JP2016176063A - 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 with a low drive voltage.SOLUTION: A polymer compound comprises a constitutional unit represented by formula (1).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”) can be suitably used for displays and lighting applications, and have recently attracted attention. This light-emitting element includes organic layers such as a light-emitting layer and a charge transport layer. By using a polymer compound, an organic layer can be formed by a coating method typified by an ink jet printing method. Therefore, a polymer compound used for manufacturing a light-emitting element has been studied.

  As a material used for a light emitting layer of a light emitting element, for example, a polymer compound including a triazine structural unit represented by the following formula has been proposed (Patent Document 1).

JP 2012-036388 A

  However, a light emitting device manufactured using the above polymer compound has a problem of high driving voltage.

  Accordingly, an object of the present invention is to provide a polymer compound useful for the production of a light emitting device having a low driving voltage. Another object of the present invention is to provide a composition containing the polymer compound and a light emitting device containing the polymer compound.

  The present invention first provides a polymer compound containing a structural unit represented by the following formula (1).

［式中、
Ｚ^１、Ｚ^２およびＺ^３は、それぞれ独立に、窒素原子または−ＣＲ^Ｚ＝を表す。Ｒ^Ｚ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、アリールオキシ基または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。但し、Ｚ^１、Ｚ^２およびＺ^３からなる群から選ばれる少なくとも１つは窒素原子である。
Ｘ^１は、単結合、−ＮＲ^Ｘ−で表される基、酸素原子または硫黄原子を表す。Ｒ^Ｘ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、アリールオキシ基または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。
Ｙ^１は、−ＣＲ^Ｙ１Ｒ^Ｙ２−で表される基、−ＣＲ^Ｙ３Ｒ^Ｙ４−ＣＲ^Ｙ５Ｒ^Ｙ６−で表される基、−ＣＲ^Ｙ７＝ＣＲ^Ｙ８−で表される基、−ＮＲ^Ｙ９−で表される基、酸素原子または硫黄原子を表す。Ｒ^Ｙ１、Ｒ^Ｙ２、Ｒ^Ｙ３、Ｒ^Ｙ４、Ｒ^Ｙ５、Ｒ^Ｙ６、Ｒ^Ｙ７、Ｒ^Ｙ８およびＲ^Ｙ９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。Ｒ^Ｙ１とＲ^Ｙ２、Ｒ^Ｙ３とＲ^Ｙ４、Ｒ^Ｙ３とＲ^Ｙ５、Ｒ^Ｙ４とＲ^Ｙ６、Ｒ^Ｙ５とＲ^Ｙ６、Ｒ^Ｙ７とＲ^Ｙ８は、それぞれ互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。
Ａｒ^１およびＡｒ^２は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。但し、Ｘ^１が単結合であり、Ｙ^１が−ＣＲ^Ｙ１Ｒ^Ｙ２−で表される基である場合、Ａｒ^１およびＡｒ^２は、それぞれ独立に、置換基を有していてもよいフェニレン基または置換基を有していてもよいナフタレンジイル基である。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５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^１は、同一でも異なっていてもよく、隣接するＲ^１同士は互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^４とＲ^５は、それぞれ互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。］

[Where:
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or —CR ^Z ═. R ^Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. . However, at least one selected from the group consisting of Z ¹ , Z ² and Z ³ is a nitrogen atom.
X ¹ represents a single bond, a group represented by —NR ^X —, an oxygen atom or a sulfur atom. R ^X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. .
Y ¹ represents a group represented by —CR ^Y1 R ^Y2 —, a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, a group represented by —CR ^Y7 = CR ^Y8 —, —NR ^Y9 — Represents a group represented by the formula: oxygen atom or sulfur atom. R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8 and R ^Y9 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl Represents a group, an aryloxy group or a monovalent heterocyclic group, and these groups optionally have a substituent. R ^Y1 and R ^Y2 , R ^Y3 and R ^Y4 , R ^Y3 and R ^Y5 , R ^Y4 and R ^Y6 , R ^Y5 and R ^Y6 , R ^Y7 and R ^Y8 are bonded to each other and together with the carbon atoms to which they are bonded A ring may be formed.
Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, when X ¹ is a single bond and Y ¹ is a group represented by —CR ^Y1 R ^Y2 —, Ar ¹ and Ar ² are each independently a phenylene group optionally having a substituent. Or it is a naphthalenediyl group which may have a substituent.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent. A plurality of R ¹ may be the same or different, and adjacent R ¹ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]

  Secondly, the present invention provides at least one selected from the group consisting of the above-described polymer compound, 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. And a composition containing the following materials.

  Thirdly, the present invention provides a light emitting device containing the above polymer compound.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element with a low drive voltage can be provided. Moreover, according to this invention, the composition containing this high molecular compound and the 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.

  The hydrogen atom may be a deuterium atom or a light hydrogen atom.

  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, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, Hexyl group, heptyl group, octyl group, 2-butyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group, dodecyl group 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 and 6-ethyloxyhexyl group may be mentioned.
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.

“P-valent heterocyclic group” (p represents an integer of 1 or more) is a p-group 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, this is an 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 carbon atom number 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, 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 a group 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 cycloalkynyl group may have a substituent, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 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および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、アリール基または１価の複素環基を表す。複数存在するＲおよび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 each is bonded. ]

The carbon atom number of a bivalent heterocyclic group is 2-60 normally without including the carbon atom number of a substituent, Preferably it is 3-20, More preferably, it is 4-15.
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および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 generating a new bond by being subjected to heating, ultraviolet irradiation, near ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction, etc. B-1) is a group represented by any one of (B-17). These groups may have a substituent.

  “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.

<Polymer compound>
The polymer compound of the present invention is a polymer compound containing a structural unit represented by the formula (1).

  [Structural Unit Represented by Formula (1)]

Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or —CR ^Z ═.

R ^Z is preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom, because the synthesis of the polymer compound of the present invention is easy.

Examples of the substituent that the group have to be represented by R ^Z, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group are preferable, an alkyl group or an aryl group is more preferable.

Z ¹ , Z ² and Z ³ each have at least two selected from the group consisting of Z ¹ , Z ² and Z ³ because the luminance life of the light emitting device containing the polymer compound of the present invention is excellent. Are preferred, and it is more preferred that all of Z ¹ , Z ² and Z ³ are nitrogen atoms.

X ¹ represents a single bond, a group represented by —NR ^X —, an oxygen atom or a sulfur atom.

R ^X is preferably an alkyl group, a cycloalkyl group, or an aryl group, and more preferably an aryl group, because synthesis of the polymer compound of the present invention is easy.

The substituent that the group represented by R ^X may have is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group.

X ¹ is preferably a single bond because the polymer compound of the present invention can be easily synthesized.

Y ¹ represents a group represented by —CR ^Y1 R ^Y2 —, a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, a group represented by —CR ^Y7 = CR ^Y8 —, —NR ^Y9 — Represents a group represented by the formula: oxygen atom or sulfur atom.

R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8, and R ^Y9 are excellent in luminance lifetime of the light-emitting element containing the polymer compound of the present invention. It is preferably an alkyl group or an aryl group.

The substituents that the groups represented by R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8, and R ^Y9 may have include an alkyl group, a cycloalkyl group, An aryl group or a monovalent heterocyclic group is preferable, and an alkyl group or an aryl group is more preferable.

When Y ¹ is a group represented by —CR ^Y1 R ^Y2 —, the driving voltage of the light-emitting device containing the polymer compound of the present invention is lower, so that R ^Y1 and R ^Y2 are an alkyl group, cycloalkyl More preferably an alkyl group or an aryl group, one of R ^Y1 and R ^Y2 is an aryl group, and the other of R ^Y1 and R ^Y2 is an alkyl group or an aryl group. It is particularly preferred.

When Y ¹ is a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, since the synthesis of the polymer compound of the present invention is easy, R ^Y3 , R ^Y4 , R ^Y5 and R ^Y6 are: An alkyl group or a cycloalkyl group is more preferable, and an alkyl group is still more preferable.

When R ^Y3 , R ^Y4 , R ^Y5 and R ^Y6 are alkyl groups, R ^Y3 and R ^Y5 are bonded to each other to form a ring together with the carbon atoms to which they are bonded, and R ^Y4 and R ^Y6 Are preferably bonded to each other to form a ring together with the carbon atoms to which they are bonded. The ring formed by bonding R ^Y3 and R ^Y5 to each other is preferably a 5-membered ring. The ring formed by combining R ^Y4 and R ^Y6 with each other is preferably a 5-membered ring.

Since Y ¹ is easy to synthesize the polymer compound of the present invention, Y ¹ is a group represented by —CR ^Y1 R ^Y2 —, a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, an oxygen atom or It is preferably a sulfur atom, more preferably a group represented by —CR ^Y1 R ^Y2 —, a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, or an oxygen atom. Since the luminance lifetime of the light-emitting element containing the molecular compound is excellent, a group represented by —CR ^Y1 R ^Y2 — or a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 — is more preferable. .

Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, when X ¹ is a single bond and Y ¹ is a group represented by —CR ^Y1 R ^Y2 —, Ar ¹ and Ar ² are each independently a phenylene group optionally having a substituent. Or it is a naphthalenediyl group which may have a substituent.

The arylene group represented by Ar ¹ and Ar ² is more preferably a phenylene group, a naphthalenediyl group, a formula (A-7)-(A-12), a formula (A-19) or a formula (A-20) These groups may have a substituent.

The divalent heterocyclic group represented by Ar ¹ and Ar ² is more preferably a formula (AA-1)-(AA-5), a formula (AA-10)-(AA-15), a formula (AA -24), a group represented by formula (AA-25) or formula (AA-26), and these groups optionally have a substituent.

Ar ¹ and Ar ² may be a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent, since synthesis of the polymer compound of the present invention is easy. Particularly preferred is a phenylene group which may have a substituent. Ar ¹ and Ar ² are preferably the same group because the synthesis of the polymer compound of the present invention is easy.

As the substituent that the group represented by Ar ¹ and Ar ² may have, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable, and an alkyl group or an aryl group is more preferable.

Examples of Ar ¹ and Ar ² include groups represented by formulas (Ar-1) to (Ar-13), and the synthesis of the polymer compound of the present invention is easy. ) To (Ar-3), the formula (Ar-6), the formula (Ar-7), the formula (Ar-12) or the group represented by the formula (Ar-13) is preferable, and the formula (Ar-1) to A group represented by (Ar-3), formula (Ar-6) or formula (Ar-12) is more preferred, represented by formula (Ar-1), formula (Ar-2) or formula (Ar-12). Are more preferable, and a group represented by the formula (Ar-1) or the formula (Ar-2) is particularly preferable.

［式中、Ｒ^Ａｒは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表す。複数存在するＲ^Ａｒは、同一でも異なっていてもよい。］

[Wherein, R ^Ar represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ^Ar may be the same or different. ]

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are excellent in the luminance life of the light emitting device containing the polymer compound of the present invention, and therefore may be a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. preferable.

As the substituent that the group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ may have, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable. An alkyl group or an aryl group is more preferable.

R ¹ is more preferably a hydrogen atom because it facilitates the synthesis of the polymer compound of the present invention.

R ² and R ⁵ are more preferably a hydrogen atom, an alkyl group, or an aryl group, and even more preferably a hydrogen atom, because a compound that is a raw material for the polymer compound of the present invention is easily available.

R ³ and R ⁴ are more preferably a hydrogen atom, an alkyl group, or an aryl group because the driving voltage of the light-emitting device containing the polymer compound of the present invention is lower, and one of R ³ and R ⁴ is More preferably, it is a hydrogen atom or an alkyl group, and the other of R ³ and R ⁴ is a hydrogen atom, an alkyl group or an aryl group, one of R ³ and R ⁴ is a hydrogen atom, and R ³ and R ⁴ It is particularly preferred that the other is a hydrogen atom, an alkyl group or an aryl group, and it is particularly preferred that one of R ³ and R ⁴ is a hydrogen atom and the other of R ³ and R ⁴ is an aryl group.

  The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (2) or the formula (3) since the synthesis of the polymer compound of the present invention is easy. It is more preferable that it is a structural unit represented by.

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｘ^１、Ｙ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、前記と同じ意味を表す。
Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４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。Ｒ^１１とＲ^１２、Ｒ^１３とＲ^１４は、それぞれ互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above.
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, These groups may have a substituent. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom because the synthesis of the polymer compound of the present invention is easy.

As the substituent that the group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may have, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable. An aryl group is more preferred.

  Since the structural unit represented by the formula (2) has a lower driving voltage of the light-emitting element containing the polymer compound of the present invention, the formula (2-1), the formula (2-2), or the formula (2- It is preferable that it is a structural unit represented by 3), and it is more preferable that it is a structural unit represented by Formula (2-1) or Formula (2-2).

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^Ｙ１、Ｒ^Ｙ２、Ｒ^Ｙ３、Ｒ^Ｙ４、Ｒ^Ｙ５およびＲ^Ｙ６は、前記と同じ意味を表す。
Ｘ^２は、酸素原子または硫黄原子を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 And R ^Y6 represents the same meaning as described above.
X ² represents an oxygen atom or a sulfur atom. ]

X ² is preferably an oxygen atom because the synthesis of the polymer compound of the present invention is easy.

  In the structural unit represented by the formula (3), the driving voltage of the light-emitting element containing the polymer compound of the present invention is lower, so the formula (3-1), the formula (3-2), or the formula (3- The structural unit represented by 3) is preferred, and the structural unit represented by formula (3-1) or formula (3-2) is more preferred.

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１１、Ｒ^１３、Ｒ^１４、Ｒ^Ｙ１、Ｒ^Ｙ２、Ｒ^Ｙ３、Ｒ^Ｙ４、Ｒ^Ｙ５およびＲ^Ｙ６は、前記と同じ意味を表す。
Ｘ^３は、酸素原子または硫黄原子を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹³ , R ¹⁴ , R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 And R ^Y6 represents the same meaning as described above.
X ³ represents an oxygen atom or a sulfur atom. ]

X ³ is preferably an oxygen atom because the synthesis of the polymer compound of the present invention is easy.

  As a structural unit represented by Formula (1), the structural unit represented by Formula (1-101)-Formula (1-136) is mentioned, for example.

  The structural unit represented by the formula (1) is based on the total amount of the structural units contained in the polymer compound from the viewpoint of achieving both the electron transport property and the luminance life of the light emitting device containing the polymer compound of the present invention. 1 to 30 mol%, preferably 3 to 20 mol%, more preferably 5 to 15 mol%.

  As for the structural unit represented by Formula (1), only 1 type may be contained in the polymer compound of this invention, and 2 or more types may be contained.

  [Structural Unit Represented by Formula (Y)]

  The polymer compound of the present invention preferably further contains a structural unit represented by the formula (Y) because the luminance life of the light-emitting device containing the polymer compound of the present invention is excellent.

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の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。］

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ]

The arylene group represented by Ar ^Y1 is more preferably the formula (A-1), the formula (A-2), the formula (A-6)-(A-10), the formula (A-19) or the formula (A A-20), more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19) And particularly preferably a group represented by the formula (A-1), the formula (A-2) or the formula (A-9), and these groups have a substituent. May be.

The divalent heterocyclic group represented by Ar ^Y1 is more preferably a formula (AA-1)-(AA-4), a formula (AA-10)-(AA-15), a formula (AA-18) -(AA-21), a group represented by formula (AA-33) or formula (AA-34), and more preferably a group represented by formula (AA-4), formula (AA-10), formula (AA- 12) a group represented by formula (AA-14) or formula (AA-33), and these groups may have a substituent.

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^Y1 and at least one divalent heterocyclic group are directly bonded, and further preferable. The ranges are the same as the more preferable ranges and further preferable ranges of the above-mentioned arylene group and divalent heterocyclic group represented by Ar ^Y1 .

  Examples of the “divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded” include groups represented by the following formulas, which have a substituent. You may do it.

［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。］

[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.

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 formulas (Y-1)-(Y-6), and brightness of the light-emitting element containing the polymer compound of the present invention. From the viewpoint of lifetime, it is preferably a structural unit represented by the formula (Y-1)-(Y-3), and preferably from the viewpoint of charge transportability of the light-emitting device containing the polymer compound of the present invention. Is a structural unit represented by the formula (Y-4)-(Y-6).

［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 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^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, and these groups optionally have a substituent.

［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)−または−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^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. You may do it.

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 the formula (Y-A1)-(Y-A5), more preferably a group represented by the 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 the formula (Y-B1)-(Y-B5), more preferably a group represented by the 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および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および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. ]

  The structural unit represented by the formula (Y-3) is preferably a structural unit represented by the formula (Y-3 ′).

［式中、Ｒ^Y11およびＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y11 and X ^Y1 represent the same meaning as described above. ]

［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。］

[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.

  As the structural unit represented by the formula (Y), for example, a structural unit comprising an arylene group represented by the formula (Y-101)-(Y-121), a formula (Y-201)-(Y-206) The structural unit which consists of a bivalent heterocyclic group represented by these is mentioned.

The constitutional unit represented by the formula (Y), wherein Ar ^Y1 is an arylene group, is excellent in luminous efficiency of the light-emitting device containing the polymer compound of the present invention, and is therefore included in the polymer compound Preferably it is 0.5-90 mol% with respect to the total amount of a unit, More preferably, it is 30-80 mol%.

A structural unit represented by formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group, or at least one arylene group and at least one divalent heterocyclic group directly bonded to each other. The structural unit which is a group is preferably 0.5 to 50 mol% with respect to the total amount of the structural units contained in the polymer compound because the charge transport property of the light-emitting device containing the polymer compound of the present invention is excellent. Yes, more preferably 3 to 30 mol%.

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

[Structural Unit Represented by Formula (X)]
The polymer compound of the present invention may further contain a structural unit represented by the following formula (X), since the hole transport property of the light-emitting device containing the polymer compound of the present invention is excellent.

［式中、
ａ^X1およびａ^X2は、それぞれ独立に、０以上の整数を表す。
Ａｒ^X1およびＡｒ^X3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^X2およびＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の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およびＡｒ^X4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。
Ｒ^X1、Ｒ^X2および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。Ｒ^X2およびＲ^X3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。］

[Where:
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
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 at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different from each other.
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 optionally have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different. ]

a ^X1 is preferably an integer of 2 or less, more preferably 1, since the light emitting device containing the polymer compound of the present invention has excellent luminous efficiency.

a ^X2 is preferably an integer of 2 or less, and more preferably 0, because the light-emitting device containing the polymer compound of the present invention is excellent in luminous efficiency.

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, and these groups have a substituent. Also good.

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

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

Ar ^X1 and Ar ^X3 are preferably an arylene group which may have a substituent.

As the arylene group represented by Ar ^X2 and Ar ^X4 , more preferably, the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9)-(A-11) Or it is group represented by a formula (A-19), and these groups may have a substituent.

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

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and the at least one divalent heterocyclic group are directly bonded to each other Further preferred ranges are the same as the more preferred ranges and further preferred ranges of the arylene group and divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 , respectively.

The divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and at least one divalent heterocyclic group are directly bonded to each other is at least represented by Ar ^Y1 in the formula (Y) Examples thereof include the same divalent groups in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.

Ar ^X2 and Ar ^X4 are preferably an arylene group which may 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.

  The structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1)-(X-7), more preferably the formula (X-1)-(X-6) And more preferably a structural unit represented by the formula (X-3)-(X-6).

［式中、Ｒ^X4およびＲ^X5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価の複素環基またはシアノ基を表し、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は、同一でも異なっていてもよい。複数存在するＲ^X5は、同一でも異なっていてもよく、隣接するＲ^X5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 and R ^X5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or cyano. Represents a group, and these groups may have a substituent. A plurality of R ^X4 may be the same or different. A plurality of R ^X5 may be the same or different, and adjacent R ^X5 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

  Since the structural unit represented by the formula (X) is excellent in the hole transport property of the light-emitting device containing the polymer compound of the present invention, it is preferably based on the total amount of the structural units contained in the polymer compound. It is 0.1-50 mol%, More preferably, it is 1-40 mol%, More preferably, it is 5-30 mol%.

  Examples of the structural unit represented by the formula (X) include structural units represented by the formula (X1-1)-(X1-11), preferably the formula (X1-3)-(X1-10). ).

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

  Examples of the polymer compound of the present invention include polymer compounds P-101 to P-107 shown in Table 1, and the polymer compound P-101 and P-101 and The polymer compound P-104 is preferable, and the polymer compound P-101a and the polymer compound P-104a are more preferable. Here, the “other structural unit” means a structural unit other than the structural units represented by Formula (1), Formula (Y-1) to Formula (Y-6), and Formula (X).

［表中、ｐ、ｑ、ｒ、ｓおよび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 (1), the formula (Y-1) to the formula (Y-6) and the formula (X) in the polymer compounds P-101 to P-107 are as described above. It is as follows.

［表中、ｐ、ｑ、ｒ、ｓおよびｔは、前記と同じ意味を表す。］

[In the table, p, q, r, s, and t represent the same meaning 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 is represented, for example, by a compound represented by the formula (M-1) and another compound (for example, a compound represented by the formula (M-2), a formula (M-3) And at least one compound selected from the group consisting of compounds represented by formula (M-4)) can be produced by condensation polymerization. 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、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ａｒ^Y1、ａ¹、ａ²、Ａｒ^X1〜Ａｒ^X4およびＲ^X1〜Ｒ^X3は、前記と同じ意味を表す。
Ｚ^C1〜Ｚ^C8は、それぞれ独立に、置換基Ａ群および置換基Ｂ群からなる群から選ばれる基を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Ar ^Y1 , a ¹ , a ² , Ar ^{X1 to} Ar ^X4 And R ^{X1 to} R ^X3 represent the same meaning as described above.
Z ^{C1 to} Z ^C8 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 and Z ^{C5 to} Z ^C8 are groups selected from the substituent group A, Z ^C3 and Z ^C4 select groups selected from the substituent group B.

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

<Substituent group A>
Chlorine atom, bromine atom, iodine atom or —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 bonded 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 bonded 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.

  The compound having a group selected from the substituent group A and the compound having a group selected from the substituent group B are subjected to condensation polymerization by a known coupling reaction, and the group selected from the substituent group A and the 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 dichlorobis (triphenylphosphine) palladium, dichlorobis (tris-o-methoxyphenylphosphine) palladium, palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate and the like. Transition of nickel complexes such as palladium complexes of nickel, nickel [tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, [bis (1,4-cyclooctadiene)] nickel Metal complexes; these transition metal complexes may further include complexes having ligands such as triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl, etc. . 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, and tripotassium phosphate; organics such as tetrabutylammonium fluoride and tetrabutylammonium hydroxide. Examples of the base include 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 recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

<Compound>
Next, the compound which is a raw material monomer of the polymer compound of the present invention will be described.

  The compound represented by the formula (M-1) is useful as a raw material monomer for the polymer compound of the present invention.

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｚ^C1およびＺ^Ｃ2は、前記と同じ意味を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Z ^C1 and Z ^C2 represent the same meaning as described above. ]

  A method for producing the compound represented by the formula (M-1) will be described.

  The compound represented by the formula (M-1) is, for example, a method in which a compound represented by the formula (M-1-a) and a compound represented by the formula (M-1-b) are subjected to a coupling reaction. Can be manufactured.

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｚ^C1およびＺ^Ｃ2は、前記と同じ意味を表す。
Ｗ^１およびＷ^２は、それぞれ独立に、置換基Ａ群および置換基Ｂ群からなる群から選ばれる基を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Z ^C1 and Z ^C2 represent the same meaning as described above.
W ¹ and W ² each independently represent a group selected from the group consisting of Substituent Group A and Substituent Group B. ]

When W ¹ is a group selected from the substituent group A, W ² is preferably a group selected from the substituent group B.
When W ¹ is a group selected from the substituent group B, W ² is preferably a group selected from the substituent group A.

  The compound having a group selected from the substituent group A and the compound having a group selected from the substituent group B are a group selected from a group selected from the substituent group A and a group selected from the substituent group B by a known coupling reaction. Carbon atoms bonded to each other are bonded to each other. Therefore, if a compound having a group selected from the substituent group A and a compound having a group selected from the substituent group B are subjected to a known coupling reaction, a coupling product of these compounds can be obtained. .

  In the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b), a catalyst such as a palladium catalyst is usually used.

  Examples of the palladium catalyst include palladium acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium ( II), tris (dibenzylideneacetone) dipalladium (0).

  The palladium catalyst may be used in combination with a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, 1,1′-bis (diphenylphosphino) ferrocene. .

  In the case of using a palladium catalyst in the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b), the amount of the palladium catalyst used is the formula (M It is 0.00.0-10 mol equivalent normally in conversion of palladium element with respect to the number-of-moles of the compound represented by -1-b).

  The coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b) is usually performed in a solvent.

  Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol, and 2-ethoxyethanol; ether solvents such as tetrahydrofuran, dioxane, cyclopentylmethyl ether, and diglyme; Halogen solvents such as chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene and mesitylene; amide systems such as N, N-dimethylformamide and N, N-dimethylacetamide Solvents: acetone, dimethyl sulfoxide, and water.

  In the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b), the amount of the compound represented by the formula (M-1-b) used Is usually 0.05 to 20 molar equivalents relative to the number of moles of the compound represented by the formula (M-1-a), and the yield of the compound represented by the formula (M-1) is excellent. Therefore, it is preferable that it is 1.5-20 molar equivalent.

  The reaction time of the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b) is usually 0.5 to 150 hours, and the reaction temperature Is usually between the melting point and boiling point of the solvent present in the reaction system.

  In the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b), a base may be added.

  The compound represented by the formula (M-1-a1), which is one embodiment of the compound represented by the formula (M-1-a), is represented by, for example, the formula (M-1-a2). It can be produced by reacting a compound with a compound represented by the formula (B-0) by Ishiyama-Miyaura-Hartwig.

［式中、
Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、前記と同じ意味を表す。
Ｗ^３は、置換基Ａ群から選ばれる基を表す。］

[Where:
X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above.
W ³ represents a group selected from the substituent group A. ]

  In the Ishiyama-Miyaura-Hartwig reaction between the compound represented by the formula (M-1-a2) and the compound represented by the formula (B-0), a catalyst such as a palladium catalyst is usually used.

  As an example of a palladium catalyst, the same thing as the example of the palladium catalyst in the coupling reaction of the compound represented by Formula (M-1-a) and the compound represented by Formula (M-1-b) is mentioned. . The palladium catalyst may be used in combination with a phosphorus compound. As an example of a phosphorus compound, the same thing as the phosphorus compound in the coupling reaction of the compound represented by a formula (M-1-a) and the compound represented by a formula (M-1-b) is mentioned.

  In the Ishiyama-Miyaura-Hartwig reaction between the compound represented by the formula (M-1-a2) and the compound represented by the formula (B-0), when a palladium catalyst is used, the amount of the palladium catalyst used is represented by the formula ( It is 0.00001-10 molar equivalent normally in conversion of palladium element with respect to the number-of-moles of the compound represented by M-1-a2).

  The Ishiyama-Miyaura-Hartwig reaction between the compound represented by the formula (M-1-a2) and the compound represented by the formula (B-0) is usually performed in a solvent.

  As an example of a solvent, the same thing as the example of the solvent in the coupling reaction of the compound represented by Formula (M-1-a) and the compound represented by Formula (M-1-b) is mentioned.

  The reaction time of the Ishiyama-Miyaura-Hartwig reaction between the compound represented by the formula (M-1-a2) and the compound represented by the formula (B-0) is usually 0.5 to 150 hours. The temperature is usually between the melting point and boiling point of the solvent present in the reaction system.

  In the Ishiyama-Miyaura-Hartwig reaction between the compound represented by the formula (M-1-a2) and the compound represented by the formula (B-0), a base may be added.

  The compound represented by the formula (M-1-a3), which is one embodiment of the compound represented by the formula (M-1-a2), is represented by, for example, the formula (M-1-a4). It can be produced by a reaction of brominating a compound.

［式中、Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、前記と同じ意味を表す。］

[Wherein, X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above. ]

  In the reaction for brominating the compound represented by the formula (M-1-a4), a brominating agent such as bromine, N-bromosuccinimide, and benzyltrimethylammonium tribromide is usually used.

  The reaction for brominating the compound represented by the formula (M-1-a4) is usually performed in a solvent.

  Examples of the solvent include water; alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol, and 2-ethoxyethanol; ether solvents such as tetrahydrofuran, dioxane, cyclopentylmethyl ether, and diglyme; Halogen solvents such as methylene and chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene, and mesitylene; N, N-dimethylformamide, N, N-dimethylacetamide and the like Amide solvents; dimethyl sulfoxide

  In the reaction for brominating the compound represented by the formula (M-1-a4), the amount of the brominating agent used is usually relative to the number of moles of the compound represented by the formula (M-1-a4). 0.8 to 1.3 molar equivalents.

  The reaction time for the reaction for brominating the compound represented by the formula (M-1-a4) is usually 0.5 to 150 hours, and the reaction temperature is usually from the melting point of the solvent present in the reaction system to the boiling point. Between.

  In the reaction for brominating the compound represented by the formula (M-1-a4), iron powder, acid, or iodine may be added.

  Examples of the acid include acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, sulfuric acid, and hydrochloric acid.

  The compound represented by the formula (M-1-b1), which is one embodiment of the compound represented by the formula (M-1-b), is represented by the formula (M-1-b2), for example. A compound and a compound represented by the formula (M-1-b3) can be produced by a coupling reaction method.

［式中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ¹およびＺ^C1は、前記と同じ意味を表す。
Ｗ^４は、置換基Ａ群および置換基Ｂ群からなる群から選ばれる基を表す。］

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ and Z ^C1 represent the same meaning as described above.
W ⁴ represents a group selected from the group consisting of the substituent group A and the substituent group B. ]

  Conditions for the coupling reaction between the compound represented by the formula (M-1-b2) and the compound represented by the formula (M-1-b3) are as follows: The conditions for the coupling reaction with the compound represented by the formula (M-1-b) are the same.

<Composition>
The composition of the present invention is at least one selected from the group consisting of the polymer compound of the present invention, 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. Material.

  The composition containing the polymer compound of the present invention and a solvent (hereinafter sometimes referred to as “ink”) is suitable for manufacturing 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 depending on the type of printing method, but when applying a printing method in which a solution such as an ink jet printing method 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 weight 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 each classified into a low molecular compound and a high molecular compound. 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 includes 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.

[Luminescent 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.

  In the composition of the present invention, the blending amount of the light emitting material is usually 1 to 150 parts by weight, preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  The light emitting material may include a low molecular compound and a high molecular compound, and preferably includes 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および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価の複素環基また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および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および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、酸素原子または窒素原子を表し、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または３を表し、ｎ_D2は、１または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 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 triplet light emitting 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 triplet light emitting complex represented by the formula Ir-2, at least one of R ^{D11 to} R ^D20 is preferably a group represented by the formula (DA).

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

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

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

［式中、
ｍ^DA1、ｍ^DA2および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、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2および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 optionally 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.
^TDA 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 ^DA1 is preferably a group represented by the formulas (GDA-11) to (GDA-15), and these groups may have a substituent.

［式中、
＊、＊＊および＊＊＊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、アリール基または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。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および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および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またはハロゲン原子を表す。Ｒ^p1および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または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 0 or 1, 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.
As the triplet light emitting complex, a metal complex represented by the formula Ir-11, a metal complex represented by the formula Ir-21, and a metal complex represented by the formula Ir-32 are preferable.

［式中、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。ｎ_D2は、１または２を表す。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^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^ＤＤは、同一でも異なっていてもよい。］

[Wherein, D represents a group represented by the formula (DA). A plurality of D may be the same or different. n _D2 represents 1 or 2. R ^DC 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 ^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.

[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 contains the polymer compound of the present invention.

  The membrane includes an insolubilized membrane obtained by insolubilizing the polymer compound of the present invention in a solvent by crosslinking. The insolubilized film is a film obtained by crosslinking the polymer compound of the present invention by an external stimulus such as heating or light irradiation. Since the insolubilized film is substantially insoluble in a solvent, the insolubilized film can be suitably used for stacking light emitting elements.

  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.

  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 light emitting layer in a light emitting element.

  The film is made of an 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 such as organic electroluminescence containing the polymer compound of the present invention. Examples of the light emitting device include a light emitting device containing the polymer compound of the present invention, There is a light-emitting element containing a cross-linked molecular compound. Here, the crosslinked product of the polymer compound of the present invention is a product obtained by crosslinking the polymer compound of the present invention within a molecule, between molecules, or both.
As a structure of the light emitting element of this invention, it has the electrode which consists of an anode and a cathode, for example, and the layer containing the high molecular compound of this invention provided between this electrode.

[Layer structure]
The layer containing 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 light emitting layer. . Each of these layers includes 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 element 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 a 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 one or more species with one or more of silver, copper, manganese, titanium, cobalt, nickel, tungsten, 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 the examples, the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Determined by The SEC measurement conditions are as follows.

[Measurement condition]
The polymer compound to be measured was dissolved in THF at a concentration of about 0.05% by weight, and 10 μL was injected into SEC. THF was used as the mobile phase of SEC and flowed 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.

Liquid chromatograph mass spectrometry (LC-MS) was performed by the following method.
The measurement sample was dissolved in chloroform or THF to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). The LC-MS mobile phase was used while changing the ratio of acetonitrile and THF, 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 measurement was performed by the following method.
About 5 to 10 mg of a measurement sample was added to about 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated tetrahydrofuran (THF-d ₈ ), deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated acetone (CD _3- (C = O) -CD ₃ ), heavy N, N-dimethylformamide (DMF-d ₇ ), heavy toluene (C ₆ D ₅ -CD ₃ ), heavy methanol (CD ₃ OD), heavy ethanol (CD ₃ CD ₂ OD), heavy 2- It was dissolved in propanol (CD ₃ -CDOD-CD ₃ ) or methylene chloride (CD ₂ Cl ₂ ) and measured using an NMR apparatus (trade name: INOVA300 or MERCURY 400VX manufactured by Agilent).

  High performance liquid chromatography (HPLC) area percentage values were used as indicators of compound purity. Unless otherwise specified, this value is a value at 254 nm by HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in THF or chloroform so that the concentration was 0.01 to 0.2% by weight, and 1 to 10 μL was injected into HPLC depending on the concentration. As the mobile phase of HPLC, acetonitrile and THF were used and allowed to flow at a flow rate of 1 mL / min in a gradient analysis of acetonitrile / THF = 100/0 to 0/100 (volume ratio). 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 M1

(Stage 1: Synthesis of Compound M1c)
After making the inside of the reaction vessel an argon gas atmosphere, compound M1a (81 g), compound M1b (8.9 g), tetrahydrofuran (1 L), tetrakis (triphenylphosphine) synthesized according to the method described in International Publication No. 2009/131255. Palladium (0) (7.0 g) and a 20 wt% tetraethylammonium hydroxide aqueous solution (370 g) were added, and the mixture was stirred at 60 ° C for 5 hours. The resulting reaction mixture was cooled to room temperature and then concentrated under reduced pressure. Thereafter, toluene (500 mL) was added thereto, the obtained organic layer was washed with ion-exchanged water, and the obtained organic layer was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then the solvent was distilled off under reduced pressure to obtain compound M1c (28 g, yield 91%) as a colorless oil. It was. The HPLC area percentage value of Compound M1c was 99.5% or more.

(Stage 2: Synthesis of Compound M1d)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M1c (24 g), Compound B0 (12 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (2.8 g) , Potassium acetate (8.6 g) and 1,2-dimethoxyethane (150 mL) were added, and the mixture was stirred at 80 ° C. for 4 hours. The resulting reaction mixture was cooled to room temperature, toluene (100 mL) was added, the mixture was filtered using celite and silica gel, and the obtained filtrate was concentrated under reduced pressure. Toluene (150 mL) and activated carbon (3 g) were added to the obtained residue, and the mixture was stirred at 60 ° C. for 1 hour. The obtained mixture was cooled to room temperature, filtered through Celite, and the obtained filtrate was concentrated under reduced pressure to obtain Compound M1d (20 g, yield 87%) as a colorless solid. The HPLC area percentage value of Compound M1d was 99.1%.

(Stage 3: Synthesis of Compound M1)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M1d (5.3 g), Compound T0 (21 g) synthesized according to the method described in International Publication No. 2011/049241, Toluene (1.9 L), Ethanol (190 mL) , Ion exchange water (460 mL), tetrakis (triphenylphosphine) palladium (0) (1.0 g) and sodium carbonate (3.6 g) were added, and the mixture was stirred at 35 ° C. for 49 hours. The obtained reaction mixture was washed with ion exchange water, and then the obtained organic layer was concentrated under reduced pressure. Hexane (560 mL) was added to the resulting residue, and the mixture was stirred at room temperature for 90 minutes, filtered, and the obtained filtrate was concentrated under reduced pressure. Hexane (20 mL) was added to the obtained residue, and the resulting precipitate was collected by filtration to obtain a solid. The obtained solid was purified by crystallization using a mixed solvent of toluene and methanol, and silica gel column chromatography using a mixed solvent of toluene and hexane in order, and then the solvent was distilled off under reduced pressure. Compound M1 (2.4 g, 22% yield) was obtained as a colorless solid. The HPLC area percentage value of Compound M1c was 99.4%.

TLC / MS (DART positive): m / z = 1006 [M + H] ^+
1 H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 8.90 (s, 1H), 8.81 (d, 1H), 8.64 (dd, 4H), 8.03 (d , 2H), 7.80-7.74 (multit, 6H), 7.59 (dd, 2H), 7.50 (dd, 2H), 7.36 (d, 4H), 7.17 (d, 4H), 1.78-1.34 (multit, 29H), 0.90 (t, 6H).

  <Synthesis Example 2> Synthesis of Compound M2

(Stage 1: Synthesis of Compound M2b)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M1a (790 g) and tetrahydrofuran (dehydrated product, 7.9 L) were added, and the mixture was cooled to −70 ° C. with stirring. Thereafter, a hexane solution of sec-butyllithium (1.1 mol / L, 1.1 L) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at −60 ° C. or lower. Thereafter, 1-iodobutane (450 g) was added dropwise thereto while stirring at −60 ° C., followed by stirring at −60 ° C. for 1.5 hours. The resulting reaction mixture was warmed to room temperature and then stirred at room temperature for 2 hours. Thereafter, 15% by weight ammonium chloride aqueous solution (1.6 L) and toluene (1.6 L) were added thereto, the obtained organic layer was washed with ion-exchanged water, and the obtained organic layer was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using hexane, and then the solvent was distilled off under reduced pressure to obtain compound M2b (460 g, yield 61%) as an oil. The HPLC area percentage value of Compound M2b was 78.1%.

(Stage 2: Synthesis of Compound M2c)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M2b (460 g), Compound B0 (380 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (37 g), acetic acid Potassium (220 g) and 1,2-dimethoxyethane (820 mL) were added, and the mixture was stirred at 85 ° C. for 5 hours. The obtained reaction mixture was cooled to room temperature, toluene (2.3 L) was added, and the mixture was filtered through celite and silica gel. The obtained filtrate was concentrated under reduced pressure. Hexane and activated carbon were added to the resulting residue and stirred at room temperature for 2 hours. The obtained mixture was filtered using Celite, and the obtained filtrate was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane, and then the solvent was distilled off under reduced pressure to obtain compound M2c (370 g, yield 75%) as an oil. It was. The HPLC area percentage value of Compound M2c was 99.3%.

(Stage 3: Synthesis of Compound M2)
After the inside of the reaction vessel was filled with an argon gas atmosphere, compound M2c (25 g), compound T0 (32 g), toluene (2.5 L), ethanol (360 mL), ion-exchanged water (720 mL), tetrakis (triphenylphosphine) palladium ( 0) (3.5 g) and sodium carbonate (12 g) were added, and the mixture was stirred at 65 ° C. for 15 hours. The obtained reaction mixture was cooled to room temperature, washed with ion exchange water, and the obtained organic layer was concentrated under reduced pressure. Hexane (360 mL) was added to the resulting residue, followed by filtration, and the resulting filtrate was concentrated under reduced pressure. The obtained residue was subjected to amino group surface-modified silica gel column chromatography using hexane (Fuji Silysia Chemical Co., Ltd., CHROMATOREX NH-DM1020), GPC (gel permeation chromatography) (manufactured by Japan Analytical Industrial Co., Ltd., JAIGEL). -2H and JAIGEL-2.5H), and crystallization using a mixed solvent of ethyl acetate and methanol were sequentially performed to obtain Compound M2 (21 g, yield 60%) as a colorless solid. The HPLC area percentage value of Compound M2 was 99.5% or more.

TLC / MS (DART positive): m / z = 930 [M + H] ^+
1 H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 8.83 (dd, 2H), 8.66 (td, 4H), 7.99 (d, 1H), 7.87 (d , 1H), 7.77 (td, 4H), 7.36 (s, 1H), 7.29-7.23 (multit, 5H), 7.10 (d, 4H), 2.68 (t, 2H), 1.76 (s, 4H), 1.69-1.55 (multit, 6H), 1.45-1.28 (multit, 14H), 0.97-0.86 (multit, 9H) .

  <Synthesis Example 3> Synthesis of Compound M3

(Stage 1: Synthesis of Compound M3b)
After making the inside of the reaction vessel a nitrogen gas atmosphere, compound M3a (54 g) synthesized according to the method described in JP2012-144722A and tetrahydrofuran (dehydrated product, 540 mL) were added, and the mixture was cooled to −75 ° C. with stirring. . Thereafter, a hexane solution of n-butyllithium (1.6 mol / L, 61 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at −75 to −70 ° C., and −70 ° C. For 2 hours. Then, after adding ion-exchange water (270 mL) there, the obtained reaction mixture was heated up to room temperature. Thereafter, toluene (270 mL) was added thereto, the obtained organic layer was washed with ion-exchanged water, the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure. . The obtained oil was purified by silica gel column chromatography using hexane, and then the solvent was distilled off under reduced pressure to obtain compound M3b (32 g, yield 70%) as a colorless oil. The HPLC area percentage value of Compound M3b was 99.5% or more.

(Stage 2: Synthesis of Compound M3c)
After the inside of the reaction vessel was filled with a nitrogen gas atmosphere, Compound M3b (32 g), Compound B0 (18 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, dichloromethane adduct (1.6 g) , Potassium acetate (19 g) and 1,4-dioxane (190 mL) were added, and the mixture was stirred at 110 ° C. for 7 hours. After the obtained reaction mixture was cooled to room temperature, ion exchange water (180 mL) and chloroform (180 mL) were added, and the resulting organic layer was washed with ion exchange water. The obtained mixture was filtered using celite and silica gel, and the obtained filtrate was concentrated under reduced pressure. Toluene (44 mL) and activated carbon (3.8 g) were added to the obtained residue, and the mixture was stirred at room temperature for 30 minutes. The obtained mixture was filtered using Celite, and the obtained filtrate was concentrated under reduced pressure to obtain Compound M3c (34.5 g, yield 98%) as a brown oil. The HPLC area percentage value of Compound M3c was 99.0%.

(Stage 3: Synthesis of Compound M3)
After the inside of the reaction vessel was filled with an argon gas atmosphere, compound M3c (5.5 g), compound T0 (9.0 g), toluene (560 mL), ethanol (120 mL), ion-exchanged water (160 mL), tetrakis (triphenylphosphine) Palladium (0) (0.58 g) and sodium carbonate (6.4 g) were added, and the mixture was stirred at 70 ° C. for 19 hours. The obtained reaction mixture was cooled to room temperature, washed with ion exchange water, and the obtained organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography using a mixed solvent of toluene and hexane, and then crystallized using a mixed solvent of ethyl acetate and ethanol to give compound M3 (5.7 g, yield). 72%) was obtained as a colorless solid. The HPLC area percentage value of Compound M3 was 99.5% or more.

LC / MS (APCI positive): m / z = 812 [M + H] ^+
1 H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 8.83 (dd, 1H), 8.72 (d, 1H), 8.68 (td, 4H), 8.03 (d , 1H), 7.96 (td, 1H), 7.77 (td, 4H), 7.44-7.32 (multit, 3H), 6.99 (d, 2H), 6.88 (s, 1H), 2.01 (s, 3H), 1.76 (s, 4H), 1.57 (q, 4H), 1.35 to 1.20 (multit, 12H), 0.84 (t, 6H) ).

  <Example 1> Synthesis of polymer compound P1

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, compound M4 (0.861 g) synthesized according to the method described in JP2010-189630A, synthesized according to the method described in WO2009 / 131255. Compound M5 (0.904 g), Compound M1 (0.353 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.5 mg) and toluene (30 mL) were added and heated to 105 ° C.
(Step 2) Thereafter, a 20 wt% tetraethylammonium hydroxide aqueous solution (12 mL) was dropped therein and refluxed for 6 hours.
(Step 3) Thereafter, phenylboronic acid (85 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.5 mg) were added thereto and refluxed for 15 hours.
(Step 4) Thereafter, a sodium diethyldithiacarbamate aqueous solution was added thereto, followed by stirring at 80 ° C. for 2 hours. After cooling the obtained reaction mixture, it was washed twice with water, twice with a 3 wt% aqueous acetic acid solution and twice with water, and the resulting solution was added dropwise to methanol, resulting in precipitation. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.07 g of polymer compound P1. The Mn of the polymer compound P1 was 7.1 × 10 ⁴ and the Mw was 1.7 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound P1 is 50: a structural unit derived from the compound M4, a structural unit derived from the compound M5, and a structural unit derived from the compound M1. It is a copolymer formed by a molar ratio of 40:10.

<Example 2> Synthesis of polymer compound P2 (Step 1) in the synthesis of polymer compound P1 was performed according to the method described in Japanese Patent Application Laid-Open No. 2010-189630 after setting the inside of the reaction vessel to an inert gas atmosphere. Compound M4 (0.859 g), Compound M5 (0.904 g) synthesized according to the method described in WO2009 / 131255, Compound M2 (0.328 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium ( 1.5 mg) and toluene (30 mL) were added, and the mixture was heated to 105 ° C., except that 0.99 g of the polymer compound P2 was obtained in the same manner as the synthesis of the polymer compound P1. The Mn of the polymer compound P2 was 6.4 × 10 ⁴ and the Mw was 1.4 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material for the polymer compound P2 is 50: a structural unit derived from the compound M4, a structural unit derived from the compound M5, and a structural unit derived from the compound M2. It is a copolymer formed by a molar ratio of 40:10.

<Example 3> Synthesis of polymer compound P3 (Step 1) in the synthesis of polymer compound P1 was performed according to the method described in Japanese Patent Application Laid-Open No. 2010-189630 after setting the inside of the reaction vessel to an inert gas atmosphere. Compound M4 (0.859 g), Compound M5 (0.904 g) synthesized according to the method described in WO2009 / 131255, Compound M3 (0.287 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium ( 1.5 mg) and toluene (30 mL) were added, and the mixture was heated to 105 ° C., except that 0.99 g of the polymer compound P3 was obtained in the same manner as the synthesis of the polymer compound P1. The Mn of the polymer compound P3 was 6.5 × 10 ⁴ and the Mw was 1.5 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for polymer compound P3 was 50: a structural unit derived from compound M4, a structural unit derived from compound M5, and a structural unit derived from compound M3. It is a copolymer formed by a molar ratio of 40:10.

  <Comparative example 1> Synthesis of polymer compound CP1

  Compound M6 was synthesized according to the method described in JP2012-036388.

The polymer compound CP1 was synthesized using the compound M4, the compound M5, and the compound M6 according to the method of “polymer compound B” described in JP2012-36388A. The Mn of the polymer compound CP1 was 9.6 × 10 ⁴ and the Mw was 2.2 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for polymer compound CP1 was 50: a structural unit derived from compound M4, a structural unit derived from compound M5, and a structural unit derived from compound M6. It is a copolymer formed by a molar ratio of 40:10.

  <Synthesis Example 4> Synthesis of Polymer Compound IP1

Compound M7 was synthesized according to the method described in JP2011-174062.
Compound M8 was synthesized according to the method described in JP-T-2007-512249.
Compound M9 was a commercially available product.
Compound M10 was synthesized according to the method described in JP-A-2008-106241.

The polymer compound IP1 was synthesized by a known coupling reaction using the compound M7, the compound M8, the compound M9, and the compound M10 according to the method of “Polymer 9” described in JP2012-144722A. The Mn of the polymer compound IP1 was 8.4 × 10 ⁴ and the Mw was 3.4 × 10 ⁵ .

  From the theoretical values determined from the amounts of the raw materials used, the polymer compound IP1 is derived from the structural unit derived from the compound M7, the structural unit derived from the compound M8, the structural unit derived from the compound M9, and the compound M10. The derived structural unit is a copolymer composed of a molar ratio of 50: 30: 12.5: 7.5.

  <Synthesis Example 5> Synthesis of Compound M11

(Stage 1: Synthesis of Compound M11c)
After the inside of the reaction vessel was filled with a nitrogen gas atmosphere, Compound M11a (22 g, commercially available), Compound M11b (21 g), 28 wt% sodium methoxide methanol solution (40 g) and methanol (1.3 L) were added at 65 ° C. Stir for 11 hours. The obtained reaction mixture was cooled to room temperature, 35% by weight hydrochloric acid (23 g) was added, and the mixture was stirred for 1.5 hours. Then, the obtained mixture was filtered to obtain Compound M11c (21 g, yield 52%) as a brown solid. The HPLC area percentage value of Compound M11c was 95.5%. By repeating this operation, the required amount of Compound M11c was obtained.

LC-MS (ESI positive): m / z = 715 [M + K] ^+
1 H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 11.31 (br, 2H), 7.82 (s, 2H), 7.59 (d, 2H), 7.41 (d, 2H) ), 4.70 (s, 2H), 4.04 (s, 6H), 3.03 (s, 6H).

(Stage 2: Synthesis of Compound M11d)
After making the inside of the reaction vessel a nitrogen gas atmosphere, Compound M11c (47 g), acetic acid (380 g) and ion-exchanged water (47 g) were added, and the mixture was stirred at 98 ° C. for 7 hours. The obtained reaction liquid was cooled to room temperature, and then the obtained mixture was filtered to obtain Compound M11d (26 g, yield 84%) as a brown solid. The HPLC area percentage value of Compound M11d was 93.6%.

LC-MS (APPI negative): m / z = 443 [M−H] ^−
1 H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 8.00 (d, 2H), 7.52 (dd, 2H), 7.27 (d, 2H), 2.89 (d, 4H) ), 2.64 (d, 4H).

(Stage 3: Synthesis of Compound M11e)
The reaction vessel was filled with a nitrogen gas atmosphere, then Compound M11d (25 g), hydrazine monohydrate (11 g), sodium hydroxide (13 g) and ethylene glycol (700 mL) were added, and the mixture was stirred at 130 ° C. for 9.5 hours. . The obtained reaction solution was cooled to room temperature, and then toluene was added thereto, followed by washing with ion-exchanged water and drying with anhydrous sodium sulfate. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was crystallized from a mixed solvent of toluene and acetonitrile to give M11e (17 g, yield 73%) as a colorless solid. The HPLC area percentage value of Compound M11e was 99.2%.

LC-MS (APPI positive): m / z = 416 [M] ^+
1 H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 7.93 (d, 2H), 7.42 (dd, 2H), 7.24 (d, 2H), 2.20-2.08 (Multit, 4H), 2.00-1.86 (multit, 4H), 1.72-1.55 (multit, 2H), 1.51-1.36 (multit, 2H).

(Stage 4: Synthesis of Compound M11f)
After making the inside of the reaction vessel an argon gas atmosphere, magnesium (1.8 g, shaved shape) and cyclopentyl methyl ether (dehydrated product, 35 mL) were added, and compound A0 (10 g) was added dropwise, followed by stirring at 70 ° C. for 2 hours. Then, the Grignard reagent was prepared by cooling the obtained reaction mixture to room temperature. Next, after putting another reaction vessel into an argon gas atmosphere, Compound M11e (13 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.05 g), and Cyclopentyl methyl ether (dehydrated product, 250 mL) was added, and the mixture was heated to 40 ° C. with stirring. Thereafter, the previously prepared Grignard reagent was added dropwise thereto over 1 hour, and the mixture was stirred at 45 ° C. for 3 hours. The obtained reaction mixture was cooled to 0 ° C., 6 wt% hydrochloric acid was added and stirred, and then the mixture was filtered using celite. Then, after adding heptane (250 mL) to the obtained filtrate and stirring, the aqueous layer was separated and removed, the obtained organic layer was washed with ion-exchanged water, and anhydrous magnesium sulfate was added to the obtained organic layer. Dried. Thereafter, activated carbon (1.3 g) was added thereto and stirred, followed by filtration, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified successively by silica gel column chromatography using heptane and then reverse phase column chromatography using a mixed solvent of ethyl acetate and acetonitrile to give compound M11f (7.5 g, yield 52%). Was obtained as a colorless oil. The HPLC area percentage value of Compound M11f was 99.5% or more.

(Stage5: Synthesis of Compound M11g)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M11f (8.0 g), Compound B0 (6.3 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct ( 0.20 g), potassium acetate (3.2 g) and cyclopentyl methyl ether (dehydrated product, 80 mL) were added and stirred at 100 ° C. for 4 hours, and then the resulting reaction mixture was cooled to room temperature. Thereafter, toluene (80 mL) and ion-exchanged water (40 mL) were added thereto and stirred, and then the aqueous layer was separated and removed, and the resulting organic layer was washed with ion-exchanged water (40 mL), and the resulting organic Anhydrous magnesium sulfate was added to the layer and dried, followed by filtration. The obtained filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then the obtained solid was washed with acetonitrile to obtain Compound M11g (6.1 g, yield 70%). Obtained as a colorless solid. The HPLC area percentage value of Compound M11g was 99.5% or more.

(Stage6: Synthesis of Compound M11)
After making the inside of reaction container argon atmosphere, Compound M11g (3.3g), Compound T0 (4.0g), Toluene (120mL), Ethanol (20mL), Tetrakis (triphenylphosphine) palladium (0) (0. 73 g), 20 wt% tetraethylammonium hydroxide aqueous solution (21 g) and ion-exchanged water (35 mL) were added, and the mixture was stirred at 50 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature, washed with ion exchange water, dried over anhydrous magnesium sulfate added to the resulting organic layer, filtered, and the resulting filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of hexane and toluene, and then crystallized using a mixed solvent of toluene and ethanol, whereby compound M11 (3.4 g, yield) was obtained. 68%) as a colorless solid. The HPLC area percentage value of Compound M11 was 99.5% or more.

LC / MS (APCI positive): m / z = 788 [M + H] ^+
1 H-NMR (CDCl ₃ , 400 MHz): δ (ppm) = 9.29 (s, 1H), 8.65 (d, 4H), 8.57 (d, 1H), 7.94 (s, 1H) ), 7.72 (d, 4H), 7.58 (d, 1H), 7.34 (d, 1H), 7.19 (d, 1H), 2.73-2.68 (multit, 2H) 2.7-1.98 (multit, 8H), 1.74-1.64 (multit, 4H), 1.55-1.27 (multit, 13H), 0.95-0.88 (multit, 6H).

  <Synthesis Example 6> Synthesis of Compound M12

(Stage 1: Synthesis of Compound M12b)
The reaction vessel was filled with an argon gas atmosphere, magnesium (5.4 g, shaved shape) and cyclopentyl methyl ether (dehydrated product, 180 mL) were added, compound A0 (45 g) was added dropwise, and the mixture was stirred at 45 ° C. for 1 hr. Grignard reagent was prepared. Next, after making another reaction vessel into an argon gas atmosphere, Compound M12a (35 g, commercially available), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.18 g) ) And cyclopentyl methyl ether (dehydrated product, 700 mL) were added, and the mixture was heated to 40 ° C. with stirring. Then, the Grignard reagent prepared previously was dripped there, and it stirred at 40 degreeC for 1 hour. The obtained reaction mixture was cooled to 0 ° C., 6 wt% hydrochloric acid was added and stirred, and then the mixture was filtered using celite. Thereafter, the aqueous layer was separated and removed, and then the obtained organic layer was washed with ion-exchanged water, dried over anhydrous magnesium sulfate added to the obtained organic layer, filtered, and the obtained filtrate was concentrated under reduced pressure. This gave compound M12b (51 g, 123% yield) as a yellow oil. The HPLC area percentage value of Compound M12b was 58.1%.

(Stage 2: Synthesis of Compound M12c)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M12b (51 g), Compound B0 (41 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (3.2 g) , Potassium acetate (16 g) and dimethoxyethane (620 mL) were added, and the mixture was stirred at 100 ° C. for 5 hours. The resulting reaction mixture was cooled to room temperature and then filtered using celite and silica gel. The obtained organic layer was washed with ion exchange water and then concentrated under reduced pressure. To the obtained residue, heptane (700 mL) and activated carbon (23 g) were added, and the mixture was stirred at room temperature for 1 hour. The obtained mixture was filtered using Celite, and the obtained filtrate was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate, and the solvent was evaporated under reduced pressure to give compound M12c (29 g, yield 61%) as a colorless oil. Obtained. The HPLC area percentage value of Compound M12c was 98.0%.

(Stage 3: Synthesis of Compound M12)
After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound M12c (3.5 g), Compound T0 (5.1 g), toluene (130 mL), ethanol (30 mL), tetrakis (triphenylphosphine) palladium (0) (0. 93 g) and 20 wt% tetraethylammonium hydroxide aqueous solution (27 g) were added, and the mixture was stirred at 50 ° C for 1.5 hours. The obtained reaction mixture was cooled to room temperature and then washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered through celite and silica gel, and the obtained filtrate was concentrated under reduced pressure. . The obtained residue was subjected to silica gel column chromatography using a mixed solvent of hexane and chloroform, and then crystallized with toluene to give Compound M12 (5.7 g, yield 72%) as a colorless solid. Got as. The HPLC area percentage value of Compound M12 was 99.5% or more.

LC / MS (ESI positive): m / z = 696 [M + H] ^+
1 H-NMR (CDCl ₃ , 400 MHz): δ (ppm) = 9.02 (s, 1H), 8.80 (d, 1H), 8.59 (d, 4H), 7.89 (s, 1H ), 7.69 (d, 4H), 7.63 (d, 1H), 7.49 (d, 1H), 7.32 (d, 1H), 2.78 (dd, 2H), 1.68 (Td, 2H), 1.48-1.42 (multit, 1H), 1.39-1.33 (multit, 10H), 0.93 (t, 6H).

  <Example 4> Synthesis of polymer compound P4

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, compound M13 (0.768 g), compound M14 (0.271 g, commercially available) synthesized according to the method described in International Publication No. 2012/088671, Compound M15 (0.631 g), compound M2 (0.281 g) synthesized according to the method described in JP 2012-144722 A, compound M16 (0.167 g) synthesized according to the method described in JP-A-2004-143419 , Dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.3 mg) and toluene (30 mL) were added and heated to 90 ° C.
(Step 2) Thereafter, a 16% by weight tetraethylammonium hydroxide aqueous solution (21 g) was added dropwise thereto and refluxed for 5 hours.
(Step 3) Thereafter, phenylboronic acid (73 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.3 mg) were added thereto and refluxed for 15 hours.
(Step 4) The obtained reaction mixture was cooled to room temperature, washed twice with 10 wt% aqueous hydrochloric acid, twice with 3 wt% aqueous ammonia, and twice with water, and the resulting solution was added dropwise to methanol. However, 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. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.23 g of polymer compound P4. The Mn of the polymer compound P4 was 5.4 × 10 ⁴ , and the Mw was 1.3 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound P4 is that the structural unit derived from the compound M13, the structural unit derived from the compound M14, the structural unit derived from the compound M15, and the compound M2 This is a copolymer comprising a derived structural unit and a structural unit derived from the compound M16 in a molar ratio of 36: 14: 32.5: 10: 7.5.

<Example 5> Synthesis of polymer compound P5 (Step 1) in the synthesis of polymer compound P4 was carried out as follows: "After making the inside of the reaction vessel an inert gas atmosphere, compound M13 (0.768 g), compound M14 (0. 271 g), compound M15 (0.631 g), compound M12 (0.210 g), compound M16 (0.167 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.3 mg) and toluene (30 mL) were added. , Heated to 90 ° C. ”
(Step 2) is the same as the synthesis of the polymer compound P4 except that “after that, 16 wt% tetrabutylammonium hydroxide aqueous solution (20 g) was dropped therein and refluxed for 7 hours”. As a result, 1.18 g of the polymer compound P5 was obtained. The Mn of the polymer compound P5 was 5.3 × 10 ⁴ , and the Mw was 1.3 × 10 ⁵ .

  The theoretical value obtained from the amount of raw materials used for the polymer compound P5 is that the structural unit derived from the compound M13, the structural unit derived from the compound M14, the structural unit derived from the compound M15, and the compound M12 This is a copolymer comprising a derived structural unit and a structural unit derived from the compound M16 in a molar ratio of 36: 14: 32.5: 10: 7.5.

<Example 6> Synthesis of polymer compound P6 (Step 1) in the synthesis of polymer compound P4 was made as follows: "After making the inside of the reaction vessel an inert gas atmosphere, compound M13 (0.767 g), compound M14 (0. 271 g), compound M15 (0.631 g), compound M11 (0.237 g), compound M16 (0.167 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.3 mg) and toluene (30 mL) were added. , Heated to 90 ° C. ”
(Step 2) is the same as the synthesis of the polymer compound P4 except that “after that, a 16 wt% tetrabutylammonium hydroxide aqueous solution (20 g) was dropped therein and refluxed for 5 hours”. As a result, 1.16 g of the polymer compound P6 was obtained. The Mn of the polymer compound P6 was 5.1 × 10 ⁴ and the Mw was 1.3 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound P6 is that the structural unit derived from the compound M13, the structural unit derived from the compound M14, the structural unit derived from the compound M15, and the compound M11 This is a copolymer comprising a derived structural unit and a structural unit derived from the compound M16 in a molar ratio of 36: 14: 32.5: 10: 7.5.

  <Comparative example 2> Synthesis of polymer compound CP2

Polymer compound CP2 is synthesized by a known coupling reaction using Compound M13, Compound M14, Compound M15, Compound M6 and Compound M16 according to the method of “Polymer Compound F” described in International Publication No. 2012/008550. did. The Mn of the polymer compound CP2 was 8.5 × 10 ⁴ and the Mw was 2.4 × 10 ⁵ .

  The theoretical value obtained from the amount of raw materials used for the polymer compound CP2 is that the structural unit derived from the compound M13, the structural unit derived from the compound M14, the structural unit derived from the compound M15, and the compound M6 This is a copolymer comprising a derived structural unit and a structural unit derived from the compound M16 in a molar ratio of 36: 14: 32.5: 10: 7.5.

<Example D1> Fabrication and evaluation of light-emitting element D1 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, was formed on the anode at a thickness of 65 nm by a spin coating method, and was 170 ° C. on a hot plate in an air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of hole transport layer)
The polymer compound IP1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
Polymer compound P1 and metal complex COM-4 synthesized according to the method described in International Publication No. 2009/131255 were dissolved in xylene at a concentration of 2.2% by weight (polymer compound P1 / metal complex). COM-4 = 60 wt% / 40 wt%). Using the obtained xylene solution, a film having a thickness of 80 nm was formed on the hole transport layer by a spin coating method, and heated at 150 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. Formed.

(Formation of cathode)
After reducing the pressure of the substrate on which the light emitting layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride is about 4 nm on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was deposited at about 80 nm. After vapor deposition, the light emitting element D1 was produced by sealing using a glass substrate.

(Evaluation of light emitting element)
By applying a voltage to the light emitting element D1, EL light emission having a maximum peak wavelength of an emission spectrum at 520 nm was observed. The external quantum efficiency at 1000 cd / m ² was 14.1%, and the drive voltage at a current density of 10 mA / cm ² was 6.3V. The results are shown in Table 2.

<Example D2> Production and Evaluation of Light-Emitting Element D2 A light-emitting element D2 was produced in the same manner as in Example D1, except that the polymer compound P2 was used instead of the polymer compound P1 in Example D1.

By applying a voltage to the light emitting element D2, EL light emission having a maximum peak of the emission spectrum at 520 nm was observed. The external quantum efficiency at 1000 cd / m ² was 14.0%, and the drive voltage at a current density of 10 mA / cm ² was 6.4V. The results are shown in Table 2.

<Example D3> Production and Evaluation of Light-Emitting Element D3 A light-emitting element D3 was produced in the same manner as in Example D1, except that the polymer compound P3 was used instead of the polymer compound P1 in Example D1.

By applying a voltage to the light emitting element D3, EL light emission having a maximum peak of the emission spectrum at 520 nm was observed. The external quantum efficiency at 1000 cd / m ² was 14.0%, and the drive voltage at a current density of 10 mA / cm ² was 6.5V. The results are shown in Table 2.

<Comparative Example CD1> Production and Evaluation of Light-Emitting Element CD1 The polymer compound CP1 was used in place of the polymer compound P1 in Example D1, and the polymer compound CP1 and the metal complex COM-4 were 1.8% by weight. A light emitting device CD1 was produced in the same manner as in Example D1 except that a xylene solution (polymer compound CP1 / metal complex COM-4 = 60 wt% / 40 wt%) dissolved in xylene at a concentration was used.

By applying a voltage to the light emitting device CD1, EL light emission having the maximum peak of the emission spectrum at 520 nm was observed. The external quantum efficiency at 1000 cd / m ² was 14.0%. The drive voltage at a current density of 10 mA / cm ² was 7.0V. The results are shown in Table 2.

<Example D4> Fabrication and evaluation of light-emitting element D4 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, was formed on the anode at a thickness of 65 nm by a spin coating method, and was 170 ° C. on a hot plate in an air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of hole transport layer)
The polymer compound IP1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
Polymer compound P1 and metal complex COM-8 synthesized according to the method described in JP2011-105701A were dissolved in xylene at a concentration of 2.2% by weight (polymer compound P1 / metal complex). COM-8 = 92.5 wt% / 7.5 wt%). 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 light is emitted by heating at 150 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. A layer was formed.

(Formation of cathode)
After reducing the pressure of the substrate on which the light emitting layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride is about 4 nm on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was deposited at about 80 nm. After vapor deposition, the light emitting element D4 was produced by sealing using a glass substrate.

(Evaluation of light emitting element)
By applying a voltage to the light emitting element D4, EL light emission having a maximum peak of the emission spectrum at 610 nm was observed. The external quantum efficiency at 1000 cd / m ² was 9.0%, and the driving voltage at a current density of 10 mA / cm ² was 6.4V. The results are shown in Table 4.

<Example D5> Production and Evaluation of Light-Emitting Element D5 A light-emitting element D5 was produced in the same manner as in Example D4, except that the polymer compound P2 was used instead of the polymer compound P1 in Example D4.

By applying a voltage to the light emitting element D5, EL light emission having the maximum peak of the emission spectrum at 610 nm was observed. The external quantum efficiency at 1000 cd / m ² was 7.2%, and the drive voltage at a current density of 10 mA / cm ² was 7.8V. The results are shown in Table 4.

<Example D6> Production and evaluation of light-emitting element D6 Light-emitting element D6 was produced in the same manner as in Example D4, except that polymer compound P3 was used instead of polymer compound P1 in Example D4.

By applying a voltage to the light emitting element D6, EL light emission having the maximum peak of the emission spectrum at 610 nm was observed. The external quantum efficiency at 1000 cd / m ² was 7.0%, and the driving voltage at a current density of 10 mA / cm ² was 7.1V. The results are shown in Table 4.

<Comparative Example CD2> Production and Evaluation of Light-Emitting Element CD2 The polymer compound CP1 was used instead of the polymer compound P1 in Example D4, and the polymer compound CP1 and the metal complex COM-8 were mixed at 1.8% by weight. The light emitting device CD2 was prepared in the same manner as in Example D4 except that a xylene solution (polymer compound CP1 / metal complex COM-8 = 92.5 wt% / 7.5 wt%) dissolved in xylene at a concentration was used. Was made.

By applying a voltage to the light emitting device CD2, EL light emission having the maximum peak of the emission spectrum at 615 nm was observed. The external quantum efficiency at 1000 cd / m ² was 5.4%, and the driving voltage at a current density of 10 mA / cm ² was 10.5V. The results are shown in Table 4.

<Example D7> Production and Evaluation of Light-Emitting Element D7 In place of metal complex COM-8 in Example D4, metal complex COM-5 synthesized according to the method described in JP-A-2006-188673 was used. A light emitting element D7 was produced in the same manner as in Example D4, except for the above.

By applying a voltage to the light-emitting element D7, EL light emission having a maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 7.9%, and the driving voltage at a current density of 10 mA / cm ² was 6.3V. The results are shown in Table 5.

<Example D8> Production and evaluation of light-emitting device D8 A light-emitting device D8 was produced in the same manner as in Example D5 except that metal complex COM-5 was used instead of metal complex COM-8 in Example D5. .

By applying a voltage to the light emitting element D8, EL light emission having the maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 7.0%, and the driving voltage at a current density of 10 mA / cm ² was 6.8V. The results are shown in Table 5.

<Example D9> Production and evaluation of light-emitting device D9 Light-emitting device D9 was produced in the same manner as in Example D6, except that metal complex COM-5 was used instead of metal complex COM-8 in Example D6. did.

By applying a voltage to the light-emitting element D9, EL light emission having a maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 7.0%, and the driving voltage at a current density of 10 mA / cm ² was 6.7V. The results are shown in Table 5.

<Comparative Example CD3> Production and Evaluation of Light-Emitting Element CD3 In Comparative Example CD2, instead of metal complex COM-8, metal complex COM-5 was used, and polymer compound CP1 and metal complex COM-5 were converted to 1.8. A light emitting device CD3 was produced in the same manner as Comparative Example CD2, except that it was dissolved in xylene at a concentration of% by weight.

By applying a voltage to the light emitting device CD3, EL light emission having the maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 5.6%, and the driving voltage at a current density of 10 mA / cm ² was 8.3V. The results are shown in Table 5.

  From these results, it can be seen that the light emitting device containing the polymer compound P1, the polymer compound P2 or the polymer compound P3 of the present invention has a lower driving voltage than the light emitting device containing the polymer compound CP1. .

<Example D10> Fabrication and evaluation of light-emitting element D10 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering. On the anode, ND-3202 (manufactured by Nissan Chemical Industries), which is a hole injection material, was formed into a film with a thickness of 65 nm by spin coating. In an air atmosphere, a hole injection layer was formed by heating on a hot plate at 50 ° C. for 3 minutes and further heating at 230 ° C. for 15 minutes.

(Formation of hole transport layer)
The polymer compound IP1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
Polymer compound P5 and metal complex COM-8 were dissolved in xylene at a concentration of 2.0% by weight (polymer compound P5 / metal complex COM-8 = 92.5% by weight / 7.5% by 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 light is emitted by heating at 150 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. A layer was formed.

(Formation of cathode)
After reducing the pressure of the substrate on which the light emitting layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride is about 4 nm on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was deposited at about 80 nm. After vapor deposition, the light emitting element D10 was produced by sealing using a glass substrate.

(Evaluation of light emitting element)
By applying a voltage to the light emitting device D10, EL light emission having the maximum peak of the emission spectrum at 615 nm was observed. The external quantum efficiency at 1000 cd / m ² was 13.9%, and the drive voltage at a current density of 10 mA / cm ² was 4.8V. The results are shown in Table 6.

<Comparative Example CD4> Production and Evaluation of Light-Emitting Element CD4 A light-emitting element CD4 was produced in the same manner as in Example D10, except that polymer compound CP2 was used instead of polymer compound P5 in Example D10.

By applying a voltage to the light emitting device CD4, EL light emission having the maximum peak of the emission spectrum at 615 nm was observed. The external quantum efficiency at 1000 cd / m ² was 13.3%, and the drive voltage at a current density of 10 mA / cm ² was 5.0V. The results are shown in Table 6.

<Example D11> Production and evaluation of light-emitting element D11 Light-emitting element D11 was produced in the same manner as Example D10, except that metal complex COM-5 was used instead of metal complex COM-8 in Example D10. did.

By applying a voltage to the light emitting element D11, EL light emission having the maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 11.1%, and the drive voltage at a current density of 10 mA / cm ² was 4.8V. The results are shown in Table 7.

<Example D12> Production and evaluation of light-emitting device D12 A light-emitting device D12 was produced in the same manner as in Example D11, except that polymer compound P4 was used instead of polymer compound P5 in Example D11.

By applying a voltage to the light emitting element D12, EL light emission having the maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 10.8%, and the drive voltage at a current density of 10 mA / cm ² was 4.8V. The results are shown in Table 7.

<Example CD5> Production and Evaluation of Light-Emitting Element CD5 A light-emitting element CD5 was produced in the same manner as in Example D11 except that polymer compound CP2 was used instead of polymer compound P5 in Example D11.

By applying a voltage to the light emitting device CD5, EL light emission having the maximum peak of the emission spectrum at 625 nm was observed. The external quantum efficiency at 1000 cd / m ² was 10.5%, and the drive voltage at a current density of 10 mA / cm ² was 5.0V. The results are shown in Table 7.

  From these results, it can be seen that the light emitting element containing the polymer compound P5 or the polymer compound P4 of the present invention has a lower driving voltage than the light emitting element containing the polymer compound CP2.

Claims (12)

The high molecular compound containing the structural unit represented by following formula (1).

[Where:
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or —CR ^Z ═. R ^Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. . However, at least one selected from the group consisting of Z ¹ , Z ² and Z ³ is a nitrogen atom.
X ¹ represents a single bond, a group represented by —NR ^X —, an oxygen atom or a sulfur atom. R ^X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. .
Y ¹ represents a group represented by —CR ^Y1 R ^Y2 —, a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, a group represented by —CR ^Y7 = CR ^Y8 —, —NR ^Y9 — Represents a group represented by the formula: oxygen atom or sulfur atom. R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8 and R ^Y9 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl Represents a group, an aryloxy group or a monovalent heterocyclic group, and these groups optionally have a substituent. R ^Y1 and R ^Y2 , R ^Y3 and R ^Y4 , R ^Y3 and R ^Y5 , R ^Y4 and R ^Y6 , R ^Y5 and R ^Y6 , R ^Y7 and R ^Y8 are bonded to each other and together with the carbon atoms to which they are bonded A ring may be formed.
Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. However, when X ¹ is a single bond and Y ¹ is a group represented by —CR ^Y1 R ^Y2 —, Ar ¹ and Ar ² are each independently a phenylene group optionally having a substituent. Or it is a naphthalenediyl group which may have a substituent.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent. A plurality of R ¹ may be the same or different, and adjacent R ¹ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ] The polymer compound according to claim 1, wherein Ar ¹ and Ar ² are a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent. The polymer compound according to claim 1, wherein X ¹ is a single bond. The Y ¹ is a group represented by —CR ^Y1 R ^Y2 — or a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —. High molecular compound. Y ¹ is a group represented by —CR ^Y1 R ^Y2 —,
The polymer compound according to claim 4, wherein R ^Y1 and R ^Y2 are an alkyl group, a cycloalkyl group, or an aryl group. The high molecular compound as described in any one of Claims 1-5 whose structural unit represented by said Formula (1) is a structural unit represented by following formula (2) or (3).

[Where:
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above.
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, These groups may have a substituent. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ] The polymer compound according to any one of claims 1 to 6, wherein Z ¹ , Z ² and Z ³ are nitrogen atoms. The polymer compound according to any one of claims 1 to 7, wherein Ar ¹ and Ar ² are the same group. Furthermore, the high molecular compound as described in any one of Claims 1-8 containing the structural unit represented by a following formula (Y).

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ] Furthermore, the high molecular compound as described in any one of Claims 1-9 containing the structural unit represented by following formula (X).

[Where:
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
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 at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different from each other.
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 optionally have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different. ] The polymer compound according to any one of claims 1 to 10,
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.   The light emitting element containing the high molecular compound as described in any one of Claims 1-10.