液が室温まで冷却した後、トルエン２０ｍｌ、化合物Ｆ５.１７ｇ（１５.７ｍｍｏｌ）、臭化トリブチルアンモニウム１．５２ｇ（４.７２ｍｍｏｌ）を加え、５０℃に昇温した。臭化ｎ−オクチルを滴下し、滴下終了後５０℃で９時間反応させた。反応終了後トルエンで有機層を抽出し、２回水洗し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｇ５．１３ｇ（収率７４％）を黄色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．５２（ｍ、２Ｈ）、０．７９（ｔ、６Ｈ）、１．００〜１．２０（ｍ、２２Ｈ）、２．０５（ｔ、４Ｈ）、７．３４（ｄ、１Ｈ）、７．４０〜７．５３（ｍ、２Ｈ）、７．６３（ｍ、３Ｈ）、７．８３（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３１（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４４１ (Synthesis of Compound G)

Compound G
Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound F and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. Purification by a silica gel column using hexane as a developing solvent gave 5.13 g (yield 74%) of Compound G as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

化合物Ｇ 化合物Ｈ
１Lオートクレーブに化合物Ｇを16.33g(37.05mmol)、トリエチルボランの1.0Mヘキサン溶液18.5ml(18.5mmol)およびヘプタン370mlを加えた後、水素圧を100kg/cm2に調整した。200℃まで昇温し、24時間保温した。室温まで冷却し、不溶物をろ過した後、溶媒を留去した。ヘキサンを展開溶媒としたシリカゲルカラムで精製することにより、化合物Ｈを9.81ｇ得た。


¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．６１（ｔ、６Ｈ）、０．９２〜１．２１（ｍ、２４Ｈ）、１．９０（ｍ、８Ｈ）、２．８６（ｔ、２Ｈ）、３．１８（ｔ、２Ｈ）、６．９９〜７．０９（ｍ、２Ｈ）、７．２３〜７．３５（ｍ、３Ｈ）、７．８５（ｄｄ、１Ｈ） Synthesis of Compound H

Compound G Compound H
After adding 16.33 g (37.05 mmol) of Compound G, 18.5 ml (18.5 mmol) of 1.0 M hexane solution of triethylborane and 370 ml of heptane to a 1 L autoclave, the hydrogen pressure was adjusted to 100 kg / cm2. The temperature was raised to 200 ° C. and kept warm for 24 hours. After cooling to room temperature and filtering insolubles, the solvent was distilled off. Purification by a silica gel column using hexane as a developing solvent gave 9.81 g of Compound H.


¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.61 (t, 6H), 0.92-1.21 (m, 24H), 1.90 (m, 8H), 2.86 (t, 2H), 3.18 (t, 2H), 6 .99 to 7.09 (m, 2H), 7.23 to 7.35 (m, 3H), 7.85 (dd, 1H)

化合物Ｈ 化合物Ｉ
化合物Ｈを8.67g(19.5mmol)、ジクロロメタン(脱水)74.53g、塩化亜鉛7.97g(58.5mmol)および酢酸57.96gを4つ口フラスコに加え、45℃に昇温した。40〜45℃でベンジルトリメチルアンモニウムトリブロミド15.97g(40.95mmol)を添加し、50℃で1.5時間保温した。室温に冷却し、クロロホルム80mlと水120mlを加えて攪拌し、分液した。水層をクロロホルム80mlで2回抽出し、先に分液したクロロホルム層と合わせて5％チオ硫酸ナトリウム水溶液80mlで洗浄した。さらに順次水80ml、5％炭酸カリウム水溶液80ml×2回、水80ml×2回洗浄した。硫酸マグネシウムでクロロホルム層を乾燥した後、溶媒を留去した。ヘキサンを展開溶媒としたシリカゲルカラムで精製することにより、化合物Ｉを7.40ｇ得た。

¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．５７（ｔ、６Ｈ）、０．７９〜１．２０（ｍ、２４Ｈ）、１．８６（ｍ、８Ｈ）、２．８２（ｔ、２Ｈ）、３．１０（ｔ、２Ｈ）、７．３２（ｓ、１Ｈ）、７．３５（ｓ、１Ｈ）、７．４２（ｄｄ、１Ｈ）７．６７（ｄ、１Ｈ）
Example 1 (Synthesis of Compound I)

Compound H Compound I
8.67 g (19.5 mmol) of Compound H, 74.53 g of dichloromethane (dehydrated), 7.97 g (58.5 mmol) of zinc chloride and 57.96 g of acetic acid were added to a four-necked flask, and the temperature was raised to 45 ° C. Benzyltrimethylammonium tribromide 15.97g (40.95mmol) was added at 40-45 degreeC, and it heat-retained at 50 degreeC for 1.5 hours. After cooling to room temperature, 80 ml of chloroform and 120 ml of water were added and stirred for liquid separation. The aqueous layer was extracted twice with 80 ml of chloroform, combined with the previously separated chloroform layer, and washed with 80 ml of 5% aqueous sodium thiosulfate solution. Further, 80 ml of water, 80 ml of 5% aqueous potassium carbonate solution was washed twice and 80 ml of water was washed twice. After drying the chloroform layer with magnesium sulfate, the solvent was distilled off. Purification by a silica gel column using hexane as a developing solvent gave 7.40 g of Compound I.

¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.57 (t, 6H), 0.79 to 1.20 (m, 24H), 1.86 (m, 8H), 2.82 (t, 2H), 3.10 (t, 2H), 7 .32 (s, 1H), 7.35 (s, 1H), 7.42 (dd, 1H) 7.67 (d, 1H)

Example 2 (Synthesis of Polymer Compound 1)
2.7 g of Compound I and 1.68 g of 2,2′-bipyridyl were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 150 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 3.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this reaction solution was cooled, and then a mixed solution of 150 ml of methanol / 150 ml of ion-exchanged water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with about 1 N hydrochloric acid, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 3% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol and re-precipitated. Since it was difficult to recover the precipitate by filtration, the solvent was distilled off under reduced pressure to recover the polymer. Next, this precipitate was washed with methanol and then dried under reduced pressure to obtain 0.9 g of a polymer. This polymer is referred to as polymer compound 1. The obtained polymer compound 1 had a polystyrene equivalent weight average molecular weight of 2.5 × 10 ⁴ and a number average molecular weight of 1.3 × 10 ⁴ .

Example 3 (Synthesis of Polymer Compound 2)
After charging 1.9 g of Compound I, 1.0 g of Compound C, and 1.68 g of 2,2′-bipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 150 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 3.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this reaction solution was cooled, and then a mixed solution of 150 ml of methanol / 150 ml of ion-exchanged water was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with about 1 N hydrochloric acid, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 3% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol and re-precipitated.
Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 1.0 g of a polymer. This polymer is referred to as polymer compound 2. The obtained polymer compound 2 had a polystyrene equivalent weight average molecular weight of 1.7 × 10 ⁴ and a number average molecular weight of 8.6 × 10 ³ .

Comparative Example 1 (Synthesis of Polymer Compound 3)
2,7-dibromo-9,9-dioctylfluorene (287 mg, 0.523 mmol), 2,7- (9,9-dioctyl) fluorenediboronic acid ethylene glycol cyclic ester (305 mg, 0. 0) under inert atmosphere. 575 mmol), aliquot 336 (15 mg) was dissolved in toluene (4.3 g), and potassium carbonate (231 mg, 1.67 mmol) was added to this as an approximately 1 g aqueous solution. Further, tetrakis (triphenylphosphine) palladium (0.39 mg, 0.00034 mmol) was added, and the mixture was heated to reflux for 20 hours. Subsequently, bromobenzene (11.5 mg) was added, and the mixture was further heated to reflux for 5 hours. After completion of heating, the reaction mass was added dropwise to a mixed solution of methanol (40 ml) and 1N aqueous hydrochloric acid (2.2 ml), and the deposited precipitate was separated by filtration. The resulting precipitate was washed with methanol and water and dried under reduced pressure to obtain a solid. Subsequently, the solid was dissolved in 50 ml of toluene, passed through a silica column, and concentrated to 20 ml. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered off and dried under reduced pressure to obtain polymer compound 3. Yield 340 mg.
The obtained polymer compound 3 had a molecular weight in terms of polystyrene of Mn = 1.2 × 10 ³ and Mw = 3.2 × 10 ³ .

Example 4 (Glass transition temperature measurement)
The glass transition temperature was measured by DSC (DSC2920, manufactured by TA Instruments). The sample was held at 200 ° C. for 5 minutes, then rapidly cooled to −50 ° C. and held for 30 minutes. After raising the temperature to 30 ° C., the measurement was carried out to 300 ° C. at a rate of 5 ° C. per minute.
The obtained glass transition points are shown in Table 1 below. It can be seen that the polymer compounds 1 and 2 of the present invention have a high glass transition temperature and excellent heat resistance.

高分子化合物４ 高分子化合物５

高分子化合物４及び高分子化合物５に対して、Hatree-Fock（HF）法により構造最適化した。その際、基底関数としては6-31g*を用いた。さらに、最適化された構造に対し、構造最適化と同一の基底を使用し、b3p86レベルの時間依存型密度汎関数（TDDFT）法により、励起三重項エネルギーを求めた。その結果、高分子化合物４及び高分子化合物５の励起三重項エネルギーは、各々、約２．９３eV及び約２．５４eVであり、本発明に含まれる高分子化合物４の励起三重項エネルギーは、本発明に含まれない高分子化合物５の励起三重項エネルギーよりも大きい値であった。従って高分子化合物４は、三重項錯体発光材料のホスト材料として、より好ましい。
Reference example (calculation of excited triplet energy of polymer compound)
As computer chemistry methods, molecular orbital methods and density functional methods based on semi-empirical methods and non-empirical methods are known. For example, to obtain the excitation energy, the Hartree-Fock (HF) method or the density functional method may be used. In the present invention, the triplet excitation energy of the conjugated polymer compound was determined using the quantum chemical calculation program Gaussian 98. Calculation of the excited triplet energy for the conjugated polymer compound is performed for the monomer (n = 1), dimer (n = 2), and trimer (n = 3). The excitation energy is calculated by linearly extrapolating n = 0 with the result at n = 1 to 3 as 1 / n function E (1 / n) (where E is the excitation triplet energy). Use the technique.
(Calculation example)

Polymer compound 4 Polymer compound 5

The structures of the polymer compound 4 and the polymer compound 5 were optimized by the Hatree-Fock (HF) method. At that time, 6-31 g * was used as a basis function. Furthermore, the excited triplet energy was calculated for the optimized structure by the time-dependent density functional (TDDFT) method at the b3p86 level, using the same basis as the structure optimization. As a result, the excited triplet energies of the polymer compound 4 and the polymer compound 5 are about 2.93 eV and about 2.54 eV, respectively, and the excited triplet energy of the polymer compound 4 included in the present invention is The value was larger than the excited triplet energy of the polymer compound 5 not included in the invention. Therefore, the polymer compound 4 is more preferable as a host material of the triplet complex light-emitting material.

東京システム開発（株）製有機ＥＬテストシステムＳＴ−Ｐを用いて、塗布薄膜のＵＶ光励起の発光スペクトルを測定した。励起光の波長は３７５ｎｍであった。塗布薄膜の発光スペクトルのピーク波長５５５ｎｍにおける発光強度を表２に示した。 Measurement of emission intensity of thin film doped with triplet complex luminescent material.
To 100 parts by weight of the polymer compound, 2 parts by weight of a yellow-green triplet complex luminescent material (ADS078GE manufactured by American Dye Source) represented by the following formula was added and dissolved in toluene. The solution was applied to a glass substrate by spin coating and air-dried. The film thickness measured with a stylus film thickness meter was 100 nm.

Using an organic EL test system ST-P manufactured by Tokyo System Development Co., Ltd., the emission spectrum of UV light excitation of the coated thin film was measured. The wavelength of the excitation light was 375 nm. The emission intensity at the peak wavelength of 555 nm of the emission spectrum of the coated thin film is shown in Table 2.

When the polymer compound 1 is used as a host material for a yellow-green triplet complex light-emitting material, the emission intensity obtained from the triplet complex light-emitting material is large, indicating that it is excellent as a host material for a triplet complex light-emitting material. It was.

Claims (26)

The repeating unit has a structure in which a tetralin ring is condensed to an indene ring. A polymer compound which shares carbon atoms and has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ . The polymer compound according to claim 1, wherein the repeating unit has a structure represented by the following formula (1).

Wherein R ₁ and R ₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or Represents a cyano group. a represents an integer of 0 to 3, and b represents an integer of 0 to 5. When a plurality of R ₁ and R ₂ are present, they may be the same or different. R ₃ and R ₄ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Represents a group, and R ₃ and R ₄ may be bonded to each other to form a ring. ] 3. The polymer compound according to claim 2, wherein a = b = 0 in the formula (1). Furthermore, the high molecular compound in any one of Claims 1-3 containing the repeating unit shown by following formula (3), Formula (4), Formula (5), or Formula (6).
-Ar _1- (3)

—Ar ₄ —X ₂ — (5)
-X _3- (6)

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₉ ═CR ₁₀ —, —C≡C—, —N (R ₁₁ ) —, or — (SiR ₁₂ R ₁₃ ) _m —.
R ₉ and R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents an integer of 0-2. m represents an integer of 1 to 12. When there are a plurality of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , they may be the same or different. ] The repeating unit represented by the above formula (3) is a repeating unit represented by the following formula (7), (8), (9), (10), (11) or (12): Item 5. The polymer compound according to any one of Items 1 to 4.

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

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

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

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

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

Wherein R ₂₈ and R ₃₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or represents a cyano group. v and w each independently represent an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. ] 6. The polymer compound according to claim 5, wherein the repeating unit represented by the formula (4) is a repeating unit represented by the following formula (13).

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ] Following formula (14 )

[Wherein R ₃₄ and R ₃₅ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or Represents a cyano group. a represents an integer of 0 to 3, and b represents an integer of 0 to 5. When a plurality of R ₃₄ and R ₃₅ are present, they may be the same or different. R ₃₆ and R ₃₇ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Represents a group. R ₃₆ and R ₃₇ may form a ring bonded to physicians each other. Y ₁ and Y ₂ represent a substituent involved in condensation polymerization are each independently. ]
The method for producing a polymer compound according to any one of claims 1 to 6, wherein the compound represented by the above is used as one of raw materials for condensation polymerization. The production method according to claim 7, wherein Y ₁ and Y ₂ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group, and condensation polymerization is performed in the presence of a nickel zero-valent complex. . Y ₁ and Y ₂ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, —B (OH) ₂ , or a borate group, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and The ratio of the total number of moles of arylalkyl sulfonate groups to the total number of moles of —B (OH) ₂ and borate group is substantially 1, and is characterized by condensation polymerization using a nickel or palladium catalyst. The manufacturing method according to claim 7. A compound represented by formula (14 ):

[Wherein R ₃₄ and R ₃₅ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or Represents a cyano group. a represents an integer of 0 to 3, and b represents an integer of 0 to 5. When a plurality of R ₃₄ and R ₃₅ are present, they may be the same or different. R ₃₆ and R ₃₇ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Represents a group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. Y ₁ and Y ₂ each independently represent a substituent involved in condensation polymerization. ] In addition to the compound represented by the above formula (14), the compound represented by any one of the following formulas (15) to (18) is subjected to condensation polymerization as a raw material. The manufacturing method as described in.

_{Y 5 -Ar 1 -Y 6 (15} )

_{Y 9 -Ar 4 -X 2 -Y 10} (17)
_{Y 11 -X 3 -Y 12 (18} )

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ ff, X ₁ , X ₂ and X ₃ represent the same meaning as described above. Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ each independently represent a substituent involved in condensation polymerization. ] Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group, and a nickel zero-valent complex exists. The production method according to claim 11, wherein the condensation polymerization is performed under. Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, —B (OH) ₂ , Or a borate group, and the ratio of the total number of moles of halogen atom, alkyl sulfonate group, aryl sulfonate group, and arylalkyl sulfonate group to the total number of moles of —B (OH) ₂ and borate group is substantially The production method according to claim 11, wherein condensation polymerization is performed using a nickel or palladium catalyst.   A composition comprising at least one material selected from a hole transport material, an electron transport material, and a light emitting material, and the polymer compound according to any one of claims 1 to 6.   An ink composition comprising the polymer compound according to claim 1.   The ink composition according to claim 15, wherein the viscosity is 1 to 20 mPa · s at 25 ° C.   The luminescent thin film containing the polymer compound in any one of Claims 1-6.   The electroconductive thin film containing the high molecular compound in any one of Claims 1-6.   The organic-semiconductor thin film containing the high molecular compound in any one of Claims 1-6.   A polymer light emitting device comprising an organic layer between electrodes composed of an anode and a cathode, wherein the organic layer contains the polymer compound according to any one of claims 1 to 6.   21. The polymer light emitting device according to claim 20, wherein the organic layer is a light emitting layer.   The polymer light emitting device according to claim 21, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material.   A planar light source comprising the polymer light-emitting device according to claim 20.   A segment display device using the polymer light-emitting device according to any one of claims 20 to 22.   A dot matrix display using the polymer light-emitting device according to claim 20.   23. A liquid crystal display device comprising the polymer light-emitting device according to claim 20 as a backlight.