JP6707909B2 - Polymer compound and light-emitting device using the same - Google Patents

Description

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

Organic electroluminescent elements (hereinafter, also referred to as “light emitting elements”) can be suitably used for display and lighting applications, and have been drawing attention in recent years. This light emitting device includes an organic layer 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 inkjet printing method. Therefore, a polymer compound used for manufacturing a light emitting device has been studied.

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

JP 2012-036388 A

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

Therefore, an object of the present invention is to provide a polymer compound useful for manufacturing 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 firstly 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。］

[In the formula,
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 —, and —NR ^Y9 —. Represents a group represented by, an oxygen atom or a 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 may 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 , and R ^Y7 and R ^Y8 are bonded to each other, together with the carbon atom to which they are bonded. It may form a ring.
Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups may 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 which may have a substituent. Alternatively, 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, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group. Represents, and these groups may have a substituent. Plural R ^{1 s} may be the same or different, and adjacent R ^{1 s} may be bonded to each other to form a ring together with the carbon atom to which they are bonded. R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ]

Secondly, the present invention comprises at least one selected from the group consisting of the above-mentioned 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 material containing the same.

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. Further, according to the present invention, it is possible to provide a composition containing the polymer compound and a light emitting device containing the polymer compound.

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

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

Me is a methyl group, Et is an ethyl group, Bu is a butyl group, i-Pr is an isopropyl group, and t-Bu is 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 a polystyrene-equivalent number average molecular weight of 1×10 ³ to 1×10 ⁸ .

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

The “constituent unit” means a unit present in one or more units in the polymer compound.

The “alkyl group” may be linear or branched. The number of carbon atoms in the straight-chain alkyl group, not including the number of carbon atoms in the substituent, is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20. The number of carbon atoms of the branched alkyl group, not including the number of carbon atoms of the substituent, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
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 and the like, for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluoromethyl group, Fluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-hexylphenyl)propyl group, 6-ethyloxy A hexyl group can be mentioned.
The number of carbon atoms of the "cycloalkyl group" is usually 3 to 50, not including the number of carbon atoms of the substituent, preferably 3 to 30, and more preferably 4 to 20.
The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

The "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 number of carbon atoms in the aryl group, not including the number of carbon atoms in the substituent, is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 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 atom in these groups However, there may be mentioned 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 in the linear alkoxy group is usually 1 to 40, preferably 4 to 10, not including the number of carbon atoms in the substituent. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, not including the number of carbon atoms of the substituent, and preferably 4 to 10.
The alkoxy group may have a substituent, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and hydrogen atom in these groups, cycloalkyl group, alkoxy group, Examples thereof include a cycloalkoxy group, an aryl group, and a group substituted with a fluorine atom.
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.
Aryloxy group may have a substituent, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples thereof include a pyrenyloxy group and groups in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like.

The “p-valent heterocyclic group” (p represents an integer of 1 or more) means that, from a heterocyclic compound, p of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring. Means the rest of the atomic groups excluding the hydrogen atoms. Among the p-valent heterocyclic groups, it is the remaining atomic group obtained by removing p hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or hetero atoms constituting the ring from the aromatic heterocyclic compound. The "p-valent aromatic heterocyclic group" is preferable.
The "aromatic heterocyclic compound" is a heterocyclic compound such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole. A compound in which the ring itself exhibits aromaticity, and a heterocycle such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilole, benzopyran, etc., which does not exhibit aromaticity, has an aromatic ring condensed to the heterocycle. 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, a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group, a triazinyl group, and these A group in which a hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like can be mentioned.

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

The "alkenyl group" may be linear or branched. The number of carbon atoms of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, not including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkenyl group is usually 3 to 30, not including the number of carbon atoms of the substituent, and preferably 4 to 20.
The number of carbon atoms of the "cycloalkenyl group" is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkenyl group and cycloalkenyl group may have a substituent, for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4- Examples thereof include a pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which these groups have a substituent.

The “alkynyl group” may be linear or branched. The carbon atom number of the alkynyl group is usually 2 to 20, not including the carbon atom of the substituent, and preferably 3 to 20. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, and preferably 4 to 20, not including the carbon atoms of the substituents.
The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, and preferably 4 to 20, not including the carbon atoms of the substituents.
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 thereof include a pentynyl group, a 1-hexynyl group, a 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 carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the number of carbon atoms in the substituent.
The arylene group may have a substituent, for example, a phenylene group, a naphthalenediyl group, an anthracene diyl group, a phenanthrene diyl group, a dihydrophenanthren diyl group, a naphthacene diyl group, a fluorenediyl group, a pyrenediyl group, a perylene diyl group, Examples thereof include a chrysenediyl group and a group in which these groups have a substituent, and a group represented by formula (A-1) to formula (A-20) is 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。］

[In the formula, R and R ^a each independently represent 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 with the atoms to which they are bonded. ]

The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20 and more preferably 4 to 15, not including the number of carbon atoms of the substituent.
The divalent heterocyclic group may have a substituent, and examples thereof include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, Dihydroacridine, furan, thiophene, azole, diazole, triazole include a divalent group obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting a ring, and are preferable. Are groups 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 are as defined above. ]

The ``crosslinking group'' is a group capable of forming a new bond by being subjected to heating, ultraviolet irradiation, near-ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction, etc., and preferably has the formula ( A group represented by any one of B-1)-(B-17). These groups may have a substituent.

The "substituent" means a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group. Represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substituent may be a bridging 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 polymer compound of the present invention can be easily synthesized.

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

Z ^1, Z ² and Z ^3, that the luminance lifetime of the light-emitting device containing the polymer compound of the present invention is excellent, at least two of the nitrogen atom selected from the group consisting of Z ^1, Z ² and Z ³ Is 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 the polymer compound of the present invention can be easily synthesized.

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, and 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 —, and —NR ^Y9 —. Represents a group represented by, an oxygen atom or a sulfur atom.

R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8 and R ^Y9 have an excellent brightness life of the light emitting device containing the polymer compound of the present invention. It is preferably an alkyl group or an aryl group.

As the substituent which the group represented by R ^Y1 , R ^Y2 , R ^Y3 , R ^Y4 , R ^Y5 , R ^Y6 , R ^Y7 , R ^Y8 and R ^Y9 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.

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, and thus R ^Y1 and R ^Y2 are an alkyl group, a cycloalkyl group or a cycloalkyl group. Group or aryl group, 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 preferable that

When Y ¹ is a group represented by —CR ^Y3 R ^Y4 —CR ^Y5 R ^Y6 —, since the polymer compound of the present invention is easily synthesized, 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 with the carbon atom 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 atom to which they are bonded. The ring formed by combining R ^Y3 and R ^Y5 with 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.

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 Y ^{1 because} the polymer compound of the present invention can be easily synthesized. 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, A group represented by -CR ^Y1 R ^Y2- or a group represented by -CR ^Y3 R ^Y4 -CR ^Y5 R ^Y6- is more preferable because the light-emitting element containing a molecular compound has excellent luminance life. ..

Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups may 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 which may have a substituent. Alternatively, 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). And 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) or a formula (AA). -24), a group represented by the formula (AA-25) or a formula (AA-26), and these groups may have a substituent.

Ar ¹ and Ar ² are each preferably a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent, because the polymer compound of the present invention can be easily synthesized. It is particularly preferably a phenylene group which may have a substituent. Further, Ar ¹ and Ar ² are preferably the same group because the polymer compound of the present invention can be easily synthesized.

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

Examples of Ar ¹ and Ar ² include groups represented by formulas (Ar-1) to (Ar-13). Since the polymer compound of the present invention can be easily synthesized, ) To (Ar-3), formula (Ar-6), formula (Ar-7), formula (Ar-12) or formula (Ar-13) are preferred, and formula (Ar-1) to A group represented by (Ar-3), formula (Ar-6) or formula (Ar-12) is more preferable, and a group represented by formula (Ar-1), formula (Ar-2) or formula (Ar-12) Is more preferable, and the group represented by formula (Ar-1) or 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。］

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

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently 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. Represents, and these groups may have a substituent.

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

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

R ¹ is more preferably a hydrogen atom because the polymer compound of the present invention can be easily synthesized.

R ² and R ⁵ are more preferably hydrogen atoms, alkyl groups or aryl groups, and more preferably hydrogen atoms, since compounds that are raw materials for the polymer compound of the present invention are 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 a 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, the other of R ³ and R ⁴ is a hydrogen atom, an alkyl group or an aryl group, and one of R ³ and R ⁴ is a hydrogen atom, and R ³ and R ⁴ The other is particularly preferably a hydrogen atom, an alkyl group or an aryl group, one of R ³ and R ⁴ is a hydrogen atom, and the other of R ³ and R ⁴ is particularly preferably an aryl group.

The constitutional unit represented by the formula (1) is preferably the constitutional unit represented by the formula (2) or the formula (3) because the polymer compound of the present invention can be easily synthesized. It is more preferable that the structural unit is 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。］

[In the formula,
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings 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 , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ]

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms because the polymer compound of the present invention can be easily synthesized.

The substituent that the group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may have is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and an alkyl group or Aryl groups are more preferred.

The constitutional unit represented by the formula (2) has a lower driving voltage of the light emitting device containing the polymer compound of the present invention, and thus the formula (2-1), the formula (2-2) or the formula (2- It is preferably a structural unit represented by 3), and more preferably 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。］

[In the formula,
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 have the same meanings as described above.
X ² represents an oxygen atom or a sulfur atom. ]

X ² is preferably an oxygen atom because the polymer compound of the present invention can be easily synthesized.

The constitutional unit represented by the formula (3) has a lower driving voltage of the light emitting device containing the polymer compound of the present invention, and thus the formula (3-1), the formula (3-2) or the formula (3-). It is preferably a structural unit represented by 3), and more preferably a structural unit represented by formula (3-1) or formula (3-2).

［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。］

[In the formula,
^{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 have the same meanings as described above.
X ³ represents an oxygen atom or a sulfur atom. ]

X ³ is preferably an oxygen atom because the polymer compound of the present invention can be easily synthesized.

Examples of the constitutional unit represented by the formula (1) include constitutional units represented by the formulas (1-101) to (1-136).

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

The constitutional unit represented by the formula (1) may be contained in the polymer compound of the present invention in only one kind or in two or more kinds.

[Structural Unit Represented by Formula (Y)]

Since the polymer compound of the present invention is excellent in the luminance life of a light emitting device containing the polymer compound of the present invention, it is preferable that the polymer compound further contains a structural unit represented by the formula (Y).

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、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。］

[ ^Wherein 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, The group of may have a substituent. ]

The arylene group represented by Ar ^Y1 is more preferably a formula (A-1), a formula (A-2), a formula (A-6)-(A-10), a formula (A-19) or a formula (A-19). A-20) is a group represented by, more preferably, formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19). Is a group represented by, particularly preferably a group represented by formula (A-1), formula (A-2) or formula (A-9), 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) or a formula (AA-18). -(AA-21), a group represented by formula (AA-33) or formula (AA-34), more preferably 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 preferred range of the arylene group and 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 preferred The ranges are the same as the more preferable range and the more preferable range, respectively, of the arylene group and divalent heterocyclic group represented by Ar ^Y1 described above.

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

［式中、Ｒ^XXは、水素原子、アルキル基、シクロアルキル基、アリール基または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。］

[In the formula, R ^XX 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. ]

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

The substituent which 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 constitutional unit represented by the formula (Y) include constitutional units represented by the formulas (Y-1)-(Y-6), and the luminance of a light emitting device containing the polymer compound of the present invention. From the viewpoint of life, it is preferably a structural unit represented by the formula (Y-1)-(Y-3), from the viewpoint of charge transportability of the light emitting device containing the polymer compound of the present invention, preferably Is a constitutional 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。］

[In the formula, 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 may have a substituent. .. A plurality of R ^Y1s may be the same or different, and adjacent R ^Y1s may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ]

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

The constitutional unit represented by the formula (Y-1) is preferably a constitutional 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。］

[In the formula, 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 may 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 may 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。］

[In the formula,
R ^Y1 has 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's may be the same or different, and R ^Y2's may be bonded to each other to form a ring together with the carbon atom to which they are 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 each have a substituent. You may have.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C(R ^Y2 ) ₂ — is preferably both an alkyl group or a cycloalkyl group, both aryl groups, and both monovalent heterocycles. A ring group, or one of which is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, and more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group; May have a substituent. Two existing 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 's form a ring, as a 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. 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 is an alkyl group. Alternatively, the other is a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In X ^Y1 , the four R ^Y2 in the group represented by —C(R ^Y2 ) ₂ —C(R ^Y2 ) ₂ — are preferably an alkyl group or cycloalkyl group which may have a substituent. Is. A plurality of R ^Y2's may be bonded to each other to form a ring together with the atoms to which they are bonded. When R ^Y2 's form 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。］

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

The constitutional unit represented by the formula (Y-2) is preferably a constitutional 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 have the same meanings 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 have the same meanings as described above. ]

The constitutional unit represented by the formula (Y-3) is preferably a constitutional 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 have the same meanings 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。］

[In the formula,
R ^Y1 has 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 may 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 composed of an arylene group represented by the formula (Y-101)-(Y-121), a formula (Y-201)-(Y-206) A structural unit composed of a divalent heterocyclic group represented by

The structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, has a high luminous efficiency of the light emitting device containing the polymer compound of the present invention, and thus is contained in the polymer compound. It is preferably 0.5 to 90 mol% and more preferably 30 to 80 mol% based on the total amount of the units.

A structural unit represented by the formula (Y), wherein Ar ^Y1 is 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. The structural unit which is a group is excellent in charge transporting property of the light emitting device containing the polymer compound of the present invention, so that the content of the structural unit contained in the polymer compound is preferably 0.5 to 50 mol %. %, and more preferably 3 to 30 mol %.

As for the structural unit represented by the formula (Y), only one type 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)]
Since the polymer compound of the present invention is excellent in the hole transport property of the light emitting device containing the polymer compound of the present invention, it may further contain a structural unit represented by the following formula (X).

［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。］

[In the formula,
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 may 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. 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.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different. ]

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

a ^X2 is preferably an integer of 2 or less, more preferably 0, because the light emitting device containing the polymer compound of the present invention has excellent emission 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 each have a substituent. Good.

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

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

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

The arylene group represented by Ar ^X2 and Ar ^X4 is more preferably the formula (A-1), the formula (A-6), the formula (A-7), or the formula (A-9)-(A-11). Alternatively, it is a group represented by the 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 preferred 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. The more preferable ranges are the same as the more preferable ranges and further preferable ranges of the arylene group and the 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 is at least represented by Ar ^Y1 in the formula (Y). The same divalent group in which one type of arylene group and at least one type of divalent heterocyclic group are directly bonded can be used.

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

The substituent which the groups represented by Ar ^{X1 to} Ar ^X4 and R ^{X1 to} R ^X3 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups each have a substituent. You may have.

The structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1)-(X-7), and more preferably the formula (X-1)-(X-6). Is a structural unit represented by the formula (1), 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 are each independently 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. The plurality of R ^X4 present may be the same or different. A plurality of R ^X5's may be the same or different, and adjacent R ^X5's may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ]

Since the structural unit represented by the formula (X) is excellent in the hole transporting property of the light emitting device containing the polymer compound of the present invention, it is preferable that the total amount of the structural units contained in the polymer compound is preferable. It is 0.1 to 50 mol %, more preferably 1 to 40 mol %, and further preferably 5 to 30 mol %.

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

The polymer unit of the present invention may contain only one type of structural unit represented by formula (X), or may include two or more types thereof.

As the polymer compound of the present invention, for example, polymer compounds P-101 to P-107 shown in Table 1 can be mentioned, and the polymer compound P-101 and Polymer compound P-104 is preferable, and polymer compound P-101a and polymer compound P-104a are more preferable. Here, the "other constitutional unit" means a constitutional unit other than the constitutional unit represented by the formula (1), the formula (Y-1) to the formula (Y-6), and the 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 constituent units represented by formula (1), formula (Y-1) to formula (Y-6) and 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 have the same meanings as described above. ]

The terminal group of the polymer compound of the present invention, if the polymerization active group remains as it is, may cause a decrease in light emission characteristics and luminance life when the polymer compound is used in the production of a light emitting device, and therefore, it is preferable. It is a stable group. The terminal group is preferably a group which is conjugated to the main chain, and examples thereof include a group which 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, a graft copolymer, and may be other embodiments, but a plurality of kinds of raw materials It is preferably a copolymer obtained by copolymerizing monomers.

<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 by, for example, a compound represented by the formula (M-1), another compound (for example, a compound represented by the formula (M-2), or a formula (M-3)). Compound 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 producing the polymer compound of the present invention may be collectively referred to as “raw material monomer”.

［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。］

[In the formula,
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 have the same meanings 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 a group 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 B group, Z ^C3 and Z ^C4 select a group selected from the substituent group A.

<Substituent Group A>
A chlorine atom, in a bromine atom, an iodine atom or _{-O-S (= O) 2} R C1 ( wherein, R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, 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 Which may be the same or different and may be bonded to each other to form a ring structure together with the oxygen atom to which they are bonded).
A group represented by —BF ₃ Q′ (in the formula, 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 May be the same or different, and may be bonded to each other to form a ring structure together with the tin atom to which they are bonded).

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

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 to give a group selected from the substituent group A and a substituent group B. The carbon atoms bonded to the 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 polymerization of these compounds will occur by condensation polymerization. A polymer can be obtained.

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

Examples of the catalyst include dichlorobis(triphenylphosphine)palladium, dichlorobis(tris-o-methoxyphenylphosphine)palladium, palladium [tetrakis(triphenylphosphine)], [tris(dibenzylideneacetone)]dipalladium, palladium acetate and the like. Transitions of nickel complexes such as palladium complexes of nickel, nickel [tetrakis(triphenylphosphine)], [1,3-bis(diphenylphosphino)propane]dichloronickel, and [bis(1,4-cyclooctadiene)]nickel Metal complexes; those transition metal complexes further include complexes having ligands such as triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, and bipyridyl. .. The catalyst may be used alone or in combination of two or more.

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

Examples of the base and the phase transfer catalyst include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate; organic bases such as tetrabutylammonium fluoride and tetrabutylammonium hydroxide. Base; 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 amount of each of the base and the phase transfer catalyst used is usually 0.001 to 100 molar equivalent based on the total number of moles of the raw material monomers.

Examples of the solvent include organic solvents such as toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N,N-dimethylacetamide and N,N-dimethylformamide, and water. The solvent may be used alone or in combination of two or more.

The amount of the solvent used is usually 10 to 100,000 parts by weight based on 100 parts by weight of the total 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.

The 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 the polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying. These methods are performed 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, or column chromatography.

<Compound>
Next, the compound that 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。］

[In the formula,
^{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} are as defined above. ]

The method for producing the compound represented by 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 by.

［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。］

[In the formula,
^{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} are as defined above.
W ¹ and W ² each independently represent a group selected from the group consisting of the substituent group A and the substituent group B. ]

When W ¹ is a group selected from Substituent group A, W ² is preferably a group selected from Substituent group B.
When W ¹ is a group selected from Substituent group B, W ² is preferably a group selected from 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 the substituent group A and a group selected from the substituent group B by a known coupling reaction. The carbon atoms that bind to are bound to each other. Therefore, by subjecting a compound having a group selected from the substituent group A and a compound having a group selected from the substituent group B 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) and 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, and 1,1′-bis(diphenylphosphino)ferrocene. ..

When a palladium catalyst is used in the coupling reaction between the compound represented by Formula (M-1-a) and the compound represented by Formula (M-1-b), the amount of the palladium catalyst used is It is usually 0.00001 to 10 molar equivalents in terms 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 formula (M-1-a) and the compound represented by 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; methylene chloride. Halogen-based solvents such as chloroform; Nitrile-based solvents such as acetonitrile and benzonitrile; Hydrocarbon-based solvents such as hexane, decalin, toluene, xylene, mesitylene; Amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide Solvents: acetone, dimethylsulfoxide, and water.

Use amount of the compound represented by the formula (M-1-b) in 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 0.05 to 20 molar equivalents relative to the number of moles of the compound represented by formula (M-1-a), and the yield of the compound represented by formula (M-1) is excellent. Therefore, it is preferably 1.5 to 20 molar equivalents.

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

A base may be added 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 compound represented by the formula (M-1-a1), which is one of the embodiments 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 subjecting a compound and a compound represented by the formula (B-0) to an Ishiyama-Miyaura-Hartwig reaction.

［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。］

[In the formula,
X ¹ , Y ¹ , R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.
W ³ represents a group selected from the substituent group A. ]

In the Ishiyama-Miyaura-Hartwig reaction of 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.

Examples of the palladium catalyst include the same as the example of the 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 palladium catalyst may be used in combination with the phosphorus compound. Examples of the phosphorus compound include the same phosphorus compounds in the coupling reaction between the compound represented by the formula (M-1-a) and the compound represented by the formula (M-1-b).

In the Ishiyama-Miyaura-Hartwig reaction of the compound represented by formula (M-1-a2) and the compound represented by formula (B-0), when a palladium catalyst is used, the amount of the palladium catalyst used is It is usually 0.00001 to 10 molar equivalents in terms 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 formula (M-1-a2) and the compound represented by formula (B-0) is usually performed in a solvent.

Examples of the solvent include the same solvents as those used in the coupling reaction between the compound represented by formula (M-1-a) and the compound represented by formula (M-1-b).

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 the boiling point of the solvent present in the reaction system.

A base may be added 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).

The compound represented by the formula (M-1-a3), which is one of the embodiments 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 have the same meanings 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 or 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-based solvents such as methylene and chloroform; Nitrile-based solvents such as acetonitrile and benzonitrile; Hydrocarbon-based solvents such as hexane, decalin, toluene, xylene and mesitylene; N,N-dimethylformamide, N,N-dimethylacetamide and the like Amide-based solvent; dimethyl sulfoxide can be mentioned

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). It is 0.8 to 1.3 molar equivalents.

The reaction time of 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 to the boiling point of the solvent present in the reaction system. Is in 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 of the embodiments of the compound represented by the formula (M-1-b), is represented by, for example, the formula (M-1-b2). The compound and the compound represented by 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。］

[In the formula,
Z ¹ , Z ² , Z ³ , Ar ¹ and Z ^C1 have the same meanings as described above.
W ⁴ represents a group selected from the group consisting of the substituent group A and the substituent group B. ]

The 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 the same as those for the compound represented by the formula (M-1-a). The conditions are the same as those for the coupling reaction with the compound represented by formula (M-1-b).

<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. And the materials of.

The composition containing the polymer compound and the solvent of the present invention (hereinafter sometimes referred to as “ink”) is suitable for producing a light emitting device 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.However, when the solution such as inkjet printing method is applied to the printing method in which the solution passes through the ejection device, in order to prevent clogging and flight bending during ejection, , Preferably 1 to 20 mPa·s at 25°C.

The solvent contained in the ink is preferably a solvent capable of dissolving or uniformly dispersing the solid content in the ink. Examples of the solvent include chlorine-based solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether-based 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; polyhydric alcohol solvents such as ethylene glycol, glycerin, 1,2-hexanediol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N An amide-based solvent such as N-dimethylformamide can be used. The solvent may be used alone or in combination of two or more.

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

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

Examples of the polymer compound include polyvinylcarbazole and its derivative; polyarylene having an aromatic amine structure in its side chain or main chain and its derivative. The polymer compound may be a compound having an electron-accepting site bound thereto. Examples of the electron-accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and the like, with fullerene being preferred.

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, based on 100 parts by weight of the polymer compound of the present invention.

The hole transport materials may be used alone or in combination of two or more.

[Electron transport material]
Electron transport materials are classified into low molecular weight compounds and high molecular weight 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, based on 100 parts by weight of the polymer compound of the present invention.

The electron transport materials may be used alone or in combination of two or more.

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

Examples of the low molecular weight compound include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; 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 their derivatives; polymers containing an aromatic amine structure in its main chain or side chain, etc. The conductive polymer of

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

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

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

The types of ions to be doped are anions for hole injection materials and cations for electron injection materials. 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.

The ions to be doped may be one kind or two or more kinds.

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

Examples of the low molecular weight compound include naphthalene and its derivative, anthracene and its derivative, perylene and its derivative, and a triplet light emitting complex having iridium, platinum or europium as a central metal.

Examples of the polymer compound include a phenylene group, a naphthalene diyl group, a fluorenediyl group, a phenanthrendiyl group, a dihydrophenanthrendiyl group, a group represented by the formula (X), a carbazolediyl group, a phenoxazinediyl group, and a phenothiazinediyl group. Examples of the polymer compound include a group, an anthracene diyl group, a pyrenediyl group, and the like.

In the composition of the present invention, the compounding amount of the light emitting material is usually 1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 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.

The triplet light emitting complex is preferably an iridium complex such as a metal complex represented by the formula Ir-1 to Ir-5.

［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。］

[In the formula,
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, or aryl. It represents an oxy group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. When a plurality of R ^{D1 to} R ^D8 , R ^{D11 to} R ^D20 , R ^{D21 to} R ^D26 and R ^{D31 to} R ^D37 are present, 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 of may be a ring-constituting atom. When there are a plurality of -A ^D1 --- A ^D2 -, 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。］

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

m ^DA1 , m ^DA2 and m ^DA3 are generally integers of 10 or less, preferably 5 or less, more preferably 0 or 1. It is preferable that m ^DA1 , m ^DA2 and m ^DA3 are the same integer.

G ^DA1 is preferably a group represented by 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。］

[In the formula,
*, **, and *** represent the binding to Ar ^DA1 , Ar ^DA2 , and Ar ^DA3 , respectively.
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 R ^DA , 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 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。］

[In the formula,
R ^DA has 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 R ^DB , they may be the same or different. ]

T ^DA is preferably a group represented by formulas (TDA-1) to (TDA-3).

［式中、Ｒ^DAおよびＲ^DBは前記と同じ意味を表す。］

[In the formula, R ^DA and R ^DB have the same meanings 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。］

[In the formula,
R ^p1 , R ^p2 and R ^p3 each independently represent 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. The plurality of np1s may be the same or different. ]

np1 is preferably 0 or 1, and more preferably 1. np2 is preferably 0 or 1, and more preferably 0. np3 is preferably 0.

R ^p1 , R ^p2 and R ^p3 are preferably alkyl groups or cycloalkyl groups.

-A ^D1 --- A ^D2 - The anionic bidentate ligand represented, for example, be the ligand represented by the following formula.

［式中、＊は、Ｉｒと結合する部位を表す。］

[In the formula, * represents a site that binds to 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 formulas Ir-31 to Ir-33. The metal complex represented by the formula Ir-4 is preferably a metal complex represented by the formulas Ir-41 to Ir-43. The metal complex represented by the formula Ir-5 is preferably a metal complex represented by the formulas 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。］

[In the formula, D represents a group represented by the formula (DA). Multiple Ds 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 may have a substituent. A plurality of R ^DCs may be the same or different. R ^DD represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^DD may be the same or different. ]

Examples of the triplet light emitting complex include the following metal complexes.

[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, and examples thereof include a phenol-based antioxidant and a phosphorus-based antioxidant.

In the composition of the present invention, the compounding amount of the antioxidant is usually 0.001 to 10 parts by weight based on 100 parts by weight of the polymer compound of the present invention.

The antioxidants may be used alone or in combination of two or more.

<Membrane>
The membrane contains the polymer compound of the present invention.

The film also includes an insolubilized film in which the polymer compound of the present invention is insolubilized 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 the solvent, it can be suitably used for stacking light emitting devices.

The heating temperature for cross-linking the film is usually 25 to 300° C., and since the luminous efficiency is improved, it is preferably 50 to 250° C., more preferably 150 to 200° C.

The type of light used for light irradiation for crosslinking the film is, for example, ultraviolet light, near-ultraviolet light, or visible light.

The film is suitable as a light emitting layer in a light emitting device.

The film is formed by using ink, for example, spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method. The flexographic printing method, the offset printing method, the inkjet printing method, the capillary coating method, and the nozzle coating method can be used.

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, and the light emitting device includes, for example, a light emitting device containing the polymer compound of the present invention, a high light emitting device of the present invention. There is a light emitting element containing a cross-linked body of a molecular compound. Here, the cross-linked product of the polymer compound of the present invention is a polymer compound of the present invention which is cross-linked intramolecularly, intermolecularly, or both.
The structure of the light-emitting device of the present invention has, for example, electrodes comprising an anode and a cathode, and a layer provided between the electrodes and containing the polymer compound of the present invention.

[Layer structure]
The layer containing the polymer compound of the present invention is usually one or more layers of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer, preferably a light emitting layer. .. These layers include a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material, respectively. These layers are the same as those used in the above-described film formation by dissolving the light-emitting material, the hole-transporting material, the hole-injecting material, the electron-transporting material, and the electron-injecting material in the above-mentioned solvent to prepare an ink. Can be formed using a method.

The light emitting element has a light emitting layer between an anode and a cathode. From the viewpoint of hole injecting property and hole transporting property, the light emitting device of the present invention preferably has at least one layer of a hole injecting layer and a hole transporting layer between the anode and the light emitting layer. From the viewpoint of injectability and electron transportability, 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.
Examples of materials for the hole transport layer, electron transport layer, light emitting layer, hole injection layer, and electron injection layer include the above-described hole transport material, electron transport material, and light emission, in addition to the polymer compound of the present invention. Materials, hole injection materials, and electron injection materials.

The material for the hole-transporting layer, the material for the electron-transporting layer, and the material for the light-emitting layer are used for forming a hole-transporting layer, an electron-transporting layer, and a layer adjacent to the light-emitting layer, respectively, in manufacturing a light-emitting element. When dissolved in the solvent described above, 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, when a low molecular compound is used 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, for example, vacuum deposition from powder Method, a method of forming a film from a solution or a molten state, and when a polymer compound is used, a method of forming a film from a solution or a molten state can be used.

The order, number, and thickness of the layers to be laminated may be adjusted in consideration of light emission efficiency and device life.

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

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

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

[Use]
In order to obtain planar light emission using the light emitting element, the planar anode and cathode may be arranged so as to overlap each other. In order to obtain a patterned light emission, a method of providing a mask with a patterned window on the surface of a planar light emitting element, and forming a layer to be a non-light emitting portion with an extremely thick layer to make it 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 some electrodes so that they can be turned ON/OFF independently, a segment type display device capable of displaying numbers, letters, etc. 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 so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer compounds having different luminescent colors or a method of using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively or can be driven actively in combination with a TFT or the like. These display devices can be used for displays of computers, televisions, mobile terminals and the like. The planar light emitting element can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar light source for illumination. If a flexible substrate is used, it can be used as a curved light source and a display device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

In the examples, the polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Sought 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 was flowed at a flow rate of 2.0 mL/min. PLgel MIXED-B (manufactured by Polymer Laboratories) was used as a column. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

Liquid chromatography mass spectrometry (LC-MS) was performed by the following method.
The measurement sample was dissolved in chloroform or THF so as to have a concentration of about 2 mg/mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). As the mobile phase of LC-MS, acetonitrile and THF were used while changing the ratio thereof, and flowed at a flow rate of 0.2 mL/min. As the column, L-column 2 ODS (3 μm) (manufactured by Chemical Substances Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle diameter 3 μm) was used.

The NMR measurement was performed by the following method.
Approximately 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 dichloride (CD ₂ Cl ₂ ) and measured using an NMR apparatus (Agilent product name: INOVA300 or MERCURY 400VX).

The value of high performance liquid chromatography (HPLC) area percentage was used as an index of the purity of the compound. Unless otherwise specified, this value is the value at 254 nm measured by HPLC (Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in THF or chloroform so as to have a concentration of 0.01 to 0.2% by weight, and 1 to 10 μL was injected into HPLC depending on the concentration. Acetonitrile and THF were used as the mobile phase of HPLC, and a flow rate of 1 mL/min was used for the 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

(Stage1: 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 WO 2009/131255. Palladium (0) (7.0 g) and 20 wt% tetraethylammonium hydroxide aqueous solution (370 g) were added, and the mixture was stirred at 60°C for 5 hr. The obtained 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 oily substance was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and the solvent was distilled off under reduced pressure to obtain compound M1c (28 g, yield 91%) as a colorless oily substance. It was The HPLC area percentage value of the compound M1c was 99.5% or more.

(Stage2: Synthesis of Compound M1d)
After making the inside of the reaction vessel 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 hr. The obtained reaction mixture was cooled to room temperature, toluene (100 mL) was added, the mixture was filtered through 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 hr. The obtained mixture was cooled to room temperature, filtered through Celite, and the obtained filtrate was concentrated under reduced pressure to give compound M1d (20 g, yield 87%) as a colorless solid. The HPLC area percentage value of the compound M1d was 99.1%.

(Stage3: Synthesis of Compound M1)
After making the inside of the reaction vessel an argon gas atmosphere, compound M1d (5.3 g), compound T0 (21 g) synthesized according to the method described in International Publication No. 2011/049421, toluene (1.9 L), ethanol (190 mL). , Ion-exchanged 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 deionized water, and the obtained organic layer was concentrated under reduced pressure. Hexane (560 mL) was added to the obtained residue, 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 is purified by sequentially performing crystallization using a mixed solvent of toluene and methanol and silica gel column chromatography using a mixed solvent of toluene and hexane, and then the solvent is distilled off under reduced pressure. , Compound M1 (2.4 g, yield 22%) was obtained as a colorless solid. The HPLC area percentage value of the 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 (multi, 6H), 7.59 (dd, 2H), 7.50 (dd, 2H), 7.36 (d, 4H), 7.17 (d, 4H), 1.78-1.34 (multi, 29H), 0.90 (t, 6H).

<Synthesis example 2> Synthesis of compound M2

(Stage1: Synthesis of Compound M2b)
After making the inside of the reaction vessel 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. Then, a hexane solution of sec-butyllithium (1.1 mol/L, 1.1 L) was added dropwise thereto with stirring while maintaining the temperature of the reaction mixture at -60°C or lower. Then, 1-iodobutane (450 g) was added dropwise thereto with stirring at -60°C, and then the mixture was stirred at -60°C for 1.5 hours. The obtained reaction mixture was warmed to room temperature and then stirred at room temperature for 2 hours. Then, a 15 wt% 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 the solvent was evaporated under reduced pressure to give compound M2b (460 g, yield 61%) as an oil. The HPLC area percentage value of the compound M2b was 78.1%.

(Stage2: Synthesis of compound M2c)
After making the inside of the reaction vessel 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, the mixture was filtered through Celite and silica gel, and the obtained filtrate was concentrated under reduced pressure. Hexane and activated carbon were added to the obtained residue, and the mixture was 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 oily substance was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane, and the solvent was evaporated under reduced pressure to give compound M2c (370 g, yield 75%) as an oily substance. It was The HPLC area percentage value of the compound M2c was 99.3%.

(Stage3: Synthesis of Compound M2)
After making the inside of the reaction vessel an argon gas atmosphere, the compound M2c (25 g), the 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 hr. The obtained reaction mixture was cooled to room temperature, washed with ion-exchanged water, and the obtained organic layer was concentrated under reduced pressure. Hexane (360 mL) was added to the obtained residue and then filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was subjected to amino group surface modification silica gel column chromatography using hexane (Fuji Silysia Chemical Ltd., CHROMATOREX NH-DM1020), GPC (gel permeation chromatography) (Nippon Analytical Industry Co., Ltd., JAIGEL). -2H and JAIGEL-2.5H) and crystallization with 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 the 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 (multi, 5H), 7.10 (d, 4H), 2.68 (t, 2H), 1.76 (s, 4H), 1.69-1.55 (multi, 6H), 1.45-1.28 (multi, 14H), 0.97-0.86 (multi, 9H). ．

<Synthesis Example 3> Synthesis of compound M3

(Stage1: 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 JP 2012-144722 A and tetrahydrofuran (dehydrated product, 540 mL) were added, and the mixture was cooled to -75°C while stirring. .. Thereafter, a hexane solution of n-butyllithium (1.6 mol/L, 61 mL) was added dropwise thereto with stirring while maintaining the temperature of the reaction mixture at -75 to -70°C. It was stirred for 2 hours. Then, ion-exchanged water (270 mL) was added thereto, and the obtained reaction mixture was heated to room temperature. Then, 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 and then filtered, and the obtained filtrate was concentrated under reduced pressure. .. The obtained oil was purified by silica gel column chromatography using hexane, and the solvent was evaporated under reduced pressure to give compound M3b (32 g, yield 70%) as a colorless oil. The HPLC area percentage value of the compound M3b was 99.5% or more.

(Stage2: Synthesis of compound M3c)
After 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 hr. The obtained reaction mixture was cooled to room temperature, ion-exchanged water (180 mL) and chloroform (180 mL) were added, and the obtained organic layer was washed with ion-exchanged 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 give compound M3c (34.5 g, yield 98%) as a brown oil. The HPLC area percentage value of the compound M3c was 99.0%.

(Stage3: Synthesis of Compound M3)
After making the inside of the reaction vessel 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 hr. The obtained reaction mixture was cooled to room temperature, washed with ion-exchanged 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%) as a colorless solid. The HPLC area percentage value of the 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 (multi, 3H), 6.99 (d, 2H), 6.88 (s, 1H), 2.01 (s, 3H), 1.76 (s, 4H), 1.57 (q, 4H), 1.35-1.20 (multi, 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 JP 2010-189630 A, synthesized according to the method described in WO 2009/131255. The compound M5 (0.904 g), the compound M1 (0.353 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.5 mg) and toluene (30 mL) were added, and the mixture was heated to 105°C.
(Step 2) After that, a 20 wt% tetraethylammonium hydroxide aqueous solution (12 mL) was added dropwise thereto, and the mixture was refluxed for 6 hours.
(Step 3) After that, phenylboronic acid (85 mg) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.5 mg) were added thereto, and the mixture was refluxed for 15 hours.
(Step 4) Thereafter, an aqueous solution of sodium diethyldithiacarbamate was added thereto, and the mixture was stirred at 80°C for 2 hours. The obtained reaction mixture was cooled, washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and the resulting solution was added dropwise to methanol, whereupon precipitation occurred. The obtained precipitate was dissolved in toluene and passed through an alumina column and a silica gel column in that order for purification. The obtained solution was added dropwise to methanol and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 1.07 g of polymer compound P1. Mn of the polymer compound P1 was 7.1×10 ⁴ , and Mw was 1.7×10 ⁵ .

The polymer compound P1 has a theoretical value obtained from the amount of the charged raw material, in which the constitutional unit derived from the compound M4, the constitutional unit derived from the compound M5 and the constitutional unit derived from the compound M1 are 50: It is a copolymer composed of a molar ratio of 40:10.

<Example 2> Synthesis of polymer compound P2 (Step 1) in the synthesis of polymer compound P1 was "synthesized according to the method described in Japanese Patent Application Laid-Open No. 2010-189630 after an inert gas atmosphere in the reaction vessel. Compound M4 (0.859 g), compound M5 (0.904 g) synthesized according to the method described in WO 2009/131255, 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.”, and 0.99 g of polymer compound P2 was obtained by the same procedure as the synthesis of polymer compound P1. The Mn of the polymer compound P2 was 6.4×10 ⁴ , and the Mw thereof was 1.4×10 ⁵ .

In the polymer compound P2, the theoretical value obtained from the amount of the charged raw materials is such that the structural unit derived from the compound M4, the structural unit derived from the compound M5 and the structural unit derived from the compound M2 are 50: It is a copolymer composed of a molar ratio of 40:10.

<Example 3> Synthesis of polymer compound P3 (Step 1) in the synthesis of polymer compound P1 was "synthesized according to the method described in JP-A-2010-189630 after an inert gas atmosphere in the reaction vessel. Compound M4 (0.859 g), compound M5 (0.904 g) synthesized according to the method described in WO 2009/131255, 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.”, and 0.99 g of polymer compound P3 was obtained in the same manner as in the synthesis of polymer compound P1. The Mn of the polymer compound P3 was 6.5×10 ⁴ , and the Mw thereof was 1.5×10 ⁵ .

With respect to the polymer compound P3, the theoretical value obtained from the amount of the charged raw material was such that the structural unit derived from the compound M4, the structural unit derived from the compound M5, and the structural unit derived from the compound M3 were 50: It is a copolymer composed of a molar ratio of 40:10.

<Comparative Example 1> Synthesis of polymer compound CP1

The compound M6 was synthesized according to the method described in JP 2012-036388 A.

The polymer compound CP1 was synthesized by using the compound M4, the compound M5 and the compound M6 according to the method of “polymer compound B” described in JP 2012-36388 A. The Mn of the polymer compound CP1 was 9.6×10 ⁴ , and the Mw thereof was 2.2×10 ⁵ .

In the polymer compound CP1, the theoretical value obtained from the amount of the charged raw materials is such that the structural unit derived from the compound M4, the structural unit derived from the compound M5, and the structural unit derived from the compound M6 are 50: It is a copolymer composed of a molar ratio of 40:10.

<Synthesis Example 4> Synthesis of polymer compound IP1

The compound M7 was synthesized according to the method described in JP2011-174062A.
Compound M8 was synthesized according to the method described in Japanese Patent Publication No. 2007-512249.
As the compound M9, a commercially available product was used.
Compound M10 was synthesized according to the method described in JP 2008-106241 A.

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. Mn of the polymer compound IP1 was 8.4×10 ⁴ , and Mw was 3.4×10 ⁵ .

The polymer compound IP1 has the theoretical value obtained from the amount of the charged raw materials, 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

(Stage1: Synthesis of Compound M11c)
After making the inside of the reaction vessel a nitrogen gas atmosphere, compound M11a (22 g, commercial product), compound M11b (21 g), 28 wt% sodium methoxide methanol solution (40 g) and methanol (1.3 L) were added, and 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 hr. Then, the obtained mixture was filtered to obtain compound M11c (21 g, yield 52%) as a brown solid. The HPLC area percentage value of the compound M11c was 95.5%. By repeating this operation, the required amount of the 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 solution was cooled to room temperature, and the obtained mixture was filtered to give compound M11d (26 g, yield 84%) as a brown solid. The HPLC area percentage value of the 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).

(Stage3: Synthesis of Compound M11e)
After making the inside of the reaction vessel a nitrogen gas atmosphere, 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 liquid 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 using a mixed solvent of toluene and acetonitrile to give M11e (17 g, yield 73%) as a colorless solid. The HPLC area percentage value of the 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 (Multi, 4H), 2.00-1.86 (multi, 4H), 1.72-1.55 (multi, 2H), 1.51-1.36 (multi, 2H).

(Stage4: Synthesis of Compound M11f)
After making the inside of the reaction vessel an argon gas atmosphere, magnesium (1.8 g, shavings) 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 making another reaction container 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 while stirring. Thereafter, the Grignard reagent prepared above 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 the mixture was stirred, and then the mixture was filtered through Celite. Then, heptane (250 mL) was added to the obtained filtrate and stirred, 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. Then, activated carbon (1.3 g) was added thereto, and the mixture was stirred, filtered, and the obtained filtrate was concentrated under reduced pressure. Compound M11f (7.5 g, yield 52%) was obtained by sequentially purifying the obtained residue by silica gel column chromatography using heptane and then reverse phase column chromatography using a mixed solvent of ethyl acetate and acetonitrile. Was obtained as a colorless oil. The HPLC area percentage value of the compound M11f was 99.5% or more.

(Stage 5: Synthesis of Compound M11g)
After making the inside of the reaction vessel 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 the mixture was stirred at 100° C. for 4 hr, and then the obtained reaction mixture was cooled to room temperature. Then, toluene (80 mL) and ion-exchanged water (40 mL) were added thereto, and the mixture was stirred, the aqueous layer was separated and removed, and the obtained organic layer was washed with ion-exchanged water (40 mL) to obtain the obtained organic layer. Anhydrous magnesium sulfate was added to the layer to dry it, followed by filtration, and 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 give Compound M 11 g (6.1 g, yield 70%). Obtained as a colorless solid. The HPLC area percentage value of Compound M11g was 99.5% or more.

(Stage 6: Synthesis of Compound M11)
After making the inside of the reaction container an argon gas atmosphere, compound M11g (3.3g), compound T0 (4.0g), toluene (120mL), ethanol (20mL), tetrakis (triphenylphosphine) palladium (0) (0. 73 g), a 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 obtained reaction mixture was cooled to room temperature, washed with ion-exchanged water, anhydrous magnesium sulfate was added to the obtained organic layer to dry it, and the mixture was filtered, and the obtained 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 to give compound M11 (3.4 g, yield). 68%) as a colorless solid. The HPLC area percentage value of the 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 (multi, 2H). , 2.27-1.98 (multi, 8H), 1.74-1.64 (multi, 4H), 1.55-1.27 (multi, 13H), 0.95-0.88 (multi, 6H).

<Synthesis Example 6> Synthesis of compound M12

(Stage1: Synthesis of Compound M12b)
After making the inside of the reaction vessel an argon gas atmosphere, magnesium (5.4 g, shavings) and cyclopentyl methyl ether (dehydrated product, 180 mL) were added, and compound A0 (45 g) was added dropwise, followed by stirring at 45° C. for 1 hour. Then, Grignard reagent was prepared. Next, another reaction vessel was placed in an argon gas atmosphere, and then compound M12a (35 g, commercial product), [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. Thereafter, the Grignard reagent prepared above was added dropwise thereto, and the mixture was stirred at 40° C. for 1 hour. The obtained reaction mixture was cooled to 0° C., 6 wt% hydrochloric acid was added and the mixture was stirred, and then the mixture was filtered through Celite. After that, the aqueous layer was separated and removed, and the obtained organic layer was washed with ion-exchanged water, and anhydrous magnesium sulfate was added to the obtained organic layer to dry it, followed by filtration, and the obtained filtrate was concentrated under reduced pressure. By doing so, compound M12b (51 g, yield 123%) was obtained as a yellow oil. The HPLC area percentage value of the compound M12b was 58.1%.

(Stage2: Synthesis of Compound M12c)
After making the inside of the reaction vessel 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 hr. The obtained reaction mixture was cooled to room temperature and then filtered using Celite and silica gel. The obtained organic layer was washed with ion-exchanged water and then concentrated under reduced pressure. Heptane (700 mL) and activated carbon (23 g) were added to the obtained residue, and the mixture was stirred at room temperature for 1 hr. 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 the compound M12c was 98.0%.

(Stage3: Synthesis of Compound M12)
After making the inside of the reaction container an argon gas atmosphere, the compound M12c (3.5 g), the compound T0 (5.1 g), toluene (130 mL), ethanol (30 mL), tetrakis(triphenylphosphine)palladium (0)(0. 93 g) and a 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, washed with ion-exchanged water, the obtained organic layer was dried over anhydrous magnesium sulfate, and then filtered using 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 using toluene to give compound M12 (5.7 g, yield 72%) as a colorless solid. Got as. The HPLC area percentage value of the 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 (multi, 1H), 1.39-1.33 (multi, 10H), 0.93 (t, 6H).

<Example 4> Synthesis of polymer compound P4

(Step 1) Compound M13 (0.768 g), compound M14 (0.271 g, commercially available product), which was synthesized according to the method described in International Publication No. 2012/086661, after the inside of the reaction vessel was made an inert gas atmosphere, Compound M15 (0.631 g), compound M2 (0.281 g), which was synthesized according to the method described in JP 2012-144722 A, Compound M16 (0.167 g), which was synthesized according to the method described in JP 2004-143419 A. , Dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.3 mg) and toluene (30 mL) were added, and the mixture was heated to 90°C.
(Step 2) Thereafter, a 16 wt% tetraethylammonium hydroxide aqueous solution (21 g) was added dropwise thereto, and the mixture was refluxed for 5 hours.
(Step 3) After that, phenylboronic acid (73 mg) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.3 mg) were added thereto, and the mixture was refluxed for 15 hours.
(Step 4) After the obtained reaction mixture was cooled to room temperature, it was washed twice with a 10 wt% hydrochloric acid aqueous solution, twice with a 3 wt% ammonia aqueous solution, and twice with water, and the obtained solution was added dropwise to methanol. However, precipitation occurred. The obtained precipitate was dissolved in toluene and passed through an alumina column and a silica gel column in that order for purification. The obtained solution was added dropwise to methanol and stirred, and then the obtained 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 thereof was 1.3×10 ⁵ .

The polymer compound P4 is the theoretical value obtained from the amount of the charged raw materials, and 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 It is a copolymer in which the derived structural unit and the structural unit derived from the compound M16 are composed 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 the polymer compound P4 was described as "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.",
The same as in the synthesis of the polymer compound P4 except that in (Step 2), "after that, a 16 wt% tetrabutylammonium hydroxide aqueous solution (20 g) was dropped and refluxed for 7 hours." Thus, 1.18 g of polymer compound P5 was obtained. The Mn of the polymer compound P5 was 5.3×10 ⁴ , and the Mw thereof was 1.3×10 ⁵ .

The polymer compound P5 has a theoretical value obtained from the amount of the charged raw materials, from 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. It is a copolymer in which the derived structural unit and the structural unit derived from the compound M16 are composed 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 described as "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.",
The same as in the synthesis of the polymer compound P4 except that in (Step 2), "after that, a 16 wt% tetrabutylammonium hydroxide aqueous solution (20 g) was added dropwise and refluxed for 5 hours." Thus, 1.16 g of polymer compound P6 was obtained. The Mn of the polymer compound P6 was 5.1×10 ⁴ , and the Mw thereof was 1.3×10 ⁵ .

The polymer compound P6 is the theoretical value obtained from the amount of the charged raw materials, and 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 It is a copolymer in which the derived structural unit and the structural unit derived from the compound M16 are composed in a molar ratio of 36:14:32.5:10:7.5.

<Comparative Example 2> Synthesis of polymer compound CP2

The polymer compound CP2 is synthesized by a known coupling reaction using the compound M13, the compound M14, the compound M15, the compound M6 and the compound M16 according to the method of “polymer compound F” described in WO 2012/008550. did. The Mn of the polymer compound CP2 was 8.5×10 ⁴ , and the Mw thereof was 2.4×10 ⁵ .

The polymer compound CP2 has the theoretical value obtained from the amount of the charged raw materials, from 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. It is a copolymer in which the derived structural unit and the structural unit derived from the compound M16 are composed in a molar ratio of 36:14:32.5:10:7.5.

<Example D1> Production and evaluation of light emitting device D1 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by a sputtering method. A film of AQ-1200 (manufactured by Plextronics), which is a polythiophene/sulfonic acid-based hole injecting agent, was formed on the anode to a thickness of 65 nm by a spin coating method, and was heated to 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 the hole was formed by heating the film on a hot plate at 180° C. for 60 minutes in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
The polymer compound P1 and the metal complex COM-4 synthesized according to the method described in WO 2009/131255 were dissolved in xylene at a concentration of 2.2% by weight (polymer compound P1/metal complex). COM-4=60% by weight/40% by weight). 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 to emit the light emitting layer. Formed.

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

(Evaluation of light emitting element)
By applying a voltage to the light emitting device D1, EL light emission having the maximum peak wavelength of the emission spectrum at 520 nm was observed. The external quantum efficiency at 1000 cd/m ² was 14.1%, and the driving 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 in Example D1 was used instead of the polymer compound P1.

By applying a voltage to the light emitting device 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 driving 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 device 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 driving 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 In Example D1, the polymer compound CP1 was used in place of the polymer compound P1, and the polymer compound CP1 and the metal complex COM-4 were used in an amount of 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% by weight/40% by weight) 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 driving voltage at a current density of 10 mA/cm ² was 7.0V. The results are shown in Table 2.

<Example D4> Production and evaluation of light emitting device D4 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by a sputtering method. A film of AQ-1200 (manufactured by Plextronics), which is a polythiophene/sulfonic acid-based hole injecting agent, was formed on the anode to a thickness of 65 nm by a spin coating method, and was heated to 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 the hole was formed by heating the film on a hot plate at 180° C. for 60 minutes in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
The polymer compound P1 and the 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% by weight/7.5% by weight). 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 to emit light. Layers were formed.

(Formation of cathode)
The substrate on which the light emitting layer was formed was depressurized to 1.0×10 ⁻⁴ Pa or less in a vapor deposition machine, and sodium fluoride was then applied on the light emitting layer as a cathode to a thickness of about 4 nm, and then on the sodium fluoride layer. Aluminum was vapor-deposited at about 80 nm. After vapor deposition, a light emitting device D4 was produced by sealing with a glass substrate.

(Evaluation of light emitting element)
By applying a voltage to the light emitting device 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 in Example D4 was used instead of the polymer compound P1.

By applying a voltage to the light emitting device D5, 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 7.2%, and the driving 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 A 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 device D6, 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 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 In Example D4, the polymer compound CP1 was used in place of the polymer compound P1, and the polymer compound CP1 and the metal complex COM-8 were used in an amount of 1.8% by weight. A light-emitting element CD2 was manufactured in the same manner as in Example D4 except that a xylene solution (polymer compound CP1/metal complex COM-8=92.5% by weight/7.5% by weight) dissolved in xylene at a concentration was used. Was produced.

By applying a voltage to the light emitting device CD2, EL light emission having a 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 Instead of the metal complex COM-8 in Example D4, a metal complex COM-5 synthesized according to the method described in JP-A-2006-188673 was used. A light emitting device D7 was made in the same manner as Example D4 except for the above.

By applying a voltage to the light emitting device 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 Element D8 A light-emitting element D8 was produced in the same manner as in Example D5 except that the metal complex COM-5 in Example D5 was used instead of the metal complex COM-8. .

By applying a voltage to the light emitting device D8, 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 6.8V. The results are shown in Table 5.

<Example D9> Production and Evaluation of Light-Emitting Element D9 A light-emitting element D9 was produced in the same manner as in Example D6 except that the metal complex COM-5 in Example D6 was used in place of the metal complex COM-8. did.

By applying a voltage to the light emitting device 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 place of the metal complex COM-8 in Comparative Example CD2, the metal complex COM-5 was used, and the polymer compound CP1 and the metal complex COM-5 were set to 1.8. A light emitting device CD3 was produced in the same manner as Comparative Example CD2, except that the light emitting device CD3 was dissolved in xylene at a concentration of wt %.

By applying a voltage to the light emitting device CD3, 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 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 is found that the light-emitting element 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 element containing the polymer compound CP1. ..

<Example D10> Production and evaluation of light emitting device D10 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by a sputtering method. A film of ND-3202 (manufactured by Nissan Chemical Industries, Ltd.), which is a hole injection material, was formed on the anode by a spin coating method to a thickness of 65 nm. In an air atmosphere, a hole injection layer was formed by heating on a hot plate at 50° C. for 3 minutes and further 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 the hole was formed by heating the film on a hot plate at 180° C. for 60 minutes 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 wt% (polymer compound P5/metal complex COM-8=92.5 wt%/7.5 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 to emit light. Layers were formed.

(Formation of cathode)
The substrate on which the light emitting layer was formed was depressurized to 1.0×10 ⁻⁴ Pa or less in a vapor deposition machine, and sodium fluoride was then applied on the light emitting layer as a cathode to a thickness of about 4 nm, and then on the sodium fluoride layer. Aluminum was vapor-deposited at about 80 nm. After vapor deposition, a light emitting device D10 was produced by sealing with a glass substrate.

(Evaluation of light emitting element)
By applying a voltage to the light emitting device D10, EL light emission having a 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 driving voltage at a current density of 10 mA/cm ² was 4.8 V. 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 in place of polymer compound P5 in Example D10.

By applying a voltage to the light emitting device CD4, EL light emission having a 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 driving 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 A light-emitting element D11 was produced in the same manner as in Example D10, except that the metal complex COM-5 in Example D10 was used instead of the metal complex COM-8. did.

By applying a voltage to the light emitting device D11, 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 11.1%, and the driving voltage at a current density of 10 mA/cm ² was 4.8 V. The results are shown in Table 7.

Example D12 Production and Evaluation of Light Emitting Element D12 A light emitting element D12 was produced in the same manner as 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 device D12, 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 10.8%, and the driving 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 in Example D11 was used instead of polymer compound P5.

By applying a voltage to the light emitting device CD5, 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 10.5%, and the driving 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 device containing the polymer compound P5 or the polymer compound P4 of the present invention has a lower driving voltage than the light emitting device containing the polymer compound CP2.

Claims (12)

A polymer compound containing a structural unit represented by the following formula (1).

[In the formula,
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 two selected from the group consisting 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 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 —, and —NR ^Y9 —. Represents a group represented by, an oxygen atom or a 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 may 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 , and R ^Y7 and R ^Y8 are bonded to each other, together with the carbon atom to which they are bonded. It may form a ring.
Ar ¹ and Ar ² each independently represent an arylene group or a divalent heterocyclic group, and these groups may 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 which may have a substituent. Alternatively, 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, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group. Represents, and these groups may have a substituent. Plural R ^{1 s} may be the same or different, and adjacent R ^{1 s} may be bonded to each other to form a ring together with the carbon atom to which they are bonded. R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atom 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 —. Polymer compounds. 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 polymer compound according to claim 1, wherein the constitutional unit represented by the formula (1) is a constitutional unit represented by the following formula (2) or (3).

[In the formula,
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , X ¹ , Y ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings 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 , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ] The polymer compound according to claim ¹ , wherein Z ¹ , Z ² and Z ³ are nitrogen atoms. The polymer compound according to claim 1, wherein Ar ¹ and Ar ² are the same group. The polymer compound according to claim 1, further comprising a structural unit represented by the following formula (Y).

[ ^Wherein 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, The group of may have a substituent. ] The polymer compound according to claim 1, further comprising a structural unit represented by the following formula (X).

[In the formula,
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 may 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. 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.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^X2 and R ^X3 , they may be the same or different. ] The polymer compound according to any one of claims 1 to 10,
A composition containing at least one material selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant and a solvent. A light emitting device containing the polymer compound according to claim 1.