JP5860235B2 - Polymer compound and composition containing the polymer compound - Google Patents

Description

  The present invention relates to a polymer compound, a composition containing the polymer compound, and a device including these.

  It is known that a light-emitting element including a composition obtained by doping a host material with a light-emitting organometallic complex as a dopant as a material of a light-emitting layer exhibits high-efficiency light-emitting characteristics (Patent Document 1).

JP 2010-31246 A

  However, Patent Document 1 specifically describes a material that provides a long-life element when used in the production of a light-emitting element such as an organic electroluminescence element (hereinafter referred to as “organic EL element”). It wasn't.

  Therefore, an object of the present invention is to provide a material that provides a long-life element when used for manufacturing a light-emitting element such as an organic EL element.

（式中、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、１価の芳香族複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、又はシアノ基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵のうち少なくとも一つは水素原子以外の基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵のうち隣接する基同士が結合して環を形成していてもよい。
Ａｒ₁及びＡｒ₂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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、１価の芳香族複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、及びシアノ基からなる群から選ばれる置換基を有していてもよい２価の芳香族基を表す。
Ａｒ₃は、アリール基又は１価の芳香族複素環基を表す。
Ａｒ₄は、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の芳香族複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、又はシアノ基を表す。
Ｒ⁶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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の芳香族複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、又はシアノ基を表す。Ｒ⁶が複数個存在する場合には、それらは同一であっても異なっていてもよい。
ａは０又は１を表す。２個存在するａは同一であっても異なっていてもよい。） The present invention first provides a polymer compound containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

(Where
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, Arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio Represents a group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group, and at least one of R ¹ , R ² , R ³ , R ^4, and R ⁵ represents a group other than a hydrogen atom. Of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , adjacent groups may be bonded to form a ring.
Ar ₁ and Ar ₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted carboxyl And a divalent aromatic group which may have a substituent selected from the group consisting of a group and a cyano group.
Ar ₃ represents an aryl group or a monovalent aromatic heterocyclic group.
Ar ₄ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group , Imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl Represents a group, a substituted carboxyl group, or a cyano group.
R ⁶ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue Group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted Represents a carboxyl group or a cyano group. When a plurality of R ⁶ are present, they may be the same or different.
a represents 0 or 1; Two a's may be the same or different. )

（式中、Ａｒ₅はアリーレン基又は２価の芳香族複素環基を表す。） Secondly, the present invention provides a polymer containing a repeating unit represented by the following formula (5) in addition to the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2). A compound is provided.

(In the formula, Ar ₅ represents an arylene group or a divalent aromatic heterocyclic group.)

  Thirdly, the present invention provides a composition containing the polymer compound and a light-emitting organometallic complex compound.

  Fourthly, the present invention provides an element having an electrode composed of an anode and a cathode, and an organic layer containing the polymer compound provided between the electrodes.

  The polymer compound and composition of the present invention (hereinafter, also referred to as “polymer compound of the present invention”) provides a long-life device when used for production of an organic EL device or the like. In a preferred embodiment, the polymer compound or the like of the present invention provides a device that is further excellent in luminous efficiency (that is, high quantum yield). Therefore, the polymer compound of the present invention is particularly useful for the production of light emitting devices such as organic EL devices.

Hereinafter, the present invention will be described in detail.
[Explanation of terms]
Hereinafter, terms commonly used in this specification will be described.

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

  “Repeating unit” means a unit present in two or more in a polymer compound.

The term “C _{m to} C _n ” (m and n are positive integers satisfying m <n) indicates that the organic group described immediately after the term has m to n carbon atoms. .

  The term “unsubstituted” appended immediately before a group means that the hydrogen atom of the group is not substituted with a substituent. The term “substituted” immediately before a group means that part or all of the hydrogen atoms of the group are substituted with a substituent. The term “which may have a substituent” attached immediately before a group means that when a hydrogen atom of the group is not substituted with a substituent, and a part or all of the hydrogen atoms of the group Means when both are substituted with a substituent.

  The term “optionally substituted” may be rephrased as “optionally substituted”. Unless otherwise specified, examples of the substituent include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms. Among these, a halogen atom and 1 to 30 carbon atoms are exemplified. 18 hydrocarbyl groups and hydrocarbyloxy groups having 1 to 18 carbon atoms are preferred, halogen atoms, hydrocarbyl groups having 1 to 12 carbon atoms and hydrocarbyloxy groups having 1 to 12 carbon atoms are more preferred, halogen atoms and carbon atoms A hydrocarbyl group having 1 to 12 carbon atoms is more preferable, and a halogen atom and a hydrocarbyl group having 1 to 6 carbon atoms are particularly preferable.

The alkyl group means an unsubstituted alkyl group and an alkyl group substituted with a substituent such as a halogen atom, an amino group, or a mercapto group. The alkyl group includes both a linear alkyl group and a cyclic alkyl group (cycloalkyl group). The alkyl group may have a branch. The carbon atom number of an alkyl group is 1-20 normally without including the carbon atom number of a substituent. As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, Nonyl group, decyl group, 4-methyldodecyl group, pentadecyl group, 2,2,4,4,6,8,8-heptamethylnonyl group, heptadecyl group, octadecyl group, 2,6,10,14-tetramethyl Pentadecyl group, nonadecyl group, 3,7-dimethyloctyl group, dodecyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, trifluoropropyl group, trideca Fluoro-1,1,2,2-tetrahydrooctyl group, heptadecafluoro 1,1,2,2-tetrahydronaphthalene-decyl group, mercaptopropyl group, and mercaptopropyl-octyl radical and mercaptodecyl group. The C ₁ -C ₂₀ alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, tert- butyl group, a pentyl group, an isoamyl group, a hexyl group, cyclohexyl Group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group.

The alkoxy group means an unsubstituted alkoxy group and an alkoxy group substituted with a substituent such as a halogen atom and an alkoxy group. The alkoxy group includes both a linear alkoxy group and a cyclic alkoxy group (cycloalkoxy group). The alkoxy group may have a branch. The carbon atom number of an alkoxy group is 1-20 normally without including the carbon atom number of a substituent, Preferably it is 1-15, More preferably, it is 1-10. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy Group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl Group, methoxymethyloxy group and 2-methoxyethyloxy group. The C ₁ -C ₁₂ alkoxy group include a methoxy group, an ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert- butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy Examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a dodecyloxy group.

The alkylthio group means an unsubstituted alkylthio group and an alkylthio group substituted with a substituent such as a halogen atom. The alkylthio group includes both a linear alkylthio group and a cyclic alkylthio group (cycloalkylthio group). The alkylthio group may have a branch. The carbon atom number of an alkylthio group is 1-20 normally without including the carbon atom number of a substituent, Preferably it is 1-15, More preferably, it is 1-10. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2- Examples include an ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a dodecylthio group, and a trifluoromethylthio group. The C ₁ -C ₁₂ alkylthio group include a methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio, tert- butylthio, pentylthio, hexylthio group, cyclohexylthio group, heptylthio group, Examples include octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, and dodecylthio group.

The aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon. The aryl group means an unsubstituted aryl group and an aryl group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. An aryl group has a condensed ring; a single bond of two or more rings selected from independent benzene rings and condensed rings; and two or more rings selected from independent benzene rings and condensed rings are divalent And those bonded via an organic group (for example, alkenylene group such as vinylene group) are also included. The carbon atom number of an aryl group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48, More preferably, it is 7-30. Examples of the aryl group include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9- include anthracenyl group and a pentafluorophenyl group, C ₁ -C ₁₂ alkoxyphenyl group or a C ₁ -C ₁₂ alkylphenyl group are preferred.

The C ₁ -C ₁₂ alkoxyphenyl group, for example, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, tert- butoxyphenyl, pentyloxyphenyl group Hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxyphenyl group and dodecyloxy A phenyl group is mentioned.

The C ₁ -C ₁₂ alkylphenyl group, for example, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, tert -Butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group and dodecylphenyl group.

The aryloxy group means an unsubstituted aryloxy group and an aryloxy group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The carbon atom number of an aryloxy group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48, More preferably, it is 7-30. The aryloxy group include a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, and a 2-naphthyloxy group and a pentafluorophenyl group, C ₁ -C ₁₂ alkoxy phenoxy group or a C ₁ -C ₁₂ alkylphenoxy group are preferable.

Examples of the C ₁ -C ₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, a tert-butoxyphenoxy group, and a pentyloxyphenoxy group. Hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxyphenoxy group and dodecyloxy A phenoxy group is mentioned.

Examples of the C _{1 to} C ₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, and a butylphenoxy group. Group, isobutylphenoxy group, tert-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group and dodecylphenoxy group.

The arylthio group means an unsubstituted arylthio group and an arylthio group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The carbon atom number of an arylthio group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48, More preferably, it is 7-30. The arylthio group, for example, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, and a 2-naphthylthio group and a pentafluorophenylthio group.

The arylalkyl group means an unsubstituted arylalkyl group and an arylalkyl group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The carbon atom number of an arylalkyl group is 7-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48, More preferably, it is 7-30. The aryl alkyl group, e.g., phenyl -C ₁ -C ₂₀ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₂₀ alkyl group, 1-naphthyl -C ₁ -C ₂₀ alkyl group and 2-naphthyl -C ₁ -C ₂₀ alkyl group.

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

The arylalkylthio group means an unsubstituted arylalkylthio group and an arylalkylthio group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The carbon atom number of an arylalkylthio group is 7-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48, More preferably, it is 7-30. Arylalkylthio group, for example, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group and a 2-naphthyl -C ₁ -C ₁₂ alkylthio group.

The arylalkenyl group means an unsubstituted arylalkenyl group and an arylalkenyl group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The number of carbon atoms of the arylalkenyl group is usually 8 to 60, preferably 8 to 48, more preferably 8 to 30, excluding the number of carbon atoms of the substituent. Arylalkenyl group, for example, phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group and 2-naphthyl -C ₂ -C ₁₂ alkenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group or a C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The C ₂ -C ₁₂ alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, Examples include 2-hexenyl group and 1-octenyl group.

The arylalkynyl group means an unsubstituted arylalkynyl group and an arylalkynyl group substituted with a substituent such as a halogen atom, an alkoxy group and an alkyl group. The number of carbon atoms of the arylalkynyl group is usually 8 to 60, preferably 8 to 48, more preferably 8 to 30, excluding the number of carbon atoms of the substituent. The arylalkynyl group, a 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 and 2-naphthyl -C ₂ -C ₁₂ alkynyl group and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl or C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The C ₂ -C ₁₂ alkynyl group include an ethynyl group, 1-propynyl, 2-propynyl, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, Examples include 2-hexynyl group and 1-octynyl group.

The heteroaryloxy group means an unsubstituted heteroaryloxy group and a substituted heteroaryloxy group. The carbon atom number of heteroaryloxy group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48. The heteroaryl group, e.g., C ₁ -C ₁₂ alkoxy pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, thienyloxy group, C ₁ -C ₁₂ alkoxide Shichie sulfonyloxy group, pyridyloxy group, and isoquinolyl include oxy group, C ₁ -C ₁₂ alkoxy pyridyl group or a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

Examples of the C ₁ -C ₁₂ alkoxypyridyloxy group include methoxypyridyloxy group, ethoxypyridyloxy group, propyloxypyridyloxy group, isopropyloxypyridyloxy group, butoxypyridyloxy group, isobutoxypyridyloxy group, sec-butoxy Pyridyloxy group, tert-butoxypyridyloxy group, pentyloxypyridyloxy group, hexyloxypyridyloxy group, cyclohexyloxypyridyloxy group, heptyloxypyridyloxy group, octyloxypyridyloxy group, 2-ethylhexyloxypyridyloxy group, nonyl Examples include oxypyridyloxy group, decyloxypyridyloxy group, 3,7-dimethyloctyloxypyridyloxy group, and dodecyloxypyridyloxy group.

The C ₁ -C ₁₂ alkyl pyridyl group, e.g., methyl pyridyl group, ethyl pyridyloxy group, dimethylpyridyl group, propyl pyridyloxy group, 1,3,5-trimethyl-pyridyl group, methyl ethyl pyridyl group , Isopropylpyridyloxy group, butylpyridyloxy group, isobutylpyridyloxy group, sec-butylpyridyloxy group, tert-butylpyridyloxy group, pentylpyridyloxy group, isoamylpyridyloxy group, hexylpyridyloxy group, heptylpyridyloxy group, Examples include octylpyridyloxy group, nonylpyridyloxy group, decylpyridyloxy group and dodecylpyridyloxy group.

The heteroarylthio group means an unsubstituted heteroarylthio group and a substituted heteroarylthio group. The carbon atom number of heteroarylthio group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 7-48. The heteroarylthio group, for example, pyridylthio group, C ₁ -C ₁₂ alkoxy pyridylthio groups include C ₁ -C ₁₂ alkylpyridylthio group and an isoquinolylthio group, C ₁ -C ₁₂ alkoxy pyridylthio group or a C ₁ -C ₁₂ alkylpyridylthio group.

  The monovalent aromatic heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from an aromatic heterocyclic compound, and includes those having a condensed ring. . The monovalent aromatic heterocyclic group means an unsubstituted monovalent aromatic heterocyclic group and a monovalent aromatic heterocyclic group substituted with a substituent such as an alkyl group. Heterocyclic compounds are not only carbon atoms but also hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms and silicon atoms as elements constituting the ring among organic compounds having a cyclic structure. The thing containing an atom. Examples of the heterocyclic compound having aromaticity include heterocyclic compounds containing heteroatoms such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phospho-isoquinoline, carbazole and dibenzophosphole. Heterocycle itself is aromatic; heterocyclic compounds containing heteroatoms, such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol and dibenzopyran, including heteroatoms contained in the compound Heterocycles themselves do not exhibit aromaticity, but those having a structure in which an aromatic ring is condensed to a heterocyclic ring can be mentioned.

The number of carbon atoms of the monovalent aromatic heterocyclic group is usually 4 to 60, preferably 4 to 30, not including the number of carbon atoms of the substituent. Examples of the monovalent aromatic heterocyclic group, for example, thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, and a quinolyl group and an isoquinolyl group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group or a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

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

The silyl group includes an unsubstituted silyl group and a silyl group substituted with one, two, or three substituents selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent aromatic heterocyclic group. Group (hereinafter referred to as “substituted silyl group”). The substituent may have a secondary substituent. The carbon atom number of a substituted silyl group is 1-60 normally without including the carbon atom number of a secondary substituent, Preferably it is 3-48, More preferably, it is 3-40. Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, tert-butylsilyldimethylsilyl group, and pentyldimethylsilyl group. Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C _{1 ~C 12} alkyl Silyl 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, Examples thereof include a tert-butyldiphenylsilyl group and a dimethylphenylsilyl group.

The substituted silyloxy group is one, two, or three substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, an alkoxy group, an aryloxy group, an arylalkoxy group, and a monovalent heterocyclic oxy group. Means a silyloxy group substituted by The substituent may have a secondary substituent. The number of carbon atoms of the substituted silyloxy group is usually 1 to 60, preferably 3 to 48, not including the number of carbon atoms of the secondary substituent. Examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-isopropylsilyloxy group, dimethyl-isopropylsilyloxy group, diethyl-isopropylsilyloxy group, tert-butyldimethylsilyloxy group Group, pentyldimethylsilyloxy group, hexyldimethylsilyloxy group, heptyldimethylsilyloxy group, octyldimethylsilyloxy group, 2-ethylhexyl-dimethylsilyloxy group, nonyldimethylsilyloxy group, decyldimethylsilyloxy group, 3, 7 - dimethyloctyl - butyldimethylsilyloxy group, dodecyl dimethyl silyl group, a phenyl -C ₁ -C ₁₂ alkyl silyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ A Kill silyloxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl silyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl silyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group , phenyl -C ₁ -C ₁₂ alkyl dimethyl silyloxy group, triphenyl silyloxy group, tri -p- xylyl silyloxy group, tribenzyl silyl group, diphenylmethyl silyl group, tert- butyldiphenylsilyl group and A dimethylphenylsilyloxy group is mentioned.

The substituted silylthio group is one, two, or three substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, an alkylthio group, an arylthio group, an arylalkylthio group, and a monovalent heterocyclic thio group. A substituted silylthio group is meant. The substituent may have a secondary substituent. The carbon atom number of the substituted silylthio group is usually 1 to 60, preferably 3 to 48, not including the carbon atom number of the secondary substituent. Examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, tri-isopropylsilylthio group, dimethyl-isopropylsilylthio group, diethyl-isopropylsilylthio group, tert-butyldimethylsilylthio group. Group, pentyldimethylsilylthio group, hexyldimethylsilylthio group, heptyldimethylsilylthio group, octyldimethylsilylthio group, 2-ethylhexyl-dimethylsilylthio group, nonyldimethylsilylthio group, decyldimethylsilylthio group, 3,7 - dimethyloctyl - dimethylsilylene group, a heteroarylthio group, dodecyl dimethylsilylene thio group, a phenyl -C ₁ -C ₁₂ alkylsilylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilylthio group, C ₁ -C ₁₂ Archi Phenyl -C ₁ -C ₁₂ alkylsilylthio group, a 1-naphthyl -C ₁ -C ₁₂ alkylsilylthio group, a 2-naphthyl -C ₁ -C ₁₂ alkylsilylthio group, a phenyl -C ₁ -C ₁₂ alkyl dimethylsilylene Examples include a ruthio group, a triphenylsilylthio group, a tri-p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

  The heterocyclic thio group means a group in which a hydrogen atom of a mercapto group is substituted with a monovalent aromatic heterocyclic group. Examples of the heterocyclic thio group include a heteroarylthio group (for example, a pyridylthio group, a pyridazinylthio group, a pyrimidylthio group, a pyrazinylthio group, and a triazinylthio group).

The substituted silylamino group is one, two or three selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, an alkylamino group, an arylamino group, an arylalkylamino group and a monovalent heterocyclic amino group. A silylamino group substituted with a substituent is meant. The substituent may have a secondary substituent. The number of carbon atoms of the substituted silylamino group is usually 1 to 60, preferably 3 to 48, not including the number of carbon atoms of the secondary substituent. Examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, tri-isopropylsilylamino group, dimethyl-isopropylsilylamino group, diethyl-isopropylsilylamino group, tert-butyldimethylsilylamino. Group, pentyldimethylsilylamino group, hexyldimethylsilylamino group, heptyldimethylsilylamino group, octyldimethylsilylamino group, 2-ethylhexyl-dimethylsilylamino group, nonyldimethylsilylamino group, decyldimethylsilylamino group, 3,7 - dimethyloctyl - dimethylsilyl group, dodecyl dimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkyl silyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ A Kill silyl amino 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 amino group , phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- xylyl silyl group, tribenzylsilyl group, diphenylmethylsilyl amino group, tert- butyldiphenylsilyl Oh amino group And a dimethylphenylsilylamino group.

  The acyl group means an unsubstituted acyl group and an acyl group substituted with a substituent such as a halogen atom. The carbon atom number of an acyl group is 1-20 normally without including the carbon atom number of a substituent, Preferably it is 2-18, More preferably, it is 2-16. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group.

  The acyloxy group means an unsubstituted acyloxy group and an acyloxy group substituted with a substituent such as a halogen atom. The carbon number of an acyloxy group is 1-20 normally without including the carbon atom number of a substituent, Preferably it is 2-18, More preferably, it is 2-16. Examples of the acyloxy group include formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, and pentafluorobenzoyloxy group.

The imine residue means a residue obtained by removing one hydrogen atom in the structure from an imine compound having a structure represented by at least one of the formula: H—N═C <and the formula: —N═CH—. To do. Examples of the structure include aldimine; ketimine; a compound in which a hydrogen atom bonded to a nitrogen atom in aldimine is substituted with a substituent such as an alkyl group, aryl group, arylalkyl group, arylalkenyl group, and arylalkynyl group. Is mentioned. The carbon atom number of an imine residue is 2-20 normally without including the carbon atom number of a substituent, Preferably it is 2-18, More preferably, it is 2-16. Examples of the imine residue include a general formula: —CR′═N—R ″ or a general formula: —N═C (R ″) ₂ (wherein R ′ represents a hydrogen atom, an alkyl group, an aryl group, Represents an arylalkyl group, an arylalkenyl group or an arylalkynyl group, and R ″ represents an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an arylalkynyl group. In the latter general formula, two R ′ 'May be the same or different from each other. Two R ″' s are bonded to each other to form a divalent group (for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group). And a group represented by the formula (1) may be formed together with the remaining atomic groups to form a ring.

（式中、Ｍｅはメチル基を表す。） Examples of the imine residue include groups represented by the following structural formulas.

(In the formula, Me represents a methyl group.)

  An amide group means a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid amide. In this specification, an acid amide is a primary or secondary amide in which the hydrogen atom of ammonia is substituted by one or two acyl groups (except for a secondary amide having a cyclic structure, ie, an acid imide). .) The amide group means an unsubstituted amide group and an amide group substituted with a substituent such as a halogen atom. The carbon atom number of an amide group is 2-20 normally without including the carbon atom number of a substituent, Preferably it is 2-18, More preferably, it is 2-16. Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, Examples include a ditrifluoroacetamide group and a dipentafluorobenzamide group.

（式中、Ｍｅはメチル基を表す。） The acid imide group means a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide. An acid imide group means an unsubstituted acid imide group and a substituted acid imide group. The carbon atom number of an acid imide group is 4-20 normally without including the carbon atom number of a substituent, Preferably it is 4-18, More preferably, it is 4-16. Examples of the acid imide group include the following groups.

(In the formula, Me represents a methyl group.)

  The carboxyl group is an unsubstituted carboxyl group and a carboxyl group substituted with a substituent such as an alkyl group, an aryl group, an arylalkyl group, and a monovalent aromatic heterocyclic group (hereinafter referred to as “substituted carboxyl group”). .) The substituent may have a secondary substituent. The carbon atom number of a substituted carboxyl group is 1-60 normally without including the carbon atom number of a secondary substituent, Preferably it is 2-48, More preferably, it is 2-45. Examples of the substituted carboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, and a pentyloxycarbonyl group. Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxy Carbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohe Sill oxycarbonyl group, perfluorooctyl group, phenoxycarbonyl group, and a naphthoxycarbonyl group and pyridyloxycarbonyl group.

  The divalent aromatic group means an atomic group formed by removing two hydrogen atoms from either an aromatic hydrocarbon or an aromatic heterocyclic compound. The divalent aromatic group includes an unsubstituted divalent aromatic group and a substituted divalent aromatic group. Examples of the divalent aromatic group include an arylene group and a divalent aromatic heterocyclic group.

  An arylene group means an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon. Arylene groups include those having an independent benzene ring or fused ring. An arylene group means an unsubstituted arylene group and a substituted arylene group. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 48, more preferably 6 to 30, and further preferably 6 to 18. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  The divalent aromatic heterocyclic group means an atomic group remaining after removing two hydrogen atoms directly bonded to an aromatic ring from an aromatic heterocyclic compound, and includes those having a condensed ring. Here, examples of the heterocyclic compound having aromaticity are the same as those described for the monovalent aromatic heterocyclic group. The divalent aromatic heterocyclic group means an unsubstituted divalent aromatic heterocyclic group and a divalent aromatic heterocyclic group substituted with a substituent such as an alkyl group.

<Polymer compound>
Since the polymer compound of the present invention can improve the film-forming property when the polymer compound is used in the production of a light emitting device and the light emitting efficiency and life of the resulting light emitting device, the number average molecular weight in terms of polystyrene is usually 2 × 10 ³ or more, preferably 2 × 10 ³ to 1 × 10 ⁸ , and preferably 1 × 10 ⁴ to 1 × 10 ⁶ . In the present specification, a compound having a polystyrene-equivalent number average molecular weight of 2 × 10 ³ or more is referred to as a polymer compound, and a compound having a polystyrene-equivalent number average molecular weight of less than 2 × 10 ³ is a low molecular compound. That's it. As long as the number average molecular weight in terms of polystyrene is 2 × 10 ³ or more, dendrimers and oligomers are also included in the polymer compound of the present invention.

The polymer compound of the present invention contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). First, the repeating unit represented by formula (1) will be described.

In formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryl Represents an oxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group, and at least one of R ¹ , R ² , R ³ , R ^4, and R ⁵ is other than a hydrogen atom Represents a group. R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other. Of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , adjacent groups may be bonded to form a ring.

In formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a group other than a hydrogen atom. At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is preferably a group containing an alkyl group. Examples of the group containing an alkyl group include the alkyl group itself and a group containing the alkyl group as a part thereof (for example, an alkoxy group; an alkylthio group; and a candidate for the above R ^{1 to} R ⁵ substituted with an alkyl group). Group). From the viewpoint of the lifetime of the light emitting device obtained using the polymer compound of the present invention, the group containing an alkyl group is preferably an alkyl group. Moreover, from the viewpoint of heat resistance of a light-emitting device obtained using the polymer compound of the present invention, the group containing an alkyl group is preferably an aryl group substituted with an alkyl group.

  The number of aliphatic carbon atoms constituting the alkyl group in the group containing the alkyl group is determined by the solubility in a solvent when the polymer compound of the present invention is used for the production of a light-emitting element and the lifetime of the light-emitting element obtained. Since it is compatible, it is preferably 6 or more, and more preferably 12 or more. In addition, since the lifetime and heat resistance of the light-emitting device obtained using the polymer compound of the present invention can be improved, the number of aliphatic carbon atoms is preferably 100 or less, more preferably 60 or less, More preferably, it is 30 or less. The number of aliphatic carbon atoms means the number of carbon atoms contained in the aliphatic skeleton portion of the target group.

Among them, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ in formula (1) is preferably an alkyl group having 6 or more carbon atoms, and has 12 or more carbon atoms. The alkyl group is more preferably.

Further, R ³ is more preferably an alkyl group having 12 or more carbon atoms. At least one of R ¹ and R ⁵ is preferably a hydrogen atom. At least one of R ² and R ⁴ is preferably an alkyl group, an aryl group, or an aryl group substituted with an alkyl group, and R ² and R ⁴ are more preferably an aryl group substituted with an alkyl group. preferable.

In formula (1), Ar ₁ and Ar ₂ 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, or an acyl group. , Acyloxy group, amide group, acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, It represents a divalent aromatic group which may have a substituent selected from the group consisting of an arylalkynyl group, a substituted carboxyl group, and a cyano group.

  Here, examples of the divalent aromatic group include an arylene group and a divalent aromatic heterocyclic group.

Examples of the arylene group represented by Ar ₁ and Ar ₂ include phenylene groups such as 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group; 2,7-biphenylylene group and 3, Biphenylylene groups such as 6-biphenylylene group; naphthalene-diyl groups such as 1,4-naphthalene-diyl group, 1,5-naphthalene-diyl group and 2,6-naphthalene-diyl group; 1,4-anthracene-diyl group Anthracene-diyl group such as 1,5-anthracenediyl group, 2,6-anthracene-diyl group and 9,10-anthracene-diyl group; phenanthrene-diyl group such as 2,7-phenanthrene-diyl group; Naphthacene diyl groups such as 7-naphthacene-diyl group, 2,8-naphthacene-diyl group and 5,12-naphthacene-diyl group; Fluorene-diyl groups such as 7-fluorene-diyl group and 3,6-fluorene-diyl group; 1,6-pyrene-diyl group, 1,8-pyrene-diyl group, 2,7-pyrene-diyl group and 4 , 9-pyrene-diyl groups, etc .; perylene-diyl groups such as 3,9-perylene-diyl groups and 3,10-perylene-diyl groups; biphenyl-diyl groups; terphenyl-diyl groups; benzofluorene- And dibenzofluorene-diyl group, preferably phenylene group or fluorenediyl group.

The number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar ₁ and Ar ₂ is usually 4 to 60, preferably 4 to 30 and more preferably not including the number of carbon atoms of the substituent. Is 6-12. Examples of the divalent aromatic heterocyclic group include pyridine-diyl groups such as 2,5-pyridine-diyl group and 2,6-pyridine-diyl group; and thiophenes such as 2,5-thiophene-diyl group. Diyl group; furan-diyl group such as 2,5-furan-diyl group; quinoline-diyl group such as 2,6-quinoline-diyl group; 1,4-isoquinoline-diyl group and 1,5-isoquinoline diyl group Isoquinoline-diyl group; quinoxaline-diyl group such as 5,8-quinoxaline-diyl group; benzo [1,2,5] thiadiazole-diyl such as 4,7-benzo [1,2,5] thiadiazole-diyl group A benzothiazole-diyl group such as a 4,7-benzothiazole-diyl group; a carbazol such as a 2,7-carbazole-diyl group and a 3,6-carbazole-diyl group A phenoxazine-diyl group such as a 3,7-phenoxazine-diyl group; a phenothiazine-diyl group such as a 3,7-phenothiazine-diyl group; and a dibenzosilole such as a 2,7-dibenzosilol-diyl group -A diyl group is mentioned, Preferably, it is a pyridine-diyl group, a quinoline-diyl group, or a quinoxaline-diyl group.

At least one of Ar ₁ and Ar ₂ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, Acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, And an arylene group or a divalent aromatic heterocyclic group which may have a substituent selected from the group consisting of cyano groups.

Examples of the arylene group represented by Ar ₁ and Ar ₂ include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (for example, the following formulas 4 to 13), and a biphenyl-diyl group (for example, the following formula 20-25), terphenyl-diyl groups (for example, the following formulas 26 to 28), phenanthrene-diyl groups (for example, the following formula 29), biphenylylene groups having a condensed ring (for example, the following formulas 31 and 32), indene- Diyl group (for example, formulas 34 and 35), fluorene-diyl group (for example, the following formulas 36 to 38), benzofluorene-diyl group (for example, the following formulas A-1 to A-3) and dibenzofluorene-diyl group ( For example, the following formula A-4) is mentioned.

（式中、Ｒは、水素原子又は置換基を表す。複数個のＲは、互いに同一であっても異なっていてもよい。）

(In the formula, R represents a hydrogen atom or a substituent. A plurality of R may be the same or different from each other.)

  In the above formulas 1 to 29, 31 to 38 and A-1 to A-4, examples of the substituent represented by R include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, and an arylthio group. , Arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent aromatic Examples include a heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group, a substituted silyloxy group, a substituted silylthio group, a heteroaryloxy group, and a heteroarylthio group. The hydrogen atom contained in these substituents may be substituted with a fluorine atom. Since the solubility of the polymer compound of the present invention in a solvent and the device characteristics of the resulting light-emitting device can be improved, at least one of a plurality of R is a group other than a hydrogen atom (that is, the above substituent). It is preferable that The substituent represented by R is preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group or a monovalent aromatic heterocyclic group, More preferably, it is an alkyl group, an alkoxy group or an aryl group.

Examples of the divalent aromatic heterocyclic group represented by Ar ₁ and Ar ₂ include a pyridine-diyl group (for example, the following formulas 45 to 50), a diazaphenylene group (for example, the following formulas 51 to 54), Quinolinediyl groups (for example, the following formulas 55 to 69), quinoxaline diyl groups (for example, the following formulas 70 to 74), bipyridyldiyl groups (for example, the following formulas 79 to 81), phenanthroline diyl groups (for example, the following formulas 82 to 84) A divalent aromatic heterocyclic group containing a nitrogen atom which is a hetero atom, such as a group having a carbazole structure (for example, the following formulas 85 to 87); an oxygen atom, a silicon atom, a nitrogen atom, a sulfur atom and a selenium atom 5-membered aromatic heterocyclic groups containing heteroatoms such as (for example, the following formulas 88 to 92); and 5-membered condensed aromatic heterocyclic groups containing heteroatoms such as oxygen atoms, silicon atoms, nitrogen atoms and selenium atoms (For example, the following formulas 93 to 103).

（式中、Ｒは、水素原子又は置換基を表す。複数個のＲは、互いに同一であっても異なっていてもよい。）

(In the formula, R represents a hydrogen atom or a substituent. A plurality of R may be the same or different from each other.)

  In the above formulas 45 to 74 and 79 to 103, examples of the substituent represented by R are the same as the examples of the substituent represented by R in the formula 1. In addition, since the solubility of the polymer compound of the present invention in a solvent and the device characteristics of the obtained light-emitting device can be improved, at least one of a plurality of R is a group other than a hydrogen atom (that is, the above-described substitution). Group).

式（３）及び（４）において、Ｒ’は水素原子又はアルキル基を示す。 At least one of Ar ₁ and Ar _2, is preferably a divalent aromatic group represented by the following formula (3) or (4), Ar ₁ and Ar ₂ are, each independently, the following equation (3 Or a divalent aromatic group represented by (4). Among the divalent aromatic groups represented by the following formula (3) or (4), an unsubstituted divalent aromatic group represented by the following formula (3) is more preferable.

In the formulas (3) and (4), R ′ represents a hydrogen atom or an alkyl group.

（式中、Ｍｅはメチル基を表す。） Preferable examples of the divalent aromatic group represented by the formula (3) include divalent groups represented by the following formulas 3-1 to 3-15.

(In the formula, Me represents a methyl group.)

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） Preferable examples of the divalent aromatic group represented by the formula (4) include divalent groups represented by the following formulas 4-1 to 4-14.

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

  The repeating unit represented by formula (1) may be contained alone or in combination of two or more in the polymer compound of the present invention.

  Preferable examples of the repeating unit represented by the formula (1) include repeating units represented by the following formulas 1-1 to 1-52.

（式中、Ａｒ₁及びＡｒ₂は、前記と同じ意味を表す。）

(In the formula, Ar ₁ and Ar ₂ represent the same meaning as described above.)

Then, the repeating unit represented by Formula (2) contained in the high molecular compound of this invention is demonstrated.

In formula (2), Ar ₃ represents an aryl group or a monovalent aromatic heterocyclic group. Ar ₃ is preferably an aryl group because the lifetime of the light-emitting device obtained using the polymer compound of the present invention can be improved.

In the formula (2), Ar ₄ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, Amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, An arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group is represented. Ar ₄ is preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and more preferably a hydrogen atom, an alkyl group or an aryl group.

In the formula (2), R ⁶ 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 acyl group, an acyloxy group, an amide group, Acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group Represents an arylalkynyl group, a substituted carboxyl group, or a cyano group. When a plurality of R ⁶ are present, they may be the same or different.

  In formula (2), a represents 0 or 1. Two a's may be the same or different.

（式（２０）中、Ａｒ₃及びＡｒ₄の定義は、式（２）のＡｒ₃及びＡｒ₄の定義と同じである。） Among the repeating units represented by the formula (2), a repeating unit represented by the following formula (20) is preferable.

(Defined in the formula (20), Ar ₃ and Ar ₄ are as defined for Ar ₃ and Ar ₄ of formula (2).)

In Formula (20), Ar ₄ is preferably a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and more preferably a hydrogen atom, an alkyl group, or an aryl group.

In the formula (20), when Ar ₃ or Ar ₄ is an aryl group, the solubility of the polymer compound of the present invention in a solvent can be improved. Therefore, the aryl group has a substituent having 2 or more carbon atoms. It is preferable to have.

（式中、ｎ−Ｂｕはｎ−ブチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） Examples of the repeating unit represented by the formula (20) include repeating units represented by the following formulas 1e to 8e.

(In the formula, n-Bu represents an n-butyl group, and t-Bu represents a tert-butyl group.)

  The repeating unit represented by the formula (2) may be contained alone or in combination of two or more in the polymer compound of the present invention.

  The ratio of the repeating unit represented by the formula (1) to the total repeating units constituting the polymer compound of the present invention is preferably larger from the viewpoint of electron transportability (that is, to improve electron transportability), From the viewpoint of the lifetime of the light-emitting element obtained when the polymer compound is used for production of a light-emitting element, a smaller one is preferable. Therefore, the ratio is preferably 10 mol% or more and 30 mol% or less, more preferably 10 mol% or more and 20 mol% or less, and particularly preferably 10 mol% or more and 15 mol% or less. On the other hand, the ratio of the repeating unit represented by the formula (2) with respect to all repeating units constituting the polymer compound of the present invention is the thermal stability and when the polymer compound is used for the production of a light emitting device. Since the lifetime of the light-emitting element obtained can be improved, it is preferably 20 mol% or more. The upper limit of the ratio is not particularly limited, but is usually 75 mol% or less. The total ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) with respect to all repeating units constituting the polymer compound of the present invention is determined using the polymer compound of the present invention. Since the electron transport property and lifetime of the light-emitting element to be obtained can be improved, the content is preferably 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more.

The polymer compound of the present invention may further contain a repeating unit represented by the following formula (5).

In formula (5), Ar ₅ represents an arylene group or a divalent aromatic heterocyclic group. Examples of the arylene group in Ar ₅ are the same as the arylene groups described above for Ar ₁ and Ar ₂ . Examples of the divalent aromatic heterocyclic group for Ar ₅ are the same as the divalent aromatic heterocyclic group described above for Ar ₁ and Ar ₂ .

As a repeating unit represented by Formula (5), the repeating unit represented by following formula (6) is illustrated.

In the formula (6), Ar ₆ and Ar ₇ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, or an acyloxy group. Amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, A substituted carboxyl group or a cyano group is represented. R ⁷ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue Group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted Represents a carboxyl group or a cyano group. It is preferable that at least one of Ar ₆ and Ar ₇ is a hydrogen atom or an alkyl group, since the solubility of the polymer compound of the present invention in a solvent and the lifetime of the resulting light-emitting element can be improved.

In formula (6), a represents 0 or 1. Two a's may be the same or different. When a plurality of R ⁷ are present, they may be the same or different.

  Examples of the repeating unit represented by the formula (5) further include a repeating unit represented by the following formula (7) and a repeating unit represented by the following formula (8).

In formula (7), R ⁸ and R ⁹ 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, or an acyl group. , Acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, hetero An arylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group is represented. R ⁸ and R ⁹ may be the same or different from each other.

In formula (7), R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, or a monovalent aromatic, from the viewpoint of the balance between the heat resistance of the polymer compound of the present invention and the solubility in an organic solvent. It is preferably a heterocyclic group, an alkoxy group, an aryloxy group, an arylalkyl group or a substituted amino group, more preferably an alkyl group or an arylalkyl group, still more preferably an alkyl group, a propyl group, an isopropyl group Group, butyl group, sec-butyl group, isobutyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclohexylmethyl group, nonyl group, decyl group, 3,7- A dimethyloctyl group or a dodecyl group is particularly preferable. R ⁸ and R ⁹ may be the same or different from each other, but are preferably the same.

In the formula (8), R ¹⁰ and R ¹¹ 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, or an acyl group. , Acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, hetero An arylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group is represented. R ¹⁰ and R ¹¹ may be the same or different from each other.

In formula (8), at least one of R ¹⁰ and R ¹¹ is an alkyl group, an aryl group, a monovalent aromatic complex from the viewpoint of the balance between the heat resistance of the polymer compound of the present invention and the solubility in an organic solvent. It is preferably a cyclic group, an arylalkyl group or an amino group, more preferably an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an amino group, an alkyl group, an aryl group or a monovalent aromatic group. It is more preferably a heterocyclic group, and particularly preferably an alkyl group or an aryl group. R ¹⁰ and R ¹¹ may be the same or different from each other.

  In formula (8), b represents 0 or 1.

  Examples of the repeating unit represented by the formula (7) include repeating units represented by the following formulas 7-001 to 7-019 and 7-101 to 7-105.

（式中、Ｍｅはメチル基を表す。）

(In the formula, Me represents a methyl group.)

  Examples of the repeating unit represented by the formula (8) include repeating units represented by the following formulas 8-001 to 8-017, 8-101 to 8-113, and 8-201 to 8-208.

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表し、ｉ−Ｐｒはイソプロピル基を表し、ｎ−Ｂｕはｎ−ブチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, n-Bu represents an n-butyl group, and t-Bu represents a tert-butyl group.)

  The repeating unit represented by formula (5) may be contained alone or in combination of two or more in the polymer compound of the present invention. The polymer compound of the present invention is represented by the repeating unit represented by the formula (5), the repeating unit represented by the formula (6), the repeating unit represented by the formula (7), and the formula (8). One type of repeating unit selected from repeating units or a combination of two or more types of repeating units may be included. Moreover, as a repeating unit represented by Formula (5), the repeating unit represented by Formula (6), the repeating unit represented by Formula (7), and the repeating unit represented by Formula (8) are each Two or more types may be combined and contained in the polymer compound of the present invention.

  The proportion of the repeating unit represented by the formula (5) with respect to all repeating units constituting the polymer compound of the present invention is usually 0 mol% or more and 80 mol% or less, and 5 mol% or more and 70 mol% or less. It is preferably 10 mol% or more and 60 mol% or less, more preferably 10 mol% or more and 50 mol% or less. The total ratio of the repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the repeating unit represented by the formula (5) with respect to all the repeating units is 80 mol% or more. Preferably, it is 85 mol% or more, more preferably 90 mol% or more.

The polymer compound of the present invention preferably further contains a repeating unit represented by the following formula (9).

In formula (9), Ar ₈ , Ar ₉ , Ar ₁₀ and Ar ₁₄ each independently represent an arylene group or a divalent aromatic heterocyclic group.

In formula (9), Ar ₁₁ , Ar ₁₂ and Ar ₁₃ each independently represent an aryl group or a monovalent aromatic heterocyclic group.

In formula (9), Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ may each independently have a substituent.

  In formula (9), x and y are each independently 0 or 1. However, the value of x + y is 0 or 1.

In the formula (9), when Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , Ar ₁₃ or Ar ₁₄ has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, Aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent aromatic heterocyclic group, carboxyl group, nitro group And an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, more preferably an alkyl group, An alkoxy group or an aryl group.

In the formula (9), examples of the arylene group represented by Ar ₈ , Ar ₉ , Ar ₁₀ and Ar ₁₄ include a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-naphthalenediyl group, Examples include 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12-naphthacenediyl group, and 2,7-fluorenediyl group.

In the formula (9), the number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar ₈ , Ar ₉ , Ar ₁₀ and Ar ₁₄ is usually 4 to 4 without including the number of carbon atoms of the substituent. 60, preferably 4-20, more preferably 4-9. Examples of the divalent aromatic heterocyclic group include 2,5-thiophenediyl group, N-methyl-2,5-pyrrolediyl group, 2,5-furandiyl group, and benzo [2,1,3] thiadiazole. Examples include -4,7-diyl, 3,7-phenoxazinediyl group and 3,6-carbazolediyl group.

In formula (9), examples of Ar ₈ , Ar ₉ , Ar ₁₀ and Ar ₁₄ include divalent groups represented by the following formulas 1b to 3b.

In formula (9), Ar ₈ and Ar ₁₀ are preferably arylene groups, more preferably 1,3-phenylene groups, 1,4-phenylene groups, 1,4-naphthalenediyl groups, 2,6 -A naphthalenediyl group or a group represented by the above formula 1b, more preferably a 1,4-phenylene group or a 1,4-naphthalenediyl group, and particularly preferably a 1,4-phenylene group.

In the formula (9), Ar ₉ is preferably 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthalenediyl group, 2,7-fluorenediyl group, benzo [2,1, 3] a thiadiazole-4,7-diyl group, a 3,7-phenoxazinediyl group, or a group represented by the formula 1b, preferably a 1,4-phenylene group, a 1,4-naphthalenediyl group, A 2,7-fluorenediyl group or a group represented by the formula 1b, more preferably a 1,4-phenylene group or a group represented by the formula 1b.

In the formula (9), Ar ₁₁ , Ar ₁₂ and Ar ₁₃ are each independently preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, more preferably an alkyl group or an aryl group. Group, and more preferably an aryl group.

Preferable examples of the repeating unit represented by the formula (9) include the repeating units represented by the following formulas 1c to 4c. In formulas 1c to 4c, R ²¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, or a substituted amino group. , A halogen atom, an acyl group, an acyloxy group, a monovalent aromatic heterocyclic group, a carboxyl group, a nitro group, or a cyano group. A plurality of R ²¹ may be the same or different.

Among the repeating units represented by the formula (9), a repeating unit represented by the following formula (10) is preferable.

In formula (10), R ³¹ , R ⁴¹ and R ⁵¹ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a phenylalkyl group having 7 to 26 carbon atoms. , Phenyl alkoxy group having 7 to 26 carbon atoms, phenyl group, phenoxy group, alkylphenyl group having 7 to 26 carbon atoms, alkoxyphenyl group having 7 to 26 carbon atoms, alkylcarbonyl group having 2 to 21 carbon atoms Represents a formyl group, an alkoxycarbonyl group having 2 to 21 carbon atoms, or a carboxyl group. Alternatively, R ³¹ and R ⁴¹ may be combined to form a ring instead of representing the above group. When a plurality of R ³¹ are present, they may be the same or different. When a plurality of R ⁴¹ are present, they may be the same or different, and a plurality of R ⁵¹ are present. They may be the same or different.

  In formula (10), s and t are each independently an integer of 0 to 4. u is 1 or 2. v is an integer of 0-5.

In the formula (10), when R ³¹ and R ⁴¹ are combined to form a ring, examples of the ring include a C _{5 to} C ₁₄ heterocyclic ring optionally having a substituent. . Examples of the heterocyclic ring include a morpholine ring, a thiomorpholine ring, a pyrrole ring, a piperidine ring, and a piperazine ring.

Examples of the repeating unit represented by the formula (10) include repeating units represented by the following formulas 1d to 10d.

  The ratio of the repeating unit represented by the formula (5) to all repeating units constituting the polymer compound of the present invention is usually 0 mol% or more and 20 mol% or less, and 0 mol% or more and 10 mol% or less. Preferably there is. The repeating unit represented by Formula (1), the repeating unit represented by Formula (2), the repeating unit represented by Formula (5), and the repeating unit represented by Formula (9) with respect to all the repeating units. Is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and 100 mol% (excluding inevitable impurities). It is particularly preferred.

  Hereafter, the preferable manufacturing method of the high molecular compound of this invention is demonstrated. The polymer compound of the present invention can be produced, for example, by condensation polymerization.

Examples of the condensation polymerization method include polymerization by the Suzuki reaction (Chem. Rev., 95, 2457 (1995)), polymerization by the Grignard reaction (Kyoritsu Shuppan, Polymer Functional Material Series Volume 2, Polymer Synthesis and Reaction (2), pages 432-433), Method of Polymerization by Yamamoto Coupling Reaction (Progressive Polymer Science (Prog. Polym. Sci.), Volume 17, 1153 1205, 1992), a method of polymerizing with a zerovalent nickel complex, a method of polymerizing with an oxidizing agent such as FeCl _3, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group A method of polymerizing by a Suzuki coupling reaction, Gr A method of polymerizing by an ignition reaction and a method of polymerizing by a zerovalent nickel complex are preferable from the viewpoint of structure control.

The polymer compound can be produced, for example, by subjecting a compound represented by the formula: Y ³ —W ¹ —Y ⁴ and a compound represented by the formula: Y ⁵ —W ² —Y ⁶ to condensation polymerization. . In the formula, W ¹ and W ² each independently represent a repeating unit represented by the formula (1), the formula (2), the formula (5), or the formula (9). Y ³ , Y ⁴ , Y ⁵ and Y ⁶ each independently represent a polymerization reactive group. When the polymer compound of the present invention has a repeating unit other than those described above, it may be subjected to condensation polymerization in the presence of a compound having two polymerizable reactive groups that become a repeating unit other than those described above.

Examples of the polymerization reactive group include a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid ester residue, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a monohalogenated methyl group, and boric acid. Residues (—B (OH) ₂ ), formyl group, cyano group, vinyl group and the like can be mentioned.

  Examples of the halogen atom that is the polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl sulfonate group that is the polymerization reactive group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.

  Examples of the aryl sulfonate group that is the polymerization reactive group include a benzene sulfonate group and a p-toluene sulfonate group.

  Examples of the arylalkyl sulfonate group that is the polymerization reactive group include a benzyl sulfonate group.

（式中、Ｍｅはメチル基、Ｅｔはエチル基を表す。） Examples of the boric acid ester residue that is the polymerization reactive group include a group 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 that is the polymerization reactive group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X 0-}} , -CH 2 S + Ph 2 X 0-
(In the formula, X ⁰ represents a halogen atom and Ph represents a phenyl group.)

Examples of the phosphonium methyl group that is the polymerization reactive group include groups represented by the following formulas.
-CH ₂ P ⁺ Ph ₃ X ^0-
(In the formula, X ⁰ represents a halogen atom.)

Examples of the phosphonate methyl group that is the polymerization reactive group include groups represented by the following formulas.
-CH ₂ PO (OR ″) ₂
(In the formula, R ″ represents an alkyl group or an aryl group.)

  Examples of the monohalogenated methyl group that is the polymerization reactive group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

  The polymerization-reactive group is, for example, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, or the like when using a zerovalent nickel complex such as a Yamamoto coupling reaction, and a Suzuki coupling reaction or the like. When a nickel catalyst or a palladium catalyst is used, an alkyl sulfonate group, a halogen atom, a boric acid ester residue, a boric acid residue, or the like.

  As the method for producing the polymer compound of the present invention, since the synthesis of the polymer compound is easy, the polymerization reactive group includes a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid residue, and A total (J) of the number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups selected from one or more groups consisting of borate ester residues and possessed by all raw material compounds; , The ratio of the total number of moles of boric acid residues and boric acid ester residues (K) is substantially 1 (usually K / J is 0.7 to 1.2), and the nickel catalyst or palladium catalyst A production method in which condensation polymerization is performed is preferred.

As a combination of the compounds as the raw materials (that is, a compound represented by the formula: Y ³ -W ¹ -Y ⁴ and a compound represented by the formula: Y ⁵ -W ² -Y ⁶ ), a dihalogenated compound, bis ( Examples thereof include a combination of an alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound with a diboric acid compound or a diboric acid ester compound.

  In the case of producing a polymer compound with a controlled sequence, examples of the compound include a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, and an aryl sulfonate- A boric acid compound, an aryl sulfonate-boric acid ester compound, an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid ester compound, or the like may be used.

（式中、Ｒ^ａ、Ｒ^ｆ及びＲ^ｇは、それぞれ独立に、水素原子又はアルキル基を表し、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ及びＲ^ｅは、それぞれ独立に、アルキル基、又はアルキル基で置換されたアリール基を表す。Ａｒ¹及びＡｒ²は、それぞれ、式（１）中のＡｒ₁及びＡｒ₂と同じ意味を示す。Ｘは、ハロゲン原子、ホウ酸エステル残基、ホウ酸残基、下記式（ａ−１）で表される基、下記式（ａ−２）で表される基、下記式（ａ−３）で表される基、又は下記式（ａ−４）で表される基を表す。２個存在するＸは同一であっても異なっていてもよい。）

（式中、Ｒ^Ｔは、アルキル基又はアリール基を表し、置換基を有していてもよい。Ｘ^Ａは、ハロゲン原子を表す。なお、式（ａ−４）中、３個存在するＲ^Ｔは同一であっても異なっていてもよい。） Here, among the compounds represented by the formula: Y ³ —W ¹ —Y ⁴ , the compound that yields the repeating unit represented by the formula (1) is preferably a compound represented by the following formula (i).

(In the formula, R ^a , R ^f and R ^g each independently represent a hydrogen atom or an alkyl group, and R ^b , R ^c , R ^d and R ^e are each independently an alkyl group or an alkyl group. .Ar ¹ and Ar ² represents a substituted aryl group, respectively, .X indicating the same meaning as Ar ₁ and Ar ₂ in the formula (1) is a halogen atom, a boric acid ester residue, a boric acid residue A group represented by the following formula (a-1), a group represented by the following formula (a-2), a group represented by the following formula (a-3), or a group represented by the following formula (a-4). The two X's may be the same or different.)

(In the formula, ^RT represents an alkyl group or an aryl group, and may have a substituent. X ^A represents a halogen atom. In the formula (a-4), three Rs exist. ^T may be the same or different.)

  It is preferable that the organic solvent used for the condensation polymerization is sufficiently subjected to deoxygenation treatment and dehydration treatment in order to suppress side reactions. However, this is not the case in the case of reaction in a two-phase system with water such as Suzuki coupling reaction.

  Examples of the organic solvent used in the condensation polymerization 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, Halogenated saturated hydrocarbons such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, isopropanol Alcohols such as butanol and tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether and methyl-te Ethers such as t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, etc., amines such as trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, pyridine, N, N-dimethylformamide, N, N— Examples include amides such as dimethylacetamide, N, N-diethylacetamide, and N-methylmorpholine oxide, ethers are preferable, and tetrahydrofuran and diethyl ether are particularly preferable. These organic solvents may be used alone or in combination of two or more.

  In the condensation polymerization, an alkali and / or a catalyst may be added to promote the reaction. The alkali and catalyst are preferably those that are sufficiently dissolved in the solvent used in the reaction. To mix the alkali and / 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, add the alkali and / or catalyst solution to the alkali and / or catalyst solution. What is necessary is just to add a reaction liquid slowly.

  When the polymer compound of the present invention is used for the production of a light-emitting device or the like, its purity affects the performance of the light-emitting device such as the light-emitting properties. Polymerization is preferred after purification by the method. Further, after the polymerization, it is preferable to perform a purification treatment such as purification by reprecipitation and fractionation by chromatography.

<Composition>
The composition of the present invention contains the polymer compound of the present invention and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.

  Examples of the light emitting material include a low molecular fluorescent light emitting material, a light emitting organometallic complex compound, and a polymer fluorescent light emitting material.

  In general, when a composition obtained by doping the above-described polymer compound with a light-emitting organometallic complex compound as a dopant is used as a light-emitting material of a light-emitting element, the host material preferably has a high minimum triplet excitation energy. Therefore, in the composition of the present invention, when a light-emitting organometallic complex compound that emits red light having a light emission peak wavelength of 600 nm or more is used as the light-emitting material, the polymer compound of the present invention contained in the composition contains It is preferable that the repeating unit represented by the formula (5) further includes a repeating unit represented by the formula (6). On the other hand, in the composition of the present invention, when a light-emitting organometallic complex compound that emits green light having an emission peak wavelength of 500 nm or more and less than 600 nm is used as the light-emitting material, the polymer compound of the present invention contained in the composition is The repeating unit represented by the formula (5) preferably further includes a repeating unit represented by the formula (7) and / or a repeating unit represented by the formula (8).

  The emission peak wavelength of the luminescent metal complex compound is evaluated by, for example, dissolving the compound in an organic solvent such as xylene, toluene and chloroform, preparing a diluted solution, and measuring the PL spectrum of the diluted solution. obtain.

  Examples of the light-emitting organometallic complex compound include known compounds such as triplet light-emitting complexes, compounds conventionally used as light-emitting materials for low-molecular organic EL devices, and 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. MoI. 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, Inorg. Chem. , (2003), 42, 8609, Inorg. Chem. , (2004), 43, 6513, Journal of the SID 11/1, 161 (2003), WO2002 / 066552, WO2004 / 020504, WO2004 / 020448, and the like. Since a light-emitting element with high luminous efficiency can be obtained, the light-emitting organometallic complex compound includes a square of the orbital coefficient of the outermost shell d orbit of the central metal in the highest occupied molecular orbital (HOMO) of the metal complex. Is preferably a compound having a ratio of 1/3 or more to the sum of squares of all atomic orbital coefficients. Examples of the compound include ortho-metalated complexes in which the central metal is a transition metal belonging to the sixth period of the periodic table.

  The central metal of the light-emitting organometallic complex compound has, for example, an atomic number of 50 or more, can exhibit spin-orbit interaction with the complex, and causes an intersystem crossing between the singlet state and the triplet state. The metal obtained is mentioned. The central metal is preferably gold, platinum, iridium, osmium, rhenium, tungsten, europium, terbium, thulium, dysprosium, samarium, praseodymium, gadolinium or ytterbium, more preferably gold, platinum, iridium, It is osmium, rhenium or tungsten, more preferably gold, platinum, iridium, osmium or rhenium, particularly preferably gold, platinum, iridium or rhenium, particularly preferably platinum or iridium.

  Examples of the ligand of the light-emitting organometallic complex compound include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, and 2-phenyl-pyridine and derivatives thereof.

  Since the ligand of the light-emitting organometallic complex compound can improve solubility in a solvent, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a substituent Having a substituent selected from the group consisting of an aryl group which may have a substituent and a heteroaryl group which may have a substituent (hereinafter referred to as a “ligand substituent”). Is more preferable. The total number of atoms other than hydrogen atoms contained in the ligand substituent is preferably 3 or more, more preferably 5 or more, further preferably 7 or more, and 10 or more. It is particularly preferred. Moreover, it is preferable that a ligand substituent exists for every ligand, The kind may be the same for each ligand, or may differ.

（式中、Ｒ^1ｐ、Ｒ^2ｐ、Ｒ^3ｐ、Ｒ^4ｐ、Ｒ^5ｐ、Ｒ^6ｐ、Ｒ^7ｐ及びＲ^8ｐは、それぞれ独立に、水素原子、又はアリール基を表す。
下記式

で表される部分は、モノアニオン性の２座配位子を表す。Ｒ^x及びＲ^yは、中心金属Ｉｒに配位する原子であり、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表す。ｍは１〜３の整数を表し、ｎは０〜２の整数を表す。） As the light-emitting organometallic complex compound having a light emission peak wavelength of 500 nm or more and less than 600 nm, an organometallic complex compound having a structure represented by the following formula (11) is preferably exemplified.

(In the formula, R ^1p , R ^2p , R ^3p , R ^4p , R ^5p , R ^6p , R ^7p and R ^8p each independently represents a hydrogen atom or an aryl group.
Following formula

The portion represented by represents a monoanionic bidentate ligand. R ^x and R ^y are atoms coordinated to the central metal Ir, and each independently represents a carbon atom, an oxygen atom, or a nitrogen atom. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. )

（式中、＊は配位原子の位置を示す。） As the monoanionic bidentate ligand, a monoanionic property in which the arc portion connecting R ^x and R ^y in the formula (11) is a divalent group having 3 to 30 atoms other than hydrogen atoms The bidentate ligand is preferably, for example, a ligand having a structure represented by the following formula.

(In the formula, * indicates the position of the coordination atom.)

  In the formula (11), the ligand shown on the left side and the ligand shown on the right side may each independently have the ligand substituent, and the solubility in a solvent can be improved. It preferably has the ligand substituent.

（式中、ｔＢｕはｔｅｒｔ−ブチル基を表し、Ｒは水素原子又は置換基を表す。複数個存在するＲは、同一であっても異なっていてもよい。） Among these, the following compounds are preferable as the light-emitting organometallic complex compound having an emission peak wavelength of 500 nm or more and less than 600 nm.

(Wherein tBu represents a tert-butyl group, R represents a hydrogen atom or a substituent. A plurality of R may be the same or different.)

As the luminescent organometallic complex compound exhibiting a red luminescent color having an emission peak wavelength of 600 nm or more, a compound having a structure represented by the following formula (12), (12-1) or (12-2) is preferable. Illustrated.

In formulas (12), (12-1) and (12-2), R ^9p , R ^10p , R ^11p , R ^12p , R ^13p , R ^14p , R ^15p , R ^16p , R ^17p , R ^18p , R ^19p , R ^20p , R ^21p , R ^22p , R ^23p , R ^24p and R ^25p are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl Alkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent Represents an aromatic heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group. These groups may have a substituent. m represents an integer of 0 to 3.
The part represented by the following formula represents the same meaning as described above in formula (11).

In formulas (12) and (12-1), Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ each independently represent —C (R ^* ) ═ or a nitrogen atom. R ^* represents a hydrogen atom or a substituent.

In the formulas (12), (12-1) and (12-2), R ^9p , R ^10p , R ^11p , R ^12p , R ^13p , R ^14p , R ^15p , R ^16p , R ^17p , R ^18p , R ^19p , R ^20p , R ^21p , R ^22p , R ^23p , R ^24p , R ^25p , Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are the same or different when there are a plurality of each. May be. However, at least two of Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are nitrogen atoms.

（式中、ｔＢｕはｔｅｒｔ−ブチル基を表し、Ｍｅはメチル基を表す。） Among these, the following compounds are preferable as the light-emitting organometallic complex compound having a light emission peak wavelength of 600 nm or more.

(In the formula, tBu represents a tert-butyl group, and Me represents a methyl group.)

  The said luminescent organometallic complex compound may be used individually by 1 type, or may use 2 or more types together.

  The low-molecular fluorescent material is usually a material having a maximum peak of fluorescence emission in a wavelength range of 400 nm or more and 700 nm or less, and its molecular weight is usually less than 3000, preferably 100 to 2000, more preferably 100-1000.

  The low molecular fluorescent material may be any material known as a light emitting material for an organic EL element. Examples of the low molecular fluorescent material include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, quinacridone derivatives, xanthene dyes, coumarin dyes, cyanine dyes, triphenylamine derivatives, oxadiazole derivatives, pyrazolo derivatives. Dye-based materials such as quinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine ring compounds, and oligothiophene derivatives; aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, The central metal such as benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, and europium complex has Al, Zn, Be, or a rare earth metal (eg, Tb, Eu, Dy, etc.), etc. Oxadiazole child, thiadiazole, phenylpyridine, phenylbenzimidazole, or a metal complex-based material having a quinoline structure and the like.

  Examples of the polymeric fluorescent material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and dye-based materials exemplified in the low molecular fluorescent materials. And a chromophore containing.

  In the composition of the present invention, the ratio of “at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material” to the polymer compound is 100 parts by weight of the polymer compound. “At least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material” is usually set to be 0.01 to 400 parts by weight for each material, preferably It is set to be 0.05 to 150 parts by weight.

  The said hole transport material should just be a well-known material as a hole transport material of an organic EL element. Examples of the hole transport material include polyvinyl carbazole and derivatives thereof; polysilane and derivatives thereof; polysiloxane derivatives having an aromatic amine in the side chain or main chain; pyrazoline derivatives; arylamine derivatives; stilbene derivatives; Polythiophene and derivatives thereof; polyarylamine and derivatives thereof; polypyrrole and derivatives thereof; poly (p-phenylene vinylene) and derivatives thereof; poly (2,5-thienylene vinylene) and derivatives thereof. The hole transport material may have an arylene group or a divalent aromatic heterocyclic group as a copolymerization component (structural unit).

  The electron transport material may be any material known as an electron transport material for organic EL elements. Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, Examples include diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, triaryltriazine and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof. The electron transport material may have an arylene group or a divalent aromatic heterocyclic group as a copolymerization component (structural unit).

  In addition, in the composition of this invention, each component may be used individually by 1 type, or may use 2 or more types together.

<Liquid composition>
The liquid composition of the present invention comprises the polymer compound of the present invention and a solvent or dispersion medium.

The solvent and dispersion medium used in the liquid composition of the present invention can be selected from known solvents that can uniformly dissolve or disperse the components of the thin film and are stable. Examples of such a solvent include the following.
Aromatic hydrocarbon solvents: toluene, xylene (each isomer or a mixture thereof), 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, mesitylene (1,3,5-trimethylbenzene), Ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, 2-phenylbutane, tert-butylbenzene, pentylbenzene, neopentylbenzene, isoamylbenzene, hexylbenzene, cyclohexylbenzene, heptylbenzene, octylbenzene, 3-propyltoluene 4-propyltoluene, 1-methyl-4-propylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, 1,4-di-tert-butylbenzene, indane, and tetralin (1,2,3 , - tetrahydronaphthalene), and the like.
Aliphatic hydrocarbon solvents: n-pentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, decalin and the like.
Aromatic ether solvents: anisole, ethoxybenzene, propoxybenzene, butyroxybenzene, pentyloxybenzene, cyclopentyloxybenzene, hexyloxybenzene, cyclohexyloxybenzene, heptyloxybenzene, octyloxybenzene, 2-methylanisole, 3-methyl Anisole, 4-methylanisole, 4-ethylanisole, 4-propylanisole, 4-butylanisole, 4-pentylanisole, 4-hexylanisole, diphenylether, 4-methylphenoxybenzene, 4-ethylphenoxybenzene, 4-propylphenoxy Benzene, 4-butylphenoxybenzene, 4-pentylphenoxybenzene, 4-hexylphenoxybenzene, 4-phenoxytoluene, 3-phenyl Nokishitoruen, 1,3-dimethoxybenzene, 2,6-dimethyl anisole, 2,5-dimethyl anisole, 2,3-dimethyl anisole, and 3,5-dimethyl anisole, and the like.
Aliphatic ether solvents: tetrahydrofuran, dioxane, dioxolane and the like.
Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and the like.
Ester solvents: ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate and the like.
Chlorinated solvents: methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, and the like.
Alcohol solvents: methanol, ethanol, propanol, isopropanol, cyclohexanol, phenol and the like.
Polyhydric alcohol and its derivatives: ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, and 1,2- Hexanediol and the like.
Aprotic polar solvents: dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
These solvents may be used alone or in combination of two or more.
When using a mixed solvent, it is preferable to combine two or more of the above solvent groups. In that case, one or more of the solvent groups of different systems may be combined even if a plurality of solvent groups of the same system are selected and combined. You may select and combine. The composition ratio of the mixed solvent can be determined in consideration of the physical properties of each solvent and the solubility of the polymer compound and the like.

As a preferred example of a mixed solvent obtained by selecting and combining a plurality of solvents from the same solvent group, a mixed solvent selected by combining a plurality of aromatic hydrocarbon solvents and a combination of selected from an aromatic ether solvent are combined. And a mixed solvent. Preferable examples of the mixed solvent obtained by selecting and combining one or more kinds from different solvent groups include the following combinations.
Combination of aromatic hydrocarbon solvent and aliphatic hydrocarbon solvent, combination of aromatic hydrocarbon solvent and aromatic ether solvent, combination of aromatic hydrocarbon solvent and aliphatic ether solvent, aromatic hydrocarbon Combinations of system solvents and aprotic polar solvents, combinations of aromatic ether solvents and aprotic polar solvents, and the like.
Moreover, you may add water to said single solvent or mixed solvent.
From the viewpoint of viscosity and film formability, a single solvent or a mixed solvent containing an organic solvent having a structure containing a benzene ring, a melting point of 0 ° C. or less, and a boiling point of 100 ° C. or more is preferable. A single solvent or a mixed solvent containing a hydrocarbon solvent or an aromatic ether solvent is preferred.

  The solvent may be a single solvent or a mixed solvent, but it is preferable to use a mixed solvent from the viewpoint of film formability. As the solvent, a solvent purified by a purification method such as washing, distillation, and contact with an adsorbent may be used.

According to the liquid composition of the present invention, an organic thin film containing the polymer compound can be easily produced. For example, an organic thin film containing the polymer compound can be obtained by applying the liquid composition of the present invention on a substrate and distilling off the solvent by heating, blowing, or reducing pressure. The conditions for distilling off the solvent can be changed according to the organic solvent used. Examples of the conditions include an atmospheric temperature (heating atmosphere) of about 50 to 150 ° C. and a reduced pressure atmosphere of about 10 ⁻³ Pa.

  The suitable viscosity of the liquid composition of the present invention varies depending on the printing method, but is preferably 0.5 to 1000 mPa · s, more preferably 0.5 to 500 mPa · s at 25 ° C. Further, when the liquid composition passes through a discharge device as in the ink jet printing method, the viscosity at 25 ° C. of the liquid composition is preferably 0.5 to prevent clogging or flight bending at the time of discharge. 50 mPa · s, more preferably 0.5 to 20 mPa · s. The content of the polymer compound of the present invention in the liquid composition is not particularly limited, but is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight.

<Thin film>
The thin film of the present invention contains the polymer compound of the present invention and is a luminescent thin film or a conductive thin film.

  The thin film of the present invention is prepared by spin coating, casting, micro gravure coating, gravure printing, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing. , Offset printing, ink jet, capillary coating, nozzle coating, and the like.

  When a thin film is produced using the liquid composition of the present invention, although it depends on the glass transition temperature of the polymer compound contained in the liquid composition, the temperature is usually 100 ° C. or higher (eg, 130 ° C., 160 ° C.). It may be produced by baking.

  The light emission quantum yield of the thin film of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, from the viewpoint of the luminance and light emission voltage of the device. Particularly preferred is 60% or more.

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

<Light emitting element>
The element of the present invention contains the polymer compound of the present invention, and includes, for example, an electrode composed of an anode and a cathode, and an organic layer containing the polymer compound of the present invention provided between the electrodes. It is. Hereinafter, the case where the element of this invention is light emitting elements, such as an organic EL element, is demonstrated as the typical thing.

When the light emitting device of the present invention is a single layer type light emitting device (anode / light emitting layer / cathode), the light emitting layer is composed of the thin film, and the light emitting layer contains the polymer compound of the present invention. Moreover, when the light emitting element of this invention is a multilayer type which has two or more layers between an anode and a cathode, those at least one layer consists of the said thin film. Examples of the layer structure of the multilayer light emitting device include the following (a) to (c).
(A) Anode / hole injection layer (hole transport layer) / light emitting layer / cathode (b) anode / light emitting layer / electron injection layer (electron transport layer) / cathode (c) anode / hole injection layer (holes) (Transport layer) / light emitting layer / electron injection layer (electron transport layer) / cathode (where “/” indicates that the layers are laminated adjacently).

  The anode of the light emitting element of the present invention has a function of supplying holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like. It is effective that the anode has a work function of 4.5 eV or more. The anode material can be a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. Specific examples of the anode material include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel; the conductive metals A mixture or laminate of an oxide and a metal; an inorganic conductive material such as copper iodide and copper sulfide; an organic conductive material such as polyaniline, polythiophene (such as PEDOT), and polypyrrole; A laminate of two or more materials and ITO is exemplified.

  The cathode of the light emitting element of the present invention has a function of supplying electrons to the electron injection layer, the electron transport layer, the light emitting layer, and the like. As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Examples of cathode materials include alkali metals (lithium, sodium, potassium, cesium, etc.) and their fluorides and oxides; alkaline earth metals (magnesium, calcium, barium, etc.) and their fluorides and oxides; gold, Metals such as silver, lead and aluminum; alloys and mixed metals (sodium-potassium alloy, sodium-potassium mixed metal, lithium-aluminum alloy, lithium-aluminum mixed metal, magnesium-silver alloy, magnesium-silver mixed metal, etc.) And rare earth metals (such as ytterbium) and indium.

  The hole injection layer and the hole transport layer of the light-emitting element of the present invention have any one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. A known material can be selected and used for the material of these layers. Examples of such materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene. Derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organic Examples thereof include silane derivatives and polymers containing these; conductive polymer oligomers such as aniline copolymers, thiophene oligomers, and polythiophene. The said material may be used individually by 1 type, or may use 2 or more types together. In addition, the hole injection layer and the hole transport layer may each independently have a single layer structure composed of one or more of the above materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. There may be.

  The electron injection layer and the electron transport layer of the light-emitting element of the present invention have one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. A known material can be selected and used for the material of these layers. Examples of such materials include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane. Derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes (for example, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole as a ligand) And metal complexes having benzothiazole as a ligand), and organosilane derivatives. The electron injection layer and the electron transport layer may each independently have a single layer structure composed of one or two or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

  In the light-emitting element of the present invention, an inorganic compound such as an insulator and a semiconductor may be used as a material for the electron injection layer and the electron transport layer. If the electron injection layer and the electron transport layer are made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved. Examples of the insulator include at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. Preferable examples of the alkali metal chalcogenide include CaO, BaO, SrO, BeO, BaS and CaSe. Moreover, as a semiconductor which comprises an electron injection layer and an electron carrying layer, the group which consists of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn, for example And oxides, nitrides and oxynitrides containing at least one element selected from These oxides, nitrides, and oxynitrides may be used alone or in combination of two or more.

  In the light emitting device of the present invention, a reducing dopant may be added to the interface region between the cathode and the thin film in contact with the cathode. Reducing dopants include alkali metals, alkaline earth metal oxides, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal Preference is given to at least one compound selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal complexes, alkaline earth metal complexes and rare earth metal complexes.

  The light emitting layer of the light emitting device of the present invention can inject holes from the anode, hole injection layer or hole transport layer when voltage is applied, and inject electrons from the cathode, electron injection layer or electron transport layer. Or the function of moving injected charges (electrons and holes) by the force of an electric field, and the function of providing a field for recombination of electrons and holes to connect to light emission. The light emitting layer of the light emitting device of the present invention preferably contains at least the polymer compound of the present invention. The polymer compound in the light emitting layer is usually 10% by weight to 100% by weight, preferably 50% by weight to 100% by weight, and preferably 80% by weight to 100% by weight with respect to the weight of the whole light emitting layer. It is more preferable that In the light emitting device of the present invention, the light emitting layer preferably contains the polymer compound of the present invention as a light emitting material.

  In the light emitting device of the present invention, a method for forming each layer is not particularly limited, and a known method may be used. Examples of such methods include vacuum deposition methods (resistance heating deposition method, electron beam method, etc.), sputtering methods, LB methods, molecular lamination methods, coating methods (casting methods, spin coating methods, bar coating methods, blade coating methods, rolls). Coating method, gravure printing, screen printing, ink jet method and the like). Especially, since a manufacturing process can be simplified, it is preferable to form into a film by the apply | coating method. In the coating method, a coating liquid can be prepared by dissolving the polymer compound of the present invention in a solvent, and the coating liquid can be formed on a desired layer (or electrode) by coating and drying. The coating solution may contain a resin as a binder, and the resin may be dissolved or dispersed in a solvent. As the resin, a non-conjugated polymer (for example, polyvinyl carbazole) or a conjugated polymer (for example, a polyolefin-based polymer) can be used. More specifically, for example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin. , Polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicone resin, and may be selected according to the purpose. The coating solution may contain optional components such as an antioxidant and a viscosity modifier depending on the purpose.

  Although the preferable thickness of each layer of the light emitting element of this invention changes with kinds of materials and layer structure, it is 1 nm-100 nm normally, and several nm-1 micrometer are preferable.

  Applications of the light emitting device of the present invention include a planar light source, an illumination light source (or light source), a sign light source, a backlight light source, a display device (display device), and a printer head. As the display device, a configuration such as a segment type or a dot matrix type can be selected using a known driving technique, a driving circuit, or the like.

  The present invention will be specifically described with reference to examples.

(Number average molecular weight and weight average molecular weight)
The number average molecular weight and the weight average molecular weight were determined as a number average molecular weight and a weight average molecular weight in terms of polystyrene by size exclusion chromatography (SEC). When the mobile phase is an organic solvent in SEC, it is called gel permeation chromatography (gel permeation chromatography, GPC). In addition, the method shown in the following analysis condition 1 or analysis condition 2 was used as analysis conditions of this GPC.

[Analysis condition 1]
The measurement sample was dissolved in tetrahydrofuran at a concentration of about 0.05% by weight, and 30 μL was injected into GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

[Analysis condition 2]
The measurement sample was dissolved in tetrahydrofuran at a concentration of about 0.05% by weight, and 10 μL was injected into GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 2.0 mL / min. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

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

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

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

(Evaluation of emission spectrum peak)
In the examples, the emission spectrum peak of the luminescent organometallic complex compound was evaluated by the following method unless otherwise specified. The phosphorescent light-emitting compound was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). At this time, the solution was prepared so that the concentration of the solid content would be 0.0008% by weight. This solution was excited at a wavelength of 350 nm using a fluorescence spectrophotometer (manufactured by JASCO Corporation, FP-6500), and the PL spectrum of the solution was measured to evaluate the emission spectrum peak.

(Measurement of MALDI-TOFMS)
In the examples, MALDI-TOFMS was measured under the following measurement conditions 1.
[Measurement condition 1]
α-Cyano-4-hydroxycinnamic acid was dissolved in methanol to prepare a saturated solution, which was used as a matrix solution. 200 μL of chloroform was added to and dissolved in about 4 mg of the polymer compound to be measured, and 20 μL of the resulting solution was diluted with 200 μL of chloroform to obtain a sample solution. 20 μL of the matrix solution and 20 μL of the sample solution were mixed and applied to a MALDI plate, and MALDI-TOFMS was measured. The measurement was performed using a MALDI-TOFMS apparatus: Voyager-DE STR (Applied Biosystems) in a measurement mode: Reflector, an acceleration voltage: 20 kV, and a laser: N ₂ (337 nm).

<Synthesis Example 1>
(Synthesis of Compound M-1)

  1,4-dihexyl-2,5-dibromobenzene (compound CM-1, 8.08 g, 20.0 mmol), bis (pinacolato) diboron (12.19 g, 48.0 mmol) in an flask under an argon gas atmosphere, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.98 g, 1.2 mmol), potassium acetate (11.78 g, 120.0 mmol), and dehydrated 1,4-dioxane (100 ml ) And stirred for 6 hours under heating to reflux. Toluene and ion-exchanged water were added, and the mixture was separated and washed with ion-exchanged water. Anhydrous sodium sulfate and activated carbon were added, and the mixture was filtered through a funnel pre-coated with Celite. The filtrate was concentrated to obtain a crude product (11.94 g). The crystals were recrystallized from hexane and washed with methanol. The obtained crystals are dried under reduced pressure to obtain 1,4-dihexyl-2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) which is the target product. Benzene (4.23 g, 42% yield, compound M-1) was obtained as white needle crystals.

The results of ¹ H-NMR analysis and LC / MS of compound M-1 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.95 (t, 6H), 1.39 to 1.42 (bd, 36H), 1.62 (m, 4H), 2.88 (T, 4H), 7.59 (bd, 2H)
LC / MS (ESI posi KCl addition): [M + K] ⁺ 573

<Synthesis Example 2>
(Synthesis of Compound M-2)

  Under an argon gas atmosphere, a small amount of dehydrated tetrahydrofuran and 1,2-dibromoethane (1.50 g, 8 mmol) were sequentially added to a small piece of magnesium (19.45 g, 800 mmol) in a flask. After confirming that magnesium was activated by heat generation and foaming, a solution of 2,6-dibromotoluene (49.99 g, 200 mmol) dissolved in dehydrated tetrahydrofuran (200 ml) was added dropwise over about 2 hours. After completion of dropping, the mixture was heated in an oil bath at 80 ° C. and stirred for 1 hour under reflux. The oil bath was removed, diluted with dehydrated tetrahydrofuran (400 ml), cooled in an ice bath, and then 2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (148. 85 g, 800 mmol) was added. The ice bath was removed, and the mixture was heated in an oil bath at 80 ° C., and stirred for 1.5 hours under reflux. After removing the oil bath and further cooling in an ice bath, a saturated aqueous ammonium chloride solution (50 ml) was added and stirred for 30 minutes. The ice bath was removed, hexane (1500 ml) was added, and the mixture was vigorously stirred for 30 minutes. Stirring was stopped, and the mixture was allowed to stand for 15 minutes, and then filtered through a glass filter spread with silica gel. The silica gel was washed with hexane (1000 ml), and the combined filtrate was concentrated under reduced pressure to give a crude product (72. 0 g) was obtained. The same operation was performed again to obtain a crude product (75.4 g).

  Next, methanol (740 ml) was added to the total of the crude products, and the mixture was stirred under reflux with heating for 1 hour using an oil bath at 85 ° C. After removing the oil bath and cooling to room temperature with stirring, the solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain white crystals (59.7 g). After the dried crystals are dissolved in isopropanol by heating, the crystals are precipitated by slowly cooling to room temperature while standing, filtered, washed with methanol, and dried under reduced pressure at 50 ° C. overnight. Compound M-2 (50.8 g, HPLC area percentage (ultraviolet wavelength 254 nm) 99.8%, yield 37%) was obtained as white crystals.

The results of ¹ H-NMR analysis of compound M-2 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.34 (s, 24H), 2.74 (s, 3H), 7.14 (t, 1H), 7.79 (d, 2H) )

で表される化合物ＣＭ−３を得た（収率７４％）。 <Synthesis Example 3>
(Synthesis of Compound M-3)
-Synthesis | combination of compound CM-3 The gas inside a 4-neck flask was substituted with nitrogen gas, 2,7- dibromofluorenone (1 equivalent) was put, and it was made to suspend in diphenyl ether (27 equivalent). The obtained suspension was heated to 120 ° C. to dissolve 2,7-dibromofluorenone, and then potassium hydroxide (5.7 equivalents) was added thereto, and the temperature was raised to 160 ° C. Stir for hours. After allowing to cool to room temperature, hexane (23 equivalents) was added, filtered, and washed with hexane to obtain a crude product. The gas inside the four-necked flask was replaced with nitrogen gas, and the resulting crude product was added and dissolved in dehydrated DMF (40 equivalents). The resulting solution was heated to 90 ° C., and methyl iodide (7.7 equivalents) was gradually added. Then, it was made to react for 10 hours. The resulting reaction solution was allowed to cool to room temperature, then dropped into water (340 equivalents) cooled to 0 ° C., and extracted twice with hexane (46 equivalents). The obtained extract was filtered through a glass filter laid with silica gel, and the obtained organic layer was concentrated. This was purified by silica gel column chromatography, and the following formula:

The compound CM-3 represented by this was obtained (yield 74%).

The results of ¹ H-NMR analysis and ¹³ C-NMR analysis of compound CM-3 are shown below.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 3.68 (s, 3H), 7.15 (d, 2H), 7.20 (d, 1H), 7.52 (d, 2H), 7.65 (d, 1H), 8.00 (brs, 1H)

¹³ C-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 52.6, 121.8, 122.2, 130.1, 131.6, 132.3, 132.4, 133.2, 134.7, 139.4, 140.6, 167 .8

で表される化合物ＣＭ−４を得た（収率２７％）。 Synthesis of Compound CM-4 A 3-neck round bottom flask was charged with 1-bromo-4-n-hexylbenzene (1 equivalent) and anhydrous tetrahydrofuran (hereinafter also referred to as THF) (34 equivalents) and cooled to -78 ° C. . Thereto was slowly added n-butyllithium (n-BuLi) (1.6 M hexane solution) (1 equivalent), and the mixture was stirred at −78 ° C. for 2 hours to obtain a reaction solution. A solution prepared by dissolving Compound CM-3 (0.43 equivalent) in anhydrous THF (5.6 equivalents) was charged into a dropping funnel and added dropwise at a dropping rate such that the temperature of the reaction solution did not exceed −70 ° C. or less. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours and slowly warmed to room temperature. Thereafter, about half the volume of anhydrous THF to which a saturated aqueous solution of ammonium chloride was added was added and stirred, and the mixture was transferred to a separatory funnel to remove the aqueous layer. The obtained organic layer was washed twice with water, and anhydrous sodium sulfate was added to the obtained organic layer for drying. A silica gel layer was laid on the glass filter, filtered through a THF solution, and then washed with THF. The resulting solution was concentrated and dried. Repulp washed with hexane, following formula:

The compound CM-4 represented by this was obtained (yield 27%).

で表される化合物Ｍ−３を得た（収率９２％）。 -Synthesis | combination of compound M-3 Compound CM-4 (1 equivalent) and dichloromethane (38 equivalent) were prepared to the 3 necked flask, and it cooled to 0 degreeC using the ice bath. Boron trifluoride diethyl ether complex (22 equivalents) was charged into a dropping funnel and added dropwise thereto. The reaction solution was stirred at 0 ° C. for 2 hours, and then poured into a beaker charged with water and ice to stop the reaction. The reaction solution was transferred to a separatory funnel and separated, and extracted with dichloromethane. The organic layers were combined, washed twice with water, and dried over anhydrous sodium sulfate. A silica gel layer was spread on a glass filter, and sodium sulfate was filtered through a THF solution and concentrated. Toluene was added to the obtained oil and heated to reflux. Next, after cooling to 70 ° C., isopropyl alcohol was added and stirred, and when it was allowed to stand at room temperature, crystals were formed. The crystals were filtered and dried, then charged into an eggplant flask, heated by adding hexane and activated carbon, and refluxed for 2 hours to obtain a mixture. Radiolite was laid on a glass filter, celite was laid thereon, and the mixture was heated to 70 ° C. in an oven, and the mixture was filtered using this. The obtained solution was concentrated in half, and the concentrate was heated to reflux and then stirred at room temperature for 1 hour. The mixture was further stirred for 2 hours while cooling in an ice bath, and the resulting crystals were collected by filtration.

The compound M-3 represented by this was obtained (yield 92%).

The results of ¹ H-NMR analysis and ¹³ C-NMR analysis of Compound M-3 are shown below.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 0.87 (t, 6H), 1.28 to 1.37 (m, 12H), 1.50 to 1.62 (m, 4H), 2.54 (t, 4H), 7 .04 (s, 8H), 7.45 (d, 2H), 7.49 (s, 2H), 7.55 (d, 2H)

¹³ C-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 14.4, 22.9, 29.4, 31.6, 32.0, 35.8, 65.4, 121.8, 122.1, 128.1, 128.7, 129 .7, 131.1, 138.3, 141.9, 142.1, 153.7

<Synthesis Example 4>
(Synthesis of Compound M-4)

  Under a nitrogen atmosphere, a solution of 1,4-dibromobenzene (27.1 g) in dehydrated diethyl ether (217 ml) was cooled using a dry ice / methanol mixed bath. A 2.77M n-butyllithium (n-BuLi) hexane solution (37.2 ml) was slowly added dropwise to the resulting suspension, and the mixture was stirred for 1 hour to prepare a lithium reagent.

  Under a nitrogen atmosphere, a suspension of cyanuric chloride (10.0 g) in dehydrated diethyl ether (68 ml) was cooled using a dry ice / methanol mixed bath, the lithium reagent was slowly added, and the temperature was raised to room temperature. Reacted. The resulting product was filtered and dried under reduced pressure. The obtained solid (16.5 g) was purified to obtain 13.2 g of acicular crystals (Compound CM-11).

  Under a nitrogen atmosphere, a solution of 4-dodecylbromobenzene (14.2 g) in anhydrous tetrahydrofuran (15 ml) was added little by little to a suspension of magnesium (1.37 g) in anhydrous tetrahydrofuran (65 ml) and heated. Stir under reflux. After allowing to cool, magnesium (0.39 g) was added to the reaction solution, heated again and reacted under reflux to prepare a Grignard reagent.

  Under a nitrogen atmosphere, the Grignard reagent was added to a suspension of the acicular crystals (12.0 g, compound CM-11) in dehydrated tetrahydrofuran (100 ml) with stirring, and the mixture was heated to reflux. After cooling, the reaction solution was washed with dilute hydrochloric acid aqueous solution. The organic layer and the aqueous layer were separated, and the aqueous layer was extracted with diethyl ether. The obtained organic layers were combined and washed again with water. The organic layer was dehydrated with anhydrous magnesium sulfate, filtered, and concentrated. The obtained white solid was purified with a silica gel column and further recrystallized to obtain 6.5 g of Compound M-4 as a white solid.

<Synthesis Example 5>
(Synthesis of Compound M-5)
In the same manner as in Synthesis Example 4, 13.2 g of acicular crystals (Compound CM-11) was obtained.

  Under a nitrogen atmosphere, a solution of 4-hexylbromobenzene (14.2 g) in dehydrated tetrahydrofuran (15 ml) was added little by little to a suspension of magnesium (1.37 g) in dehydrated tetrahydrofuran (65 ml) and heated. Stir under reflux. After allowing to cool, magnesium (0.39 g) was added to the reaction solution, heated again and reacted under reflux to prepare a Grignard reagent.

  Under a nitrogen atmosphere, the Grignard reagent was added to a suspension of the acicular crystals (12.0 g) in dehydrated tetrahydrofuran (100 ml) with stirring, and the mixture was heated to reflux. After cooling, the reaction solution was washed with dilute hydrochloric acid aqueous solution. The organic layer and the aqueous layer were separated, and the aqueous layer was extracted with diethyl ether. The obtained organic layers were combined and washed again with water. The organic layer was dehydrated with anhydrous magnesium sulfate, filtered, and concentrated. The obtained white solid was purified with a silica gel column and further recrystallized to obtain Compound M-5 (6.5 g) as a white solid.

The results of ¹ H-NMR analysis of compound M-5 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.90 (t, J = 6.2 Hz, 3H), 1.25-1.42 (m, 6H), 1.63-1. 73 (m, 2H), 2.71 (t, J = 7.6 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), 7.65 (d, J = 7.9 Hz, 4H) ), 8.53-8.58 (m, 6H)
LC-MS (APCI, positive): m / z ⁺ = 566 [M + H] ⁺

（式中、Ｍｅはメチル基を表す。） <Synthesis Example 6>
(Synthesis of Compound M-6)

(In the formula, Me represents a methyl group.)

  Palladium (II) acetate (0.90 g), tris (2-methylphenyl) phosphine (2.435 g) and toluene (125 mL) are placed in a reaction vessel in which the internal gas is replaced with nitrogen gas, and the mixture is stirred at room temperature for 15 minutes. did. There, 2,7-dibromo-9,9-dioctylfluorene (27.4 g), (4-methylphenyl) phenylamine (22.91 g) and sodium-tert-butoxide (tert-BuONa, 19.75 g) were added. In addition, the mixture was heated to reflux overnight, cooled to room temperature, and washed with water. The organic layer was taken out and the solvent was distilled off under reduced pressure. The residue was dissolved in toluene, and the resulting solution was passed through an alumina column. The eluate was concentrated under reduced pressure, and methanol was added thereto to form a precipitate. The precipitate was collected by filtration and recrystallized from p-xylene. The crystals were redissolved in toluene, and the resulting solution was passed through an alumina column. The solution was concentrated and poured into stirred methanol, resulting in precipitation. The precipitate was collected and dried at room temperature under reduced pressure for 18 hours. As a result, white 2,7-bis [N- (4-methylphenyl) -N-phenyl] amino-9,9-dioctylfluorene (25.0 g) was collected. )was gotten.

  2,7-bis [N- (4-methylphenyl) -N-phenyl] amino-9,9-dioctylfluorene (12.5 g) and dichloromethane (95 mL) are added to a reaction vessel in which the internal gas is replaced with nitrogen gas, and the mixture is stirred. The reaction solution was then cooled to -10 ° C. A solution of 5.91 g of N-bromosuccinimide (NBS) dissolved in 20 mL of dimethylformamide (DMF) was slowly added dropwise thereto. After stirring for 3.5 hours, the mixture was mixed with cold methanol, and the resulting precipitate was collected by filtration and recrystallized from p-xylene. The obtained crystals were recrystallized again using toluene and methanol to obtain 12.1 g of Compound M-6 as a white solid.

The results of ¹ H-NMR analysis of compound M-6 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.61-0.71 (m, 4H), 0.86 (t, J = 6.8 Hz, 6H), 0.98-1. 32 (m, 20H), 1.72-1.77 (m, 4H), 2.32 (br, 6H), 6.98-7.08 (m, 16H), 7.29 (d, J = 8.3Hz, 4H), 7.44 (br, 2H)

で表される化合物ＣＭ−５の粗生成物を得た（４２％）。精製は行わず、次の工程に用いた。 <Synthesis Example 7>
(Synthesis of Compound M-7)
Synthesis of Compound CM-5 The gas inside the three-necked flask was replaced with nitrogen gas, 1-bromo-3-n-hexylbenzene (1 equivalent) was weighed and dissolved in dehydrated tetrahydrofuran (33 equivalents). . The obtained solution was cooled to −75 ° C. or lower, and 2.5 M n-butyllithium / n-hexane solution (0.95 equivalent) was added dropwise, and the mixture was stirred for 5 hours while maintaining at −75 ° C. or lower. A solution prepared by dissolving 2-methoxycarbonyl-4,4′-dibromobiphenyl (0.43 equivalent) in dehydrated tetrahydrofuran (5.3 equivalent) was added dropwise to the obtained solution while maintaining at −70 ° C. or lower. The resulting solution was slowly warmed to room temperature and stirred overnight. While stirring the reaction solution at 0 ° C., water was added dropwise thereto. After the solvent was distilled off, water was added to the residue and the mixture was extracted once with hexane and twice with hexane. The organic layers were combined, washed with saturated brine, the aqueous layer was re-extracted with hexane, and the obtained organic layer was dried over magnesium sulfate. When the solvent was distilled off, the following formula:

To give a crude product of compound CM-5 (42%). The product was used for the next step without purification.

  In addition, 2-methoxycarbonyl-4,4'-dibromobiphenyl is described in Journal of the American Chemical Society (1956), 78, 3196-3198. It was synthesized by the method described in 1.

で表される化合物ＣＭ−６を得た（収率４７％）。 Synthesis of Compound CM-6 Compound CM-5 (1 equivalent) was weighed in a three-necked flask and dissolved in dichloromethane (35 equivalents), and the gas in the flask was replaced with nitrogen gas. The resulting solution was cooled to 0 ° C. or lower, and boron trifluoride diethyl ether complex (4.8 equivalents) was added dropwise while maintaining the temperature at 5 ° C. or lower. After slowly warming to room temperature, the mixture was stirred overnight. The reaction solution was poured into ice water with stirring and stirred for 30 minutes. The obtained solution was separated, and the aqueous layer was extracted with dichloromethane. The organic layers were combined, 10% by weight aqueous potassium phosphate solution was added for liquid separation, and the organic layer was washed twice with water. After drying the organic layer with magnesium sulfate, the solvent was distilled off and the oil obtained was dissolved in toluene and filtered through a glass filter covered with silica gel. After the solvent was distilled off, methanol was added and stirred vigorously. The obtained crystals were filtered and washed with methanol. By recrystallization with a hexane / butyl acetate mixed solvent, the following formula:

The compound CM-6 represented by this was obtained (47% of yield).

The results of ¹ H-NMR analysis of Compound CM-6 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ); δ (ppm) = 0.86 (6H, t), 1.26 (12H, m), 1.52 (4H, m), 2.51 (4H, t ), 6.87 (2H, d), 7.00 (2H, s), 7.04 (2H, d), 7.12 (2H, t), 7.46 (2H, dd), 7.48. (2H, d), 7.55 (2H, d)

で表されるＭ−７を得た（収率６０％）。 -Synthesis | combination of compound M-7 CM-6 (1 equivalent) was weighed in the 3 necked flask, and the gas in this flask was substituted with nitrogen gas. Thereto, dehydrated tetrahydrofuran (80 equivalents) was added and cooled to -70 ° C or lower. A 2.5 M n-butyllithium / n-hexane solution (2.2 equivalents) was added dropwise while keeping the obtained solution at −70 ° C. or lower. After dropping, the mixture was stirred for 4 hours while maintaining the temperature. 2-Isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.9 equivalents) was added, and the mixture was slowly warmed to room temperature and stirred overnight. The reaction was cooled to -30 ° C. A 2M hydrochloric acid / diethyl ether solution (2 equivalents) was added dropwise thereto, and the temperature was raised to room temperature. After distilling off the solvent, toluene was added to dissolve it, followed by filtration through a glass filter covered with silica gel. When the solvent of the resulting solution was distilled off, a crude product was obtained. By recrystallization from toluene / acetonitrile solvent under nitrogen atmosphere, the following formula:

M-7 represented by the formula (1) was obtained (60% yield).

The results of ¹ H-NMR analysis of compound M-7 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ); δ (ppm) = 0.86 (6H, t), 1.26 to 1.29 (12H, m), 1.31 (24H, s), 1.52 -1.53 (4H, m), 2.50 (4H, t), 6.92 (2H, d), 7.00 (2H, d), 7.08 (2H, t), 7.13 ( 2H, s), 7.77 (2H, d), 7.81-7.82 (4H, m)

<Synthesis Example 8>
(Synthesis of Compound M-8)

・ Composition of CM-8

  Under a stream of argon, 1-bromo-3,5-di-n-hexylbenzene (1 equivalent) and tetrahydrofuran (36 equivalents) were charged into a reaction vessel to prepare a homogeneous solution, and the solution was cooled to -69 ° C. A 2.76 M n-butyllithium hexane solution (1 equivalent) was added dropwise to the solution at −68 ° C. over 1.5 hours, and the mixture was further stirred at −70 ° C. for 1.5 hours. Next, a solution consisting of Compound CM-3 (0.4 eq) and tetrahydrofuran (3.6 eq) was added dropwise at −70 ° C. over 1 hour and stirred at −70 ° C. for 2 hours. Subsequently, methanol (2.4 equivalents) and distilled water (5.5 equivalents) were added and stirred at −70 ° C., and then the mixture was warmed to room temperature and stirred overnight at room temperature. Subsequently, the reaction mixture was filtered, the filtrate was concentrated, heptane and water were added and stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and liquid-separated. A saturated saline solution was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated to obtain the target compound CM-8 (yield 46%).

Synthesis of compound CM-9

Under a stream of argon, Compound CM-8 (1 equivalent) and dichloromethane (29 equivalents) were charged into a reaction vessel to prepare a homogeneous solution, and cooled to −30 ° C. Boron trifluoride diethyl ether complex (BF ₃ · OEt ₂ , 1 equivalent) was added dropwise to the solution over 30 minutes. Then, it stirred at room temperature overnight. Next, the reaction mixture was cooled to −20 ° C., distilled water (112 equivalents) was added, and the mixture was stirred for 1 hour, and then left to separate and separate liquid debris from the organic layer. Next, water (57 equivalents) was added and stirred, and the aqueous layer which was allowed to stand and liquid-separated was removed from the organic layer. A 10% by weight aqueous sodium hydrogen carbonate solution (22 equivalents) was added to the obtained organic layer, and the mixture was stirred and allowed to stand to separate and separate the aqueous layer from the organic layer. The organic layer was concentrated to remove the solvent. Subsequently, the residue was purified by silica gel column chromatography using toluene and heptane as developing solvents, and concentrated to remove the solvent. Subsequently, the target compound CM-9 was obtained by recrystallization using butyl acetate and methanol (yield 57%).

Synthesis of compound M-8

Under a stream of argon, compound CM-9 (1 equivalent), compound CM-10 (2.2 equivalents), 1,4-dioxane (87 equivalents), potassium acetate (6.1 equivalents), 1, 1′-bis (diphenylphosphino) ferrocene (dppf, 1.5 mol%) and 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (PdCl ₂ dppf · CH ₂ Cl ₂ 1.5 mol%) and stirred at 100 to 102 ° C. for 5 hours. Subsequently, after cooling the obtained reaction mixture to room temperature, it filtered with the filter which spread Celite and the silica gel, and the obtained filtrate was concentrated and the solvent was removed. Subsequently, activated carbon was added to the solution prepared by adding hexane, and the mixture was stirred at a temperature at which hexane was refluxed for 1 hour. After cooling to room temperature, the mixture was filtered with a filter packed with celite and concentrated to remove the solvent. Subsequently, recrystallization was performed with toluene and acetonitrile to obtain the target compound M-8 (95%).

内部の気体をアルゴンガスで置換したセパラブルフラスコに、化合物Ｌ−５（４．０ｇ、８．５ｍｍｏｌ）、化合物ＣＭ−１１（１６ｇ、３７．６ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）（Ｐｄ（ＰＰｈ_３）_４、４９４ｍｇ、０．４３ｍｍｏｌ、５ｍｏｌ％）、トルエン（７８０ｍＬ）、及びエタノール（２６０ｍＬ）を加え、撹拌しながら３５℃に加熱した。次いで、イオン交換水（２６０ｍＬ）に炭酸カリウム（３．５４ｇ、２６ｍｍｏｌ）を溶解させた水溶液を滴下し、６４時間撹拌した。反応液を分液ロートに移し、イオン交換水及び１０重量％食塩水で洗浄し、有機層を硫酸ナトリウムにて脱水した後、シリカゲルを敷き詰めたロートに通液し、溶媒を減圧留去した。得られた残渣を、中圧分取カラムクロマトグラフィー（シリカゲルカラム、展開溶媒：クロロホルム／ヘキサン＝４／６（体積比））にて精製した後、トルエンにて再結晶し、得られた固体を真空乾燥機で十分に乾燥させることにより、目的とする化合物Ｍ−９を白色粉末として得た（１．５ｇ、収率２４％）。
なお、化合物Ｌ−５は、ＷＯ０２／６６５５２に記載の方法に準じて合成した。 <Synthesis Example 9>
(Synthesis of Compound M-9)

In a separable flask in which the internal gas was replaced with argon gas, compound L-5 (4.0 g, 8.5 mmol), compound CM-11 (16 g, 37.6 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 494 mg, 0.43 mmol, 5 mol%), toluene (780 mL), and ethanol (260 mL) were added and heated to 35 ° C. with stirring. Next, an aqueous solution in which potassium carbonate (3.54 g, 26 mmol) was dissolved in ion-exchanged water (260 mL) was added dropwise and stirred for 64 hours. The reaction solution was transferred to a separatory funnel, washed with ion exchange water and 10 wt% saline, the organic layer was dehydrated with sodium sulfate, and then passed through a funnel filled with silica gel, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative column chromatography (silica gel column, developing solvent: chloroform / hexane = 4/6 (volume ratio)), and then recrystallized from toluene. By sufficiently drying with a vacuum dryer, the target compound M-9 was obtained as a white powder (1.5 g, yield 24%).
Compound L-5 was synthesized according to the method described in WO02 / 66552.

内部の気体をアルゴンガスで置換したセパラブルフラスコに、化合物ＣＭ−１３（４．０ｇ、４．５ｍｍｏｌ）、化合物ＣＭ−１１（８．４ｇ、２０．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）（Ｐｄ（ＰＰｈ_３）_４、２６１ｍｇ、０．２３ｍｍｏｌ、５ｍｏｌ％）、トルエン（７８０ｍＬ）及びエタノール（２６０ｍＬ）を加え撹拌しながら３５℃に加熱した。次いで、イオン交換水（２６０ｍＬ）に炭酸カリウム（１．８７ｇ、１４ｍｍｏｌ、３当量）を溶解させた水溶液を滴下し、２３時間撹拌した。反応液を分液ロートに移し、イオン交換水及び１０重量％食塩水で洗浄し、有機層を硫酸ナトリウムにて脱水した後、シリカゲルを敷き詰めたロートに通液し、溶媒を減圧留去した。
上記の作業を２回行い、得られた残渣をまとめて秤量したところ、残渣の合計は２２ｇであった。得られた残渣を、中圧分取カラムクロマトグラフィー（シリカゲルカラム、展開溶媒：クロロホルム／ヘキサン＝４／６（体積比））にて精製した後、ヘキサンにてリパルブ洗浄及び熱時濾過を行い、得られた粉末を真空乾燥機で十分に乾燥させることにより、目的とする化合物Ｍ−１０を白色粉末として得た（５ｇ、収率５０％）。 <Synthesis Example 10>
(Synthesis of Compound M-10)

In a separable flask in which the internal gas was replaced with argon gas, compound CM-13 (4.0 g, 4.5 mmol), compound CM-11 (8.4 g, 20.0 mmol), tetrakis (triphenylphosphine) palladium ( 0) (Pd (PPh ₃ ) ₄ , 261 mg, 0.23 mmol, 5 mol%), toluene (780 mL) and ethanol (260 mL) were added and heated to 35 ° C. with stirring. Next, an aqueous solution in which potassium carbonate (1.87 g, 14 mmol, 3 equivalents) was dissolved in ion-exchanged water (260 mL) was added dropwise and stirred for 23 hours. The reaction solution was transferred to a separatory funnel, washed with ion exchange water and 10 wt% saline, the organic layer was dehydrated with sodium sulfate, and then passed through a funnel filled with silica gel, and the solvent was distilled off under reduced pressure.
When the above operation was performed twice and the obtained residues were weighed together, the total amount of residues was 22 g. The resulting residue was purified by medium pressure preparative column chromatography (silica gel column, developing solvent: chloroform / hexane = 4/6 (volume ratio)), then repulb washed with hexane and filtered while hot. The obtained powder was sufficiently dried with a vacuum dryer to obtain the target compound M-10 as a white powder (5 g, yield 50%).

で表される２−（３'−ブロモフェニル）ピリジンを得た。 <Synthesis Example 11>
(Synthesis of Luminescent Organometallic Complex Compound MC-1)
A phosphorescent compound A was synthesized according to the synthesis method described in International Publication No. 2002/066652. Specifically, Suzuki coupling of 2-bromopyridine and 1.2 equivalent of 3-bromophenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M sodium carbonate Aqueous solution, solvent: ethanol, toluene), the following formula:

2- (3′-bromophenyl) pyridine represented by the formula:

で表されるブロモ化合物を得た。 Next, Suzuki coupling of tribromobenzene and 2.2 equivalents of 4-tert-butylphenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution) , Solvent: ethanol, toluene) and the following formula:

The bromo compound represented by this was obtained.

で表されるホウ酸化合物を得た。 Under a nitrogen atmosphere, the bromo compound was dissolved in anhydrous THF, cooled to −78 ° C., and a small excess of tert-butyllithium was added dropwise. Under cooling, B (OC ₄ H ₉ ) ₃ was further added dropwise and reacted at room temperature. The resulting reaction solution was post-treated with 3M aqueous hydrochloric acid to give the following formula:

The boric acid compound represented by this was obtained.

で表される配位子（即ち、配位子となる化合物）を得た。 Suzuki coupling of 2- (3′-bromophenyl) pyridine and 1.2 equivalents of the boric acid compound (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution, solvent: ethanol , Toluene), the following formula:

Was obtained (that is, a compound to be a ligand).

で表される化合物を黄色粉体として得た。 Under an argon atmosphere, IrCl ₃ .3H ₂ O, 2.2 equivalents of the ligand, 2-ethoxyethanol, and ion-exchanged water were charged and refluxed. The precipitated solid was suction filtered. The obtained solid was washed with ethanol and ion-exchanged water in this order and then dried, and the following formula:

Was obtained as a yellow powder.

で表される発光性有機金属錯体化合物ＭＣ−１を得た。 Under an argon atmosphere, 2 equivalents of the ligand and 2 equivalents of silver trifluoromethanesulfonate are added to the yellow powder and heated in diethylene glycol dimethyl ether to obtain the following formula:

A light-emitting organometallic complex compound MC-1 represented by the formula:

The results of ¹ H-NMR analysis and LC-MS of the light-emitting organometallic complex compound MC-1 are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.38 (s, 54H), 6.93 (dd, J = 6.3 Hz and 6.6 Hz, 3H), 7.04 (br, 3H), 7.30 (d, J = 7.9 Hz, 3H), 7.48 (d, J = 7.3 Hz, 12H), 7.61-7.70 (m, 21H), 7.82 ( s, 6H), 8.01 (s, 3H), 8.03 (d, J = 7.9 Hz, 3H)

LC-MS (APCI, positive): m / z ⁺ = 1677 [M + H] ⁺

  The emission spectrum peak of the luminescent organometallic complex compound MC-1 was 513 nm.

<Synthesis Example 12>
(Synthesis of Luminescent Organometallic Complex Compound MC-2)

（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, t-Bu represents a tert-butyl group.)

  First, 5-bromo-2-phenylpyridine and 4,6-bis (4-tert-butylphenyl) -2-chloro-1,3,5-triazine are prepared according to the method described in JP2008-179617A. Synthesized.

Under a nitrogen stream, 5-bromo-2-phenylpyridine (103.0 g, 440 mmol) and 1320 mL of dehydrated diethyl ether were weighed into a reaction vessel and cooled to -67 ° C. To this, n-butyllithium / hexane solution (1.59M, 318.2 mL, 506 mmol) was added dropwise over 20 minutes. After completion of the dropwise addition, the resulting solution was stirred at −67 ° C. for 1.5 hours, then tri-isopropyl borate (B (Oi-Pr) ₃ , 95.2 g, 506 mmol) was added, and −67 ° C. The mixture was stirred for 4 hours and then gradually warmed to room temperature and stirred overnight. To the reaction mixture, 1N aqueous sodium hydroxide solution (440 mL) and distilled water (500 mL) were added, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was recovered from the reaction solution by a liquid separation operation, and about 400 mL of 3N hydrochloric acid was added to adjust the pH to 5. As a result, a candy-like precipitate was formed. The supernatant was removed from the reaction solution by decantation, and the precipitate was washed twice with distilled water and then dissolved in methanol to obtain a methanol solution. The supernatant was extracted twice with ethyl acetate, dried over anhydrous magnesium sulfate, and then combined with this methanol solution and concentrated under reduced pressure. Ethyl acetate was added to the obtained residue, and water was removed azeotropically to obtain Compound L-1 (82.9 g) as a light gray powder.

In a reaction vessel, 4,6-bis (4-tert-butylphenyl) -2-chloro-1,3,5-triazine (137.1 g, 361 mmol), compound L-1 (82.6 g, 415 mmol), toluene (2890 mL) and tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 8.34 g, 7.22 mmol) are weighed, and the solid content is dissolved while stirring at 50 ° C. under a nitrogen stream. It was. 2M aqueous sodium carbonate solution (722 mL) was added to the resulting solution, and the mixture was refluxed for 17 hours. The organic layer was recovered from the reaction solution and washed with 5 wt% aqueous sodium hydrogen carbonate solution and 10 wt% brine. The washed organic layer was dried over sodium sulfate and concentrated. The obtained concentrated liquid was purified by silica gel column chromatography (toluene), and the solvent was distilled off. The obtained residue was dissolved in chloroform and crystallized by adding ethanol. After the crystals were collected by filtration, the crystals were washed with ethanol and dried to obtain Compound L-2 (169.2 g).

The results of LC-MS and ¹ H-NMR analysis of Compound L-2 are shown below.
LC-MS (APPI, positive) m / z: 499 ([M + H] ⁺ )

¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm) = 1.42 (s, 18H), 7.52 (m, 3H), 7.62 (d, J = 6.8 Hz, 4H), 7.95 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 7.3 Hz, 2H), 8.69 (d, J = 6.8 Hz, 4H), 9.04 (d, J = 8.4 Hz, 1H), 10. 02 (s, 1H)

  In a reaction vessel, compound L-2 (22.17 g, 44 mmol), iridium chloride trihydrate (6.95 g, 20 mmol), 2-ethoxyethanol (96 mL), and water (32 mL) were weighed, under an argon stream. And heated at 140 ° C. for 15 hours. After air cooling, the obtained mixture was filtered, and the residue was washed with methanol, water, and methanol in this order to obtain a red solid. This red solid was dissolved in chloroform, ethanol was added and the mixture was refluxed for 2 hours. After air cooling, the precipitated solid was collected by filtration and washed with ethanol. After repeating this operation three times, the obtained solid was collected and dried under reduced pressure to obtain metal complex complex 1 (20.03 g).

  In a reaction vessel, weigh metal complex complex 1 (759 mg, 0.30 mmol), compound L-3 (330 mg, 0.61 mmol) synthesized according to the method described in WO 2006/062226, and diglyme (9 mL). The resulting mixture was added with silver trifluoromethanesulfonate (AgOTf, 157 mg, 0.61 mmol), and stirred at 100 ° C. for 10 hours under an argon stream. After air cooling, pure water (50 mL) was added to the reaction mixture, and the resulting precipitate was filtered off. Toluene / hexane (1/2 (volume basis)) mixed solvent (40 mL) was added to the precipitate, followed by filtration. The filtrate was dried with sodium sulfate. The solution was filtered and purified by silica gel column chromatography (hexane / toluene = 1 / 1.5 (volume basis)), and the solvent was distilled off. The obtained residue was washed with methanol and dried under reduced pressure to obtain a luminescent organometallic complex compound MC-2 (252 mg, 0.15 mmol).

The results of LC-MS and ¹ H-NMR analysis of the luminescent organometallic complex compound MC-2 are shown below.
LC-MS (APCI, positive) m / z: 1733 ([M + H] ⁺ )

¹ H-NMR (600 MHz, THF-d ₈ )
δ (ppm) = 1.22 (s, 18H), 1.35 (s, 18H), 1.38 (s, 18H), 6.81 (m, 1H), 6.82 (m, 1H), 6.86 (m, 1H), 6.90 (m, 1H), 6.96 (d, J = 7.1 Hz, 1H), 7.41 (d, J = 7.1 Hz, 1H), 7. 22 (d, J = 8.2 Hz, 1H), 7.24 (d, J = 8.2 Hz, 1H), 7.47 (d, J = 8.2 Hz, 4H), 7.48 (d, J = 8.5 Hz, 4H), 7.50 (d, J = 8.2 Hz, 4H), 7.66 (m, 1H), 7.66 (d, J = 8.2 Hz, 4H), 7.71 (M, 2H), 7.74 (s, 1H), 7.84 (s, 2H), 7.89 (d, J = 7.9 Hz, 1H), 7.93 (d, J = 7.9 Hz) , 1H), 8.03 (d, J = 6.4) z, 1H), 8.06 (m, 1H), 8.29 (d, J = 8.8 Hz, 1H), 8.38 (d, J = 8.5 Hz, 4H), 8.41 (d, J = 8.8 Hz, 1H), 8.43 (d, J = 8.2 Hz, 4H), 8.67 (s, 1H), 8.99 (d, J = 8.8 Hz, 1H), 9. 21 (m, 1H), 9.23 (d, J = 8.8 Hz, 1H), 9.28 (s, 1H), 9.44 (s, 1H)

  The emission spectrum peak of the luminescent organometallic complex compound MC-2 was 611 nm.

反応容器に、２，５−ジブロモピリジン（７．１１ｇ、３０ｍｍｏｌ）、トルエン（１３０ｍＬ）、フェニルホウ酸（４．５７ｇ、３７．５ｍｍｏｌ）、及びテトラキス（トリフェニルホスフィン）パラジウム（０）（１．７３ｇ、１．５ｍｍｏｌ）を量り取り、窒素気流下、５０℃で撹拌し、反応物を溶解させた。次いで、２Ｍ炭酸ナトリウム水溶液（３０ｍＬ）を加えて、８０℃で６時間撹拌した。得られた反応液の有機層を回収し、炭酸ナトリウム水溶液及び飽和食塩水で洗浄した。有機層を硫酸ナトリウムで乾燥させ、濾過した後に溶媒を留去した。この残渣をシリカゲルカラムクロマトグラフィー（ヘキサン／トルエン）で精製し、溶媒を留去して、５−ブロモ−２−フェニルピリジン（６．２１ｇ、２６．５ｍｍｏｌ）を得た。 <Synthesis Example 13>
(Synthesis of Luminescent Organometallic Complex Compound MC-3)
・ Synthesis of 5-bromo-2-phenylpyridine

In a reaction vessel, 2,5-dibromopyridine (7.11 g, 30 mmol), toluene (130 mL), phenylboric acid (4.57 g, 37.5 mmol), and tetrakis (triphenylphosphine) palladium (0) (1.73 g). 1.5 mmol), and stirred at 50 ° C. under a nitrogen stream to dissolve the reaction product. Subsequently, 2M sodium carbonate aqueous solution (30 mL) was added, and the mixture was stirred at 80 ° C. for 6 hours. The organic layer of the resulting reaction solution was collected and washed with an aqueous sodium carbonate solution and saturated brine. The organic layer was dried over sodium sulfate and filtered, and then the solvent was distilled off. The residue was purified by silica gel column chromatography (hexane / toluene), and the solvent was distilled off to give 5-bromo-2-phenylpyridine (6.21 g, 26.5 mmol).

反応容器に、５−ブロモ−２−フェニルピリジン（７．３９ｇ、３０ｍｍｏｌ）、塩化イリジウム三水和物（４．７６ｇ、１３．５ｍｍｏｌ）、２−エトキシエタノール（５８ｍＬ）、及び水（１９ｍＬ）を量り取り、窒素気流下、１４０℃で１６時間加熱した。空冷後、得られた反応混合物を濾別し、水、メタノール、及びヘキサンの順で洗浄することにより、黄色固体として、上式で表される金属錯体ｃｏｍｐｌｅｘ １（９．１０ｇ、６．５８ｍｍｏｌ）を得た。
次いで、反応容器に、金属錯体ｃｏｍｐｌｅｘ １（６．９４ｇ、５．０ｍｍｏｌ）、５−ブロモ−２−フェニルピリジン（７．３２ｇ、３０．０ｍｍｏｌ）及びジグライム（４３ｍＬ）を量り取り、トリフルオロメタンスルホン酸銀（２．５７ｇ、１０．０ｍｍｏｌ）を加え、１３０℃で１４時間撹拌した。得られた反応生成物を濾別し、固体を塩化メチレンに溶解させた。この溶液を濾過し、濾液を濃縮した。析出した固体を濾別回収し、ヘキサンで洗浄することにより、上式で表される金属錯体ｃｏｍｐｌｅｘ ２（６．３５ｇ、７．１ｍｍｏｌ）を得た。 ・ Synthesis of metal complex complex 2

In a reaction vessel, 5-bromo-2-phenylpyridine (7.39 g, 30 mmol), iridium chloride trihydrate (4.76 g, 13.5 mmol), 2-ethoxyethanol (58 mL), and water (19 mL). Weighed and heated at 140 ° C. for 16 hours under a nitrogen stream. After air cooling, the obtained reaction mixture was filtered and washed with water, methanol, and hexane in this order to obtain a metal complex complex 1 (9.10 g, 6.58 mmol) represented by the above formula as a yellow solid. Got.
Next, a metal complex complex 1 (6.94 g, 5.0 mmol), 5-bromo-2-phenylpyridine (7.32 g, 30.0 mmol) and diglyme (43 mL) were weighed into a reaction vessel, and trifluoromethanesulfonic acid was measured. Silver (2.57 g, 10.0 mmol) was added and stirred at 130 ° C. for 14 hours. The resulting reaction product was filtered off and the solid was dissolved in methylene chloride. The solution was filtered and the filtrate was concentrated. The precipitated solid was collected by filtration and washed with hexane to obtain a metal complex complex 2 (6.35 g, 7.1 mmol) represented by the above formula.

The results of LC-MS and ¹ H-NMR analysis of metal complex complex 2 are shown below.
LC-MS (positive) m / z: 890 ([M + H] ⁺ )
¹ H NMR (300 MHz, DMSO-d ₆ )
δ (ppm) = 6.51 (d, J = 7.8 Hz, 3H), 6.72 (m, 3H), 6.84 (m, 3H), 7.66 (d, J = 2.0 Hz, 3H), 7.80 (d, J = 7.8 Hz, 3H), 8.05 (dd, J = 2.0, 8.8 Hz, 3H), 8.14 (d, J = 8.8 Hz, 3H) )

窒素気流下、反応容器に、金属錯体ｃｏｍｐｌｅｘ ２（３．２７ｇ、３．７ｍｍｏｌ）、酢酸カリウム（３．２７ｇ、３３．３ｍｍｏｌ）、ビス（ピナコラート）ジボロン（３．３８ｇ、１３．３ｍｍｏｌ）、１，１’−ビス（ジフェニルホスフィノ）フェロセン（２４５ｍｇ、０．４４ｍｍｏｌ）、［１，１’−ビス（ジフェニルホスフィノ）フェロセン]ジクロロパラジウム（II）（３６１ｍｇ、０．４４ｍｍｏｌ）、及びテトラヒドロフラン（４００ｍＬ）を量り取り、３０時間還流した。得られた反応液を濃縮し、塩化メチレンを加えて溶解させた後に、ろ過した。濾液をシリカゲルクロマトグラフィー（塩化メチレン）で精製し、溶媒を留去して残渣をジエチルエーテルで洗浄することにより、上式で表される金属錯体ｃｏｍｐｌｅｘ ３（２．５５ｇ、２．４７ｍｍｏｌ）を得た。 ・ Synthesis of metal complex complex 3

Under a nitrogen stream, a metal complex complex 2 (3.27 g, 3.7 mmol), potassium acetate (3.27 g, 33.3 mmol), bis (pinacolato) diboron (3.38 g, 13.3 mmol), 1 , 1′-bis (diphenylphosphino) ferrocene (245 mg, 0.44 mmol), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (361 mg, 0.44 mmol), and tetrahydrofuran (400 mL) ) And was refluxed for 30 hours. The resulting reaction solution was concentrated, dissolved by adding methylene chloride, and then filtered. The filtrate was purified by silica gel chromatography (methylene chloride), the solvent was distilled off, and the residue was washed with diethyl ether to obtain metal complex complex 3 (2.55 g, 2.47 mmol) represented by the above formula. It was.

The results of LC-MS and ¹ H-NMR analysis of metal complex complex 3 are shown below.
LC-MS (positive) m / z: 1072 ([M + K] ⁺ )
¹ H NMR (300 MHz, CDCl ₃ )
δ (ppm) = 1.21 (s, 36H), 6.87 (m, 9H), 7.69 (d, J = 7.7 Hz, 3H), 7.82 (s, 3H), 7.86 (M, 6H)

（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） Synthesis of 2,4-di (4′-tert-butylphenyl) -6-chloro-1,3,5-triazine

(In the formula, t-Bu represents a tert-butyl group.)

Under a stream of argon, 1-bromo-4-tert-butylbenzene (125 g, 587 mmol) and tetrahydrofuran (470 mL) were charged into a reaction vessel and cooled to -70 ° C. Then, n-butyllithium / hexane solution (1.6 M, 367 mL, 587 mmol) was added dropwise at −70 ° C. over 90 minutes. After completion of dropping, the mixture was stirred at −70 ° C. for 2 hours to obtain a 4-tert-butylphenyllithium / tetrahydrofuran solution.
Under a stream of argon, another reaction vessel was charged with cyanuric chloride (50.8 g, 276 mmol) and tetrahydrofuran (463 mL) and cooled to -70 ° C. To the obtained mixture, the 4-tert-butylphenyllithium / tetrahydrofuran solution prepared earlier was slowly added dropwise while cooling so that the reaction temperature was -60 ° C or lower. After completion of dropping, the reaction solution was stirred at −40 ° C. for 4 hours and at room temperature for 4 hours. Water was added to the reaction mixture to terminate the reaction, and tetrahydrofuran was distilled off. Water and chloroform were added to the resulting residue to extract the organic layer, and the organic layer was washed with water, and then the solvent was distilled off. The residue was dissolved in acetonitrile and the insoluble solid was removed by hot filtration. The obtained filtrate was concentrated, cooled to -70 ° C, and the precipitated solid was collected by filtration. The collected solid was dissolved in a chloroform / hexane mixed solvent and purified by silica gel column chromatography (developing solvent: chloroform / hexane). The solvent was distilled off and the residue was recrystallized from acetonitrile to give 2,4-di (4′-tert-butylphenyl) -6-chloro-1,3,5-triazine (41.3 g, 109 mmol). Got.

The results of LC-MS and ¹ H-NMR analysis of 2,4-di (4′-tert-butylphenyl) -6-chloro-1,3,5-triazine are shown below.
LC-MS (APPI, positive) m / z: 380 ([M + H] ⁺ )
¹ H NMR (300 MHz, CDCl ₃ )
δ (ppm) = 1.39 (s, 18H), 7.56 (d, J = 8.4 Hz, 4H), 8.54 (d, J = 8.4 Hz, 4H)

（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） ・ Synthesis of Luminescent Organometallic Complex Compound MC-3

(In the formula, t-Bu represents a tert-butyl group.)

  Under a nitrogen stream, a metal complex complex 3 (546 mg, 0.53 mmol), 2,4-di (4′-tert-butylphenyl) -6-chloro-1,3,5-triazine (702 mg, 1 .85 mmol), cesium carbonate (1.73 g, 5.31 mmol), tetrakis (triphenylphosphine) palladium (0) (196 mg, 0.17 mmol), and tetrahydrofuran (53 mL) were weighed and refluxed for 9 hours. The reaction solution was concentrated, and toluene was added to dissolve it. This solution was filtered, and the filtrate was purified twice by silica gel chromatography (first developing solvent: toluene, second developing solvent: hexane / toluene = 1/1 (volume ratio)). The solvent was distilled off, and the residue was washed with methanol to obtain a luminescent organometallic complex compound MC-3 (257 mg, 0.15 mmol) represented by the above formula.

The results of LC-MS and ¹ H-NMR analysis of the luminescent organometallic complex compound MC-3 are shown below.
LC-MS (APCI, positive) m / z: 1686 ([M + H] ⁺ )
¹ H NMR (300 MHz, CDCl ₃ )
δ (ppm) = 1.14 (s, 54H), 6.96 (m, 9H), 7.39 (d, J = 8.4 Hz, 12H), 7.83 (d, J = 7.5 Hz, 3H), 8.18 (d, J = 8.4 Hz, 3H), 8.36 (d, J = 8.4 Hz, 12H), 9.14 (d, J = 8.4 Hz, 3H), 9. 33 (s, 3H)

で表される発光性有機金属錯体化合物ＭＣ−４を、国際公開第２００２／４４１８９号に記載の方法に従って合成した。 <Synthesis Example 14>
(Synthesis of Luminescent Organometallic Complex Compound MC-4)
Following formula:

The light-emitting organometallic complex compound MC-4 represented by the following formula was synthesized according to the method described in International Publication No. 2002/44189.

アルゴン気流下、反応容器に、発光性有機金属錯体化合物ＭＣ−１（４．２５ｇ、２．５ ｍｍｏｌ）とクロロホルム（４００ｍＬ）を量り取り、発光性有機金属錯体化合物ＭＣ−１を溶解させた。次いで、Ｎ−ブロモスクシンイミド （８７２ｍｇ、４．９ｍｍｏｌ）を加え、室温で２４時間攪拌した。溶媒を留去し、残渣にクロロホルム／ヘキサン混合溶媒（１００ｍＬ）を加えて溶解させた。得られた溶液をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム／ヘキサン混合溶媒）で精製した。溶出した溶液を回収し、溶媒を留去した後、残渣をメタノールで洗浄することにより、上式で表される金属錯体ｃｏｍｐｌｅｘ４（３．７６ｇ、２．０ｍｍｏｌ）を得た。 <Synthesis Example 15>
(Synthesis of Luminescent Organometallic Complex Compound MC-5)
・ Synthesis of metal complex complex 4

Under a stream of argon, the luminescent organometallic complex compound MC-1 (4.25 g, 2.5 mmol) and chloroform (400 mL) were weighed into the reaction vessel to dissolve the luminescent organometallic complex compound MC-1. Next, N-bromosuccinimide (872 mg, 4.9 mmol) was added, and the mixture was stirred at room temperature for 24 hours. The solvent was distilled off, and a chloroform / hexane mixed solvent (100 mL) was added to the residue to dissolve it. The resulting solution was purified by silica gel chromatography (developing solvent: chloroform / hexane mixed solvent). The eluted solution was recovered, the solvent was distilled off, and the residue was washed with methanol to obtain a metal complex complex4 (3.76 g, 2.0 mmol) represented by the above formula.

The results of MALDI-TOFMS and ¹ H-NMR analysis of metal complex Complex 4 are shown below.
MALDI-TOFMS (positive, [Measurement Method 1]) m / z: 1890 ([M])
¹ H NMR (300 MHz, THF-d ₈ )
δ (ppm) = 1.27 (s, 18H), 1.36 (s, 18H), 1.41 (s, 18H), 6.95 (m, 4H), 7.24 (m, 2H), 7.48 (m, 12H), 7.69 (m, 5H), 7.74 (m, 3H), 7.83 (s, 2H), 7.99 (d, J = 6.0 Hz, 1H) , 8.09 (m, 3H), 8.40 (m, 9H), 8.54 (d, J = 8.6 Hz, 1H), 8.68 (s, 1H), 9.05 (m, 1H) ), 9.22 (m, 2H), 9.28 (d, J = 8.6 Hz, 1H), 9.46 (s, 1H)

アルゴン気流下、反応容器に、金属錯体ｃｏｍｐｌｅｘ４（２．８４ｇ、１．５ｍｍｏｌ）、化合物Ｌ−５（１．５６ｇ、３．３ｍｍｏｌ）、２０重量％テトラエチルアンモニウムヒドロキシド水溶液（５．４２ｇ、７．４ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）（６１ｍｇ、０．０５ｍｍｏｌ）、及びテトラヒドロフラン（９０ｍＬ）を量り取り、１４時間還流した。反応液にトルエンと水を加えて洗浄し、有機層を回収した。この有機層を、飽和食塩水で洗浄し、硫酸ナトリウムで乾燥させた。得られた溶液をろ過し濃縮した。得られた濃縮液をシリカゲルクロマトグラフィー（展開溶媒：トルエン）で精製した。溶出した溶液を回収し、溶媒を留去した後、残渣に、クロロホルム／ヘキサン混合溶媒を加えて溶解させた。得られた溶液をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム／ヘキサン）で精製し、溶媒を留去した。残渣をトルエンに溶解させ、得られた溶液にアセトニトリルを加え、結晶化することにより精製した。得られた固体を濾別して回収し、上式で表される発光性有機金属錯体化合物ＭＣ−５（２．８５ｇ、１．２ｍｍｏｌ）を得た。
なお、化合物Ｌ−５は、ＷＯ０２／６６５５２に記載の方法に準じて合成した。 ・ Synthesis of Luminescent Organometallic Complex Compound MC-5

Under an argon stream, a metal complex complex4 (2.84 g, 1.5 mmol), compound L-5 (1.56 g, 3.3 mmol), 20 wt% tetraethylammonium hydroxide aqueous solution (5.42 g, 7. mmol) were placed in a reaction vessel. 4 mmol), tetrakis (triphenylphosphine) palladium (0) (61 mg, 0.05 mmol), and tetrahydrofuran (90 mL) were weighed and refluxed for 14 hours. Toluene and water were added to the reaction solution for washing, and the organic layer was recovered. The organic layer was washed with saturated brine and dried over sodium sulfate. The resulting solution was filtered and concentrated. The obtained concentrated liquid was purified by silica gel chromatography (developing solvent: toluene). The eluted solution was collected and the solvent was distilled off. The residue was dissolved by adding a chloroform / hexane mixed solvent. The resulting solution was purified by silica gel chromatography (developing solvent: chloroform / hexane), and the solvent was distilled off. The residue was dissolved in toluene, and acetonitrile was added to the resulting solution for purification by crystallization. The obtained solid was collected by filtration to obtain a luminescent organometallic complex compound MC-5 (2.85 g, 1.2 mmol) represented by the above formula.
Compound L-5 was synthesized according to the method described in WO02 / 66552.

The results of MALDI-TOFMS and ¹ H-NMR analysis of metal complex MC-5 are shown below.
MALDI-TOFMS (positive, [Measurement method 1]) m / z: 2413 ([M])
¹ H NMR (300 MHz, THF-d ₈ )
δ (ppm) = 1.26 (s, 18H), 1.37 (s, 18H), 1.38 (s, 18H), 1.40 (s, 18H), 1.42 (s, 18H), 7.26 (d, J = 8.1 Hz, 1H), 7.31 (d, J = 8.1 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.35 (d , J = 8.1 Hz, 1H), 7.39 (d, J = 8.1 Hz, 1H), 7.48 (d, J = 8.4 Hz, 4H), 7.49 (d, J = 8. 3 Hz, 4H), 7.50 (d, J = 8.1 Hz, 4H), 7.51 (d, J = 8.1 Hz, 4H), 7.52 (d, J = 8.5 Hz, 4H), 7.68 (d, J = 8.4 Hz, 4H), 7.69 (d, J = 8.5 Hz, 4H), 7.72 (d, J = 8.3 Hz, 4H), 7.74 (m , 4H), 7.75 (s, 1 ), 7.78 (s, 1H), 7.88 (s, 2H), 7.91 (s, 2H), 7.92 (s, 2H), 8.10 (m, 1H), 8.11 (D, J = 6.2 Hz, 1H), 8.35 (s, 1H), 8.39 (m, 5H), 8.44 (d, J = 8.1 Hz, 4H), 8.56 (d , J = 8.8 Hz, 1H), 8.69 (d, J = 8.8 Hz, 1H), 8.73 (s, 1H), 9.03 (d, J = 8.8 Hz, 1H), 9 .26 (m, 1H), 9.27 (d, J = 8.8 Hz, 1H), 9.38 (s, 1H), 9.51 (s, 1H)

<Hole Transport Polymer Compound HP-1>
The hole transporting polymer compound HP-1 was prepared by the following procedure.
Under an inert gas atmosphere, Compound M-8 (17.3 g), Compound M-6 (10.4 g), 9,9-dioctyl-2,7-dibromofluorene (2.62 g), 9,9-bis ( Benzocyclobuten-4-yl) -2,7-dibromofluorene (1.51 g) and toluene (580 mL) were mixed and stirred while heating. Thereto, palladium acetate (4.30 mg) and tris (2-methoxyphenyl) phosphine (27.0 mg) were added and heated to 100 ° C., and then a 20 wt% tetraethylammonium hydroxide aqueous solution (68.5 g) was added dropwise. And heated to reflux for 7 hours.
Next, phenylboric acid (0.230 g), bis (triphenylphosphine) palladium dichloride (13.4 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (68.5 g) were added, and the mixture was heated to reflux overnight.
After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (10.8 g) and ion-exchanged water (120 mL) were added and stirred at 40 ° C. for 3 hours.
In the reaction solution, after separating the organic layer and the aqueous layer, the organic layer was washed sequentially with ion-exchanged water once, twice with 10% by weight hydrochloric acid, twice with 3% by weight aqueous ammonia solution and twice with ion-exchanged water. did.
The obtained organic layer was passed through a column filled with silica gel and alumina previously passed through toluene, and the passed solution was dropped into methanol to deposit a precipitate. The precipitate was collected by filtration and dried to obtain 19.5 g of a polymer compound (hereinafter referred to as “polymer compound HP-1”). The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound HP-1 were Mn = 7.5 × 10 ⁴ and Mw = 3.6 × 10 ⁵ , respectively.
The polymer compound HP-1 has the following structural units and molar ratios from the charging ratio of raw material monomers, and the structural unit (PA) and the structural unit selected from (PB) are alternately polymerized. Presumed to be a molecular compound.

（式中、Ｍｅはメチル基、ｎ−Ｂｕはｎ−ブチル基を表す。） <Hole transporting polymer compound HP-2>
The hole transporting polymer compound HP-2 was prepared by the following procedure.
Under inert gas atmosphere, Compound M-8 (0.9339 g), N, N′-bis (4-bromophenyl) -N, N′-bis (2,6-dimethyl-4-n-butylphenyl)- 1,4-phenylenediamine (1.9223 g), 9,9-dioctyl-2,7-dibromofluorene (0.5947 g), 9,9-bis (benzocyclobuten-4-yl) -2,7-dibromo Fluorene (0.3437 g) and toluene (118 mL) were mixed and stirred while heating. To the reaction solution, palladium acetate (1.0 mg) and tris (2-methoxyphenyl) phosphine (6.1 mg) were added and heated to 100 ° C., and then a 20 wt% tetraethylammonium hydroxide aqueous solution (15.3 g). Was added dropwise and refluxed with heating for 11 hours.
Next, phenylboric acid (0.053 g), palladium acetate (1.0 mg), tris (2-methoxyphenyl) phosphine (6.1 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (15. 3g) was added and refluxed with heating overnight.
After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (2.41 g) and ion-exchanged water (48 mL) were added and stirred at 85 ° C. for 2 hours.
In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.
The obtained organic layer was dropped into methanol, and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol, and the resulting precipitate was collected by filtration and dried to obtain 3.71 g of a hole transporting polymer compound HP-2. The number average molecular weight and weight average molecular weight in terms of polystyrene measured under analysis condition 1 were Mn = 5.6 × 10 ⁴ and Mw = 1.5 × 10 ⁵ , respectively.
The hole transporting polymer compound HP-2 has the following structural units and molar ratios based on the monomer charge ratio, and the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized. It is estimated that the polymer compound.

(In the formula, Me represents a methyl group, and n-Bu represents an n-butyl group.)

[Example 1]
<Synthesis of Polymer Compound A>
In an inert gas atmosphere, compound M-1 (2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,4-dihexylbenzene) (1 .451 g), Compound M-2 (2,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -toluene) (0.424 g), Compound M- 3 (9,9-bis (4-n-hexylphenyl) -2,7-dibromofluorene) (2.120 g), compound M-4 (2,4-bis (4-bromophenyl) -6- (4 -N-dodecylphenyl) -1,3,5-triazine (0.523 g)) and toluene (59 mL) were mixed and stirred while heating. Palladium acetate (1.4 mg) and tris (2-methoxyphenyl) phosphine (8.7 mg) were added, 20 wt% tetraethylammonium hydroxide aqueous solution (14.7 g) was added dropwise, and the mixture was heated to reflux for 17 hours.

  Next, phenylboric acid (0.051 g), palladium acetate (1.4 mg), tris (2-methoxyphenyl) phosphine (8.7 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (14.7 g) were added. Heated to reflux for 17 hours.

  After removing the aqueous layer, sodium N, N-diethyldithiocarbamate trihydrate (2.28 g) and ion-exchanged water (46 mL) were added and stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed twice with ion-exchanged water, twice with a 3 wt% aqueous acetic acid solution, and twice with ion-exchanged water.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 2.43 g of a polymer compound (hereinafter referred to as “polymer compound A”). The number average molecular weight and weight average molecular weight in terms of polystyrene measured under the analysis condition 2 of the polymer compound A were Mn = 8.6 × 10 ⁴ and Mw = 2.8 × 10 ⁵ , respectively.

  Polymer compound A has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

<Production and Evaluation of Organic EL Device>
A glass substrate having an ITO film with a thickness of 45 nm formed by sputtering is applied with a solution of polythiophenesulfonic acid in ethylene glycol monobutyl ether / water (3/2 (volume ratio)) (Sigma Aldrich, trade name: Plexcore OC 1200). The film was spin-coated to form a film having a thickness of 65 nm and dried on a hot plate at 170 ° C. for 15 minutes.

  Next, the hole transporting polymer compound HP-1 was spin-coated in a 0.7 wt% xylene solution to form a film having a thickness of about 20 nm. Then, it heated at 180 degreeC for 60 minutes on the hotplate.

Subsequently, a solution of polymer compound A dissolved in xylene solvent at a concentration of 1.8% by weight, and a luminescent organometallic complex compound MC-1 dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 1 was prepared by mixing so that the weight ratio was 70:30. The composition 1 was formed by spin coating at a rotational speed of 1800 rpm. The film thickness was about 80 nm. After drying this at 130 ° C. for 10 minutes under a nitrogen gas atmosphere, about 3 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode to produce an organic EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

When voltage was applied to the obtained organic EL device, electroluminescence light emission (hereinafter referred to as EL light emission) having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light at 3.0 V, showed light emission of 1000 cd / m ^{2 at} 6.2 V, and had a maximum light emission efficiency of 60.88 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 72.1 hours, and was attenuated to 70% of the initial luminance after 235 hours.

[Example 2]
<Synthesis of polymer compound B>
Under an inert gas atmosphere, compound M-1 (2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,4-dihexylbenzene) (8 182 g), compound M-3 (9,9-bis (4-n-hexylphenyl) -2,7-dibromofluorene) (8.508 g), compound M-4 (2,4-bis (4-bromo) Phenyl) -6- (4-n-dodecylphenyl) -1,3,5-triazine) (2.097 g) and toluene (250 mL) were mixed and stirred while heating. Palladium acetate (3.7 mg) and tris (2-methoxyphenyl) phosphine (23.2 mg) were added and heated to 100 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (61.3 g) was added dropwise to the resulting solution, and the mixture was heated to reflux for 8 hours.

  Next, phenylboric acid (0.20 g), palladium acetate (3.7 mg), tris (2-methoxyphenyl) phosphine (23.3 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (58.3 g) were added. Heated to reflux for 15 hours.

  After removing the aqueous layer, sodium N, N-diethyldithiocarbamate trihydrate (9.31 g) and ion-exchanged water (60 mL) were added and stirred at 40 ° C. for 3 hours.

  After the organic layer was separated from the aqueous layer, the organic layer was washed with ion-exchanged water once, twice with 10% by weight hydrochloric acid, twice with 3% by weight aqueous ammonia solution and twice with ion-exchanged water.

The organic layer was passed through a column filled with silica gel and alumina which had been passed through toluene in advance, and the passed solution was dropped into methanol to precipitate a precipitate. The precipitate was collected by filtration and dried to obtain 9.80 g of a polymer compound (hereinafter referred to as “polymer compound B”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on the analysis condition 1 of the polymer compound B were Mn = 9.2 × 10 ⁴ and Mw = 2.3 × 10 ⁵ , respectively.

  Polymer compound B has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound B dissolved in xylene solvent at a concentration of 1.9% by weight and dissolved in xylene solvent at a concentration of 1.9% by weight An organic EL device was produced in the same manner as in Example 1 except that the composition 2 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-1 in a weight ratio of 70:30. did.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light at 2.9 V, showed light emission of 1000 cd / m ² at 5.8 V, and had a maximum light emission efficiency of 55.4 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 101.6 hours, and was attenuated to 70% of the initial luminance after 262.5 hours.

[Example 3]
<Synthesis of polymer compound C>
In an inert gas atmosphere, compound M-1 (2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,4-dihexylbenzene) (1 688 g), compound M-2 (2,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -toluene) (0.497 g), compound M- 3 (9,9-bis (4-n-hexylphenyl) -2,7-dibromofluorene) (2.484 g), compound M-5 (2,4-bis (4-bromophenyl) -6- (4 -N-hexylphenyl) -1,3,5-triazine (0.531 g)) and toluene (66 mL) were mixed and stirred while heating. Palladium acetate (1.7 mg) and tris (2-methoxyphenyl) phosphine (10.2 mg) were added, 20 wt% tetraethylammonium hydroxide aqueous solution (17.2 g) was added dropwise, and the mixture was heated to reflux for 7 hours.

  Next, phenylboric acid (0.059 g), palladium acetate (1.7 mg), tris (2-methoxyphenyl) phosphine (10.3 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (17.1 g) were added. Heated to reflux for 15 hours.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (2.68 g) and ion-exchanged water (54 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 2.81 g of a polymer compound (hereinafter referred to as “polymer compound C”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on the analysis condition 2 of the polymer compound C were Mn = 8.1 × 10 ⁴ and Mw = 2.8 × 10 ⁵ , respectively.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound C dissolved in a xylene solvent at a concentration of 1.9% by weight and a solution of the polymer compound C dissolved in a xylene solvent at a concentration of 1.9% by weight An organic EL device was produced in the same manner as in Example 1 except that the composition 3 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-1 in a weight ratio of 70:30. did.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light from 2.9 V, showed light emission of 1000 cd / m ² at 6.1 V, and had a maximum light emission efficiency of 61.8 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 44.4 hours, and was attenuated to 70% of the initial luminance after 163.5 hours.

Polymer compound C has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

[Example 4]
<Synthesis of polymer compound D>
Under an inert gas atmosphere, compound M-1 (2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,4-dihexylbenzene (2. 807 g)), compound M-3 (9,9-bis (4-n-hexylphenyl) -2,7-dibromofluorene) (2.903 g), compound M-5 (2,4-bis (4-bromo Phenyl) -6- (4-n-hexylphenyl) -1,3,5-triazine) (0.621 g) and toluene (85 mL) were mixed and stirred while heating. Palladium acetate (1.9 mg) and tris (2-methoxyphenyl) phosphine (11.9 mg) were added, 20 wt% tetraethylammonium hydroxide aqueous solution (19.9 g) was added dropwise, and the mixture was heated to reflux for 5 hours.

  Next, phenylboric acid (0.069 g), palladium acetate (1.9 mg) and tris (2-methoxyphenyl) phosphine (11.9 mg) were added, and the mixture was heated to reflux for 15.5 hours.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (3.13 g) and ion-exchanged water (63 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through the solution was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 3.52 g of a polymer compound (hereinafter referred to as “polymer compound D”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on the analysis condition 1 of the polymer compound D were Mn = 1.5 × 10 ⁵ and Mw = 4.7 × 10 ⁵ , respectively.

  Polymer compound D has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound D dissolved in a xylene solvent at a concentration of 1.5% by weight and a solution of the polymer compound D dissolved in a xylene solvent at a concentration of 1.5% by weight were used. An organic EL device was produced in the same manner as in Example 1 except that the composition 4 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-1 at a weight ratio of 70:30. did.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light from 2.9 V, showed light emission of 1000 cd / m ^{2 at} 6.0 V, and had a maximum light emission efficiency of 56.48 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 19.6 hours, and was attenuated to 70% of the initial luminance after 75.4 hours.

[Comparative Example 1]
<Synthesis of polymer compound E>
In an inert gas atmosphere, compound M-1 (2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,4-dihexylbenzene) (3 124g), 9,9-dioctyl-2,7-dibromofluorene (2.770 g), compound M-5 (2,4-bis (4-bromophenyl) -6- (4-n-hexylphenyl)- 1,3,5-triazine (0.696 g)) and toluene (82 mL) were mixed and stirred while heating. Palladium acetate (2.1 mg) and tris (2-methoxyphenyl) phosphine (13.4 mg) were added, 20 wt% tetraethylammonium hydroxide aqueous solution (22.3 g) was added dropwise, and the mixture was heated to reflux for 5 hours.

  Next, phenylboric acid (0.078 g), palladium acetate (2.1 mg), tris (2-methoxyphenyl) phosphine (13.3 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (22.3 g) were added. Heated to reflux for 17.5 hours.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (3.51 g) and ion-exchanged water (70 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water three times, 3% by weight acetic acid aqueous solution three times, and ion-exchanged water three times in this order.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 3.43 g of a polymer compound (hereinafter referred to as “polymer compound E”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on the analysis condition 2 of the polymer compound E were Mn = 1.6 × 10 ⁵ and Mw = 5.2 × 10 ⁵ , respectively.

  Polymer compound E has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized Is done.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound E dissolved in xylene solvent at a concentration of 1.6% by weight and dissolved in xylene solvent at a concentration of 1.6% by weight An organic EL device was produced in the same manner as in Example 1 except that the composition 5 was prepared by mixing a solution of the light-emitting organometallic complex compound MC-1 at a weight ratio of 70:30. did.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light at 3.0 V, showed light emission of 1000 cd / m ^{2 at} 6.7 V, and had a maximum light emission efficiency of 47.54 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 11.3 hours, and was attenuated to 70% of the initial luminance after 28.9 hours.

[Example 5]
<Synthesis of polymer compound F>
Under an inert gas atmosphere, 9,9-bis (4-n-hexylphenyl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- Fluorene (2.875 g), 9,9-dioctyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -fluorene (0.942 g), 9,9-bis (3-n-hexylphenyl) -2,7-dibromofluorene (2.194 g), compound M-4 (2,4-bis (4-bromophenyl) -6- (4-n- Dodecylphenyl) -1,3,5-triazine) (0.666 g), N, N′-bis (4-bromophenyl) -N, N′-bis (2,6-dimethyl-4-tert-butylphenyl) ) -1,4-phenylenediamine (0.580 g) And they were mixed in toluene (114 mL), and stirred with heating. Bistriphenylphosphine palladium dichloride (3.7 mg) was added and heated to 100 ° C., a 20 wt% tetraethylammonium hydroxide aqueous solution (18.5 g) was added dropwise, and the mixture was heated to reflux for 8 hours.

  Next, phenylboric acid (0.065 g), bistriphenylphosphine palladium dichloride (3.7 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (18.5 g) were added, and the mixture was heated to reflux overnight.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (2.91 g) and ion-exchanged water (58 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 4.28 g of a polymer compound (hereinafter referred to as “polymer compound F”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on Analysis Condition 2 of the polymer compound F were Mn = 9.0 × 10 ⁴ and Mw = 2.4 × 10 ⁵ , respectively.

  Polymer compound F has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, the hole transporting polymer compound HP-2 was spin-coated in a 0.7% by weight xylene solution and formed into a film having a thickness of about 20 nm. A solution of polymer compound F dissolved in xylene solvent at a concentration of 1.6% by weight; and a solution of luminescent organometallic complex compound MC-2 dissolved in xylene solvent at a concentration of 1.6% by weight; Were mixed at a weight ratio of 92.5: 7.5, and the composition 6 was prepared, and the film thickness of the composition 6 was about 80 nm at a rotational speed of 1550 rpm by spin coating. An organic EL element was produced in the same manner as in Example 1 except that the film was formed so that

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-2 was obtained from this device. The device started to emit light at 2.3 V, showed light emission of 1000 cd / m ² at 4.7 V, and had a maximum light emission efficiency of 21.15 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 525 hours, and was attenuated to 70% of the initial luminance after 1244.4 hours.

[Example 6]
<Synthesis of polymer compound G>
Under an inert gas atmosphere, 9,9-bis (4-n-hexylphenyl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- Fluorene (2.021 g), 9,9-dioctyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -fluorene (0.691 g), 9,9-bis (3-n-hexylphenyl) -2,7-dibromofluorene (1.608 g), compound M-5 (2,4-bis (4-bromophenyl) -6- (4-n- (Hexylphenyl) -1,3,5-triazine) (0.423 g), N, N′-bis (4-bromophenyl) -N, N′-bis (2,6-dimethyl-4-tert-butylphenyl) ) -1,4-phenylenediamine (0.425 g) And they were mixed in toluene (82 mL), and stirred with heating. Bistriphenylphosphine palladium dichloride (2.7 mg) was added, 20 wt% tetraethylammonium hydroxide aqueous solution (13.7 g) was added dropwise, and the mixture was heated to reflux for 7 hours.

  Next, phenylboric acid (0.047 g), bistriphenylphosphine palladium dichloride (1.4 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (13.6 g) were added, and the mixture was heated to reflux for 16.5 hours.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (1.81 g) and ion-exchanged water (36 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol, and the resulting precipitate was collected by filtration and dried to obtain 3.04 g of a polymer compound (hereinafter referred to as “polymer compound G”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on the analysis condition 2 of the polymer compound G were Mn = 9.1 × 10 ⁴ and Mw = 2.5 × 10 ⁵ , respectively.

  Polymer compound G has the following repeating units and molar ratios from the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound F dissolved at a concentration of 1.5% by weight and a luminescent organometallic dissolved in a xylene solvent at a concentration of 1.5% by weight An organic EL device was produced in the same manner as in Example 5 except that the composition 7 was prepared by mixing the solution of the complex compound MC-2 in a weight ratio of 92.5: 7.5. did.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the light-emitting organometallic complex compound MC-2 was obtained from this device. The device started to emit light at 2.5 V, showed light emission of 1000 cd / m ^{2 at} 5.0 V, and the maximum light emission efficiency was 16.93 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance attenuated to 80% of the initial luminance after 105 hours, and attenuated to 70% of the initial luminance after 408 hours.

[Comparative Example 2]
<Synthesis of polymer compound H>
Under an inert gas atmosphere, 9,9-dioctyl-2,7-bis (1,3,2-dioxaborolan-2-yl) -fluorene (2.652 g), 9,9-dioctyl-2,7-dibromofluorene (1.920 g), 2,4-bis (4-bromophenyl) -6- (4-n-hexylphenyl) -1,3,5-triazine (0.531 g), N, N′-bis (4 -Bromophenyl) -N, N′-bis (2,6-dimethyl-4-tert-butylphenyl) -1,4-phenylenediamine (0.369 g), methyltrioctylammonium chloride (trade name: Aliquat 336, Aldrich) (0.65 g) and toluene (50 mL) were mixed and stirred while heating. Bistriphenylphosphine palladium dichloride (3.5 mg) was added, 17.5 wt% aqueous sodium carbonate solution (13.5 mL) was added dropwise, and the mixture was heated to reflux for 3 hours.

  Next, phenylboric acid (0.610 g), bistriphenylphosphine palladium dichloride (3.5 mg), and toluene (50 mL) were added, and the mixture was heated to reflux for 16 hours.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (3.04 g) and ion-exchanged water (30 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer was separated from the aqueous layer, and then the organic layer was washed with ion-exchanged water twice, 3% by weight aqueous acetic acid solution twice, and ion-exchanged water twice.

The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and a toluene solution was passed through a silica gel / alumina column through which toluene was passed in advance. The eluate after passing through was dropped into methanol and the resulting precipitate was collected by filtration and dried to obtain 3.48 g of a polymer compound (hereinafter referred to as “polymer compound H”). The number-average molecular weight and weight-average molecular weight in terms of polystyrene measured based on Analysis Condition 1 of the polymer compound H were Mn = 1.4 × 10 ⁵ and Mw = 3.7 × 10 ⁵ , respectively.

  Polymer compound H has the following repeating units and molar ratios based on the monomer charge ratio, and is estimated to be a polymer compound in which (PA) repeating units and repeating units selected from (PB) are alternately polymerized. Is done.

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

<Production and Evaluation of Organic EL Device>
In Example 5, in place of the composition 6, a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.6% by weight and a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.6% by weight. In the same manner as in Example 5 except that the composition 8 was prepared by mixing a solution of the light-emitting organometallic complex compound MC-2 in a weight ratio of 92.5: 7.5. An EL element was produced.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-2 was obtained from this device. The device started to emit light at 2.5 V, showed light emission of 1000 cd / m ^{2 at} 5.5 V, and the maximum light emission efficiency was 18.20 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance attenuated to 80% of the initial luminance after 63 hours, and attenuated to 70% of the initial luminance after 148.2 hours.

[Example 7]
<Synthesis of polymer compound I>
In a reaction vessel in which the internal gas was replaced with nitrogen gas, 1,4-bis (1,3,2-dioxaborolan-2-yl) -2,5-dihexylbenzene (1.11 g, 2.23 mmol), 1, 3-bis (1,3,2-dioxaborolan-2-yl) -2-methylbenzene (0.19 g, 0.56 mmol), 2,7-dibromo-9,9-bis (4-hexylphenyl) fluorene ( 1.44 g, 2.24 mmol), compound M-9 (0.43 g, 0.56 mmol), palladium acetate (II) 0.6 mg, tris (2-methoxyphenyl) phosphine 3.9 mg, and toluene 43 mL were weighed out. And mixing at 100 ° C. while heating. To the reaction solution, 10 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 5 hours. After the reaction, 69 mg of phenylboric acid, 0.6 mg of palladium (II) acetate, 3.9 mg of tris (2-methoxyphenyl) phosphine, 7 mL of toluene, and 10 ml of 20 wt% tetraethylammonium hydroxide aqueous solution were added, and the mixture was further refluxed for 15 hours. . Next, 16 ml of a 0.2 M sodium diethyldithiocarbamate aqueous solution was added, and the mixture was stirred at 85 ° C. for 2 hours. The reaction solution was cooled to room temperature, diluted with toluene, and then washed successively with water twice, 3% by weight acetic acid aqueous solution twice, and water four times. When the organic layer was dropped into methanol, precipitation occurred. The precipitate was filtered and dried to obtain a solid. This solid was dissolved in toluene, and the resulting solution was purified by passing through an alumina column and a silica gel column. When the eluate was dropped into methanol, 1.56 g of a polymer compound (hereinafter referred to as “polymer compound I”) was obtained. The polymer compound I had a polystyrene-equivalent number average molecular weight of 5.0 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ , measured based on Analysis Condition 2.

で表される繰り返し単位と、下記式：

（式中、Ｍｅはメチル基を表す。）
で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）
で表される繰り返し単位とが、４０：１０：４０：１０のモル比で含まれる共重合体である。 The polymer compound I has the following formula:

And a repeating unit represented by the following formula:

(In the formula, Me represents a methyl group.)
And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

(In the formula, t-Bu represents a tert-butyl group.)
Is a copolymer contained in a molar ratio of 40: 10: 40: 10.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound I dissolved in a xylene solvent at a concentration of 2.2% by weight and a solution of the polymer compound I at a concentration of 2.2% by weight were dissolved in the xylene solvent. The composition 9 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-1 in a weight ratio of 70:30, and the composition 9 was spin-coated at a rotational speed of 1600 rpm. An organic EL element was produced in the same manner as in Example 1 except that the film was formed in the same manner as in Example 1.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light at 2.64 V, showed light emission of 1000 cd / m ² at 5.7 V, and had a maximum light emission efficiency of 62.80 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 82 hours.

[Example 8]
<Synthesis of polymer compound J>
In a reaction vessel in which the internal gas was replaced with nitrogen gas, 1,4-bis (1,3,2-dioxaborolan-2-yl) -2,5-dihexylbenzene (1.00 g, 2.00 mmol), 1, 3-bis (1,3,2-dioxaborolan-2-yl) -2-methylbenzene (0.17 g, 0.50 mmol), 2,7-dibromo-9,9-bis (4-hexylphenyl) fluorene ( 1.29 g, 2.00 mmol), compound M-10 (0.58 g, 0.5 mmol), palladium (II) acetate 0.6 mg, tris (2-methoxyphenyl) phosphine 3.5 mg, and toluene 44 mL were weighed out. And mixing at 100 ° C. while heating. To the reaction solution, 9 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 11 hours. After the reaction, 62 mg of phenylboric acid, 0.6 mg of palladium (II) acetate, 3.5 mg of tris (2-methoxyphenyl) phosphine, 7 mL of toluene, and 9 mL of 20 wt% tetraethylammonium hydroxide aqueous solution were added, and the mixture was further refluxed for 15 hours. . Subsequently, 14 mL of 0.2 M sodium diethyldithiocarbamate aqueous solution was added, and the mixture was stirred at 85 ° C. for 2 hours. The reaction solution was cooled to room temperature, diluted with toluene, and washed successively with water twice, 3% by weight acetic acid aqueous solution twice, and water six times. When the organic layer was dropped into methanol, precipitation occurred. The precipitate was filtered and dried to obtain a solid. This solid was dissolved in toluene and purified by passing through the resulting solution alumina column and silica gel column. When the eluate was dropped into methanol, 1.46 g of a polymer compound (hereinafter referred to as “polymer compound J”) was obtained. The polymer compound J had a polystyrene-equivalent number average molecular weight of 4.9 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ , measured based on Analysis Condition 2.

で表される繰り返し単位と、下記式：

（式中、Ｍｅはメチル基を表す。）
で表される繰り返し単位と、下記式：

で表される繰り返し単位と、下記式：

（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）
で表される繰り返し単位とが、４０：１０：４０：１０のモル比で含まれる共重合体である。 The polymer compound J has the following formula:

And a repeating unit represented by the following formula:

(In the formula, Me represents a methyl group.)
And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

(In the formula, t-Bu represents a tert-butyl group.)
Is a copolymer contained in a molar ratio of 40: 10: 40: 10.

<Production and Evaluation of Organic EL Device>
In Example 1, instead of the composition 1, a solution of the polymer compound J dissolved in a xylene solvent at a concentration of 2.2% by weight and a solution of the polymer compound J dissolved in a xylene solvent at a concentration of 2.2% by weight were used. The composition 10 was prepared by mixing the light-emitting organometallic complex compound MC-1 with the solution in a weight ratio of 70:30, and the composition 10 was spin-coated at a rotational speed of 1690 rpm. An organic EL element was produced in the same manner as in Example 1 except that the film was formed in the same manner as in Example 1.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 520 nm derived from the light-emitting organometallic complex compound MC-1 was obtained from this device. The device started to emit light at 2.69 V, showed light emission of 1000 cd / m ² at 5.4 V, and had a maximum light emission efficiency of 58.50 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 100 hours.

[Example 9]
<Production and Evaluation of Organic EL Device>
In Example 7, instead of the composition 9, a solution of the polymer compound I dissolved in a xylene solvent at a concentration of 2.2% by weight and a solution of the polymer compound I at a concentration of 2.2% by weight were dissolved in the xylene solvent. The composition 11 was prepared by mixing the light-emitting organometallic complex compound MC-3 with a solution at a weight ratio of 70:30, and the composition 11 was spin-coated at a rotational speed of 1580 rpm. An organic EL element was produced in the same manner as in Example 7 except that the film was formed in the same manner as in Example 7.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 605 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.74 V, showed light emission of 1000 cd / m ² at 7.6 V, and had a maximum light emission efficiency of 27.80 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 41.9 hours.

[Example 10]
<Production and Evaluation of Organic EL Device>
In Example 8, instead of the composition 10, a solution of the polymer compound J dissolved in a xylene solvent at a concentration of 2.2% by weight and a solution of the polymer compound J dissolved in a xylene solvent at a concentration of 2.2% by weight. The composition 12 was prepared by mixing the light-emitting organometallic complex compound MC-3 with a solution at a weight ratio of 70:30, and the composition 12 was spin-coated at a rotation speed of 1620 rpm. An organic EL element was produced in the same manner as in Example 8 except that the film was formed in the same manner as in Example 8.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 605 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.82 V, showed light emission of 1000 cd / m ^{2 at} 7.7 V, and had a maximum light emission efficiency of 24.60 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 50.6 hours.

[Comparative Example 3]
<Production and Evaluation of Organic EL Device>
In Comparative Example 1, instead of the composition 5, a solution of the polymer compound E dissolved in xylene solvent at a concentration of 2.2% by weight and dissolved in xylene solvent at a concentration of 2.2% by weight. The solution of the light-emitting organometallic complex compound MC-3 was mixed at a weight ratio of 70:30 to prepare a composition 13, and the composition 13 was spin-coated at a rotational speed of 2400 rpm. An organic EL element was produced in the same manner as in Comparative Example 1 except that the film was formed in the above step.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 605 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.96 V, showed 1000 cd / m ² at 8.3 V, and had a maximum light emission efficiency of 23.00 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 5.3 hours.

[Example 11]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound F dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 14 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-4 with a weight ratio of 92.5: 7.5, and the composition 14 was prepared by spin coating. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2540 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 625 nm derived from the light-emitting organometallic complex compound MC-4 was obtained from this device. The device started light emission from 2.41 V, showed light emission of 1000 cd / m ^{2 at} 4.5 V, and the maximum light emission efficiency was 11.70 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 107.2 hours. This was 6.7 times longer than that of Comparative Example 4.

[Example 12]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound F dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The solution of the luminescent organometallic complex compound MC-3 was mixed at a weight ratio of 92.5: 7.5 to prepare the composition 15, and the composition 15 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2570 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 600 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.29 V, emitted 1000 cd / m ^{2 at} 4.2 V, and had a maximum luminous efficiency of 31.20 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 593.8 hours. This was 5.76 times longer than that of Comparative Example 5.

[Example 13]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound F dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 16 was prepared by mixing the light-emitting organometallic complex compound MC-5 with a solution at a weight ratio of 92.5: 7.5, and the composition 16 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2740 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-5 was obtained from this device. The device started to emit light at 2.39 V, showed light emission of 1000 cd / m ^{2 at} 5.0 V, and had a maximum light emission efficiency of 20.40 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 493.6 hours. This was 8.9 times longer than that of Comparative Example 6.

[Example 14]
<Synthesis of polymer compound K>
Under an inert gas atmosphere, 9,9-bis (4-n-hexylphenyl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- Fluorene (2.79 g), 9,9-dioctyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -fluorene (0.943 g), 9,9-bis (3-n-hexylphenyl) -2,7-dibromofluorene (1.86 g), 2,4-bis (4-bromophenyl) -6- (4-n-dodecylphenyl) -1 , 3,5-triazine (0.999 g), N, N′-bis (4-bromophenyl) -N, N′-bis (2,6-dimethyl-4-tert-butylphenyl) -1,4- Phenylenediamine (0.581 g) and toluene (114 L) were mixed and stirred under heating. Bis (triphenylphosphine) palladium dichloride (3.70 mg) was added to the mixture and heated to 100 ° C., 20 wt% tetraethylammonium hydroxide aqueous solution (18.5 g) was added dropwise, and the mixture was heated to reflux.
Next, phenylboric acid (0.0650 g), bis (triphenylphosphine) palladium dichloride (3.70 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (18.5 g) were added, and the mixture was heated to reflux overnight.
After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (2.91 g) and ion-exchanged water (58 mL) were added and stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer and the aqueous layer were separated, and the organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid aqueous solution twice, and ion-exchanged water three times.
The organic layer was added dropwise to methanol and the resulting precipitate was collected by filtration and then dried to obtain a solid. This solid was dissolved in toluene, and the resulting solution was passed through a silica gel / alumina column through which toluene was passed in advance. The passed solution was added dropwise to methanol to precipitate a precipitate. The precipitate was collected by filtration and dried to obtain 4.25 g of a polymer compound (hereinafter referred to as “polymer compound K”). The number-average molecular weight (Mn) and weight-average molecular weight (Mw) in terms of polystyrene measured based on analysis condition 2 of the polymer compound K are Mn = 1.4 × 10 ⁵ and Mw = 4.3 × 10, respectively. It was ⁵ .

（式中、Ｍｅはメチル基、ｎ−Ｂｕはｎ−ブチル基を表す。） Polymer compound K has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized. Is done.

(In the formula, Me represents a methyl group, and n-Bu represents an n-butyl group.)

<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound K dissolved in a xylene solvent at a concentration of 1.8% by weight and a solution of the polymer compound K at a concentration of 1.8% by weight were dissolved in the xylene solvent. The composition 17 was prepared by mixing the light-emitting organometallic complex compound MC-4 with a solution at a weight ratio of 92.5: 7.5, and the composition 17 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2000 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 625 nm derived from the light-emitting organometallic complex compound MC-4 was obtained from this device. The device started to emit light at 2.34 V, showed light emission of 1000 cd / m ^{2 at} 4.2 V, and the maximum light emission efficiency was 11.40 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 71.1 hours. This was 4.44 times longer than that of Comparative Example 4.

[Example 15]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound K dissolved in a xylene solvent at a concentration of 1.8% by weight and a solution of the polymer compound K at a concentration of 1.8% by weight were dissolved in the xylene solvent. The solution of the luminescent organometallic complex compound MC-3 was mixed at a weight ratio of 92.5: 7.5 to prepare the composition 18, and the composition 18 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2120 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 600 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.26 V, showed light emission of 1000 cd / m ^{2 at} 3.9 V, and the maximum light emission efficiency was 30.90 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 360.2 hours. This was 3.49 times longer than that of Comparative Example 5.

[Example 16]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound K dissolved in a xylene solvent at a concentration of 1.8% by weight and a solution of the polymer compound K at a concentration of 1.8% by weight were dissolved in the xylene solvent. The composition 19 was prepared by mixing the light-emitting organometallic complex compound MC-5 with a solution at a weight ratio of 92.5: 7.5, and the composition 19 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotation speed of 2090 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-5 was obtained from this device. The device started to emit light at 2.27 V, showed light emission of 1000 cd / m ^{2 at} 4.3 V, and the maximum light emission efficiency was 19.60 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 297.1 hours. This was 5.35 times longer than that of Comparative Example 6.

[Example 17]
<Synthesis of polymer compound L>
Under an inert gas atmosphere, 9,9-bis (4-n-hexylphenyl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- Fluorene (0.754 g), 9,9-dioctyl-2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -fluorene (0.259 g), 9,9-bis (3-n-hexylphenyl) -2,7-dibromofluorene (0.602 g), 2,4-bis (4-bromophenyl) -6- (3,5-bis (4-tert -Butylphenyl) phenyl) -1,3,5-triazine (0.210 g), N, N'-bis (4-bromophenyl) -N, N'-bis (2,6-dimethyl-4-tert- Butylphenyl) -1,4-phenylenediamine (0 159 g) and mixed toluene (35 mL), and stirred with heating. Bis (triphenylphosphine) palladium dichloride (1.0 mg) was added to the mixture and heated to 100 ° C., 20 wt% tetraethylammonium hydroxide aqueous solution (7.64 g) was added dropwise, and the mixture was heated to reflux for 5 hours.

  Next, phenylboric acid (0.035 g), bis (triphenylphosphine) palladium dichloride (1.0 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.64 g) were added, and the mixture was heated to reflux overnight.

  After removing the aqueous layer from the reaction solution, sodium N, N-diethyldithiocarbamate trihydrate (0.40 g) and ion-exchanged water (8 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. In the reaction solution, the organic layer and the aqueous layer were separated, and then the organic layer was washed successively with 3.6 wt% hydrochloric acid twice, 2.5 wt% aqueous ammonia solution twice, and ion-exchanged water four times.

The organic layer was added dropwise to methanol to precipitate a precipitate. The precipitate was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene, and the resulting solution was passed through a silica gel / alumina column through which toluene was passed in advance. The solution thus passed was dropped into methanol, and the resulting precipitate was collected by filtration and dried to obtain 1.21 g of a polymer compound (hereinafter referred to as “polymer compound L”). The number-average molecular weight (Mn) and weight-average molecular weight (Mw) in terms of polystyrene measured based on analysis condition 2 of the polymer compound L are Mn = 7.3 × 10 ⁴ and Mw = 2.1 × 10, respectively. It was ⁵ .

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） Polymer compound L has the following structural units and molar ratios from the monomer charge ratio, and is a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized: Presumed.

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound L dissolved in a xylene solvent at a concentration of 2.0% by weight and a solution of the polymer compound L at a concentration of 2.0% by weight were dissolved in the xylene solvent. The composition 20 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-2 with a weight ratio of 92.5: 7.5, and the composition 20 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 3500 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-2 was obtained from this device. The device started to emit light at 2.28 V, showed light emission of 1000 cd / m ^{2 at} 4.4 V, and had a maximum light emission efficiency of 18.20 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 238.2 hours. This was 3.78 times longer than that of Comparative Example 2.

[Example 18]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound L dissolved in a xylene solvent at a concentration of 2.0% by weight and a solution of the polymer compound L at a concentration of 2.0% by weight were dissolved in the xylene solvent. The composition 21 was prepared by mixing the light-emitting organometallic complex compound MC-3 with a solution at a weight ratio of 92.5: 7.5, and the composition 21 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 3000 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 600 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.24 V, showed light emission of 1000 cd / m ^{2 at} 4.2 V, and the maximum luminous efficiency was 29.80 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 517.3 hours. This was 5.02 times longer than that of Comparative Example 5.

[Example 19]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound G dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 22 was prepared by mixing the light-emitting organometallic complex compound MC-4 with a solution at a weight ratio of 92.5: 7.5, and the composition 22 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2500 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 625 nm derived from the light-emitting organometallic complex compound MC-4 was obtained from this device. The device started to emit light at 2.41 V, showed light emission of 1000 cd / m ^{2 at} 4.6 V, and the maximum light emission efficiency was 11.40 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 86.1 hours. This was 5.38 times longer than that of Comparative Example 4.

[Example 20]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound G dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 23 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-3 with a weight ratio of 92.5: 7.5, and the composition 23 was spin-coated. An organic EL element was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2370 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 600 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.31 V, emitted 1000 cd / m ^{2 at} 4.3 V, and had a maximum luminous efficiency of 31.80 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 308.1 hours. This was 2.99 times longer than that of Comparative Example 5.

[Example 21]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound G dissolved in xylene solvent at a concentration of 1.8% by weight and dissolved in xylene solvent at a concentration of 1.8% by weight. The composition 24 was prepared by mixing the light-emitting organometallic complex compound MC-5 with a solution at a weight ratio of 92.5: 7.5, and the composition 24 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2500 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-5 was obtained from this device. The device started to emit light at 2.39 V, showed light emission of 1000 cd / m ^{2 at} 5.0 V, and had a maximum light emission efficiency of 20.40 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance attenuated to 80% of the initial luminance after 443.4 hours. This was 7.99 times longer than that of Comparative Example 6.

[Comparative Example 4]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.4% by weight and a solution of the polymer compound H in a concentration of 1.4% by weight were dissolved in the xylene solvent. The composition 25 was prepared by mixing a solution of the light-emitting organometallic complex compound MC-4 with a weight ratio of 92.5: 7.5, and the composition 25 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2000 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 625 nm derived from the light-emitting organometallic complex compound MC-4 was obtained from this device. The device started to emit light at 2.59 V, showed light emission of 1000 cd / m ^{2 at} 5.1 V, and the maximum light emission efficiency was 10.80 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 16.0 hours.

[Comparative Example 5]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.5% by weight and a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.5% by weight were used. The composition 26 was prepared by mixing a solution of the light-emitting organometallic complex compound MC-3 with a weight ratio of 92.5: 7.5, and the composition 26 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotation speed of 2950 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 600 nm derived from the light-emitting organometallic complex compound MC-3 was obtained from this device. The device started to emit light at 2.46 V, showed light emission of 1000 cd / m ^{2 at} 4.5 V, and had a maximum light emission efficiency of 29.10 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 103.1 hours.

[Comparative Example 6]
<Production and Evaluation of Organic EL Device>
In Example 5, instead of the composition 6, a solution of the polymer compound H dissolved in a xylene solvent at a concentration of 1.4% by weight and a solution of the polymer compound H in a concentration of 1.4% by weight were dissolved in the xylene solvent. The composition 27 was prepared by mixing the solution of the light-emitting organometallic complex compound MC-5 in a weight ratio of 92.5: 7.5, and the composition 27 was spin-coated. An organic EL device was produced in the same manner as in Example 5 except that the film was formed at a rotational speed of 2110 rpm.

When voltage was applied to the obtained organic EL device, EL light emission having a peak at 615 nm derived from the luminescent organometallic complex compound MC-5 was obtained from this device. The device started to emit light at 2.56 V, showed 1000 cd / m ² at 5.3 V, and had a maximum luminous efficiency of 18.60 cd / A.

The organic EL element obtained above was driven at a constant current after setting the current value so that the initial luminance was 8000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was attenuated to 80% of the initial luminance after 55.5 hours.

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。） [Example 22]
<Synthesis of Compound M-11>
・ Composition of CM-16

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

  In a separable flask in which the internal gas was replaced with argon gas, 3,5-dibromo-4-methylbenzoic acid (compound CM-14, 60 g, 205 mmol), compound CM-15 (200 g, 430 mmol), bis (triphenyl) Add phosphine) palladium dichloride (8.6 g, 12 mmol, 6 mol%) and toluene (1300 mL) and heat to 90 ° C. with stirring. Then, a 20 wt% tetraethylammonium hydroxide aqueous solution (600 mL) is added dropwise. After completion of dropping, the mixture is heated to reflux for 24 hours. The reaction solution was transferred to a separatory funnel, washed with 0.5 mol / L hydrochloric acid and 10% by weight saline, the organic layer was dehydrated with magnesium sulfate, and then passed through a funnel filled with silica gel. Is distilled off under reduced pressure. The obtained residue is recrystallized in a chloroform-methanol system to obtain white compound CM-16.

（式中、Ｍｅはメチル基を表し、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。）

(In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

  Compound CM-16 (41 g, 50 mmol), monochlorobenzene (100 mL) and DMF (0.1 mL) are added to a separable flask whose internal gas is replaced with argon gas, and the mixture is heated and stirred at 60 ° C. Then thionyl chloride (12.5 g, 105 mmol, 2.1 eq) is slowly added dropwise. After stirring for 10 hours or longer, the solvent is distilled off under reduced pressure. Monochlorobenzene (200 mL) and 4-bromobenzonitrile (18 g, 100 mmol) are added to the resulting residue, and the reactor is cooled with ice and stirred. Subsequently, antimony pentachloride (15 g, 50 mmol) is slowly added dropwise, and after completion of the addition, the temperature is raised to room temperature, followed by stirring for 48 hours or more. The resulting reaction mixture is added dropwise to a 25 wt% aqueous ammonia solution with stirring. If precipitation occurs in the organic layer or an emulsion is formed, dilute with chloroform. The aqueous layer is removed from the reaction solution, and the organic layer is washed twice or more with ion-exchanged water and dehydrated with sodium sulfate. The solvent is distilled off under reduced pressure, the resulting residue is dissolved in chloroform, passed through a funnel filled with silica gel, and the solvent is distilled off under reduced pressure. By recrystallizing the obtained residue in a chloroform-methanol system, white compound M-11 is obtained.

Claims (17)

A polymer compound containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2);
A composition containing a light-emitting organometallic complex compound.

(Where
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, Arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio Represents a group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group. Of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , adjacent groups may be bonded to form a ring. However, R ³ is an alkyl group having 12 or more carbon atoms, or at least one of R ² and R ⁴ is an alkyl group, an aryl group, or an aryl group substituted with an alkyl group.
Ar ₁ and Ar ₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted carboxyl And a divalent aromatic group which may have a substituent selected from the group consisting of a group and a cyano group.
Ar ₃ represents an aryl group or a monovalent aromatic heterocyclic group.
Ar ₄ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group , Imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl Represents a group, a substituted carboxyl group, or a cyano group.
R ⁶ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue Group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted Represents a carboxyl group or a cyano group. When a plurality of R ⁶ are present, they may be the same or different.
a represents 0 or 1; Two a's may be the same or different. ) The composition according to claim 1, wherein R ² and R ⁴ are an aryl group substituted with an alkyl group. The composition according to claim 1 or 2, wherein Ar ₄ is a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group. The composition according to any one of claims 1 to 3, wherein Ar ₁ and Ar ₂ are each independently a divalent aromatic group represented by the following formula (3) or (4).

(In the formula, R ′ represents a hydrogen atom or an alkyl group.)   The total proportion of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in all repeating units constituting the polymer compound contained in the composition is 30 mol%. It is the above, The composition as described in any one of Claims 1-4. The composition according to any one of claims 1 to 5, wherein the polymer compound contained in the composition further contains a repeating unit represented by the following formula (5).

(In the formula, Ar ₅ represents an arylene group or a divalent aromatic heterocyclic group.) The composition according to claim 6, wherein the repeating unit represented by the formula (5) is a repeating unit represented by the following formula (6).

(In the formula, Ar ₆ and Ar ₇ are each independently an alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide) Group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted carboxyl R ⁷ represents an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide Group, acid imide , Imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl Represents a group, a substituted carboxyl group, or a cyano group, a represents 0 or 1. The two a may be the same or different, and when a plurality of R ⁷ are present, they are the same. It may or may not be.) The composition according to claim 6, wherein the repeating unit represented by the formula (5) is a repeating unit represented by the following formula (7) and / or a repeating unit represented by the following formula (8).

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group) Group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryl An oxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group, and b represents 0 or 1.)   Of all repeating units constituting the polymer compound contained in the composition, the repeating unit represented by the formula (1), the repeating unit represented by the formula (2) and the formula (5) The composition according to any one of claims 6 to 8, wherein the total ratio of the repeating units is 80 mol% or more. The composition according to any one of claims 1 to 9, wherein the polymer compound contained in the composition further contains a repeating unit represented by the following formula (9).

(In the formula, Ar ₈ , Ar ₉ , Ar ₁₀ and Ar ₁₄ each independently represent an arylene group or a divalent aromatic heterocyclic group. Ar ₁₁ , Ar ₁₂ and Ar ₁₃ each independently represent aryl. Represents a group or a monovalent aromatic heterocyclic group, and x and y are each independently 0 or 1, provided that x + y is 0 or 1.)   The material according to any one of claims 1 to 10, further comprising at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material (excluding a light emitting organometallic complex compound). Composition.   The liquid composition containing the composition as described in any one of Claims 1-11, and a solvent or a dispersion medium.   The thin film containing the composition as described in any one of Claims 1-11.   The element which has an electrode which consists of an anode and a cathode, and the organic layer containing the composition as described in any one of Claims 1-11 provided between this electrode.   A planar light source comprising the element according to claim 14.   A display device comprising the element according to claim 14. A polymer compound containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

(Where
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, Arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio Represents a group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, or a cyano group. Of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , adjacent groups may be bonded to form a ring. However, R ³ is an alkyl group having 12 or more carbon atoms, or at least one of R ² and R ⁴ is an alkyl group, an aryl group, or an aryl group substituted with an alkyl group.
Ar ₁ and Ar ₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, imine residue, substituted silyl group, substituted silyloxy group, substituted silylthio group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted carboxyl And a divalent aromatic group which may have a substituent selected from the group consisting of a group and a cyano group.
Ar ₃ represents an aryl group or a monovalent aromatic heterocyclic group.
Ar ₄ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group , Imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl Represents a group, a substituted carboxyl group, or a cyano group.
R ⁶ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue Group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent aromatic heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, substituted Represents a carboxyl group or a cyano group. When a plurality of R ⁶ are present, they may be the same or different.
a represents 0 or 1; Two a's may be the same or different. )