JP2017125087A - Polymer compound and light emitting element prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound useful for the production of a light emitting element having an excellent brightness life.SOLUTION: A polymer compound comprises a deuterated aryl amine constitutional unit having no crosslinking group, a constitutional unit having a crosslinking group represented by a structural formula represented by formula (1) and the like, and others, where the crosslinking group includes two crosslinking groups from a group of crosslinking groups represented by specific structural formulas. There is also provided a light emitting element including a crosslinked body thereof.SELECTED DRAWING: None

Description

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

  Organic electroluminescence elements (hereinafter also referred to as “light-emitting elements”) have high luminous efficiency and low driving voltage, and thus can be suitably used for display and lighting applications, and have recently attracted attention. . The light emitting element includes organic layers such as a light emitting layer and a hole transport layer. By using a polymer compound as the material for the organic layer, the organic layer can be formed by a coating method typified by an ink jet printing method, and thus the polymer compound has been studied.

  As the polymer compound, Patent Document 1 describes a polymer compound containing a structural unit derived from an arylamine and a structural unit derived from fluorene having a benzocyclobutene structure.

  As the polymer compound, Patent Document 2 discloses a polymer compound containing a structural unit derived from deuterated naphthalene, a structural unit derived from deuterated diamine, and a structural unit derived from fluorene having a styrene structure. And a polymer compound comprising a structural unit derived from deuterated diamine and a structural unit derived from styrene.

JP 2008-106241 A International Publication No. 2010/114583

  However, light-emitting elements manufactured using these polymer compounds do not always have a sufficient luminance life.

  Then, an object of this invention is to provide a high molecular compound useful for manufacture of the light emitting element which is excellent in a luminance lifetime.

The present invention provides the following [1] to [8].
[1] A deuterated arylamine structural unit having no bridging group and a structural unit having a bridging group represented by formula (1) or formula (1 ′), and represented by formula (XL-1) And a polymer compound having a crosslinking group represented by the formula (XL-16).

［式中、
ｎＡは０〜５の整数を表し、ｎは１又は２を表す。
Ａｒ³は、芳香族炭化水素基又は複素環基を表し、これらの基は置換基を有していてもよい。
Ｌ^Aは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’は、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｌ^Aが複数存在する場合、それらは同一でも異なっていてもよい。
Ｘは、架橋基Ａ群から選ばれる架橋基を表す。Ｘが複数存在する場合、それらは同一でも異なっていてもよい。但し、Ｘが式（ＸＬ−１）で表される架橋基である場合、該Ｘが結合するＬ^Aは、アルキレン基、シクロアルキレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。］

[Where:
nA represents an integer of 0 to 5, and n represents 1 or 2.
Ar ³ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
L ^A represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups have a substituent. Also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of ^LA are present, they may be the same or different.
X represents a crosslinking group selected from the crosslinking group A group. When two or more X exists, they may be the same or different. Provided that when X is a bridging group of the formula (XL-1), L ^A in which the X is attached is an alkylene group, a cycloalkylene group, a divalent heterocyclic group, represented by -NR'- Group, oxygen atom or sulfur atom, and these groups optionally have a substituent. ]

［式中、
ｍＡは０〜５の整数を表し、ｍは１〜４の整数を表し、ｃは０又は１を表す。ｍＡが複数存在する場合、それらは同一でも異なっていてもよい。
Ａｒ⁵は、芳香族炭化水素基、複素環基、又は、芳香族炭化水素環と複素環とが直接結合した基を表し、これらの基は置換基を有していてもよい。
Ａｒ⁴及びＡｒ⁶は、それぞれ独立に、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接又は酸素原子若しくは硫黄原子を介して結合して、環を形成していてもよい。
Ｋ^Ａは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。Ｋ^Ａが複数存在する場合、それらは同一でも異なっていてもよい。
Ｘ’は、架橋基Ａ群から選ばれる架橋基、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。但し、少なくとも１つのＸ’は、架橋基Ａ群から選ばれる架橋基である。但し、Ｘ’が式（ＸＬ−１）で表される架橋基である場合、該Ｘ’が結合するＫ^Aは、アルキレン基、シクロアルキレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子、若しくは、硫黄原子、又は、これらの基に含まれる水素原子の一部又は全部が重水素原子で置換された基を表し、これらの基は置換基を有していてもよい。］
（架橋基Ａ群）

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ⁵ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which an aromatic hydrocarbon ring and a heterocyclic ring are directly bonded, and these groups may have a substituent.
Ar ⁴ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ⁴ , Ar ⁵ and Ar ⁶ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or a sulfur atom to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good. When a plurality of K ^A are present, they may be the same or different.
X ′ represents a bridging group selected from the bridging group A group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. However, at least one X ′ is a crosslinking group selected from the crosslinking group A group. However, when X ′ is a bridging group represented by the formula (XL-1), K ^A to which X ′ is bonded is an alkylene group, a cycloalkylene group, a divalent heterocyclic group, or —NR′—. Represents a group represented by the above, an oxygen atom, a sulfur atom, or a group in which some or all of the hydrogen atoms contained in these groups are substituted with deuterium atoms, and these groups have a substituent. May be. ]
(Crosslinking group A group)

［式中、Ｒ^ＸＬは、メチレン基、酸素原子又は硫黄原子を表し、ｎ^ＸＬは、０〜５の整数を表す。Ｒ^ＸＬが複数存在する場合、それらは同一でも異なっていてもよく、ｎ^ＸＬが複数存在する場合、それらは同一でも異なっていてもよい。＊は結合位置を表す。これらの架橋基は置換基を有していてもよい。］
［２］前記架橋基を有しない重水素化アリールアミン構成単位が、式(Ｘ)で表される構成単位である、［１］に記載の高分子化合物。

[Wherein, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5. When a plurality of R ^XL are present, they may be the same or different, and when a plurality of n ^XL are present, they may be the same or different. * Represents a bonding position. These crosslinking groups may have a substituent. ]
[2] The polymer compound according to [1], wherein the deuterated arylamine structural unit having no crosslinking group is a structural unit represented by the formula (X).

［式中、
ａ¹及びａ²は、それぞれ独立に、０〜２の整数を表す。
Ａｒ^X1及びＡｒ^X3は、それぞれ独立に、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^X2及びＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、又は、アリーレン基と２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。Ａｒ^X2及びＡｒ^X4が複数存在する場合、それらは同一でも異なっていてもよい。
Ｒ^X1、Ｒ^X2及びＲ^X3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^X2及びＲ^X3が複数存在する場合、それらは同一でも異なっていてもよい。
但し、Ａｒ^X1、Ａｒ^X2、Ａｒ^X3、Ａｒ^X4、Ｒ^X1、Ｒ^X2及びＲ^X3で表される基の少なくとも１つに含まれる水素原子の一部又は全部は、重水素原子で置換されている。］
［３］前記Ａｒ^X2又はＡｒ^X4が、式（Ａ−７）、式（Ａ−９）又は式（Ａ−１９）で表される基である、［２］に記載の高分子化合物。

[Where:
a ¹ and a ² each independently represents an integer of 0 to 2;
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups are substituents You may have. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different.
However, a part or all of the hydrogen atoms contained in at least one of the groups represented by Ar ^X1 , Ar ^X2 , Ar ^X3 , Ar ^X4 , R ^X1 , R ^X2 and R ^X3 are substituted with deuterium atoms. Yes. ]
[3] The polymer compound according to [2], wherein Ar ^X2 or Ar ^X4 is a group represented by Formula (A-7), Formula (A-9), or Formula (A-19).

［式中、Ｒ及びＲ^aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ及びＲ^aは、各々、同一でも異なっていてもよく、Ｒ^a同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。］
［４］前記Ａｒ^X1、Ａｒ^X3、Ｒ^X1及びＲ^X2で表される基に含まれる水素原子の一部又は全部が重水素原子で置換されている、［２］又は［３］に記載の高分子化合物。
［５］更に、式(Ｙ)で表される構成単位を含む、［１］〜［４］のいずれかに記載の高分子化合物。

[Wherein, R and R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which they are bonded. ]
[4] The method according to [2] or [3], wherein a part or all of hydrogen atoms contained in the groups represented by Ar ^X1 , Ar ^X3 , R ^X1 and R ^X2 are substituted with deuterium atoms. High molecular compound.
[5] The polymer compound according to any one of [1] to [4], further comprising a structural unit represented by the formula (Y).

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、又は、アリーレン基と２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。］
［６］前記式(Ｙ)で表される構成単位が、式(Y-1)で表される構成単位又は式(Y-2)で表される構成単位である、［５］に記載の高分子化合物。

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. It may be. ]
[6] The structural unit represented by the formula (Y) is a structural unit represented by the formula (Y-1) or a structural unit represented by the formula (Y-2). High molecular compound.

［式中、Ｒ^Y1は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、または、１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよく、隣接するＲ^Y1同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups have a substituent. Also good. A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｘ^Y1は、−Ｃ(Ｒ^Y2)₂−、−Ｃ(Ｒ^Y2)＝Ｃ(Ｒ^Y2)−又はＣ(Ｒ^Y2)₂−Ｃ(Ｒ^Y2)₂−で表される基を表す。Ｒ^Y2は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、又は、１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y2は、同一でも異なっていてもよく、Ｒ^Y2同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］
［７］［１］〜［６］のいずれかに記載の高分子化合物と、
正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料、酸化防止剤及び溶媒からなる群より選ばれる少なくとも１種の材料とを含有する組成物。
［８］［１］〜［６］のいずれかに記載の高分子化合物及びその架橋体からなる群から選ばれる少なくとも一種を含む発光素子。

[Wherein, R ^Y1 represents the same meaning as described above. X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - , or _{^{C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]
[7] The polymer compound according to any one of [1] to [6],
A composition comprising a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and at least one material selected from the group consisting of a solvent.
[8] A light emitting device comprising at least one selected from the group consisting of the polymer compound according to any one of [1] to [6] and a crosslinked product thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element which is excellent in a luminance lifetime can be provided. Moreover, according to this invention, the composition and light emitting element containing this high molecular compound can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

<Explanation of common terms>
Terms commonly used in this specification have the following meanings unless otherwise specified.

Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

  In the formula representing the metal complex, the solid line representing the bond with the central metal means a covalent bond or a coordinate bond.

The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .

“Low molecular weight compound” means a compound having no molecular weight distribution and a molecular weight of 1 × 10 ⁴ or less.

  “Structural unit” means one or more units present in a polymer compound.

The “alkyl group” may be linear or branched. The carbon atom number of a linear alkyl group is 1-50 normally without including the carbon atom number of a substituent, Preferably it is 3-30, More preferably, it is 4-20. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3-propylheptyl, decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-hexyldecyl, dodecyl And a group in which a hydrogen atom in these groups is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, etc., for example, a trifluoromethyl group, a pentafluoroethyl group, a peroxy group, and the like. Fluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5 -Di-hexylphenyl) propyl group, 6-ethyloxyhexyl group.
The number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30 and more preferably 4 to 20 without including the number of carbon atoms of the substituent.
The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

“Aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an aryl group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-20, More preferably, it is 6-10.
The aryl group may have a substituent, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups Are groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

The “alkoxy group” may be linear or branched. The number of carbon atoms of a linear alkoxy group is 1-40 normally without including the carbon number of a substituent, Preferably it is 4-10. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The alkoxy group may have a substituent, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, And a group substituted with a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
The number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.

The number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms of the substituent.
The aryloxy group may have a substituent, for example, a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples include a pyrenyloxy group and a group in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.

The “p-valent heterocyclic group” (p represents an integer of 1 or more) is p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. This means the remaining atomic group excluding the hydrogen atom. Among the p-valent heterocyclic groups, it is the remaining atomic group obtained by removing p hydrogen atoms from an aromatic heterocyclic compound directly bonded to carbon atoms or heteroatoms constituting the ring. A “p-valent aromatic heterocyclic group” is preferable.
`` Aromatic heterocyclic compounds '' are oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. A compound in which the ring itself exhibits aromaticity and a heterocyclic ring such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran itself does not exhibit aromaticity, but the aromatic ring is condensed to the heterocyclic ring. Means a compound.

The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these And a group in which the hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

  “Halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The “amino group” may have a substituent, and a substituted amino group is preferable. As a substituent which an amino group has, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group is preferable.
Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.
Examples of the amino group include dimethylamino group, diethylamino group, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert- Butylphenyl) amino group.

The “alkenyl group” may be linear or branched. The number of carbon atoms of a linear alkenyl group is 2-30 normally without including the carbon atom number of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkenyl group is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of the substituent.
The number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkenyl group and the cycloalkenyl group may have a substituent, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, Examples include a pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which these groups have a substituent.

The “alkynyl group” may be linear or branched. The carbon atom number of an alkynyl group is 2-20 normally without including the carbon atom of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The alkynyl group and the cycloalkynyl group may have a substituent, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, 4- Examples include a pentynyl group, 1-hexynyl group, 5-hexynyl group, and groups in which these groups have a substituent.

The “arylene group” means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an arylene group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-30, More preferably, it is 6-18.
The arylene group may have a substituent. Examples include chrysenediyl groups and groups in which these groups have substituents, and groups represented by formula (A-1) to formula (A-20) are preferable. The arylene group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及びＲ^aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表す。複数存在するＲ及びＲ^aは、各々、同一でも異なっていてもよく、Ｒ^a同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。］

[Wherein, R and R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which they are bonded. ]

The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20 and more preferably 4 to 15 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, Divalent acridine, furan, thiophene, azole, diazole, and triazole include divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring, and preferably Is a group represented by formula (AA-1) to formula (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[Wherein, R and R ^a represent the same meaning as described above. ]

  The “crosslinking group” is a group capable of forming a new bond by being subjected to heating, ultraviolet irradiation, near ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction, etc. It is a crosslinking group represented by the formulas (XL-1) to (XL-16) of Group A.

  “Substituent” means a halogen atom, cyano group, alkyl group, cycloalkyl group, aryl group, monovalent heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, amino group, substituted amino group, alkenyl group. Represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substituent may be a crosslinking group.

  The “deuterium atom” may be either a double hydrogen atom D or a tritium atom T, but is preferably a double hydrogen atom.

  “Deuterated” means that at least one hydrogen atom is replaced with a deuterium atom. The proportion of deuterium atoms in the deuterated structural unit or group is higher than the natural abundance ratio.

“X% is deuterated” means that X% of the hydrogen atom H is replaced with a deuterium atom. For example, when 50% of the compound C ₆ H ₆ is double hydrogenated, 3 hydrogen atoms H of the hydrogen atoms H ₆ are replaced by the double hydrogen atom D, and the compound C ₆ H ₃ D ₃ become.

<Polymer compound>
The polymer compound of the present invention includes a deuterated arylamine structural unit having no crosslinkable group and a structural unit having a crosslinkable group represented by formula (1) or formula (1 ′). Is a polymer compound having a crosslinking group represented by formula (XL-16). In the polymer compound of the present invention, the structural unit having a crosslinking group represented by the formula (1) or the formula (1 ′) is usually represented by the crosslinking group represented by the formula (XL-1) and the formula (XL). And a crosslinking group represented by -16).

[Deuterated arylamine structural unit having no bridging group]
A deuterated arylamine structural unit having no bridging group is a structural unit having an arylamine structure in which at least one hydrogen atom is substituted with a deuterium atom without having a bridging group. The structural unit is preferably a structural unit in which at least 10% of hydrogen atoms are replaced with deuterium atoms, more preferably a structural unit in which at least 20% of hydrogen atoms are replaced with deuterium atoms, and still more preferably. Is a structural unit in which 20 to 50% of hydrogen atoms are substituted with deuterium atoms.

  The deuterated arylamine structural unit having no crosslinking group is preferably a structural unit represented by the formula (X).

[Structural Unit Represented by Formula (X)]
a ¹ is preferably an integer of 2 or less, more preferably 0 or 1, and even more preferably 1, since the luminance lifetime of the light emitting device using the polymer compound of the present invention is more excellent.

a ² is preferably 2 or less, more preferably 0 or 1, and even more preferably 0, because the luminance lifetime of the light emitting device using the polymer compound of the present invention is more excellent.

The arylene group represented by Ar ^X1 and Ar ^X3 is preferably a group represented by the formula (A-1) to the formula (A-10), the formula (A-19) or the formula (A-20), More preferably, it is a group represented by the formula (A-1) or the formula (A-9), more preferably a group represented by the formula (A-1), and these groups have a substituent. It may be.

The divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 is preferably represented by Formula (AA-1), Formula (AA-2), or Formula (AA-7) to Formula (AA-26). These groups may have a substituent.

Ar ^X1 and Ar ^X3 are preferably an arylene group, more preferably a group represented by the formula (A-1) or the formula (A-9), and still more preferably a formula (A-1). These groups may have a substituent.

The arylene group represented by Ar ^X2 and Ar ^X4 is preferably represented by formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-11) or A group represented by formula (A-19), more preferably formula (A-1), formula (A-7), formula (A-9), formula (A-10) or formula (A-19). ), More preferably a group represented by formula (A-7), formula (A-9) or formula (A-19), particularly preferably (A-7) or formula A group represented by (A-19), and these groups optionally have a substituent;

The preferred range of the divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 is the same as the preferred range of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 .

Preferred ranges, more preferred ranges, and further preferred ranges for the arylene group and the divalent heterocyclic group in the divalent group in which the arylene group represented by Ar ^X2 and Ar ^X4 and the divalent heterocyclic group are directly bonded are as follows: These are the same as the preferred range, more preferred range, and further preferred range of the arylene group and divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 , respectively.

Examples of the divalent group in which the arylene group represented by Ar ^X2 and Ar ^X4 and the divalent heterocyclic group are directly bonded include groups represented by the following formulas, and these groups have substituents. You may have.

［式中、Ｒ^XXは、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein R ^XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^XX is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

Ar ^X2 and Ar ^X4 are preferably an arylene group, more preferably a formula (A-1), a formula (A-7), a formula (A-9) to a formula (A-11) or a formula (A-19). ), More preferably a group represented by formula (A-7), formula (A-9) or formula (A-19), particularly preferably formula (A-7) or A group represented by formula (A-19), and these groups each optionally have a substituent;

R ^X1 , R ^X2 and R ^X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, still more preferably an aryl group A group, particularly preferably a phenyl group, and these groups optionally have a substituent.

The substituents that the groups represented by Ar ^{X1 to} Ar ^X4 and R ^{X1 to} R ^X3 may have are preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups further have a substituent. You may do it.

In the structural unit represented by the formula (X), preferably a part or all of hydrogen atoms contained in the groups represented by R ^X1 and R ^X2 are substituted with deuterium atoms, more preferably Ar ^X1 and Some or all of the hydrogen atoms contained in the group represented by Ar ^X3 are substituted with deuterium atoms, and some or all of the hydrogen atoms contained in the groups represented by R ^X1 and R ^X2 Substituted with a deuterium atom.

  The structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1) to the formula (X-7), more preferably the formula (X-5) to the formula (X -7), more preferably a structural unit represented by formula (X-6) or formula (X-7).

［式中、Ｒ^X4、Ｒ^X5、Ｒ^X6及びＲ^X7は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、ハロゲン原子、１価の複素環基又はシアノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^X4、Ｒ^X5、Ｒ^X6及びＲ^X7は、同一でも異なっていてもよい。Ｒ^X4、Ｒ^X5、Ｒ^X6及びＲ^X7で表される基に含まれる水素原子の一部又は全部が、重水素原子で置換されている。隣接するＲ^X4、Ｒ^X5、Ｒ^X6及びＲ^X7同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

Wherein R ^X4 , R ^X5 , R ^X6 and R ^X7 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, halogen atom, monovalent The heterocyclic group or cyano group, and these groups optionally have a substituent. A plurality of R ^X4 , R ^X5 , R ^X6 and R ^X7 may be the same or different. Part or all of the hydrogen atoms contained in the groups represented by R ^X4 , R ^X5 , R ^X6 and R ^X7 are substituted with deuterium atoms. Adjacent R ^X4 , R ^X5 , R ^X6 and R ^X7 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^X4 , R ^X5 , R ^X6 and R ^X7 are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

  Specific examples of the structural unit represented by the formula (X) include structural units represented by the formula (XX-1) to the formula (XX-20), preferably the formula (XX-2), the formula ( XX-3), a structural unit represented by formula (XX-13) to formula (XX-20), more preferably formula (XX-13) to formula (XX-16) or formula (XX-19) It is a structural unit represented by

  The proportion of the structural unit represented by the formula (X) is 0.1 to 90 mol with respect to the total amount of the structural units contained in the polymer compound because the hole transport property of the polymer compound of the present invention is excellent. %, More preferably 30 to 80 mol%, still more preferably 35 to 60 mol%.

  In the polymer compound of the present invention, the deuterated arylamine structural unit having no crosslinking group (the structural unit represented by the formula (X)) is contained alone or in combination of two or more kinds. Also good.

[Structural Unit Having a Crosslinking Group Represented by Formula (1)]
nA is preferably 0 or 1 because the luminance lifetime of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

  n is preferably 2 because the luminance life of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

Ar ³ is preferably an aromatic hydrocarbon group which may have a substituent because the luminance lifetime of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

The number of carbon atoms of the aromatic hydrocarbon group represented by Ar ³ is usually 6 to 60, preferably 6 to 30 and more preferably 6 to 18 without including the number of carbon atoms of the substituent. is there.
The arylene group portion excluding n substituents of the aromatic hydrocarbon group represented by Ar ³ is preferably a group represented by the formula (A-1) to the formula (A-20), More preferably, a group represented by formula (A-1), formula (A-2), formula (A-6) to formula (A-10), formula (A-19) or formula (A-20) And more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19), Preferably, it is a group represented by Formula (A-1) or Formula (A-9), and these groups may have a substituent.

The number of carbon atoms of the heterocyclic group represented by Ar ³ is usually 2 to 60, preferably 3 to 30 and more preferably 4 to 18 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group part excluding n substituents of the heterocyclic group represented by Ar ³ is preferably a group represented by the formula (AA-1) to the formula (AA-34). is there.

The aromatic hydrocarbon group and heterocyclic group represented by Ar ³ may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and an aryl group. , Aryloxy group, monovalent heterocyclic group and cyano group.

Alkylene group represented by L ^A is not including the carbon atom number of substituent is usually 1 to 20, preferably 1 to 15, more preferably from 1 to 10, more preferably 2 to 6. Cycloalkylene group represented by L ^A is not including the carbon atom number of substituent is usually 3 to 20.
The alkylene group and the cycloalkylene group may have a substituent, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group.

Alkylene group and cycloalkylene group represented by L ^A may have a substituent. Examples of the substituent that the alkylene group and the cycloalkylene group may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a cyano group.

The arylene group represented by L ^A may have a substituent. Examples of the arylene group include an o-phenylene group, an m-phenylene group, and a p-phenylene group. Examples of the substituent that the arylene group may have include, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a cyano group, and a bridge. Examples thereof include a crosslinking group selected from the group A.

L ^A is preferably a phenylene group or an alkylene group because the production of the polymer compound of the present invention is facilitated, and these groups may have a substituent. If X is a bridging group of the formula (XL-1), L ^A is preferably substituted is also an alkylene radical.

  The crosslinkable group represented by X is preferably a compound of the formula (XL-1), formula (XL-3), formula (XL-5), formula (XL- 7) or a crosslinking group represented by formula (XL-16), more preferably a crosslinking group represented by formula (XL-1) or formula (XL-16).

  The proportion of the structural unit represented by the formula (1) is preferably 0.5 to 50 with respect to the total amount of the structural units contained in the polymer compound because the polymer compound of the present invention is excellent in stability and crosslinkability. It is mol%, More preferably, it is 3-30 mol%, More preferably, it is 3-20 mol%.

  The structural unit represented by the formula (1) may be included in the polymer compound alone or in a combination of two or more.

  The structural unit represented by the formula (1) may be deuterated.

[Structural unit represented by formula (1 ')]
mA is preferably 0 or 1, more preferably 0, because the luminance lifetime of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

  m is preferably 2 because the luminance lifetime of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

  c is preferably 0 because the production of the polymer compound of the present invention is facilitated and the luminance life of the light emitting device obtained using the polymer compound of the present invention is more excellent.

Ar ⁵ is preferably an aromatic hydrocarbon group which may have a substituent because the luminance lifetime of the light-emitting device obtained using the polymer compound of the present invention is more excellent.

The arylene group portion excluding m substituents of the aromatic hydrocarbon group represented by Ar ⁵ is preferably the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to a group represented by formula (A-11) or formula (A-19), more preferably formula (A-1), formula (A-7), formula (A-9) A group represented by formula (A-10) or formula (A-19), more preferably a group represented by formula (A-7), formula (A-9) or formula (A-19) And these groups may have a substituent.

The divalent heterocyclic group moiety excluding m substituents of the heterocyclic group represented by Ar ⁵ is more preferably a formula (AA-1), a formula (AA-2) or a formula (AA-7 ) To (AA-26), and these groups may have a substituent.

Preferred range of the arylene group and divalent heterocyclic group in the divalent group excluding m substituents of the group in which the aromatic hydrocarbon ring represented by Ar ⁵ and the heterocyclic ring are directly bonded, and more preferred. The range and the more preferable range are the same as the preferable range, the more preferable range, and the further preferable range, respectively, of the arylene group and divalent heterocyclic group represented by Ar ⁵ .

Ar ⁴ and Ar ⁶ are preferably an arylene group which may have a substituent since the luminance life of a light-emitting device obtained using the polymer compound of the present invention is more excellent.

The arylene group represented by Ar ⁴ and Ar ⁶ is more preferably a group represented by the formula (A-1) to the formula (A-10), the formula (A-19) or the formula (A-20). More preferably a group represented by the formula (A-1) or the formula (A-9), particularly preferably a group represented by the formula (A-1), and these groups have a substituent. You may have.

The divalent heterocyclic group represented by Ar ⁴ and Ar ⁶ is more preferably represented by formula (AA-1), formula (AA-2), or formula (AA-7) to formula (AA-26). These groups may have a substituent.

The groups represented by Ar ⁴ , Ar ⁵ and Ar ⁶ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, Examples thereof include a halogen atom, a monovalent heterocyclic group, and a cyano group.

Alkylene group represented by K ^A, a cycloalkylene group, an arylene group, a divalent definitions and examples of the heterocyclic group, respectively, the alkylene group represented by L ^A, a cycloalkylene group, an arylene group, a divalent heterocyclic The definition and examples of the ring group are the same.

K ^A, since production of the polymer compound of the present invention is facilitated, it is preferable that a phenylene group or a methylene group. If X 'is a bridging group of the formula (XL-1), K ^A is preferably a methylene group.

  As the cross-linking group represented by X ′, since the cross-linking property of the polymer compound of the present invention is excellent, the formula (XL-1), the formula (XL-3), the formula (XL-5), the formula (XL -7) or a crosslinking group represented by formula (XL-16), more preferably a crosslinking group represented by formula (XL-1) or formula (XL-16).

  The proportion of the structural unit represented by the formula (1 ′) is excellent in the stability of the polymer compound of the present invention and the crosslinkability of the polymer compound of the present invention. The total amount is preferably 0.5 to 50 mol%, more preferably 3 to 30 mol%, and still more preferably 3 to 20 mol%.

  One type of structural unit represented by the formula (1 ′) may be contained in the polymer compound, or two or more types may be contained in the polymer compound.

  The structural unit represented by the formula (1 ′) may be deuterated.

[Preferred Embodiment of Structural Unit Represented by Formula (1) or Formula (1 ′)]
Examples of the structural unit represented by the formula (1) include structural units represented by the formula (1-1) to the formula (1-29), and the structural unit represented by the formula (1 ′) Examples include structural units represented by the formula (1′-1) to the formula (1′-9). Among these, since the crosslinkability of the polymer compound of the present invention is excellent, it is preferably a structural unit represented by the formula (1-1) to the formula (1-29), more preferably the formula (1-1). ~ A structural unit represented by formula (1-15), formula (1-19), formula (1-20), formula (1-23), formula (1-25) or formula (1-29) More preferably, it is a structural unit represented by formula (1-1) to formula (1-9) or formula (1-29).

  In the polymer compound of the present invention, among the structural unit having a crosslinking group represented by formula (1) and the structural unit having a crosslinking group represented by formula (1 ′), the configuration represented by formula (1) It is preferable to have a unit.

  In the polymer compound of the present invention, the total amount of the crosslinking group represented by the formula (XL-1) and the crosslinking group represented by the formula (XL-16) is excellent in crosslinkability and the polymer of the present invention. Since the luminance life of the light-emitting device obtained using the compound is excellent, it is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of crosslinking groups contained in the polymer compound. More preferably 100 mol%.

  Since the polymer compound of the present invention is excellent in crosslinkability and the luminance life of a light emitting device obtained using the polymer compound of the present invention is excellent, preferably the formula (1-1), formula (1-2) , Formula (1-5), Formula (1-6), Formula (1-9) to Formula (1-12), Formula (1-19), Formula (1-23), Formula (1-27), At least one structural unit selected from the group consisting of formula (1-29) and formula (1′-2) to formula (1′-9), formula (1-3), formula (1-4), formula (1-7), formula (1-8), formula (1-20) and at least one structural unit selected from the group consisting of formula (1-28), more preferably formula (1-1 ), Formula (1-5), Formula (1-6), Formula (1-9), Formula (1-19), Formula (1-29), and Formula (1′-9). And at least one structural unit and at least one structural unit selected from the group consisting of formula (1-3), formula (1-8), and formula (1-20).

  The polymer compound of the present invention preferably further includes a structural unit represented by the formula (Y) because the luminance life of a light-emitting device using the polymer compound of the present invention is more excellent. However, the structural unit represented by Formula (Y) is different from the structural unit represented by Formula (1).

The arylene group represented by Ar ^Y1 is more preferably a formula (A-1), a formula (A-6), a formula (A-7), a formula (A-9) to a formula (A-11), a formula (A A-13) or a group represented by formula (A-19), more preferably in formula (A-1), formula (A-7), formula (A-9) or formula (A-19). And these groups may have a substituent.

More preferably, the divalent heterocyclic group represented by Ar ^Y1 is represented by the formula (AA-4), formula (AA-10), formula (AA-13), formula (AA-15), formula (AA-18) ) Or a group represented by formula (AA-20), particularly preferably represented by formula (AA-4), formula (AA-10), formula (AA-18) or formula (AA-20) These groups may have a substituent.

In the divalent group in which the arylene group represented by Ar ^Y1 and the divalent heterocyclic group are directly bonded, more preferable ranges and further preferable ranges of the arylene group and the divalent heterocyclic group are the above-mentioned Ar. This is the same as the more preferable range and further preferable range of the arylene group and divalent heterocyclic group represented by ^Y1 .

As the divalent group in which the arylene group represented by Ar ^Y1 and the divalent heterocyclic group are directly bonded, the arylene group represented by Ar ^X2 and Ar ^X4 in the formula (X) and the divalent heterocyclic group And the same as the divalent group directly bonded to each other.

The substituent that the group represented by Ar ^Y1 may have is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups may further have a substituent.

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formula (Y-1) to the formula (Y-7), and the light emitting device using the polymer compound of the present invention. From the viewpoint of the luminance life, it is preferably a structural unit represented by the formula (Y-1) or the formula (Y-2), and from the viewpoint of electron transport properties, preferably the formula (Y-3) or the formula ( Y-4), and from the viewpoint of hole transportability, it is preferably a structural unit represented by formula (Y-5) to formula (Y-7).

［式中、Ｒ^Y1は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよく、隣接するＲ^Y1同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. . A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

  The structural unit represented by the formula (Y-1) is preferably a structural unit represented by the formula (Y-1 ′).

［式中、Ｒ^Y11は、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y11は、同一でも異なっていてもよい。］

[Wherein, R ^Y11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^Y11 may be the same or different. ]

R ^Y11 is preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group, still more preferably an alkyl group, and these groups have a substituent. It may be.

［式中、
Ｒ^Y1は前記と同じ意味を表す。
Ｘ^Y1は、−Ｃ(Ｒ^Y2)₂−、−Ｃ(Ｒ^Y2)＝Ｃ(Ｒ^Y2)−又はＣ(Ｒ^Y2)₂−Ｃ(Ｒ^Y2)₂−で表される基を表す。Ｒ^Y2は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y2は、同一でも異なっていてもよく、Ｒ^Y2同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Where:
R ^Y1 represents the same meaning as described above.
X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - , or _{^{C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. May be.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ₂ — is preferably an alkyl group or a cycloalkyl group, both are aryl groups, and both are monovalent complex. A cyclic group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group. May have a substituent. Two R ^{Y2 s} may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R ^Y2 forms a ring, the group represented by —C (R ^Y2 ) ₂ — Is preferably a group represented by formulas (Y-A1) to (Y-A5), more preferably a group represented by formula (Y-A4), and these groups have a substituent. It may be.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ═C (R ^Y2 ) — is preferably both an alkyl group or a cycloalkyl group, or one of which is an alkyl group Alternatively, a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In X ^Y1 , four R ^Y2 in the group represented by —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — are preferably an alkyl group or a cycloalkyl group which may have a substituent. It is. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded. When R ^Y2 forms a ring, —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — The group represented is preferably a group represented by formulas (Y-B1) to (Y-B5), more preferably a group represented by formula (Y-B3), and these groups are substituted. It may have a group.

［式中、Ｒ^Y2は前記と同じ意味を表す。］

[Wherein, R ^Y2 represents the same meaning as described above. ]

  The structural unit represented by the formula (Y-2) is preferably a structural unit represented by the formula (Y-2 ′).

［式中、Ｒ^Y1及びＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y1 and X ^Y1 represent the same meaning as described above. ]

［式中、
Ｒ^Y1は前記と同じ意味を表す。
Ｒ^Y3は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Where:
R ^Y1 represents the same meaning as described above.
R ^Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]

R ^Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

［式中、
Ｒ^Y1は前記を同じ意味を表す。
Ｒ^Y4は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Where:
R ^Y1 represents the same meaning as described above.
R ^Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formula (Y-11) to the formula (Y-55).

The proportion of the structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, is superior in the luminance life of the light-emitting element using the polymer compound of the present invention. Preferably it is 0.5-80 mol% with respect to the total amount of the structural unit contained, More preferably, it is 30-60 mol%.

Ratio of structural unit represented by formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded. Is excellent in charge transport property of a light-emitting device using the polymer compound of the present invention, and is preferably 0.5 to 40 mol%, more preferably 3%, based on the total amount of structural units contained in the polymer compound. ~ 30 mol%.

  One type of structural unit represented by the formula (Y) may be contained in the polymer compound, or two or more types may be contained.

  Examples of the polymer compound of the present invention include polymer compounds P-1 to P-6 shown in Table 1. Here, the “other” structural unit means a structural unit other than the structural units represented by Formula (X), Formula (1), Formula (1 ′), and Formula (Y).

［表中、ｐ、ｑ、ｒ、ｓ及びｔは、各構成単位のモル比率を表す。ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝100であり、かつ、70≦ｐ＋ｑ＋ｒ＋ｓ≦100である。］

[In the table, p, q, r, s, and t represent the molar ratio of each structural unit. p + q + r + s + t = 100 and 70 ≦ p + q + r + s ≦ 100. ]

  Examples and preferred ranges of the structural units represented by the formula (X), the formula (1), the formula (1 ′) and the formula (Y) in the polymer compounds P-1 to P-6 are as described above. .

  The terminal group of the polymer compound of the present invention preferably has a polymerization active group as it is, because when the polymer compound is used for the production of a light emitting device, the light emission characteristics and the luminance life may be lowered. It is a stable group. The terminal group is preferably a group that is conjugated to the main chain, and includes a group that is bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.

  The polymer compound of the present invention may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be in other embodiments, but a plurality of types of raw materials A copolymer obtained by copolymerizing monomers is preferred.

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

  The polymer compound of the present invention includes, for example, a compound represented by the formula (M-1), a compound represented by the formula (M-2) and / or a compound represented by the formula (M-3), It can be produced by condensation polymerization with other compounds (for example, a compound represented by the formula (M-4)). In the present specification, the compounds used for the production of the polymer compound of the present invention are sometimes collectively referred to as “raw material monomers”.

［式中、
ａ¹、ａ²、Ａｒ^X1〜Ａｒ^X4、Ｒ^X1〜Ｒ^X3、ｎＡ、ｎ、Ａｒ³、Ｌ^A、Ｘ、ｍＡ、ｍ、ｃ、Ａｒ⁴〜Ａｒ⁶、Ｋ^A、Ｘ’及びＡｒ^Y1は、前記と同じ意味を表す。
Ｚ^C1〜Ｚ^C10は、それぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれる基を表す。］

[Where:
a ¹ , a ² , Ar ^{X1 to} Ar ^X4 , R ^{X1 to} R ^X3 , nA, n, Ar ³ , L ^A , X, mA, m, c, Ar ^{4 to} Ar ⁶ , K ^A , X ′ and Ar ^Y1 Represents the same meaning as described above.
Z ^{C1 to} Z ^C10 each independently represent a group selected from the group consisting of the substituent group A and the substituent group B. ]

For example, when Z ^C1 , Z ^C2 , Z ^C3 , Z ^C4 , Z ^C5 and Z ^C6 are groups selected from the substituent group A, Z ^C7 and Z ^C8 select a group selected from the substituent group B. .
For example, when Z ^C1 , Z ^C2 , Z ^C3 , Z ^C4 , Z ^C5 and Z ^C6 are groups selected from the substituent group B, Z ^C7 and Z ^C8 select a group selected from the substituent group A. .

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. A group represented by:

<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be linked to each other to form a ring structure together with the oxygen atoms to which they are bonded.
A group represented by —BF ₃ Q ′ (wherein Q ′ represents Li, Na, K, Rb or Cs);
A group represented by —MgY ′ (wherein Y ′ represents a chlorine atom, a bromine atom or an iodine atom);
A group represented by —ZnY ″ (wherein Y ″ represents a chlorine atom, a bromine atom or an iodine atom); and
-Sn (R ^C3) ₃ (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different and may be linked to each other to form a ring structure together with the tin atoms to which they are bonded.

Examples of the group represented by —B (OR ^C2 ) ₂ include groups represented by the following formulae.

  A compound having a group selected from Substituent Group A and a compound having a group selected from Substituent Group B are subjected to condensation polymerization by a known coupling reaction, and a group selected from Substituent Group A and Substituent Group B Carbon atoms bonded to a group selected from are bonded to each other. Therefore, if a compound having two groups selected from Substituent Group A and a compound having two groups selected from Substituent Group B are subjected to a known coupling reaction, condensation of these compounds by condensation polymerization A polymer can be obtained.

  The condensation polymerization is usually performed in the presence of a catalyst, a base and a solvent, but may be performed in the presence of a phase transfer catalyst, if necessary.

  Examples of the catalyst include bis (triphenylphosphine) palladium (II) dichloride, bis (tris-o-methoxyphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone). ) Palladium (0), palladium complexes such as palladium acetate, tetrakis (triphenylphosphine) nickel (0), [1,3-bis (diphenylphosphino) propane) nickel (II) dichloride, bis (1,4- Transition metal complexes such as nickel complexes such as cyclooctadiene) nickel (0); these transition metal complexes are further triphenylphosphine, tri (o-tolyl) phosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, 1,3-bi And a complex having a ligand such as su (diphenylphosphino) propane and bipyridyl. A catalyst may be used individually by 1 type, or may use 2 or more types together.

  The amount of the catalyst used is usually 0.00001 to 3 molar equivalents as the amount of transition metal relative to the total number of moles of raw material monomers.

  Examples of the base and phase transfer catalyst include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate; tetrabutylammonium fluoride, tetraethylammonium hydroxide, tetrahydroxide Examples thereof include organic bases such as butylammonium; phase transfer catalysts such as tetrabutylammonium chloride and tetrabutylammonium bromide. Each of the base and the phase transfer catalyst may be used alone or in combination of two or more.

  The usage-amount of a base and a phase transfer catalyst is 0.001-100 molar equivalent normally with respect to the total number of moles of a raw material monomer, respectively.

  Examples of the solvent include organic solvents such as toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and water. A solvent may be used individually by 1 type, or may use 2 or more types together.

  The amount of the solvent used is usually 10 to 100,000 parts by weight with respect to a total of 100 parts by weight of the raw material monomers.

  The reaction temperature of the condensation polymerization is usually -100 to 200 ° C. The reaction time of the condensation polymerization is usually 1 hour or more.

  Post-treatment of the polymerization reaction is a known method, for example, a method of removing water-soluble impurities by liquid separation, adding the reaction solution after polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying. These methods are carried out alone or in combination. When the purity of the polymer compound is low, it can be purified by a usual method such as crystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

<Composition>
The composition of the present invention comprises at least one material selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant and a solvent, Containing molecular compounds.

  The composition containing the polymer compound and the solvent of the present invention (hereinafter sometimes referred to as “ink”) is suitable for production of a light-emitting element using a printing method such as an inkjet printing method or a nozzle printing method.

  The viscosity of the ink may be adjusted according to the type of printing method, but when applying a printing method such as an inkjet printing method to a printing method that passes through a discharge device, in order to prevent clogging and flight bending at the time of discharge. It is preferably 1 to 20 mPa · s at 25 ° C.

  The solvent contained in the ink is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink. Examples of the solvent include chlorine solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, anisole and 4-methylanisole; toluene, Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane, and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, and phenyl acetate Solvents: ethylene glycol, rubber Polyhydric alcohol solvents such as serine and 1,2-hexanediol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like And amide solvents. A solvent may be used individually by 1 type, or may use 2 or more types together.

  In the ink, the amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

[Hole transport material]
The hole transport material is classified into a low molecular compound and a high molecular compound, and a high molecular compound is preferable, and a high molecular compound having a crosslinking group is more preferable.

  Examples of the polymer compound include polyvinyl carbazole and derivatives thereof; polyarylene having an aromatic amine structure in the side chain or main chain and derivatives thereof. The polymer compound may be a compound to which an electron accepting site is bonded. Examples of the electron accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and fullerene is preferable.

  In the composition of the present invention, the compounding amount of the hole transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  A hole transport material may be used individually by 1 type, or may use 2 or more types together.

[Electron transport materials]
Electron transport materials are classified into low molecular compounds and high molecular compounds. The electron transport material may have a crosslinking group.

  Examples of the low molecular compound include a metal complex having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, and , Diphenoquinone, and derivatives thereof.

  Examples of the polymer compound include polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.

  In the composition of the present invention, the compounding amount of the electron transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  An electron transport material may be used individually by 1 type, or may use 2 or more types together.

[Hole injection material and electron injection material]
The hole injection material and the electron injection material are classified into a low molecular compound and a high molecular compound, respectively. The hole injection material and the electron injection material may have a crosslinking group.

  Examples of the low molecular weight compound include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.

  Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline, and polyquinoxaline, and derivatives thereof; polymers containing an aromatic amine structure in the main chain or side chain, etc. The conductive polymer is mentioned.

  In the composition of the present invention, the compounding amounts of the hole injection material and the electron injection material are each usually 1 to 400 parts by weight, preferably 5 to 150 parts, per 100 parts by weight of the polymer compound of the present invention. Parts by weight.

  Each of the hole injection material and the electron injection material may be used alone or in combination of two or more.

[Ion dope]
When the hole injection material or the electron injection material contains a conductive polymer, the electrical conductivity of the conductive polymer is preferably 1 × 10 ⁻⁵ S / cm to 1 × 10 ³ S / cm. In order to make the electric conductivity of the conductive polymer within such a range, the conductive polymer can be doped with an appropriate amount of ions.

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

  Only one kind or two or more kinds of ions may be doped.

[Light emitting material]
Luminescent materials are classified into low molecular compounds and high molecular compounds. The light emitting material may have a crosslinking group.

  Examples of the low molecular weight compound include naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and triplet light-emitting complexes having iridium, platinum, or europium as a central metal.

  Examples of the polymer compound include a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrene diyl group, a dihydrophenanthrene diyl group, a group represented by the formula (X), a carbazole diyl group, a phenoxazine diyl group, and a phenothiazine diyl. And polymer compounds containing a group, an anthracenediyl group, a pyrenediyl group, and the like.

  The light emitting material may contain a low molecular compound and a high molecular compound, and preferably contains a triplet light emitting complex and a high molecular compound.

  As the triplet light-emitting complex, iridium complexes such as metal complexes represented by the formulas Ir-1 to Ir-5 are preferable.

［式中、
Ｒ^D1〜Ｒ^D8、Ｒ^D11〜Ｒ^D20、Ｒ^D21〜Ｒ^D26及びＲ^D31〜Ｒ^D37は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^D1〜Ｒ^D8、Ｒ^D11〜Ｒ^D20、Ｒ^D21〜Ｒ^D26及びＲ^D31〜Ｒ^D37が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
−Ａ^D1---Ａ^D2−は、アニオン性の２座配位子を表し、Ａ^D1及びＡ^D2は、それぞれ独立に、イリジウム原子と結合する炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。−Ａ^D1---Ａ^D2−が複数存在する場合、それらは同一でも異なっていてもよい。
ｎ_D1は、１、２又は３を表し、ｎ_D2は、１又は２を表す。］

[Where:
R ^{D1 to} R ^D8 , R ^{D11 to} R ^D20 , R ^{D21 to} R ^D26 and R ^{D31 to} R ^D37 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryl group It represents an oxy group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent. When there are a plurality of R ^{D1 to} R ^D8 , R ^{D11 to} R ^D20 , R ^{D21 to} R ^D26, and R ^{D31 to} R ^D37 , they may be the same or different.
-A ^D1 --- A ^D2 -represents an anionic bidentate ligand, and A ^D1 and A ^D2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom bonded to an iridium atom, The atom may be an atom constituting a ring. When a plurality of -A ^D1 --- A ^D2 -are present, they may be the same or different.
n _D1 represents 1, 2 or 3, and n _D2 represents 1 or 2. ]

In the metal complex represented by the formula Ir-1, at least one of R ^{D1 to} R ^D8 is preferably a group represented by the formula (DA).

In the metal complex represented by the formula Ir-2, preferably at least one of R ^{D11 to} R ^D20 is a group represented by the formula (DA).

In the metal complex represented by the formula Ir-3, preferably at least one of R ^{D1 to} R ^D8 and R ^{D11 to} R ^D20 is a group represented by the formula (DA).

In the metal complex represented by the formula Ir-4, preferably at least one of R ^{21 to} R ^D26 is a group represented by the formula (DA).

In the metal complex represented by the formula Ir-5, preferably at least one of R ^{D31 to} R ^D37 is a group represented by the formula (DA).

［式中、
ｍ^DA1、ｍ^DA2及びｍ^DA3は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基又は複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1、Ａｒ^DA2及びＡｒ^DA3は、それぞれ独立に、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2及びＡｒ^DA3が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるＴ^DAは、同一でも異なっていてもよい。］

[Where:
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group, or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. The plurality of ^TDAs may be the same or different. ]

m ^DA1 , m ^DA2 and m ^DA3 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1. m ^DA1 , m ^DA2 and m ^DA3 are preferably the same integer.

G ^DA is preferably a group represented by the formula (GDA-11) ~ (GDA -15), these groups may have a substituent.

［式中、
＊、＊＊及び＊＊＊は、各々、Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3との結合を表す。
Ｒ^DAは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は更に置換基を有していてもよい。Ｒ^DAが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
*, **, and *** each represent a bond with Ar ^DA1 , Ar ^DA2 , and Ar ^DA3 .
R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may further have a substituent. When there are a plurality of ^RDA , they may be the same or different. ]

R ^DA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups have a substituent. May be.

Ar ^DA1 , Ar ^DA2 and Ar ^DA3 are preferably groups represented by the formulas (ArDA-1) to (ArDA-3).

［式中、
Ｒ^DAは前記と同じ意味を表す。
Ｒ^DBは、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^DBが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
R ^DA represents the same meaning as described above.
R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RDBs , they may be the same or different. ]

T ^DA is preferably a group represented by the formula (TDA-1) ~ (TDA -3).

［式中、Ｒ^DA及びＲ^DBは前記と同じ意味を表す。］

[Wherein R ^DA and R ^DB represent the same meaning as described above. ]

  The group represented by the formula (D-A) is preferably a group represented by the formulas (D-A1) to (D-A3).

［式中、
Ｒ^p1、Ｒ^p2及びＲ^p3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基又はハロゲン原子を表す。Ｒ^p1及びＲ^p2が複数ある場合、それらはそれぞれ同一であっても異なっていてもよい。
ｎｐ１は、０〜５の整数を表し、ｎｐ２は０〜３の整数を表し、ｎｐ３は０又は１を表す。複数あるｎｐ１は、同一でも異なっていてもよい。］

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^p1 and R ^p2 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]

  np1 is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and even more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.

R ^p1 , R ^p2 and R ^p3 are preferably an alkyl group or a cycloalkyl group.

Examples of the anionic bidentate ligand represented by -A ^D1 --- A ^D2- include a ligand represented by the following formula.

［式中、＊は、Ｉｒと結合する部位を表す。］

[In formula, * represents the site | part couple | bonded with Ir. ]

  The metal complex represented by the formula Ir-1 is preferably a metal complex represented by the formulas Ir-11 to Ir-13. The metal complex represented by the formula Ir-2 is preferably a metal complex represented by the formula Ir-21. The metal complex represented by the formula Ir-3 is preferably a metal complex represented by the formula Ir-31 to Ir-33. The metal complex represented by the formula Ir-4 is preferably a metal complex represented by the formula Ir-41 to Ir-43. The metal complex represented by the formula Ir-5 is preferably a metal complex represented by the formula Ir-51 to Ir-53.

［式中、
ｎ_D2は、１又は２を表す。
Dは、式(D-A)で表される基を表す。複数存在するDは、同一でも異なっていてもよい。
Ｒ^DCは、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^DCは、同一でも異なっていてもよい。
Ｒ^DDは、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^DDは、同一でも異なっていてもよい。］

[Where:
n _D2 represents 1 or 2.
D represents a group represented by the formula (DA). A plurality of D may be the same or different.
R ^DC represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^DCs may be the same or different.
R ^DD represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^DD may be the same or different. ]

  Examples of the triplet luminescent complex include the metal complexes shown below.

  In the composition of the present invention, the content of the light emitting material is usually 0.1 to 400 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

[Antioxidant]
The antioxidant may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission and charge transport. Examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  In the composition of the present invention, the blending amount of the antioxidant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  Antioxidants may be used alone or in combination of two or more.

<Membrane>
The membrane may contain the polymer compound of the present invention as it is, or the polymer compound of the present invention contained within a molecule or between molecules, or in a state crosslinked within a molecule and between molecules (crosslinked product). May be. The crosslinked product of the polymer compound of the present invention may be a crosslinked product of the polymer compound of the present invention and another compound crosslinked between molecules. The film containing the crosslinked product of the polymer compound of the present invention is a film obtained by crosslinking the film containing the polymer compound of the present invention by external stimulation such as heating and light irradiation. Since the film containing the crosslinked product of the polymer compound of the present invention is substantially insolubilized with respect to the solvent, it can be suitably used for laminating light-emitting elements described later.

  The heating temperature for crosslinking the film is usually 25 to 300 ° C., and the light emission efficiency becomes good. Therefore, the heating temperature is preferably 50 to 250 ° C., more preferably 150 to 200 ° C.

  The heating time for crosslinking the film is usually 10 to 180 minutes, and the light emission efficiency is improved. Therefore, the heating time is preferably 30 to 120 minutes, more preferably 30 to 60 minutes.

  Types of light used for light irradiation for crosslinking the film are, for example, ultraviolet light, near ultraviolet light, and visible light.

  The film is suitable as a hole transport layer or a hole injection layer in the light emitting element.

  The film is made of ink, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method. , Flexographic printing, offset printing, ink jet printing, capillary coating, and nozzle coating.

  The thickness of the film is usually 1 nm to 10 μm.

<Light emitting element>
The light emitting device of the present invention is a light emitting device containing at least one selected from the group consisting of the polymer compound of the present invention and a crosslinked product thereof. The crosslinked product of the polymer compound of the present invention includes a state (crosslinked product) in which the polymer compound of the present invention is crosslinked intramolecularly, between molecules, or both.
As a structure of the light emitting element of this invention, it has an electrode which consists of an anode and a cathode, for example, and the layer containing the crosslinked body of the high molecular compound of this invention provided between this electrode.

[Layer structure]
The layer containing a crosslinked product of the polymer compound of the present invention is usually one or more of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer, and preferably a positive layer. It is a hole transport layer. Each of these layers contains a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material. Each of these layers is the same as the above-described film production, in which a light-emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material are dissolved in the above-described solvent and ink is prepared and used. It can be formed using a method.

The light emitting element has a light emitting layer between an anode and a cathode. The light emitting device of the present invention preferably has at least one of a hole injection layer and a hole transport layer between the anode and the light emitting layer from the viewpoint of hole injection and hole transport. From the viewpoint of injection property and electron transport property, it is preferable to have at least one of an electron injection layer and an electron transport layer between the cathode and the light emitting layer.
As a material for the hole transport layer, the electron transport layer, the light emitting layer, the hole injection layer, and the electron injection layer, in addition to the polymer compound of the present invention, the above-described hole transport material, electron transport material, and light emission, respectively. Examples include materials, hole injection materials, and electron injection materials.

  The material of the hole transport layer, the material of the electron transport layer, and the material of the light emitting layer are used when forming the hole transport layer, the electron transport layer, and the layer adjacent to the light emitting layer, respectively, in the production of the light emitting device. When dissolved in a solvent, it is preferable that the material has a crosslinking group in order to avoid dissolution of the material in the solvent. After forming each layer using a material having a crosslinking group, the layer can be insolubilized by crosslinking the crosslinking group.

  In the light emitting device of the present invention, as a method for forming each layer such as a light emitting layer, a hole transport layer, an electron transport layer, a hole injection layer, and an electron injection layer, when using a low molecular compound, for example, vacuum deposition from powder For example, a method using film formation from a solution or a molten state may be used.

  What is necessary is just to adjust the order of the layer to laminate | stack, the number, and thickness in consideration of luminous efficiency and element lifetime.

[Substrate / Electrode]
The substrate in the light-emitting element may be any substrate that can form electrodes and does not change chemically when the organic layer is formed. For example, the substrate is made of a material such as glass, plastic, or silicon. In the case of an opaque substrate, the electrode farthest from the substrate is preferably transparent or translucent.

  Examples of the material for the anode include conductive metal oxides and translucent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc. A conductive compound of silver, palladium and copper (APC); NESA, gold, platinum, silver and copper.

Examples of the material of the cathode include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, indium; two or more kinds of alloys thereof; Alloys of at least one species and at least one of silver, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; and graphite and graphite intercalation compounds. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
Each of the anode and the cathode may have a laminated structure of two or more layers.

[Usage]
In order to obtain planar light emission using the light emitting element, the planar anode and the cathode may be arranged so as to overlap each other. In order to obtain pattern-like light emission, a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, a layer that is desired to be a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There is a method, a method of forming an anode or a cathode, or both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display device capable of displaying numbers, characters, and the like can be obtained. In order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes and arranged orthogonally. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors, or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively, or can be driven active in combination with a TFT or the like. These display devices can be used for displays of computers, televisions, portable terminals and the like. The planar light emitting element can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source and a display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  In Examples, the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound were determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the moving bed. . The SEC measurement conditions are as follows.

<Measurement conditions>
The polymer compound to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by weight, and 10 μL was injected into SEC. The mobile phase was run at a flow rate of 2.0 mL / min. As a 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.

LC-MS was measured by the following method.
The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent, trade name: 1100LCMSD). The LC-MS mobile phase was used while changing the ratio of acetonitrile and tetrahydrofuran, and was allowed to flow at a flow rate of 0.2 mL / min. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size: 3 μm) was used.

NMR was measured by the following method.
About 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated tetrahydrofuran, deuterated dimethyl sulfoxide, deuterated acetone, deuterated N, N-dimethylformamide, deuterated toluene, deuterated methanol, deuterated ethanol, deuterated 2-propanol. Alternatively, it was dissolved in methylene chloride and measured using an NMR apparatus (manufactured by Agilent, trade name: INOVA300 or MERCURY 400VX).

  A high performance liquid chromatography (HPLC) area percentage value was used as an indicator of the purity of the compound. Unless otherwise specified, this value is a value at UV = 254 nm in HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform so that the concentration was 0.01 to 0.2% by weight, and 1 to 10 μL was injected into the HPLC depending on the concentration. The HPLC mobile phase was used by changing the ratio of acetonitrile / tetrahydrofuran from 100/0 to 0/100 (volume ratio) and flowing at a flow rate of 1.0 mL / min. As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having equivalent performance was used. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

  <Synthesis Example 1> Synthesis of Compound 2

化合物１ 化合物２

Compound 1 Compound 2

A 500 mL four-necked flask equipped with a stirrer was charged with compound 1 (20 g), bispinacol diboron (B ₂ Pin; 14.0 g), potassium acetate (KOAc; 20.56 g), and [1,1′- Bis (diphenylphosphino) ferrocene] palladium dichloride (PdCl ₂ (dppf); 1.7 g) was added, and the gas in the flask was replaced with argon gas. 1,2-Dimethoxyethane (DME; 200 mL) was added thereto, and then the mixture was heated to reflux temperature and stirred for 20 hours. The reaction solution was cooled to room temperature, hexane and water were added, the mixture was stirred at room temperature, the aqueous layer was separated, and the organic layer was washed with a saturated aqueous sodium chloride solution. Magnesium sulfate was added to the obtained organic layer for drying, followed by filtration and concentration to obtain a crude product. The crude product was dissolved in hexane, activated carbon was added and stirred, filtered, and concentrated. The obtained crystals were crystallized with a mixed solvent of toluene and acetonitrile to obtain 21.0 g of Compound 2 as a white solid. The HPLC area percentage value of Compound 2 was 99.75%.

¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 0.88 (6H, t), 1.20-1.39 (60H, m), 1.47-1.54 (4H, m), 2.75-2.87 (4H, m), 7.51 (2H, s)

  <Synthesis Example 2> Synthesis of Compound 4

化合物３ 化合物４

Compound 3 Compound 4

  The gas in a 300 mL four-necked flask equipped with a stirrer was replaced with argon gas, Compound 3 (11.4 g) and acetonitrile (MeCN; 149 mL) were added, and the mixture was cooled in an ice bath. Thereafter, the entire flask was shielded from light, and N-bromosuccinimide (NBS; 15.56 g) was added to the flask a plurality of times. Water and a 10% by weight aqueous sodium sulfite solution were added and stirred, followed by extraction with chloroform, liquid separation, and the organic layer was washed with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated to obtain a crude product. The crude product was dissolved in hexane, filtered through a filter covered with silica gel and celite, and the filtrate was concentrated under reduced pressure to obtain 16.5 g of Compound 4 as a colorless transparent oil.

  <Synthesis Example 3> Synthesis of Compound 5

化合物４ 化合物５

Compound 4 Compound 5

In a 300 mL four-necked flask equipped with a stirrer, compound 4 (16.5 g), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ; 1.78 g), tri-tert-butylphosphine Tetrafluoroborate salt (tBuPHBF ₄ ; 1.02 g), sodium tert-butoxide (11.32 g), and toluene (165 mL) were added, and the gas in the flask was replaced with argon gas. Aniline-d5 (9.5 g) was added dropwise thereto, and the mixture was stirred at 50 ° C. for 2 hours. After cooling, ion-exchanged water was added and washed with stirring. The obtained organic layer was dried over magnesium sulfate and filtered, and then the filtrate was concentrated to obtain a crude product. The crude product was dissolved in hexane and purified by silica gel column chromatography (hexane) to obtain 14.9 g of compound 5 as white crystals.

¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 5.50 (2H, S), 6.42-6.55 (2H, m), 6.66-6.78 (1H, m)

  <Synthesis Example 4> Synthesis of Compound 7

化合物６ 化合物７

Compound 6 Compound 7

  In a 200 mL four-necked flask equipped with a stirrer, compound 6 (8.0 g), tris (dibenzylideneacetone) dipalladium (0) (0.43 g), tri-tert-butylphosphine tetrafluoroborate salt (0. 25 g), sodium tert-butoxide (7.35 g), and toluene (60 mL) were added, and the gas in the flask was replaced with argon gas. A solution prepared by dissolving compound 6 (10.63 g) in toluene (30 mL) was added dropwise thereto, and the mixture was stirred at 50 ° C. for 2 hours. After cooling the reaction solution, toluene and ion-exchanged water were added, dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dissolved in chloroform and hexane, treated with activated carbon, filtered through silica gel, and the filtrate was concentrated. Methanol was added to the obtained crystals, washed with repulp and dried to obtain 12.9 g of compound 7 as white crystals.

LC-MS (ESI, positive): [M + H] ⁺ 701.
¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.35-1.75 (4H, m), 1.85-2.14 (8H, m), 6.62-7.24 (14H, m), 7.68 (2H, d).

  <Synthesis Example 5> Synthesis of Compound 8

化合物７ 化合物８

Compound 7 Compound 8

  The gas in a 200 mL four-necked flask equipped with a stirrer was replaced with argon gas, Compound 7 (12.0 g) and chloroform (180 mL) were added, and the mixture was cooled in an ice bath. Thereafter, the entire flask was shielded from light, and N-bromosuccinimide (5.88 g) was added in several portions, and the mixture was warmed to room temperature and stirred for 2 hours. Water and a 10% by weight aqueous sodium sulfite solution were added, and the mixture was stirred and separated. The organic layer was washed with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated. The obtained crystals were dissolved in chloroform and toluene, treated with activated carbon, and filtered using silica gel. The filtrate was concentrated to about 1/3, acetonitrile was added dropwise, and the precipitated crystals were collected by filtration. The obtained crystal was repulp washed with toluene and dried to obtain 6.5 g of Compound 8 as a white crystal. The HPLC area percentage value of Compound 8 was 99.77%.

LC-MS (ESI, positive): [M + H] ⁺ 858.
¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.40-1.72 (4H, m), 1.85-2.15 (8H, m), 6.74 (2H, d), 6.98 (2H, d), 7.08-7.20 (8H, m), 7.70 (2H, d).

<Synthesis Example 6> Synthesis of Iridium Complex 1 Iridium complex 1 was synthesized according to the method described in International Publication No. 2009/131255.

<Synthesis Example 7> Synthesis of Compounds 9 to 18 Compound 9 was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2008-106241.
Compound 10 was synthesized according to the method described in JP 2010-215886 A.
Compound 11 was synthesized according to the method described in JP 2012-236971 A.
Compound 12 was synthesized according to the method described in JP-T-2007-528916.
Compounds 13 and 15 were synthesized according to the method described in JP 2010-189630 A.
Compound 14 was synthesized according to the method described in WO2009 / 131255.
Compound 16 was synthesized according to the method described in JP 2011-174062.
Compound 17 was synthesized according to the method described in JP 2012-144722 A.
Compound 18 was synthesized according to the method described in WO2002 / 045184.
Compound 19 was synthesized according to the method described in JP-A-2004-143419.
Compound 20 was synthesized according to the method described in JP 2010-031259 A.

<Example 1> Synthesis of polymer compound 1
(Step 1) After setting the inside of the reaction vessel to an inert gas atmosphere, Compound 2 (0.8155 g), Compound 8 (0.8589 g), Compound 9 (0.0660 g), Compound 10 (0.0576 g), dichlorobis (tris-o- Methoxyphenylphosphine) palladium (1.1 mg) and toluene (26 mL) were added and heated to 105 ° C.
(Step 2) Thereafter, a 20 wt% tetraethylammonium hydroxide aqueous solution (18 mL) was added dropwise thereto and refluxed for 5.4 hours. Furthermore, phenylboronic acid (61.1 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.1 mg) were added thereto, and the mixture was refluxed for 17.3 hours. Thereafter, the obtained reaction mixture was cooled, toluene (45 mL) was added, and the mixture was washed once with water, twice with a 10 wt% aqueous hydrochloric acid solution, twice with a 3 wt% aqueous ammonia solution, and twice with water. When the obtained solution was added dropwise to methanol and stirred, precipitation occurred. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. When the obtained solution was added dropwise to methanol and stirred, precipitation occurred. The obtained precipitate was collected by filtration and dried to obtain 1.01 g of polymer compound 1. The Mn of the polymer compound 1 was 4.7 × 10 ⁴ and the Mw was 1.8 × 10 ⁵ .
In polymer compound 1, in the deuterated arylamine structural unit having no crosslinking group, 45.8% of hydrogen atoms were substituted with deuterium atoms.

  From the theoretical values determined from the amounts of raw materials used, the polymer compound 1 is derived from the structural unit derived from the compound 2, the structural unit derived from the compound 8, the structural unit derived from the compound 9, and the compound 10. The derived structural unit is a copolymer composed of a molar ratio of 50: 40: 5: 5.

<Comparative Example 1> Synthesis of polymer compound 2 (Step 1) in Example 1 was carried out by changing the reaction vessel into an inert gas atmosphere, then compound 2 (0.8445 g), compound 11 (0.9209 g), compound 9 (0.0660 g), Compound 10 (0.0575 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.1 mg) and toluene (28 mL) were mixed and heated to 105 ° C. In the same manner as in Example 1, 1.08 g of the polymer compound 2 was obtained. The high molecular compound 2 had Mn of 6.4 × 10 ⁴ and Mw of 2.7 × 10 ⁵ .

  From the theoretical values determined from the amounts of raw materials used, the polymer compound 2 is derived from the structural unit derived from the compound 2, the structural unit derived from the compound 11, the structural unit derived from the compound 9, and the compound 10. The derived structural unit is a copolymer composed of a molar ratio of 50: 40: 5: 5.

<Comparative Example 2> Synthesis of Polymer Compound 3 (Step 1) in Example 1 was carried out by replacing "the inside of the reaction vessel with an inert gas atmosphere, then compound 2 (0.657 g), compound 8 (0.693 g), compound 12". (0.111 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (0.90 mg) and toluene (32 mL) were mixed and heated to 105 ° C. 0.761 g of molecular compound 3 was obtained. Mn of the polymer compound 3 was 4.1 × 10 ⁴ , and Mw was 1.5 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound 3 is 50: a structural unit derived from the compound 2, a structural unit derived from the compound 8, and a structural unit derived from the compound 12. A copolymer composed of a molar ratio of 40:10.

<Comparative Example 3> Synthesis of Polymer Compound 4 (Step 1) in Example 1 was carried out as follows: “After the inside of the reaction vessel was set to an inert gas atmosphere, Compound 2 (0.663 g), Compound 8 (0.693 g), Compound 9 (0.107 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (0.90 mg) and toluene (32 mL) were mixed and heated to 105 ° C. 0.456 g of molecular compound 4 was obtained. The Mn of the polymer compound 4 was 4.2 × 10 ⁴ and the Mw was 1.6 × 10 ⁵ .

  The theoretical value obtained from the amount of charged raw material of polymer compound 2 is 50: 50, 50% of the structural unit derived from compound 2, the structural unit derived from compound 8, and the structural unit derived from compound 9. A copolymer composed of a molar ratio of 40:10.

<Synthesis Example 8> Synthesis of Polymer Compound 5 Polymer compound 5 was synthesized according to the method described in JP 2012-36388 A using the compounds shown in Table 2. The Mn of the polymer compound 5 was 8.2 × 10 ⁴ and the Mw was 2.1 × 10 ⁵ . The polymer compound 5 is a copolymer in which the structural units derived from the respective compounds are composed of the molar ratios shown in Table 2 according to the theoretical values obtained from the charged raw materials.

Synthesis Example 9 Synthesis of Polymer Compound 6 Polymer compound 6 was synthesized according to the method described in JP 2012-144722 A using the compounds shown in Table 3. The Mn of the polymer compound 6 was 1.0 × 10 ⁵ and the Mw was 2.9 × 10 ⁵ . The polymer compound 6 is a copolymer in which the structural units derived from the respective compounds are composed of the molar ratios shown in Table 3 according to the theoretical values obtained from the charged raw materials.

<Example D1> Fabrication and evaluation of light-emitting element D1 (fabrication)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by sputtering. On the anode, a hole injection material (manufactured by Nissan Chemical Industries, Ltd., trade name: ND3202) was formed into a film with a thickness of 65 nm by a spin coating method. This was heated on a hot plate at 50 ° C. for 3 minutes in an air atmosphere to volatilize the solvent, and then heated on a hot plate at 230 ° C. for 15 minutes to form a hole injection layer.
Polymer compound 1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a 20 nm thick film was formed on the hole injection layer by spin coating, and heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere. A transport layer was formed.
Polymer compound 5 and iridium complex 1 were dissolved in xylene at a concentration of 2.2% by weight, respectively. And each xylene solution was mixed so that the solid content ratio of the high molecular compound 5 and the iridium complex 1 might be 70 weight%: 30 weight%. Using the obtained xylene solution, a film having a thickness of 80 nm is formed on the hole transport layer by a spin coating method, and the light emitting layer is heated by heating at 150 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. Formed.
After depressurizing the substrate on which the light emitting layer was formed to 1 × 10 ⁻⁴ Pa or less in a vapor deposition machine, about 7 nm of sodium fluoride was formed on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was deposited at about 120 nm. After vapor deposition, the light emitting element D1 was produced by sealing using a glass substrate.

(Evaluation)
By applying a voltage to the light emitting element D1, EL light emission having the maximum peak wavelength of the emission spectrum at 520 nm was observed. The current value was set so that the initial luminance was 20000 cd / m ² , the device was then driven at a constant current, and the luminance change over time was measured. The time until the luminance became 50% of the initial luminance (hereinafter referred to as “LT50”) was 298 hours. The results are shown in Table 4.

<Comparative Example CD1> Production and Evaluation of Light-Emitting Element CD1 A light-emitting element CD1 was produced in the same manner as in Example D1, except that polymer compound 2 was used instead of polymer compound 1 in Example D1. By applying a voltage to the light emitting device CD1, EL light emission having the maximum peak wavelength of the emission spectrum at 520 nm was observed. The current value was set so that the initial luminance was 20000 cd / m ² , the device was then driven at a constant current, and the luminance change over time was measured. The LT50 was 227 hours. The results are shown in Table 4.

<Comparative Example CD2> Production and Evaluation of Light-Emitting Element CD2 A light-emitting element CD2 was produced in the same manner as in Example D1, except that polymer compound 3 was used instead of polymer compound 1 in Example D1. By applying a voltage to the light emitting device CD2, EL light emission having the maximum peak wavelength of the emission spectrum at 520 nm was observed. The current value was set so that the initial luminance was 20000 cd / m ² , the device was then driven at a constant current, and the luminance change over time was measured. The LT50 was 234 hours. The results are shown in Table 4.

<Comparative Example CD3> Production and Evaluation of Light-Emitting Element CD3 A light-emitting element CD3 was produced in the same manner as in Example D1, except that polymer compound 4 was used instead of polymer compound 1 in Example D1. By applying a voltage to the light emitting device CD3, EL light emission having the maximum peak wavelength of the emission spectrum at 520 nm was observed. The current value was set so that the initial luminance was 20000 cd / m ² , the device was then driven at a constant current, and the luminance change over time was measured. The LT50 was 252 hours. The results are shown in Table 4.

  From a comparison between the light emitting element D1 and the light emitting elements CD1, CD2, and CD3, it can be seen that the light emitting element of the present invention has an excellent luminance life.

<Example D2> Fabrication and evaluation of light-emitting element D2 (fabrication)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by sputtering. On the anode, a hole injection material (trade name: ND-3202, manufactured by Nissan Chemical Industries, Ltd.) was formed to a thickness of 65 nm by a spin coating method. This was heated in an air atmosphere at 50 ° C. for 3 minutes on a hot plate to volatilize the solvent, and then heated on the hot plate at 230 ° C. for 15 minutes to form a hole injection layer.
Polymer compound 1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a 20 nm thick film was formed on the hole injection layer by spin coating, and heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere. A transport layer was formed.
Polymer compound 6 was dissolved in xylene at a concentration of 1.2% by weight. Using the obtained xylene solution, a film with a thickness of 60 nm is formed on the hole transport layer by spin coating, and heated at 150 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. Formed.
After depressurizing the substrate on which the light emitting layer was formed to 1 × 10 ⁻⁴ Pa or less in a vapor deposition machine, about 7 nm of sodium fluoride was formed on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was deposited at about 120 nm. After vapor deposition, the light emitting element D2 was produced by sealing using a glass substrate.

(Evaluation)
By applying a voltage to the light emitting element D2, EL light emission having the maximum peak wavelength of the emission spectrum at 460 nm was observed. After setting the current value so that the initial luminance was 5000 cd / m ² , the device was driven at a constant current, and the change in luminance with time was measured. The LT50 was 51 hours. The results are shown in Table 5.

<Example CD4> Production and Evaluation of Light-Emitting Element CD4 A light-emitting element CD4 was produced in the same manner as in Example D2, except that polymer compound 2 was used instead of polymer compound 1 in Example D2. By applying a voltage to the light emitting device CD4, EL light emission having the maximum peak wavelength of the emission spectrum at 460 nm was observed. After setting the current value so that the initial luminance was 5000 cd / m ² , the device was driven at a constant current, and the change in luminance with time was measured. The LT50 was 31 hours. The results are shown in Table 5.

<Comparative Example CD5> Production and Evaluation of Light-Emitting Element CD5 A light-emitting element CD5 was produced in the same manner as in Example D2, except that polymer compound 3 was used instead of polymer compound 1 in Example D2. By applying a voltage to the light emitting device CD5, EL light emission having the maximum peak wavelength of the emission spectrum at 460 nm was observed. After setting the current value so that the initial luminance was 5000 cd / m ² , the device was driven at a constant current, and the change in luminance with time was measured. The LT50 was 12 hours. The results are shown in Table 5.

<Comparative Example CD6> Production and Evaluation of Light-Emitting Element CD6 A light-emitting element CD6 was produced in the same manner as in Example D2, except that polymer compound 4 was used instead of polymer compound 1 in Example D2. By applying a voltage to the light emitting device CD6, EL light emission having the maximum peak wavelength of the emission spectrum at 460 nm was observed. After setting the current value so that the initial luminance was 5000 cd / m ² , the device was driven at a constant current, and the change in luminance with time was measured. The LT50 was 22 hours. The results are shown in Table 5.

  From the comparison between the light emitting element D2 and the light emitting elements CD4, CD5, and CD6, it can be seen that the light emitting element of the present invention has an excellent luminance life.

Claims (8)

A deuterated arylamine structural unit having no bridging group and a structural unit having a bridging group represented by formula (1) or formula (1 ′), and represented by formula (XL-1) And a polymer compound having a crosslinking group represented by the formula (XL-16).

[Where:
nA represents an integer of 0 to 5, and n represents 1 or 2.
Ar ³ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
L ^A represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups have a substituent. Also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of ^LA are present, they may be the same or different.
X represents a crosslinking group selected from the crosslinking group A group. When two or more X exists, they may be the same or different. Provided that when X is a bridging group of the formula (XL-1), L ^A in which the X is attached is an alkylene group, a cycloalkylene group, a divalent heterocyclic group, represented by -NR'- Group, oxygen atom or sulfur atom, and these groups optionally have a substituent. ]

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ⁵ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which an aromatic hydrocarbon ring and a heterocyclic ring are directly bonded, and these groups may have a substituent.
Ar ⁴ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ⁴ , Ar ⁵ and Ar ⁶ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or a sulfur atom to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good. When a plurality of K ^A are present, they may be the same or different.
X ′ represents a bridging group selected from the bridging group A group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. However, at least one X ′ is a crosslinking group selected from the crosslinking group A group. However, when X ′ is a bridging group represented by the formula (XL-1), K ^A to which X ′ is bonded is an alkylene group, a cycloalkylene group, a divalent heterocyclic group, or —NR′—. Represents a group represented by the above, an oxygen atom, a sulfur atom, or a group in which some or all of the hydrogen atoms contained in these groups are substituted with deuterium atoms, and these groups have a substituent. May be. ]
(Crosslinking group A group)

[Wherein, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5. When a plurality of R ^XL are present, they may be the same or different, and when a plurality of n ^XL are present, they may be the same or different. * Represents a bonding position. These crosslinking groups may have a substituent. ] The polymer compound according to claim 1, wherein the deuterated arylamine structural unit having no crosslinking group is a structural unit represented by the formula (X).

[Where:
a ¹ and a ² each independently represents an integer of 0 to 2;
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups are substituents You may have. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different.
However, a part or all of the hydrogen atoms contained in at least one of the groups represented by Ar ^X1 , Ar ^X2 , Ar ^X3 , Ar ^X4 , R ^X1 , R ^X2 and R ^X3 are substituted with deuterium atoms. Yes. ] The high molecular compound of Claim 2 whose said Ar ^<X2> or Ar ^<X4> is group represented by Formula (A-7), Formula (A-9), or Formula (A-19).

[Wherein, R and R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which they are bonded. ] The polymer compound according to claim 2 or 3, wherein a part or all of hydrogen atoms contained in the groups represented by Ar ^X1 , Ar ^X3 , R ^X1 and R ^X2 are substituted with deuterium atoms. Furthermore, the high molecular compound as described in any one of Claims 1-4 containing the structural unit represented by a formula (Y).

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. It may be. ] The polymer compound according to claim 5, wherein the structural unit represented by the formula (Y) is a structural unit represented by the formula (Y-1) or a structural unit represented by the formula (Y-2). .

[Wherein, R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups have a substituent. Also good. A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

[Wherein, R ^Y1 represents the same meaning as described above. X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - , or _{^{C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ] A polymer compound according to any one of claims 1 to 6;
A composition comprising a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and at least one material selected from the group consisting of a solvent.   A light emitting device comprising at least one selected from the group consisting of the polymer compound according to claim 1 and a crosslinked product thereof.