JP6244653B2 - 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 same.

  Organic electroluminescence elements (hereinafter referred to as “light-emitting elements”) can be suitably used for display applications due to their characteristics such as high luminous efficiency and low voltage drive, and are actively researched and developed. It has been broken. A light emitting material is used for manufacturing the light emitting element. As a light emitting material, there are a case where a low molecular compound is used and a case where a high molecular compound is used. In the case of using a polymer compound, a uniform organic thin film can be formed by a coating method such as an ink jet printing method, which is particularly advantageous when manufacturing a large display.

  In recent years, polymer compounds that contain an arylamine derivative represented by the following formula as a structural unit have been disclosed as polymer compounds used in the manufacture of light-emitting elements (for example, Patent Document 1, Patent Document 2, and Patent Document). 3).

International Publication No. 99/054385 International Publication No. 2009/075223 International Publication No. 2009/066666

  However, the luminance life of a light emitting device manufactured using the above polymer compound is not always sufficient.

  Then, an object of this invention is to provide a high molecular compound useful for manufacture of the light emitting element which is excellent in a luminance lifetime. Another object of the present invention is to provide a composition containing a polymer compound, an organic thin film, a light emitting device using the organic thin film, and a planar light source and a display device using the light emitting device.

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

（１）
［式中、
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価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^１およびＲ^２は、それぞれ独立に、水素原子、アルキル基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^１およびＲ^１は、直接または２価の基を介して結合して含窒素複素環を形成してもよい。Ａｒ^２およびＲ^２は、直接または２価の基を介して結合して含窒素複素環を形成してもよい。
Ｒ^３は、ハロゲン原子、シアノ基、アルキル基、−Ｏ−Ｒ^Ａで表される基、−Ｎ(Ｒ^Ａ)_２で表される基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^３が複数ある場合、それらは同一でも異なっていてもよい。Ｒ^Ａは、水素原子、アルキル基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^Ａが複数ある場合、それらは同一でも異なっていてもよく、互いに結合して環を形成してもよい。
ｎ１は、０以上６以下の整数を表す。］

(1)
[Where:
Ar ¹ and Ar ² each independently represent an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent.
Ar ¹ and R ¹ may be bonded directly or via a divalent group to form a nitrogen-containing heterocycle. Ar ² and R ² may be bonded directly or via a divalent group to form a nitrogen-containing heterocyclic ring.
R ³ represents a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group. These groups may have a substituent. When there are a plurality of R ³ , they may be the same or different. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RA , they may be the same or different and may be bonded to each other to form a ring.
n1 represents an integer of 0 or more and 6 or less. ]

  A second aspect of the present invention is a composition containing the polymer compound and at least one material selected from the group consisting of a hole injection material, a hole transport material, a light emitting material, an electron transport material and an electron injection material. Offer things.

  Thirdly, the present invention provides a liquid composition containing the polymer compound or the composition and a solvent.

  Fourthly, the present invention provides an organic thin film containing the polymer compound or the composition.

  Fifthly, the present invention provides a light emitting device comprising an anode, a cathode, and an organic layer provided between the anode and the cathode, wherein the organic layer is the organic thin film.

  Sixthly, the present invention provides a planar light source or a display device using the light emitting element.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element which is excellent in a luminance lifetime can be provided. In addition, according to the present invention, it is possible to provide a composition and an organic thin film containing a polymer compound, a light emitting element using the organic thin film, a planar light source and a display device using the light emitting element.

It is a schematic cross section of the light emitting device according to the first embodiment. It is a schematic cross section of the light emitting device according to the second embodiment. It is an example of the schematic cross section of the planar light source which concerns on this embodiment.

  Hereinafter, terms commonly used in this specification will be described with examples as necessary.

  The “structural unit” means a unit structure existing in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit (that is, a unit structure existing two or more in the polymer compound)”.

The “arylene group” means a group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
The “aryl group” means a group formed by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.

  The “N′-valent aromatic hydrocarbon group” means a group obtained by removing N ′ hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.

  The “aromatic hydrocarbon” may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48, more preferably 6-30. Specifically, benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene, chrysene, biphenyl, terphenyl, phenylnaphthalene, phenylanthracene, Examples include phenylfluorene, phenylphenanthrene, and the like, and benzene, naphthalene, anthracene, phenanthrene, naphthacene, fluorene, pyrene, perylene, biphenyl, terphenyl, phenylnaphthalene, phenylanthracene, phenylfluorene, and phenylphenanthrene are preferable.

  The “N-valent aromatic heterocyclic group” means a group formed by removing N hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound.

  "Aromatic heterocyclic compound" means not only carbon atom but also oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, boron atom, silicon as an element constituting a ring among organic compounds having a cyclic structure. It is a compound that contains heteroatoms such as an atom, selenium atom, tellurium atom, arsenic atom, etc., and exhibits aromaticity.

  The “aromatic heterocyclic compound” may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 2 to 60, preferably 3 to 30. . Specifically, oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, dibenzofuran, dibenzothiophene, etc. Heterocycles containing atoms themselves are aromatic, compounds such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran, etc. Heterocycles containing heteroatoms themselves do not show aromaticity. Examples include compounds in which aromatic hydrocarbons are condensed.

The “polymer compound (sometimes referred to as“ polymer organic material ”)” has a molecular weight distribution, and unless otherwise specified, usually has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ . It is preferably 1 × 10 ⁴ to 1 × 10 ⁶ . Moreover, since the weight average molecular weight of polystyrene conversion of this high molecular compound is 2 * 10 < ³ > -2 * 10 < ⁸ > normally and film forming property becomes favorable, it is preferably 2 * 10 < ⁴ > -2 * 10 < ⁶ >. .

  The polymer compound may be any copolymer, for example, any of a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer.

  The weight average molecular weight and the number average molecular weight of the polymer compound are usually determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight. By converting, the weight average molecular weight and the number average molecular weight are calculated.

“Low molecular compounds (sometimes referred to as“ low molecular organic materials ”)” have no molecular weight distribution .

  In the present specification, the hydrogen atom may be a deuterium atom, but is preferably a hydrogen atom.

  Hereinafter, preferred embodiments of the polymer compound, the composition, the liquid composition, the organic thin film, the light emitting element, the planar light source, and the display device of the present invention will be described in detail.

(Polymer compound)
The polymer compound of the first embodiment is a polymer compound containing a structural unit represented by the following formula (1).

（１）

(1)

In formula (1), Ar ¹ and Ar ² each independently represent an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.

Ar ¹ and Ar ² are preferably arylene groups, and these groups may have a substituent.

The arylene group represented by Ar ¹ and Ar ² may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48, more preferably 6-30.

The arylene groups represented by Ar ¹ and Ar ² are each independently benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene or chrysene. From the above, a divalent group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring is preferable, and these groups may have a substituent.

Arylene groups represented by Ar ¹ and Ar ² are each independently ^two benzene, naphthalene, anthracene, fluorene, spirobifluorene, phenanthrene, dihydrophenanthrene or pyrene, which are directly bonded to the carbon atoms constituting the ring. A divalent group obtained by removing a hydrogen atom is more preferable, and these groups may have a substituent.

The arylene groups represented by Ar ¹ and Ar ² are more preferably arylene groups represented by the following formulas (Ar1-A1) to (Ar1-A15), and the following formulas (Ar1-A1) to (Ar1- An arylene group represented by A14) is particularly preferable, and these groups may have a substituent. In the following, * represents a bond.

The arylene group represented by Ar ¹ and Ar ² is particularly preferably an arylene group represented by the following formulas (Ar1-1) to (Ar1-5), and is represented by the following formula (Ar1-1). It is especially more preferable that it is an arylene group, and these groups may have a substituent.

［式中、Ｒ^Ｙ１は、水素原子または置換基を表し、複数存在するＲ^Ｙ１は同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。＊は前記と同じ意味を表し、Ｒ^Ａは後記と同じ意味を表す。］

[Wherein, R ^Y1 represents a hydrogen atom or a substituent, and a plurality of R ^Y1 may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded. * Represents the same meaning as described above, and R ^A represents the same meaning as described later. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group, a hydrogen atom or Alkyl groups are more preferred, and the definitions and examples of these groups are the same as the definitions and examples of those groups that are substituents described later. R ^A represents the same meaning as described below.

The divalent aromatic heterocyclic group represented by Ar ¹ and Ar ² may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent. Yes, preferably 3-30.

The divalent aromatic heterocyclic groups represented by Ar ¹ and Ar ² are each independently pyridine, diazabenzene, triazine, quinoline, isoquinoline, quinoxaline, pyrrole, indole, carbazole, furan, benzofuran, dibenzofuran, thiophene, benzo Removing two hydrogen atoms directly attached to the ring carbon atom or heteroatom from thiophene, dibenzothiophene, dibenzophosphole, dibenzoborol, dibenzosilol, phenoxazine, phenothiazine, benzothiadiazole or oxadiazole It is preferable that these groups are divalent groups, and these groups may have a substituent.

The divalent aromatic heterocyclic groups represented by Ar ¹ and Ar ² are each independently pyridine, diazabenzene, triazine, quinoline, isoquinoline, carbazole, dibenzofuran, dibenzothiophene, phenoxazine, phenothiazine, benzothiadiazole or oxadiazole A group obtained by removing two hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from an azole is more preferable, and these groups may have a substituent.

The divalent aromatic heterocyclic group represented by Ar ¹ and Ar ² is more preferably a divalent aromatic heterocyclic group represented by the following, and these groups may have a substituent. Good. In the following, * represents the same meaning as described above, and R ^A represents the same meaning as described later.

In this specification, the “substituent” means a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group, or a monovalent group. Of these aromatic heterocyclic groups, and these groups may further have a substituent. When a plurality of substituents are present, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which each is bonded.

R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. Unless otherwise specified, R ^A is preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, more preferably an alkyl group or an aryl group, and these groups may have a substituent. When there are a plurality of ^RA , they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded.
The definitions and examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ^A are the alkyl group, aryl group and monovalent aromatic heterocyclic ring represented by R ¹ and R ² described later. This is the same as definitions and examples of groups.

  Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferable unless otherwise specified.

  The alkyl group as a substituent may further have a substituent, and may be any of a linear alkyl group, a branched alkyl group, or a cyclic alkyl group (cycloalkyl group). Unless otherwise specified, the number of carbon atoms of the alkyl group is usually 1 to 60 (in the case of a branched alkyl group and a cyclic alkyl group, usually 3 to 60), preferably 1 without including the number of carbon atoms of the substituent. To 20 (preferably 3 to 20 in the case of a branched alkyl group and a cyclic alkyl group).

  Examples of the alkyl group as a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a 2-ethylbutyl group, Hexyl, cyclohexyl, heptyl, cyclohexylmethyl, cyclohexylethyl, octyl, 2-ethylhexyl, 3-propylheptyl, nonyl, decyl, 3,7-dimethyloctyl, 2-ethyloctyl 2-hexyl-decyl group, dodecyl group, and unless otherwise specified, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group Group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2 -An ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group or a dodecyl group is preferable, and these groups may further have a substituent. Examples of the alkyl group having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, and a 3- (4-methylphenyl) propyl group. , 3- (3,5-di-hexylphenyl) propyl group and 6-ethyloxyhexyl group.

  The aryl group which is a substituent may further have a substituent, and unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48, more preferably 6-30.

  Unless otherwise specified, an aryl group as a substituent is a ring formed from benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene, or chrysene. It is preferably a monovalent group obtained by removing one hydrogen atom directly bonded to the constituent carbon atom, and these groups may further have a substituent.

  Unless otherwise specified, as the aryl group as a substituent, one hydrogen atom directly bonded to the carbon atom constituting the ring is removed from benzene, naphthalene, anthracene, fluorene, spirobifluorene, phenanthrene, dihydrophenanthrene or pyrene. It is more preferable that these groups are monovalent groups, and these groups may further have a substituent.

  Unless otherwise specified, the aryl group as a substituent is more preferably an aryl group represented by the following, and these groups may further have a substituent. In the following, * represents the same meaning as described above.

  The monovalent aromatic heterocyclic group as a substituent may further have a substituent, and unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 2 to 60. Yes, preferably 3-30.

  As monovalent aromatic heterocyclic groups as substituents, unless otherwise specified, pyridine, diazabenzene, triazine, quinoline, isoquinoline, quinoxaline, pyrrole, indole, carbazole, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene , Dibenzophosphole, dibenzoborol, dibenzosilol, phenoxazine, phenothiazine, benzothiadiazole or oxadiazole, a monovalent group formed by removing one hydrogen atom directly bonded to a ring carbon atom or heteroatom It is preferably a group, and these groups may further have a substituent.

  As the monovalent aromatic heterocyclic group as a substituent, unless otherwise specified, pyridine, diazabenzene, triazine, quinoline, isoquinoline, pyrrole, carbazole, furan, thiophene, or oxadiazole is used as a carbon atom or a hetero ring. More preferably, it is a monovalent group obtained by removing one hydrogen atom directly bonded to an atom, and these groups may further have a substituent.

As the monovalent aromatic heterocyclic group as a substituent, unless otherwise specified, the monovalent aromatic heterocyclic group represented by the following is more preferable, and the group may further have a substituent. In the following, * and R ^A represent the same meaning as described above.

Alkyl group which is a substituent, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group and a substituent which a monovalent aromatic heterocyclic group may have As a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group. Unless otherwise specified, a fluorine atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group is preferable, and an alkyl group, an aryl group or a monovalent aromatic heterocyclic group is preferable. Are more preferable, and an alkyl group or an aryl group is more preferable. The definitions and examples of these groups are the same as the definitions and examples of those groups that are the substituents described above. R ^A represents the same meaning as described above. In addition, the substituent which a substituent may have may have a substituent further.

Examples of the substituent that the group represented by Ar ¹ and Ar ² may have include a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , and a group represented by —N (R ^A ) ₂ . Group, aryl group or monovalent aromatic heterocyclic group, alkyl group, group represented by —O—R ^A , group represented by —N (R ^A ) ₂ , aryl group or 1 A valent aromatic heterocyclic group is preferable, an alkyl group, a group represented by —O—R ^A or an aryl group is more preferable, and an alkyl group or an aryl group is further preferable. The definitions and examples of these groups are the same as the definitions and examples of those groups that are the substituents described above. R ^A represents the same meaning as described above. In addition, the substituent which the group represented by Ar ¹ and Ar ² may have may further have a substituent.

In formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. . R ¹ and R ² are preferably an aryl group or a monovalent aromatic heterocyclic group, and more preferably an aryl group.

The definitions and examples of the alkyl group and aryl group represented by R ¹ and R ² are the same as the definitions and examples of the alkyl group and aryl group which are the aforementioned substituents.

The aryl group represented by R ¹ and R ² is particularly preferably an aryl group represented by the following formulas (R1-1) to (R1-4), and particularly preferably represented by the following formula (R1-1). Aryl groups, and these groups may have a substituent.

［式中、Ｒ^Ａ、Ｒ^Ｙ１および＊は前記と同じ意味を表す。］

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

The monovalent aromatic heterocyclic group represented by R ¹ and R ² may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent. Yes, preferably 3-30.

The monovalent aromatic heterocyclic group represented by R ¹ and R ² is pyridine, diazabenzene, triazine, quinoline, isoquinoline, quinoxaline, pyrrole, indole, carbazole, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene. , Dibenzophosphole, dibenzoborol, dibenzosilol, phenoxazine, phenothiazine, benzothiadiazole or oxadiazole, a monovalent group formed by removing one hydrogen atom directly bonded to a ring carbon atom or heteroatom It is preferable that these are groups, and these groups may have a substituent.

The monovalent aromatic heterocyclic group represented by R ¹ and R ² is selected from the group consisting of pyridine, diazabenzene, triazine, quinoline, isoquinoline, pyrrole, carbazole, furan, thiophene, and oxadiazole. It is more preferably a monovalent group formed by removing one hydrogen atom directly bonded to an atom, and these groups may have a substituent.

The monovalent aromatic heterocyclic group represented by R ¹ and R ² is more preferably a monovalent aromatic heterocyclic group represented by the following, and these groups may have a substituent. In the following, * and R ^A represent the same meaning as described above.

Definitions and examples of the substituent that the group represented by R ¹ and R ² may have include definitions and examples of the substituent that the group represented by Ar ¹ and Ar ² may have, It is the same.

Ar ¹ and R ¹ may be bonded directly or via a divalent group to form a nitrogen-containing heterocycle. Ar ² and R ² may be bonded directly or via a divalent group to form a nitrogen-containing heterocyclic ring.

The divalent group is not particularly limited, but —O—, —S—, —N (R ^A ) — or —C (R ^A ) ₂ — is preferable. ^RA represents the same meaning as described above.

Examples of the nitrogen-containing heterocycle include the following structures. In the following, * and R ^A represent the same meaning as described above.

In formula (1), R ³ represents a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group, or a monovalent fragrance. Represents a group heterocyclic group, and these groups optionally have a substituent. When there are a plurality of R ³ , they may be the same or different. R ³ is preferably an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group, an alkyl group, —O ^A group represented by —RA, an aryl group or a monovalent aromatic heterocyclic group is more preferred, an alkyl group, a group represented by —O—R ^A or an aryl group is more preferred, and an alkyl group or aryl group is more preferred. Particularly preferred are alkyl groups, and these groups may have a substituent.
The definitions and examples of the halogen atom, alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ³ are the same as the definitions and examples of those groups which are the aforementioned substituents. R ^A represents the same meaning as described above.

The definition and example of the substituent that the group represented by R ³ may have are the same as the definition and example of the substituent that the group represented by Ar ¹ and Ar ² may have. is there.

  In the formula (1), n1 represents an integer of 0 or more and 6 or less, and is preferably an integer of 0 or more and 2 or less.

  The structural unit represented by the formula (1) is preferably a structural unit represented by the following formulas (1-1) to (1-3), and a structural unit represented by the following formula (1-1). It is more preferable that

（１−１）

(1-1)

In formula (1-1), Ar ¹ , Ar ² , R ¹ , R ² , R ³ and n1 represent the same meaning as described above.

（１−２）

(1-2)

In formula (1-2), Ar ¹ , Ar ² , R ¹ , R ² , R ³ and n1 represent the same meaning as described above.

（１−３）

(1-3)

In formula (1-3), Ar ¹ , Ar ² , R ¹ , R ² , R ³ and n1 represent the same meaning as described above.

  The structural unit represented by the formula (1-1) is preferably a structural unit represented by the following formula (1-1A).

［式中、Ａｒ^１、Ａｒ^２、Ｒ^１およびＲ^２は、前記と同じ意味を表す。Ｒ^ＸＡ１〜Ｒ^ＸＡ６は水素原子、ハロゲン原子、シアノ基、アルキル基、−Ｏ−Ｒ^Ａで表される基、−Ｎ(Ｒ^Ａ)_２で表される基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein Ar ¹ , Ar ² , R ¹ and R ² represent the same meaning as described above. R ^{XA1 to} R ^XA6 are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group, or a monovalent aromatic It represents a heterocyclic group, and these groups may have a substituent. ]

R ^{XA1 to} R ^XA4 are preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group, or a monovalent aromatic heterocyclic group. More preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. May have a substituent.

R ^XA5 and R ^XA6 are preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group More preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A or an aryl group, still more preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group. And these groups may have a substituent.

The definitions and examples of the halogen atom, alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ^{XA1 to} R ^XA6 are the same as the definitions and examples of those groups represented by R ^3. .

The definition and example of the substituent that the group represented by R ^{XA1 to} R ^XA6 may have are the same as the definition and example of the substituent that the group represented by R ³ may have. is there.

  Examples of the structural unit represented by the formula (1) include structural units represented by the following formulas (1A-1) to (1A-19), preferably the following formulas (1A-1) to (1A- 13), more preferably structural units represented by the following formulas (1A-1) to (1A-8). In the following formulas (1A-1) to (1A-19), * represents the same meaning as described above, and D represents a deuterium atom.

  The polymer compound of the first embodiment may contain only one type of structural unit represented by the formula (1), or may contain two or more types.

  In the polymer compound of the first embodiment, the ratio of the total number of moles of the structural unit represented by the formula (1) to the total number of moles of all the structural units is obtained using the polymer compound of the first embodiment. Since the luminance life of the light emitting element is more excellent, 0.01 to 100% is preferable, 0.1 to 40% is more preferable, 0.5 to 20% is further preferable, and 1 to 10% is particularly preferable.

  The polymer compound of the first embodiment preferably further includes one or more structural units selected from the group consisting of structural units represented by the following formulas (2-1) to (2-4). More preferably, it contains at least one structural unit selected from the group consisting of structural units represented by formulas (2-1) to (2-2), and is a structural unit represented by the following formula (2-1) It is more preferable that 1 or more types are included. However, the structural unit represented by Formula (1) is different from the structural unit represented by Formula (2-3).

（２−１）

(2-1)

In Formula (2-1), B ¹ represents an arylene group, and the group may have a substituent.

The arylene group represented by B ¹ may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48. More preferably, it is 6-30.

Since the arylene group represented by B ¹ has a higher luminance lifetime obtained by using the polymer compound of the first embodiment, benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, inde It is preferably a divalent group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from nofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene, chrysene or dihydrodibenzocycloheptene, A divalent group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from benzene, naphthalene, anthracene, fluorene, spirobifluorene, phenanthrene, dihydrophenanthrene, pyrene or dihydrodibenzocycloheptene. There is Are more preferable, and these groups may have a substituent.

The arylene group represented by B ¹ is more preferably an arylene group represented by the following, and these groups may have a substituent. In the following, * represents the same meaning as described above.

The arylene group represented by B ¹ is particularly preferably an arylene group represented by the following, and these groups may have a substituent. In the following, * represents the same meaning as described above.

R ^B represents a hydrogen atom or a substituent. When a plurality of R ^B are present, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded.

R ^B is preferably an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group, and an alkyl group or an aryl group Alternatively, a monovalent aromatic heterocyclic group is more preferable, an alkyl group or an aryl group is more preferable, and the definitions and examples of these groups are the same as the definitions and examples of those groups that are the above-described substituents. R ^A represents the same meaning as described above.

The arylene group represented by B ¹ is preferably an arylene group represented by formulas (B1-1) to (B1-8) because the luminance life obtained using the polymer compound of the first embodiment is more excellent. And more preferably an arylene group represented by formulas (B1-1) to (B1-6), and still more preferably an arylene group represented by (B1-2) or (B1-3). In the following, ^{*, R Y1} and ^{R B} are as defined above.

The substituent that the arylene group represented by B ¹ may have is the same as the definition and examples of the substituent that the group represented by Ar ¹ and Ar ² may have.

Examples of the arylene group represented by B ¹ include the following formulas (Ar3-A1) to (Ar3-A17), formulas (Ar3-B1) to (Ar3-B15), and formulas (Ar3-C1) to (Ar3-C6). ), Formulas (Ar3-D1) to (Ar3-D7), formulas (Ar3-E1) to (Ar3-E5), formulas (Ar3-F1) to (Ar3-F5), formulas (Ar4-A1) to (Ar4) -A32), formulas (Ar4-B1) to (Ar4-B8), formulas (Ar4-C1) to (Ar4-C7), formulas (Ar4-D1) to (Ar4-D9) and formulas (Ar4-E1) to And an arylene group represented by (Ar4-E4), preferably formulas (Ar3-A11) to (Ar3-A15), formulas (Ar3-B5) to (Ar3-B15), formula (Ar3-C3) ~ (Ar3-C6), (Ar4-A1) ~ (Ar4-A2) 7), formula (Ar4-B1) to (Ar4-B6), formula (Ar4-C1) to (Ar4-C3), formula (Ar4-D1) to (Ar4-D4), formula (Ar4-D1) or formula (Ar4-D2).

  In the polymer compound of the first embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-1) to the total number of moles of all the structural units is determined using the polymer compound of the first embodiment. Since the luminance life of the obtained light emitting device is more excellent, 0.1 to 99% is preferable, 10 to 98% is more preferable, 30 to 97% is further preferable, and 50 to 95% is particularly preferable.

（２−２）

(2-2)

In formula (2-2), B ² is a divalent aromatic heterocyclic group or a group in which two or more groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are directly bonded. Represents a valent group, and the group may have a substituent, but is preferably a divalent aromatic heterocyclic group.

The divalent aromatic heterocyclic group represented by B ² is the same as the definition and examples of the divalent aromatic heterocyclic group represented by Ar ¹ and Ar ² described above.

The divalent aromatic heterocyclic group represented by B ² is particularly preferably a divalent aromatic heterocyclic group represented by the following because the hole transport property of the polymer compound of the first embodiment is excellent. These groups may have a substituent. In the following, * and R ^Y1 represent the same meaning as described above.

R ^C represents a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, more preferably an aryl group, and these groups May have a substituent.

The definitions and examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ^C are the above-mentioned alkyl group, aryl group and monovalent aromatic heterocyclic ring represented by R ¹ and R ^2. This is the same as definitions and examples of groups.

Examples of the divalent aromatic heterocyclic group represented by B ^2, for example, divalent aromatic heterocyclic group represented by the following. In the following, * represents the same meaning as described above.

The substituent that the divalent aromatic heterocyclic group represented by B ² may have is the same as the definition and example of the substituent that the group represented by Ar ¹ and Ar ² may have. is there.

An arylene group and a divalent aromatic heterocyclic group in a divalent group in which two or more groups selected from the group consisting of an arylene group represented by B ² and a divalent aromatic heterocyclic group are directly bonded to each other; Definitions and examples are the same as definitions and examples of the arylene group represented by B ¹ and the divalent aromatic heterocyclic group represented by B ² , respectively.

Examples of the divalent group in which two or more groups selected from the group consisting of an arylene group represented by B ² and a divalent aromatic heterocyclic group are directly bonded include the following divalent groups: These may be substituted. In the following, * represents the same meaning as described above.

The divalent group in which two or more groups selected from the group consisting of an arylene group represented by B ² and a divalent aromatic heterocyclic group are directly bonded is an electron transport property of the polymer compound of the first embodiment. Is preferable, it is preferably a divalent group represented by the following formula (Y-3) or (Y-4).

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｒ^Y3は、水素原子または置換基を表す。］

[Wherein, R ^Y1 represents the same meaning as described above. R ^Y3 represents a hydrogen atom or a substituent. ]

R ^Y3 is preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, more preferably an alkyl group or —O—R ^A. Group, an aryl group or a monovalent aromatic heterocyclic group, more preferably an aryl group or an aromatic heterocyclic group, particularly preferably an aryl group. Definitions and examples of these groups are as follows: The definitions and examples of those groups which are the above-described substituents are the same. R ^A represents the same meaning as described above.

  As a bivalent group represented by a formula (Y-3) or (Y-4), the bivalent group represented by the following is mentioned, for example.

  In the polymer compound of the first embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-2) to the total number of moles of all the structural units is the charge transport of the polymer compound of the first embodiment. Since the property is excellent, 0.01 to 50% is preferable, 0.1 to 30% is more preferable, and 1 to 15% is more preferable.

（２−３）

(2-3)

  In formula (2-3), n2 represents an integer of 0 or more, preferably 3 or less, more preferably 0 or 1, and further preferably 0. n3 represents an integer of 0 or more, preferably 2 or less, more preferably 1.

In formula (2-3), B ³ and B ⁵ each independently represent an arylene group or a divalent aromatic heterocyclic group, preferably an arylene group, and these groups have a substituent. It may be.

The definitions and examples of the arylene group and divalent aromatic heterocyclic group represented by B ³ and B ⁵ are the above-described arylene group and divalent aromatic heterocyclic group represented by Ar ¹ and Ar ² , respectively. This is the same as the definitions and examples.

In formula (2-3), B ⁴ and B ⁶ are an arylene group, a divalent aromatic heterocyclic group, or two or more selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group. It represents a divalent group in which groups are directly bonded, and is preferably an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent. When there are a plurality of B ⁴ and B ⁶ , they may be the same or different.

The definition and example of the arylene group represented by B ⁴ and B ⁶ are the same as the definition and example of the arylene group represented by Ar ¹ and Ar ² described above. The arylene groups represented by B ⁴ and B ⁶ are particularly preferably represented by the formulas (B1-3), (B1-5) to (B1-7) or the following formulas (2B-1) to (2B-3). Is an arylene group.

［式中、Ｒ^Ｙ１および＊は前記と同じ意味を表す。］

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

The definitions and examples of the divalent aromatic heterocyclic group represented by B ⁴ and B ⁶ are the same as the definitions and examples of the divalent aromatic heterocyclic group represented by Ar ¹ and Ar ² .

An arylene group and a divalent aromatic complex in a divalent group in which two or more groups selected from the group consisting of an arylene group represented by B ⁴ and B ⁶ and a divalent aromatic heterocyclic group are directly bonded The definitions and examples of the cyclic group are the same as the definitions and examples of the arylene group and divalent aromatic heterocyclic group represented by B ⁴ and B ⁶ , respectively.

Examples of the divalent group in which two or more groups selected from the group consisting of an arylene group represented by B ⁴ and B ⁶ and a divalent aromatic heterocyclic group are directly bonded include the following 2 Valent groups, and these may have a substituent. In the following, * represents the same meaning as described above.

Definitions and examples of substituents that B ³ , B ⁴ , B ⁵ and B ⁶ may have are definitions and examples of substituents which the groups represented by Ar ¹ and Ar ² may have. The same.

In formula (2-3), R ^C represents the same meaning as described above. If R ^C is more, they may be the same or different.

  Examples of the structural unit represented by the formula (2-3) include structural units represented by the following formulas (X-1) to (X-9), preferably the following formulas (X-4) to ( X-8) is a structural unit.

［式中、Ｒ^ｘ４およびＲ^ｘ５は、それぞれ独立に、水素原子または置換基を表す。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、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^x4 and R ^x5 each independently represent a hydrogen atom or a substituent. A plurality of R ^x4 may be the same or different. A plurality of R ^X5 may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^x4 is preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, and represented by a hydrogen atom, an alkyl group or —O—R ^A. A group or an aryl group is more preferable, a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is particularly preferable, and the definitions and examples of these groups include Same as the example. R ^A represents the same meaning as described above.

R ^x5 is preferably an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, more preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, Alkyl groups or aryl groups are more preferred, and the definitions and examples of these groups are the same as the definitions and examples of those groups that are the aforementioned substituents. R ^A represents the same meaning as described above.

  Examples of the structural unit represented by the formula (2-3) include structural units represented by the following formulas (XA-1) to (XA-28), preferably (XA-10) to (XA-26). ).

  In the polymer compound of the first embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-3) to the total number of moles of all the structural units is the hole of the polymer compound of the first embodiment. Since transportability is excellent, 0.01 to 50% is preferable, 0.1 to 30% is more preferable, and 1 to 10% is more preferable.

（２−４）

(2-4)

  In formula (2-4), n4 represents an integer of 0 or more, preferably 2 or less.

In formula (2-4), B ⁷ and B ⁹ each independently represent an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent.

The definitions and examples of the arylene group and the divalent aromatic heterocyclic group represented by B ⁷ and B ⁹ are the above-described arylene group represented by B ¹ and the divalent aromatic represented by B ² , respectively. This is the same as the definition and examples of the heterocyclic group.

In formula (2-4), B ⁸ is an arylene group, a divalent aromatic heterocyclic group, or two or more groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group. It represents a bonded divalent group, and is preferably an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent. If B ⁸ there are multiple, they may be the same or different.

An arylene group represented by B ⁸ , a divalent aromatic heterocyclic group, and a divalent group in which two or more groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are directly bonded The definition and examples of are selected from the group consisting of the above-mentioned arylene group and divalent aromatic heterocyclic group represented by B ⁴ and B ⁶ , and the arylene group and divalent aromatic heterocyclic group. This is the same as the definition and examples of the divalent group in which the above groups are directly bonded.

Wherein (2-4), ^{Z 1} and ^{Z 2} are each ^{independently, - (R XX1) C =} C (R XX1) - or -C≡C- represents, ^{if Z 2} there are multiple, they It may be the same or different.
Here, R ^XX1 represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ or an aryl group. Or it is a monovalent | monohydric aromatic heterocyclic group, More preferably, they are a hydrogen atom, an alkyl group, or an aryl group, and these groups may have a substituent. The definitions and examples of these groups are the same as the definitions and examples of those groups that are the substituents described above. ^RA represents the same meaning as described above.

  In the polymer compound of the first embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-4) to the total number of moles of all the structural units is the charge transport of the polymer compound of the first embodiment. From the standpoint of superiority, 0.1 to 50% is preferable, and 1 to 30% is more preferable.

  Examples of the polymer compound of the first embodiment include polymer compounds 1A-A1 to 1A-A12 shown in Table 4. Here, the “other structural unit” is a structural unit represented by the formula (1), the formula (2-1), the formula (2-2), the formula (2-3), and the formula (2-4). This means a structural unit other than.

［表中、ｐ^1A、ｑ^1A、ｒ^1A、ｓ^1A、ｔ^1Aおよびｕ^1Aは、第１実施形態の高分子化合物における各構成単位のモル比率を表す。ｐ^1A＋ｑ^1A＋ｒ^1A＋ｓ^1A＋ｔ^1A＋ｕ^1A＝100であり、かつ、70≦ｐ^1A＋ｑ^1A＋ｒ^1A＋ｓ^1A＋ｔ^1A≦100である。］

[In the table, p ^1A , q ^1A , r ^1A , s ^1A , t ^1A and u ^1A represent the molar ratio of each structural unit in the polymer compound of the first embodiment. p ^1A + q ^1A + r ^1A + s ^1A + t ^1A + u ^1A = 100 and 70 ≦ p ^1A + q ^1A + r ^1A + s ^1A + t ^1A ≦ 100. ]

  The polymer compound of the second embodiment includes a structural unit represented by the above formula (1), a structural unit represented by the following formula (3-1), and a structural unit represented by the following formula (3-2). It is a high molecular compound containing.

（３−１）

(3-1)

In the formula (3-1), Ar ³ is a divalent formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from benzene or an aromatic hydrocarbon condensed with two or more benzenes. Represents a group, and the group may have a substituent.

The divalent group represented by Ar ³ may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48. More preferably, it is 6-30.

The divalent group represented by Ar ³ is a divalent group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from benzene, naphthalene, anthracene, tetracene, phenanthrene, pyrene, perylene, or chrysene. It is preferable that these groups are, and these groups may have a substituent.

The divalent group represented by Ar ³ may be a divalent group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from benzene, naphthalene, anthracene, phenanthrene or pyrene. More preferably, these groups may have a substituent.

The divalent group represented by Ar ³ is more preferably an arylene group represented by the following, and these groups may have a substituent. In the following, * represents the same meaning as described above.

The divalent group represented by Ar ³ is particularly preferably an arylene group represented by the following formulas (Ar3-1) to (Ar3-5), and the following formulas (Ar3-1) to (Ar3-3) An arylene group represented by (II) is particularly preferable.

［式中、＊およびＲ^ｘ４は前記と同じ意味を表す。Ｒ^Ｄは、水素原子または置換基を表す。Ｒ^Ｄ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。］

[Wherein * and R ^x4 represent the same meaning as described above. ^RD represents a hydrogen atom or a substituent. When two or more ^RD exists, they may be the same or different. ]

R ^D is preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group, More preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A or an aryl group, still more preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group, Particularly preferred are alkyl groups, and these groups may have a substituent. The definitions and examples of these groups are the same as the definitions and examples of those groups that are the substituents described above. ^RA represents the same meaning as described above.

The substituent that the group represented by Ar ³ may have is the same as the definition and examples of the substituent that the group represented by Ar ¹ and Ar ² may have. However, when there are a plurality of such substituents, they are not bonded to each other to form a ring.

Examples of the divalent group represented by Ar ³ include the following formulas (Ar3-A1) to (Ar3-A17), (Ar3-B1) to (Ar3-B15), (Ar3-C1) to (Ar3- C6), divalent groups represented by (Ar3-D1) to (Ar3-D7), (Ar3-E1) to (Ar3-E5) and (Ar3-F1) to (Ar3-F5), Preferably, it is a divalent group represented by formulas (Ar3-A11) to (Ar3-A15), (Ar3-B5) to (Ar3-B11) or (Ar3-C3) to (Ar3-C6).

（３−２）

(3-2)

In formula (3-2), Ar ⁴ represents an arylene group, and the group may have a substituent. However, Ar ⁴ has one or more SP ³ carbon atoms constituting the ring.

The “number of SP ³ carbon atoms constituting the ring” represents the number of SP ³ carbon atoms constituting the aromatic hydrocarbon ring, including a condensed ring, a spiro ring, and a bridged ring such as a bicyclo ring. included.
However, when the ring has a substituent, the number of SP ³ carbon atoms of the substituent is not included in the number of SP ³ carbon atoms constituting the ring.

The number of SP ³ carbon atoms constituting the ring will be described using examples of arylene groups represented by the following formulas (3-a) to (3-f).

In the arylene group represented by the formula (3-a), the number of SP ³ carbon atoms constituting the ring of the arylene group is 0.

In the arylene group represented by the formula (3-b), the number of SP ³ carbon atoms constituting the ring of the arylene group is 1.

In the arylene group represented by the formula (3-c), the number of SP ³ carbon atoms constituting the ring of the arylene group is 2.

In the arylene group represented by the formula (3-d), the number of SP ³ carbon atoms constituting the ring of the arylene group is 4.

In the arylene group represented by the formula (3-d), the number of SP ³ carbon atoms constituting the ring of the arylene group is 4.

In the arylene group represented by the formula (3-e), the number of SP ³ carbon atoms constituting the ring of the arylene group is 5.

In the arylene group represented by the formula (3-f), the number of SP ³ carbon atoms constituting the ring of the arylene group is 8.

The arylene group represented by Ar ⁴ may have a substituent, and the number of carbon atoms does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48. .

The arylene group represented by Ar ⁴ has two hydrogen atoms directly bonded to the carbon atoms constituting the ring from indene, fluorene, benzofluorene, indenofluorene, spirobifluorene, dihydrophenanthrene, or dihydrodibenzocycloheptene. Is preferably a divalent group formed by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from indene, fluorene, benzofluorene, indenofluorene, spirobifluorene or dihydrophenanthrene. It is more preferable that these groups are divalent groups, and these groups may have a substituent.

The arylene group represented by Ar ⁴ is a divalent group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from fluorene, benzofluorene, spirobifluorene, dihydrophenanthrene or dihydrodibenzocycloheptene. And more preferably a divalent group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from fluorene, benzofluorene, spirobifluorene or dihydrophenanthrene. Preferably, these groups may have a substituent.

The arylene group represented by Ar ⁴ is particularly preferably an arylene group represented by the following, and these groups may have a substituent. In the following, * represents the same meaning as described above.

The arylene group represented by Ar ⁴ is particularly preferably an arylene group represented by the formula (B1-3) or (B1-5) to (B1-8), and particularly preferably a formula (B1-3). ) Or an (arylene group) represented by (B1-5) to (B1-7), particularly preferably an arylene group represented by formula (B1-3) or (B1-6).

The substituent that the group represented by Ar ⁴ may have is the same as the definition and examples of the substituent that the group represented by Ar ¹ and Ar ² may have.

The number of SP ³ carbon atoms constituting the ring of Ar ⁴ is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Examples of the divalent group represented by Ar ⁴ include the following formulas (Ar4-A1) to (Ar4-A32), (Ar4-B1) to (Ar4-B8), (Ar4-C1) to (Ar4- C7), divalent groups represented by (Ar4-D1) to (Ar4-D9) and (Ar4-E1) to (Ar4-E4) are mentioned, and preferably the formulas (Ar4-A1) to (Ar4- A27) or a divalent group represented by formulas (Ar4-C1) to (Ar4-C3).

  The polymer compound of the second embodiment may contain only one type of structural unit represented by the formula (1), or may contain two or more types.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (1) to the total number of moles of all the structural units is obtained using the polymer compound of the second embodiment. Since the luminance life of the light emitting device is more excellent, it is preferably 0.01 to 99%, more preferably 0.1 to 40%, still more preferably 0.5 to 20%, and particularly preferably 1 to 10%.

  The polymer compound of the second embodiment may contain only one type of structural unit represented by the formula (3-1), or may contain two or more types.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (3-1) to the total number of moles of all the structural units is determined using the polymer compound of the second embodiment. Since the luminance life of the obtained light emitting device is more excellent, 0.01 to 99% is preferable, 1 to 90% is more preferable, 10 to 80% is more preferable, and 30 to 70% is particularly preferable.

  The polymer compound of the second embodiment may contain only one type of structural unit represented by the formula (3-2), or may contain two or more types.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (3-2) to the total number of moles of all the structural units is determined using the polymer compound of the second embodiment. Since the luminance life of the obtained light emitting device is more excellent, 0.01 to 99% is preferable, 1 to 90% is more preferable, 10 to 80% is more preferable, and 30 to 70% is particularly preferable.

  In the polymer compound of the second embodiment, the structural unit represented by the formula (1), the structural unit represented by the formula (3-1), and the formula (3-2) with respect to the total number of moles of all the structural units. 50-100% is preferable, as for the ratio of the total number of moles of the structural unit represented, 80-100% is more preferable, and 90-100% is further more preferable.

  The polymer compound of the second embodiment may further contain one or more structural units selected from the group consisting of structural units represented by the above formulas (2-1) to (2-4), Since the polymer compound of the second embodiment has excellent charge transport properties, it may contain one or more structural units selected from the group consisting of structural units represented by formulas (2-2) to (2-4). preferable.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-2) to the total number of moles of all the structural units is the charge transport of the polymer compound of the second embodiment. Since the property is excellent, 0.01 to 50% is preferable, 0.1 to 30% is more preferable, and 1 to 15% is more preferable.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-3) to the total number of moles of all the structural units is 0.01 from the viewpoint of hole transportability. -50% is preferable, 0.1-30% is more preferable, and 1-10% is further more preferable.

  In the polymer compound of the second embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-4) to the total number of moles of all the structural units is the charge transport of the polymer compound of the second embodiment. From the standpoint of superiority, 0.1 to 50% is preferable, and 1 to 30% is more preferable.

  Examples of the polymer compound of the second embodiment include polymer compounds 1B-A1 to 1B-A8 shown in Table 5. Here, the “other structural unit” refers to Formula (1), Formula (2-2), Formula (2-3), Formula (2-4), Formula (3-1), and Formula (3-2). ) Means a structural unit other than the structural unit represented by

［表中、ｐ^2A、ｑ^2A、ｑ^2B、ｒ^2A、ｓ^2A、ｔ^2Aおよびｕ^2Aは、第２実施形態の高分子化合物における各構成単位のモル比率を表す。ｐ^2A＋ｑ^2A＋ｑ^2B＋ｒ^2A＋ｓ^2A＋ｔ^2A＋ｕ^2A＝100であり、かつ、70≦ｐ^2A＋ｑ^2A＋ｑ^2B＋ｒ^2A＋ｓ^2A＋ｔ^2A≦100である。］

[In the table, p ^2A , q ^2A , q ^2B , r ^2A , s ^2A , t ^2A and u ^2A represent the molar ratio of each structural unit in the polymer compound of the second embodiment. p ^2A + q ^2A + q ^2B + r ^2A + s ^2A + t ^2A + u ^2A = 100 and 70 ≦ p ^2A + q ^2A + q ^2B + r ^2A + s ^2A + t ^2A ≦ 100. ]

  The polymer compound of 3rd Embodiment is a polymer compound containing the structural unit represented by the said Formula (1), and the structural unit represented by following formula (4).

（４）

(4)

In Formula (4), Ar ⁵ represents an aryl group or a monovalent aromatic heterocyclic group, and these groups may have a substituent. Ar ⁵ is preferably an aryl group.

The definitions and examples of the aryl group and monovalent aromatic heterocyclic group represented by Ar ⁵ are the same as the definitions and examples of the aryl group and monovalent aromatic heterocyclic group which are the above-described substituents.

Ar ⁵ is more preferably a phenyl group which may have a substituent, and even more preferably a phenyl group having a substituent.

The definitions and examples of the substituent that the group represented by Ar ⁵ may have are the same as the definitions and examples of the substituent that the group represented by Ar ¹ and Ar ² may have. It is.

In the formula (4), R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A or a group represented by —N (R ^A ) ₂ . The group may have a substituent. R ^A represents the same meaning as described above.

R ⁴ is preferably an alkyl group which may have a substituent, and more preferably an unsubstituted alkyl group.

The definitions and examples of the halogen atom and alkyl group represented by R ⁴ are the same as the definitions and examples of the halogen atom and alkyl group which are the aforementioned substituents.

The definitions and examples of the substituent that the group represented by R ⁴ may have are the same as the definitions and examples of the substituent that the group represented by Ar ¹ and Ar ² may have. It is.

  In the formula (4), each of the ring C1 and the ring C2 independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent. An aromatic hydrocarbon ring which may have

  The aromatic hydrocarbon ring which may have a substituent represented by ring C1 and ring C2 usually has 6 to 60 carbon atoms, not including the carbon atoms of the substituent, preferably It is 6-48, More preferably, it is 6-30.

  The aromatic hydrocarbon ring which may have a substituent represented by ring C1 and ring C2 is preferably a benzene ring or an aromatic hydrocarbon ring in which two or more benzene rings are condensed.

  The aromatic hydrocarbon ring which may have a substituent represented by ring C1 and ring C2 is more preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, further preferably a benzene ring or a naphthalene ring, A ring is particularly preferred.

  The aromatic heterocycle optionally having a substituent represented by ring C1 and ring C2 has 2 to 60 carbon atoms, preferably 3 to 60, not including the carbon atoms of the substituent. ~ 30.

  Examples of the aromatic heterocycle optionally having a substituent represented by ring C1 and ring C2 include pyridine ring, diazabenzene ring, triazine ring, quinoline ring, isoquinoline ring, pyrrole ring, indole ring, carbazole ring, furan A ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, phenoxazine ring or phenothiazine ring is preferred.

Definitions and examples of the substituent that the ring C1 and the ring C2 may have are the same as the definitions and examples of the substituent that the group represented by Ar ¹ and Ar ² may have. .

  Examples of the structural unit represented by the formula (4) include structural units represented by the following formulas (4A-1) to (4A-8), preferably the following formulas (4A-1) to (4A). -4), more preferably a structural unit represented by the following formula (4A-1), which may have a substituent.

  The structural unit represented by the formula (4) is preferably a structural unit represented by the following formula (4-1).

（４−１）

(4-1)

In formula (4-1), Ar ⁵ and R ⁴ represent the same meaning as described above.

In formula (4-1), R ⁵ and R ⁶ are each independently represented by a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , or —N (R ^A ) _2. A group, an aryl group or a monovalent aromatic heterocyclic group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic A heterocyclic group is preferred, an alkyl group, a group represented by -O-R ^A or an aryl group is more preferred, an alkyl group or an aryl group is more preferred, an alkyl group is particularly preferred, and these groups have a substituent. You may do it. When there are a plurality of R ⁵ and R ⁶ , they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded. R ^A represents the same meaning as described above.
The definitions and examples of the halogen atom, alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ⁵ and R ⁶ are the same as the definitions and examples of those groups which are the aforementioned substituents. .

  In formula (4-1), n5 and n6 each independently represent an integer of 0 or more and 3 or less, and preferably 0 or 1.

  Examples of the structural unit represented by the formula (4) include structural units represented by the formulas (Ar4-A14) to (Ar4-A27) and the following formulas (4A-A1) to (4A-A7). Preferably, it is a structural unit represented by the formulas (Ar4-A14) to (Ar4-A27).

［式中、＊は前記と同じ意味を表す。］

[Wherein, * represents the same meaning as described above. ]

  The polymer compound of the third embodiment may further include one or more structural units selected from the group consisting of structural units represented by the above formulas (2-1) to (2-4). Since the luminance lifetime of the light-emitting device obtained using the polymer compound of the third embodiment is more excellent, it is preferable to include one or more structural units represented by the formula (2-1). It is preferable that the polymer compound contains one or more structural units selected from the group consisting of structural units represented by formulas (2-2) and (2-4), Since the hole transport property of the polymer compound of the third embodiment is excellent, it is preferable to include one or more structural units represented by the formula (2-3).

  The polymer compound of the third embodiment may contain only one type of structural unit represented by formula (4), or may contain two or more types.

  In the polymer compound of the third embodiment, the ratio of the total number of moles of the structural unit represented by the formula (1) to the total number of moles of all the structural units is obtained using the polymer compound of the third embodiment. Since the luminance life of the light emitting device is more excellent, 0.01 to 99% is preferable, 0.1% to 40% is more preferable, 0.5% to 20% is further preferable, and 1% to 10% is more preferable. Particularly preferred.

  In the polymer compound of the third embodiment, the ratio of the total number of moles of the structural unit represented by formula (1) and the structural unit represented by formula (4) to the total number of moles of all structural units is 20%. It is preferably 100% or less and more preferably 50% or more and 100% or less.

  In the polymer compound of the third embodiment, the structural unit represented by the formula (1), the structural unit represented by the formula (2-1), and the formula (4) with respect to the total number of moles of all the structural units. The ratio of the total number of moles of structural units is preferably 50% or more and 100% or less, and more preferably 80 to 100%.

  In the polymer compound of the third embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-2) to the total number of moles of all the structural units is the charge transport of the polymer compound of the third embodiment. Since the property is excellent, 0.01 to 50% is preferable, 0.1 to 30% is more preferable, and 1 to 15% is more preferable.

  In the polymer compound of the third embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-3) to the total number of moles of all the structural units is the hole of the polymer compound of the third embodiment. Since transportability is excellent, 0.01 to 50% is preferable, 0.1 to 30% is more preferable, and 1 to 10% is more preferable.

  In the polymer compound of the third embodiment, the ratio of the total number of moles of the structural unit represented by the formula (2-4) to the total number of moles of all the structural units is the charge transport of the polymer compound of the third embodiment. From the standpoint of superiority, 0.1 to 50% is preferable, and 1 to 30% is more preferable.

  Examples of the polymer compound of the third embodiment include polymer compounds 1C-A1 to 1C-A12 shown in Table 6. Here, the “other structural unit” refers to Formula (1), Formula (4), Formula (2-1), Formula (2-2), Formula (2-3), and Formula (2-4). Means a structural unit other than the structural unit represented.

［表中、ｐ^３A、ｑ^３A、ｑ^３B、ｒ^３A、ｓ^３A、ｔ^３Aおよびｕ^３Aは、第３実施形態の高分子化合物における各構成単位のモル比率を表す。ｐ^３A＋ｑ^３A＋ｑ^３B＋ｒ^３A＋ｓ^３A＋ｔ^３A＋ｕ^３A＝100であり、かつ、70≦ｐ^３A＋ｑ^３A＋ｑ^３B＋ｒ^３A＋ｓ^３A＋ｔ^３A≦100である。］

[In the table, p ^3A , q ^3A , q ^3B , r ^3A , s ^3A , t ^3A, and u ^3A represent the molar ratio of each structural unit in the polymer compound of the third embodiment. p ^3A + q ^3A + q ^3B + r ^3A + s ^3A + t ^3A + u ^3A = 100 and 70 ≦ p ^3A + q ^3A + q ^3B + r ^3A + s ^3A + t ^3A ≦ 100. ]

  The polymer compound of this embodiment may have a crosslinkable group described later.

  If the polymerization active group remains as it is in the terminal group of the polymer compound of this embodiment, when the polymer compound of this embodiment is used for the production of a light emitting device, the light emission characteristics and the luminance life may be reduced. Therefore, a stable group is preferable. The terminal group is preferably a group that is conjugated to the main chain, and includes a group that is bonded to an aryl group or a monovalent aromatic heterocyclic group via a carbon-carbon bond.

  The polymer compound of the present embodiment is preferably a conjugated polymer compound.

  In this specification, the “conjugated polymer compound” is not only a polymer compound in which double bonds (or triple bonds) and single bonds are alternately linked, but also a polymer compound in which a conjugated system is substantially spread. Also included.

  Examples of the polymer compound in which double bonds (or triple bonds) and single bonds are alternately connected include polyarylenes having an arylene as a structural unit such as polyfluorene and polyphenylene; divalent aromatic heterocyclic groups such as polythiophene and polydibenzofuran. And polyarylene vinylenes such as polyphenylene vinylene, or copolymers in which these structural units are combined.

  The polymer compound having a substantially conjugated system is a polymer compound in which the double bond and the single bond are not alternately connected but the conjugation is substantially connected. Specifically, a polymer compound containing a structural unit containing a hetero atom such as triphenylamine is exemplified. The polymer compound is regarded as a conjugated polymer compound because the double bond and the single bond are not alternately linked but are substantially coupled to each other.

(Method for producing polymer compound)
The polymer compound of the present invention can be produced using a known polymerization method described in Chemical Review (Chem. Rev.), Vol. 109, pages 897-1091 (2009). It is more preferable to use condensation polymerization.

  As the condensation polymerization, polymerization is performed by a coupling reaction using a transition metal catalyst such as a Suzuki reaction, a Yamamoto reaction and a Buchwald reaction, and by a reaction not using a transition metal catalyst such as a Gilch reaction, a Wittig reaction and a Knoevenagel reaction. Examples of the method include a polymerization method by a coupling reaction using a transition metal catalyst.

  As a polymerization method by a coupling reaction, a Suzuki reaction, a Yamamoto reaction, a Stille reaction, a Buchwald reaction, a Hiyama reaction, a Ullmann reaction, a Heck reaction, a Negishi reaction, a Kumada reaction, a Glaser reaction, a Sonogashira reaction, and a Suzuki z reaction are preferably used. A method of polymerizing by reaction, Yamamoto reaction or Buchwald reaction is more preferable, and a method of polymerizing by Suzuki reaction or Yamamoto reaction is more preferable.

  As a method of polymerizing by a coupling reaction, for example, a compound represented by the following formula (M-1), a compound represented by the following formula (M-2), and the following formula (M-3) are represented. A compound, a compound represented by the following formula (M-4) and at least one compound selected from the group consisting of a compound represented by the following formula (M-5) are polymerized in the presence of a transition metal catalyst. A method is mentioned. In this specification, the compounds used for the production of the polymer compound of the present invention are sometimes collectively referred to as “raw material monomers”.

［式中、Ａｒ^１、Ａｒ^２、Ｒ^１〜Ｒ^３、Ｂ^１〜Ｂ^９、ｎ１〜ｎ４、Ｚ^１、Ｚ^２およびＲ^Ｃは、前記と同じ意味を表し、Ｚ^C1〜Ｚ^C10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示す。］

[Wherein, Ar ¹ , Ar ² , R ^{1 to} R ³ , B ^{1 to} B ⁹ , n1 to n4, Z ¹ , Z ² and R ^C represent the same meaning as described above, and Z ^{C1 to} Z ^C10 represent Each independently represents a group selected from the group consisting of Substituent Group A and Substituent Group B. ]

For example, when Z ^C1 and Z ^C2 are groups selected from Substituent Group A, Z ^C3 , Z ^C4 , Z ^C5 , Z ^C6 , Z ^C7 , Z ^C8 , Z ^C9 and Z ^C10 are selected from Substituent Group B. Select the group to be chosen.
For example, when Z ^C1 and Z ^C2 are a group selected from the substituent group B, Z ^C3 , Z ^C4 , Z ^C5 , Z ^C6 , Z ^C7 , Z ^C8 , Z ^C9 and Z ^C10 are the substituent group A. A group selected from is selected.

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

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

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

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

  Although it does not specifically limit as a transition metal catalyst, A palladium catalyst and a nickel catalyst are preferable.

  Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate, dichlorobis (triphenylphosphine) palladium (II), dichlorobis [tris- ( 2-methoxyphenylphosphine)] palladium and hexachloropalladium (IV) potassium complexes, and the like, and complexes in which a ligand is coordinated to the palladium complex.

  Examples of the nickel catalyst include tetrakis (triphenylphosphine) nickel (0), [bis (1,5-cyclooctadiene)] nickel (0), [1,3-bis (diphenylphosphino) propane] dichloronickel (II ), Nickel complexes such as bis (2,4-pentanedionato) nickel (II) and nickel (II) halide, and complexes in which a ligand is coordinated to the nickel complex.

  Although it will not specifically limit if it is a ligand which can be coordinated to a transition metal as a ligand, A phosphorus ligand and a nitrogen-type ligand are preferable.

Although it will not specifically limit if it is a ligand which has a phosphorus atom which can be coordinated to a transition metal as a phosphorus type ligand, A phosphine ligand is preferable and a tertiary phosphine ligand is more preferable.
Specifically, triphenylphosphine, tris (2-methylphenyl) phosphine, tris (2-methoxyphenyl) phosphine, di-tert-butylphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, 1,1 ′ -Bis (diphenylphosphino) ferrocene (DPPF), 1,3-bis (diphenylphosphino) propane (DPPP), 1,2-bis (diphenylphosphino) ethane (DPPE), 2,2 ″ -bis ( Diphenylphosphino) -1,1′-binaphthyl (BINAP), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (SPhos), 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′- Triisopropylbiphenyl (XPhos), 2- (dicyclohexylphosphine) C) -2'-methylbiphenyl (MePhos), 2- (dicyclohexylphosphino) -2 '-(dimethylamino) biphenyl (DavePhos), 2- (di-tert-butylphosphino) biphenyl (JohnPhos), and the like. It is done. The phosphine ligand may be used as a quaternary phosphonium salt.

  The nitrogen-based ligand is not particularly limited as long as it has a nitrogen atom that can coordinate to a transition metal, but pyridine, dimethylpyridine, bipyridine, terpyridine, quinoline, isoquinoline, acridine, phenanthroline, N, N-dimethyl-4-aminopyridine (DMAP), ligands containing nitrogen-containing aromatic heterocycles such as porphyrin and salts thereof, ammonia, aniline, diisopropylamine, 1,1,1,3,3,3-hexa Methyldisilazane (HMDS), triethylamine, triphenylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), N, N, N ′, N′-tetramethylethane-1, Amine-based ligands such as 2-diamine (TMEDA) and quaternary ammonium salts thereof, and acetonitrile, Nitrile ligands such as Nzonitoriru like.

  As the above-mentioned catalyst, a previously synthesized catalyst may be used as it is, or a catalyst prepared by preparing a transition metal catalyst and a ligand in a reaction system may be used. In addition, these catalysts may be used individually by 1 type, or may use 2 or more types together.

  The amount of the catalyst used may be an effective amount as a catalyst. For example, it is usually 0.0001 to 300 in terms of the number of moles of transition metal with respect to 100 mol% of the total raw material monomers in the synthesis of the polymer compound. It is mol%, Preferably it is 0.001-50 mol%.

  In the coupling reaction using a transition metal catalyst, when a base is used, examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, butyl lithium, potassium- Organic bases such as tert-butoxide, sodium-tert-butoxide, sodium methoxide, sodium ethoxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide Can be mentioned.

  The usage-amount of a base is 10-2000 mol% normally with respect to a total of 100 mol% of the charging raw material monomer at the time of the synthesis | combination of a high molecular compound.

  The coupling reaction using a transition metal catalyst may be performed in the absence of a solvent or in the presence of a solvent, but is usually preferably performed in the presence of an organic solvent. Here, as the organic solvent, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, hydrocarbon solvents such as hexane, cyclohexane and decalin, ether solvents such as tetrahydrofuran, 1,4-dioxane and dimethoxyethane, Alcohol solvents such as methanol, ethanol, 2-propanol, tert-butyl alcohol and phenol, halogen solvents such as methylene chloride and chloroform, nitrile solvents such as acetonitrile and benzonitrile, acetone, acetic acid, ethyl acetate, 1 And acyl solvents such as methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide. In general, it is desirable to use a solvent that has been subjected to deoxygenation treatment in order to suppress side reactions. An organic solvent may be used individually by 1 type, or may use 2 or more types together. Further, a mixed solvent of an organic solvent and water may be used.

  The amount of the organic solvent used is preferably such an amount that the total concentration of raw material monomers charged during the synthesis of the polymer compound is 0.01 to 90% by mass, and 1 to 50% by mass. More preferred.

  The reaction temperature of the coupling reaction using a transition metal catalyst is preferably −100 to 200 ° C., more preferably −80 to 150 ° C., and further preferably 0 to 120 ° C. Moreover, reaction time is 1 hour or more normally, Preferably it is 2-500 hours.

  The post-treatment of the polymerization can be performed by a known method, for example, a method of removing water-soluble impurities by liquid separation, or adding a reaction solution after the polymerization reaction to a lower alcohol such as methanol to precipitate the precipitated precipitate. The methods of filtration and drying can be performed alone or in combination.

  The polymer compound obtained by the post-treatment can be purified by an ordinary method such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, etc., if necessary. When the polymer compound of the present embodiment is used for the production of a light emitting device, the purity may affect the performance of the light emitting device such as the light emitting characteristics. Therefore, after polymerization, purification by reprecipitation purification, fractionation by chromatography, etc. It is preferable to process.

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

  The composition of the present invention preferably contains the polymer compound of the present invention and at least one material selected from the group consisting of a hole transport material and a light emitting material. It is more preferable to contain at least one kind of light emitting material.

[Hole injection material]
As a hole injection material, the material which comprises the below-mentioned hole injection layer is mentioned.

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

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

[Hole transport material]
Examples of the hole transport material include materials constituting a hole injection layer described later.

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

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

[Luminescent material]
Luminescent materials are classified into fluorescent materials and phosphorescent materials, and fluorescent materials are classified into low-molecular fluorescent materials and high-molecular fluorescent materials. The light emitting material may have a crosslinking group.

  As low-molecular fluorescent materials, known compounds can be applied, such as naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, and the like. Dyes, metal complexes having 8-hydroxyquinoline as a ligand, triarylamine compounds, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, carbazole and derivatives thereof, phenoxazine and derivatives thereof, phenothiazine and derivatives thereof Derivatives, quinacridone and derivatives thereof, and stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metasic Low molecular weight compounds of the fan system and acetylenic, and the like, preferably triarylamine compound.

  As the triarylamine compound, a compound represented by the following formula (1B-B) is preferable.

［式中、
ｎ^１ＢＢは、１以上の整数を表す。
Ａｒ^１ＢＢは、ｎ^１ＢＢ価の芳香族炭化水素基、ｎ^１ＢＢ価の芳香族複素環基、または、芳香族炭化水素環および芳香族複素環からなる群から選ばれる２つ以上の環が、直接、または、−Ｏ−、−Ｓ−、−Ｃ（Ｒ^３ＢＢ）_２−、−Ｃ（Ｒ^３ＢＢ）＝（Ｒ^３ＢＢ）−若しくは−Ｃ≡Ｃ−で表される基を介して結合した構造をｎ^１ＢＢ価の基を表し、これらの基は置換基を有していてもよい。Ｒ^３ＢＢは、水素原子、アルキル基、アリール基または１価の芳香族複素環基を表し、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^３ＢＢは同一でも異なっていてもよく、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。
Ｒ^１ＢＢおよびＲ^２ＢＢは、それぞれ独立に、水素原子、アルキル基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^１ＢＢおよびＲ^２ＢＢ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。］

[Where:
n ^1BB represents an integer of 1 or more.
Ar ^1BB is an n ^1BB valent aromatic hydrocarbon group, an n ^1BB valent aromatic heterocyclic group, or two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Or a structure bonded through a group represented by —O—, —S—, —C (R ^3BB ) ₂ —, —C (R ^3BB ) = (R ^3BB ) — or —C≡C—. n ^1BB valent group is represented, and these groups may have a substituent. R ^3BB represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. A plurality of R ^3BBs may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
R ^1BB and R ^2BB each independently represent a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When there are a plurality of R ^1BB and R ^2BB , they may be the same or different. ]

Examples of the n ^1BB valent aromatic hydrocarbon group represented by Ar ^1BB include benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, ^Examples include groups obtained by removing n ^1BB hydrogen atoms directly bonded to the carbon atoms constituting the ring from perylene or chrysene, and preferably benzene, naphthalene, anthracene, fluorene, spirobifluorene, phenanthrene, dihydrophenanthrene, pyrene Or a group formed by removing n ^1BB hydrogen atoms directly bonded to carbon atoms constituting the ring from chrysene, and more preferably a ring is formed from benzene, naphthalene, anthracene, fluorene, pyrene or chrysene. A group formed by removing n ^1BB hydrogen atoms directly bonded to the carbon atoms formed, and more preferably removing n ^1BB hydrogen atoms bonded directly to the carbon atoms constituting the ring from anthracene, pyrene or chrysene These groups may have a substituent.

^Examples of the n ^1BB valent aromatic heterocyclic group represented by Ar ^1BB include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, and dihydroacridine. , Furan, thiophene, azole, diazole, triazole, benzothiadiazole or oxadiazole, a group formed by removing n ^1BB hydrogen atoms directly bonded to a ring carbon atom or hetero atom, and these groups May have a substituent.

Two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring represented by Ar ^1BB are directly or —O—, —S—, —C (R ^3BB ) ₂ —, Examples of the aromatic hydrocarbon ring in the n ^1BB valent group bonded through a group represented by —C (R ^3BB ) = (R ^3BB ) — or —C≡C— include, for example, benzene, naphthalene, anthracene , Tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene, and chrysene. Examples of the aromatic heterocycle include pyridine, diazabenzene, triazine, azanaphthalene, Diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, Mention may be made of phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, azole, diazole, triazole, benzothiadiazole and oxadiazole.

Two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring represented by Ar ^1BB are directly or —O—, —S—, —C (R ^3BB ) ₂ —, The n ^1BB valent group bonded via a group represented by —C (R ^3BB ) = (R ^3BB ) — or —C≡C— is preferably a group in which two or more aromatic hydrocarbon rings are directly or , —C (R ^3BB ) ₂ — or —C (R ^3BB ) = (R ^3BB ) — is a n ^1BB valent group bonded through a group represented by the ^formula , and the group has a substituent. Also good.

The definitions and examples of the alkyl group, aryl group or monovalent aromatic heterocyclic group represented by R ^3BB are the same as the definitions and examples of those groups which are the aforementioned substituents.

In the group represented by —C (R ^3BB ) ₂ —, R ^3BB is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably an alkyl group or an aryl group, still more preferably an alkyl group. These groups may have a substituent.

In the group represented by —C (R ^3BB ) ^═ (R ^3BB ) —, R ^3BB is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably It is a hydrogen atom, and these groups may have a substituent.

Ar ^1BB is preferably an n ^1BB valent aromatic hydrocarbon group, and the group may have a substituent.

R ^1BB and R ^2BB are preferably an aryl group or a monovalent aromatic heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

The definitions and examples of the alkyl group, aryl group or monovalent aromatic heterocyclic group represented by R ^1BB and R ^2BB are the same as the definitions and examples of those groups represented by R ¹ and R ² described above. It is.

The definition and examples of the substituent that the group represented by Ar ^1BB , R ^1BB , R ^2BB, and R ^3BB may have are the definition of the substituent that the group represented by Ar ¹ and Ar ² may have. And similar to the examples.

n ^1BB is generally an integer of 10 or less, and is preferably 4 or less, more preferably 1 or 2, and still more preferably, because the synthesis of the compound represented by the formula (1B-B) is easy. 2.

  The compound represented by the formula (1B-B) is preferably a compound represented by the formulas (1B-B1) to (1B-B3), and more preferably the formula (1B-B1).

［式中、Ｒ^ｘ４、Ｒ^１ＢＢおよびＲ^２ＢＢは前記と同じ意味を表す。］

[Wherein, R ^x4 , R ^1BB and R ^2BB represent the same meaning as described above. ]

  As a compound represented by Formula (1B-B), the compound represented by the following is mentioned, for example. In the following, D represents the same meaning as described above.

  As the phosphorescent material, a known compound such as a triplet light-emitting complex can be used. For example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc SPE. Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., 304p, 123p, 123p. , (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Inorg. Chem., (2003), 42, 8609, Inorg. Chem., (2004), 43, 6513, Journal of the SID 11/1, 161 (2003), WO2002 / 066552, WO2004 / 020504, WO2004 / 020448, etc. Metal complexes.

  As the metal complex which is a phosphorescent material, the sum of the squares of the orbital coefficients of the outermost shell d orbits of the central metal with respect to the sum of the squares of all the atomic orbital coefficients in the highest occupied orbital (HOMO) of the metal complex is It is preferable from the viewpoint of obtaining a high emission quantum efficiency that a ratio of 1/3 or more is applied. As such a metal complex, for example, an orthometalated complex in which the central metal is a transition metal belonging to the fifth period or the sixth period can be used.

  As a central metal of a metal complex which is a phosphorescent material, a metal having an atomic number of 50 or more and having a spin-orbit interaction in the complex and capable of causing an intersystem crossing between a singlet state and a triplet state can be given. Preferably ruthenium (II), rhodium (III), palladium (II), osmium (II), iridium (III) or platinum (II), more preferably platinum (II) or iridium (III). More preferably, it is iridium (III).

  Examples of the ligand of the metal complex that is a phosphorescent material include a neutral or anion that forms at least one bond selected from the group consisting of a coordination bond and a covalent bond with the central metal atom. A monodentate ligand, or a neutral or anionic polydentate ligand. Examples of the bond between the central metal atom and the ligand include a metal-nitrogen bond, a metal-carbon bond, a metal-oxygen bond, a metal-phosphorus bond, a metal-sulfur bond, and a metal-halogen bond. The multidentate ligand usually means a bidentate to hexadentate ligand.

  As the phosphorescent material, an iridium complex or a platinum complex is preferable, an iridium complex is more preferable, and an iridium complex represented by the following formulas Ir-1 to Ir-3 is more preferable.

［式中、
Ｒ^D1、Ｒ^D2、Ｒ^D3、Ｒ^D4、Ｒ^D5、Ｒ^D6、Ｒ^D7、Ｒ^D8、Ｒ^D11、Ｒ¹²、Ｒ¹³、Ｒ^D14、Ｒ¹⁵、Ｒ¹⁶、Ｒ^D17、Ｒ^D18、Ｒ^D19およびＲ^D20は、それぞれ独立に、水素原子、アルキル基、−Ｏ−Ｒ^Ａで表される基、アリール基、１価の芳香族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^Ａは、前記と同じ意味を表す。
−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す。
ｎ_D1は、１、２または３を表し、ｎ_D2は、１または２を表す。］

[Where:
R ^D1 , R ^D2 , R ^D3 , R ^D4 , R ^D5 , R ^D6 , R ^D7 , R ^D8 , R ^D11 , R ¹² , R ¹³ , R ^D14 , R ¹⁵ , R ¹⁶ , R ^D17 , R ^D18 , R ^D19 And R ^D20 each independently represents a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group, a monovalent aromatic heterocyclic group or a halogen atom, and these groups each represent a substituent. You may have. R ^A represents the same meaning as described above.
-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.
n _D1 represents 1, 2 or 3, and n _D2 represents 1 or 2. ]

The definitions and examples of alkyl groups, aryl groups, monovalent aromatic heterocyclic groups and halogen atoms represented by R ^{D1 to} R ^D8 and R ^{D11 to} R ^D20 are the definitions of those groups which are the aforementioned substituents. Same as the example.

R ^{D1 to} R ^D8 and R ^{D11 to} R ^D20 are each preferably a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, a hydrogen atom, an alkyl group, An aryl group or a monovalent aromatic heterocyclic group is more preferable, and these groups may have a substituent.

In the iridium complex represented by the formula Ir-1, at least one of R ^{D1 to} R ^D8 is preferably a group represented by the following formula (Dend-A) or (Dend-B), more preferably It is a group represented by the formula (Dend-A).

In the iridium complex represented by the formula Ir-2, at least one of R ^{D11 to} R ^D20 is preferably a group represented by the following formula (Dend-A) or (Dend-B), more preferably It is a group represented by the formula (Dend-A).

In the iridium 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 following formula (Dend-A) or (Dend-B). And more preferably a group represented by the following formula (Dend-A).

［式中、
Ｇ^ＤＡ1は、窒素原子、３価の芳香族炭化水素基または３価の芳香族複素環基を表す。
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価の芳香族複素環基を表す。
Ｔ^DA2およびＴ^DA3は、それぞれ独立に、アリール基または１価の芳香族複素環基を表す。
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。
＊は結合手を表す。］

[Where:
G ^DA1 represents a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent aromatic heterocyclic group.
T ^DA2 and T ^DA3 each independently represent an aryl group or a monovalent aromatic heterocyclic group.
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
* Represents a bond. ]

［式中、
Ｇ^ＤＡ1、Ｇ^ＤＡ2およびＧ^ＤＡ3は、それぞれ独立に、窒素原子、３価の芳香族炭化水素基または３価の芳香族複素環基を表す。
Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3、Ａｒ^DA4、Ａｒ^DA5、Ａｒ^DA6およびＡｒ^DA7は、それぞれ独立に、アリーレン基または２価の芳香族複素環基を表す。
Ｔ^DA4、Ｔ^DA5、Ｔ^DA6およびＴ^DA7は、それぞれ独立に、アリール基または１価の芳香族複素環基を表す。
ｍ^ＤＡ１、ｍ^ＤＡ２、ｍ^ＤＡ3、ｍ^ＤＡ4、ｍ^ＤＡ5、ｍ^ＤＡ6およびｍ^ＤＡ7は、それぞれ独立に、０以上の整数を表す。
＊は結合手を表す。］

[Where:
G ^DA1 , G ^DA2 and G ^DA3 each independently represent a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent aromatic heterocyclic group.
T ^DA4 , T ^DA5 , T ^DA6 and T ^DA7 each independently represent an aryl group or a monovalent aromatic heterocyclic group.
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
* Represents a bond. ]

G ^DA1 is preferably a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, more preferably from benzene, pyridine, diazabenzene, triazine or carbazole to a carbon atom or a hetero atom constituting the ring. It is a group obtained by removing three hydrogen atoms from directly bonded hydrogen atoms, and more preferably groups represented by the formulas (GDA-11) to (GDA-15), and these groups are substituent groups. You may have.

［式中、
＊１、＊２および＊３は、各々、Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3との結合を表す。
Ｒ^DAは、水素原子、アルキル基、−Ｏ−Ｒ^Ａで表される基、アリール基または１価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^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。Ｒ^Ａは前記と同じ意味を表す。］

[Where:
* 1, * 2 and * 3 represent bonds with Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , respectively.
R ^DA represents a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When there are a plurality of ^RDA , they may be the same or different. R ^A represents the same meaning as described above. ]

Alkyl group, an aryl group represented by R ^DA, 1 monovalent definitions and examples of the aromatic heterocyclic group and a halogen atom, a definition and examples of those groups is a substituted group described above is the same.

R ^DA is preferably a hydrogen atom, an alkyl group or a group represented by O—R ^A , more preferably a hydrogen atom or an alkyl group, and these groups optionally have a substituent.

G ^DA2 is preferably a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, more preferably from benzene, pyridine, diazabenzene, triazine or carbazole to a carbon atom or a hetero atom constituting the ring. Of the directly bonded hydrogen atoms, it is a group obtained by removing three hydrogen atoms, and more preferably groups represented by the following formulas (GDA-21) to (GDA-25).

［式中、
＊２、＊４および＊５は、各々、Ａｒ^DA2、Ａｒ^DA4およびＡｒ^DA5との結合を表す。
Ｒ^DAは、前記と同じ意味を表す。］

[Where:
* 2, * 4, and * 5 represent bonds with Ar ^DA2 , Ar ^DA4, and Ar ^DA5 , respectively.
R ^DA represents the same meaning as described above. ]

G ^DA3 is preferably a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, more preferably from benzene, pyridine, diazabenzene, triazine or carbazole to a carbon atom or heteroatom constituting the ring. Of the directly bonded hydrogen atoms, the group is a group obtained by removing three hydrogen atoms, and more preferably groups represented by the following formulas (GDA-31) to (GDA-35).

［式中、
＊３、＊６および＊７は、各々、Ａｒ^DA3、Ａｒ^DA6およびＡｒ^DA7との結合を表す。
Ｒ^DAは、前記と同じ意味を表す。］

[Where:
* 3, * 6 and * 7 each represent a bond with Ar ^DA3 , Ar ^DA6 and Ar ^DA7 .
R ^DA represents the same meaning as described above. ]

The definitions and examples of the arylene group and divalent aromatic heterocyclic group represented by Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are represented by Ar ¹ and Ar ^2. The definitions and examples of these groups are the same.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably groups represented by the following formulas (ArDA-1) to (ArDA-3). When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different from each other, but are preferably the same.

［式中、Ｒ^DA、Ｒ^Ａ、Ｒ^Ｃおよび＊は前記と同じ意味を表す。］

[Wherein, R ^DA , R ^A , R ^C and * represent the same meaning as described above. ]

Ar ^DA2 and Ar ^DA3 are preferably the same.

Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably the same.

Definitions and examples of aryl groups and monovalent aromatic heterocyclic groups represented by T ^DA2 , T ^DA3 , T ^DA4 , T ^DA5 , T ^DA6 and T ^DA7 are those groups represented by R ¹ and R ^2. This is the same as the definitions and examples.

T ^DA2 , T ^DA3 , T ^DA4 , T ^DA5 , T ^DA6 and T ^DA7 are preferably groups represented by the following formulas (TD-1) to (TD-3).

［式中、Ｒ^DA、Ｒ^Ａおよび＊は前記と同じ意味を表す。］

[Wherein, R ^DA , R ^A and * represent the same meaning as described above. ]

T ^DA2 and T ^DA3 are preferably the same.

T ^DA4 , T ^DA5 , T ^DA6 and T ^DA7 are preferably the same.

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1. More preferably 0.

m ^DA2 and m ^DA3 are preferably the same integer.

m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are preferably the same integer.

  The group represented by the formula (Dend-A) is preferably a group represented by the following formula (Dend-A1), (Dend-A2) or (Dend-A3), and is represented by the formula (Dend-A1) or A group represented by (Dend-A3) is more preferred, and a group represented by formula (Dend-A1) is more preferred.

［式中、
Ｒ^p1、Ｒ^p2およびＲ^p3は、それぞれ独立に、アルキル基、−Ｏ−Ｒ^Ａで表される基、アリール基、１価の芳香族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^p1およびＲ^p2が複数存在する場合、それらはそれぞれ互いに同一でも異なっていてもよい。
Ｒ^Ａおよび＊は前記と同じ意味を表す。
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。ｎｐ１が複数存在する場合、それらは互いに同一でも異なっていてもよい。］

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a group represented by —O—R ^A , an aryl group, a monovalent aromatic heterocyclic group or a halogen atom, and these groups are substituted It may have a group. When a plurality of R ^p1 and R ^p2 are present, they may be the same as or different from each other.
R ^A and * represent the same meaning as described above.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. When a plurality of np1 are present, they may be the same as or different from each other. ]

The definitions and examples of the alkyl group, aryl group, monovalent aromatic heterocyclic group and halogen atom represented by R ^p1 , R ^p2 and R ^p3 are as follows: It is the same.

R ^p1 , R ^p2 and R ^p3 are preferably an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, more preferably an alkyl group, and these groups have a substituent. Also good.

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

  The group represented by the formula (Dend-B) is preferably a group represented by the following formula (Dend-B1), (Dend-B2) or (Dend-B3), and is represented by the formula (Dend-B1) or The group represented by (Dend-B3) is more preferred, and the group represented by the formula (Dend-B1) is more preferred.

［式中、
Ｒ^p1、Ｒ^p2、Ｒ^p3、ｎｐ１、ｎｐ２、ｎｐ３および＊は前記と同じ意味を表す。］

[Where:
R ^p1 , R ^p2 , R ^p3 , np1, np2, np3 and * have the same meaning as described above. ]

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

［式中、＊＊は、イリジウム原子と結合する部位を表す。］

[In the formula, ** represents a site bonded to an iridium atom. ]

  The iridium complex represented by the formula Ir-1 is preferably an iridium complex represented by the formulas Ir-11 to Ir-13. The iridium complex represented by the formula Ir-2 is preferably an iridium complex represented by the formula Ir-21. The iridium complex represented by the formula Ir-3 is preferably an iridium complex represented by the formula Ir-31 to Ir-33.

［式中、Ｄｅｎｄは、前記式（Ｄｅｎｄ−Ａ）または（Ｄｅｎｄ−Ｂ）で表される基を表す。ｎ_D3は、前記と同じ意味を表す。］

[Wherein Dend represents a group represented by the formula (Dend-A) or (Dend-B). n _D3 represents the same meaning as described above. ]

  Examples of the phosphorescent material include the metal complexes shown below.

  Examples of the polymeric fluorescent light-emitting material include at least one selected from the group consisting of structural units represented by the formulas (2-1), (2-2), (2-3), and (2-4). Examples thereof include a polymer compound containing more than one type of structural unit, and a polymer compound obtained by binding the above-described low molecular fluorescent material to the terminal, main chain or side chain of the polymer compound.

  In the composition of the present invention, the content of the light emitting material is usually 0.01 to 400 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is 0.5-75 weight part, More preferably, it is 1-15 weight.

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

[Electron transport materials and hole blocking materials]
Examples of the electron transport material and the hole blocking material include materials constituting an electron transport layer and a hole blocking layer described later.

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

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

[Electron injection material]
As an electron injection material, the material which comprises the below-mentioned electron injection layer is mentioned.

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

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

(Liquid composition)
The liquid composition of the present invention is a composition containing the polymer compound of the present invention and a solvent, and may be a composition containing the composition of the present invention and a solvent. The liquid composition of the present invention may be referred to as a solution, an ink, or an ink composition.

  The liquid composition of the present invention is useful for device preparation by coating such as a printing method typified by an ink jet printing method. Moreover, the liquid composition of this embodiment may contain a stabilizer, a thickener, a low molecular weight compound for decreasing the viscosity, a surfactant, an antioxidant, and the like as other components.

  The ratio of the polymer compound of the present invention in the liquid composition of the present embodiment is usually 0.1 to 99.9% by mass, preferably 0.1 to 10% by mass with respect to 100% by mass of the liquid composition. %, More preferably 0.2 to 7% by mass, still more preferably 0.5 to 2% by mass.

  The viscosity of the liquid composition of the present embodiment may be adjusted depending on the type of printing method. However, in the case where a solution such as an ink jet printing method passes through a discharge device, it prevents clogging or flight bending at the time of discharge. Therefore, at 25 ° C., the range is preferably 1 to 20 mPa · s.

  The high molecular weight compound used as the thickener is not particularly limited as long as it is soluble in the same solvent as the high molecular compound of the present invention and does not inhibit light emission or charge transport. Polymethyl methacrylate can be used. These high molecular weight compounds preferably have a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more.

  The viscosity can be increased by adding a small amount of a poor solvent for the solid content in the liquid composition of the present embodiment as a thickener. When adding a poor solvent as a thickener, the type and amount of the poor solvent may be selected so that the solid content in the liquid composition does not precipitate, and considering the storage stability, the amount of the poor solvent is 50 mass% or less is preferable with respect to 100 mass% of liquid compositions, and 30 mass% or less is more preferable.

  The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport. For example, a phenol-based antioxidant or a phosphorus-based antioxidant may be used. it can.

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

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

  The solvent in the liquid composition of the present embodiment is preferably one that can dissolve or uniformly disperse the solid content in the liquid composition. Examples of the solvent include chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ethers such as tetrahydrofuran, dioxane, anisole and 4-methylanisole. Solvents, toluene, xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene and other aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n -Aliphatic hydrocarbon solvents such as nonane and n-decane, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, benzophenone, acetophenone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, vinegar Ester solvents such as phenyl, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexane Polyhydric alcohols such as diols and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, etc. Examples include amide solvents. These solvents may be used alone or in combination of two or more.

  Among these, the solubility of the polymer compound, uniformity during film formation, and viscosity characteristics can be improved, so that aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketones Preferred solvents are toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, Tetralin, anisole, 4-methylanisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin, methyl benzoate, cyclohexano , 2-propyl cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone, acetophenone, benzophenone more preferable.

  These solvents are preferably used in combination of two or more types, more preferably used in combination of two or three types, and particularly preferably used in combination of two types, because film formability and device characteristics are improved. preferable.

When two types of solvents are contained in the liquid composition of the present embodiment, one of the solvents may be in a solid state at 25 ° C. Since the film formability is improved, the one kind of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and more preferably 200 ° C. or higher.
Moreover, since favorable viscosity is obtained, it is preferable that the polymer compound of the present invention is dissolved in both of the two solvents at a concentration of 1% by mass or more at 60 ° C., and one of the two solvents is used. In the solvent, the polymer compound of the present invention is preferably dissolved at a concentration of 1% by mass or more at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition of the present embodiment, the viscosity and film formability are excellently obtained. Therefore, the solvent having the highest boiling point is 40 to 90 mass of the total solvent in the liquid composition. %, More preferably 50 to 90% by mass, and still more preferably 65 to 85% by mass.

  The polymer compound of the present invention contained in the liquid composition of the present embodiment may be one type or two or more types. In addition, a compound having a high molecular weight other than the polymer compound of the present embodiment may be included as long as the device characteristics and the like are not impaired.

  The liquid composition of the present embodiment may contain water, metal, and a salt thereof in a range of 1 to 1000 ppm based on weight. Examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, and iridium. Moreover, the liquid composition of this embodiment may contain silicon, boron, phosphorus, fluorine, chlorine, bromine, etc. in the range of 1-1000 ppm on a weight basis.

(Organic thin film)
The organic thin film of the present invention contains the polymer compound or composition of the present invention, and is, for example, a light-emitting thin film, a conductive thin film, or an organic semiconductor thin film.

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

  The heating temperature for crosslinking the organic thin film is usually 25 to 300 ° C., and the luminous efficiency of the light-emitting device obtained using the organic thin film of the present invention is improved, preferably 50 to 250 ° C. More preferably, it is 150-200 degreeC.

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

  The organic thin film of the present invention is suitable as a light emitting layer or a hole transport layer in a light emitting device.

  As the method for producing the organic thin film of the present invention, a method by film formation from the liquid composition of the present invention is preferable. For example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method The ink jet printing method, the capillary coating method, and the nozzle coating method can be used, and the screen printing method, the flexographic printing method, the offset printing method, and the ink jet printing method are preferable.

  The thickness of the organic thin film of this embodiment is 1 nm-10 micrometers normally, Preferably it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm, More preferably, it is 10 nm-200 nm.

  When producing an organic thin film using the liquid composition of this embodiment, since the glass transition temperature of the high molecular compound of this embodiment contained in a liquid composition is high, it can heat at the temperature of 100 degreeC or more.

(Light emitting element)
<Structure of light emitting element>
The light emitting device of the present invention is a light emitting device comprising an anode, a cathode, and an organic layer provided between the anode and the cathode, and the organic layer is the organic thin film of the present invention.

  The light emitting element includes a light emitting layer between an anode and a cathode.

  In the light emitting device of the present invention, the organic layer is one or more layers selected from a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, a hole blocking layer and an electron injection layer, Or it is more preferable that it is a positive hole transport layer, and it is still more preferable that it is a light emitting layer.

  The light emitting device of the present invention preferably further comprises a hole transport layer provided between the anode and the light emitting layer.

  The light emitting device of the present invention preferably further comprises a hole injection layer provided between the anode and the hole transport layer.

  The light emitting device of the present invention may further include an arbitrary layer such as an insulating layer.

  The hole injection layer is a layer having a function of injecting holes from the anode. The hole transport layer is a layer having a function of transporting holes and a function of supplying holes to the light emitting layer and the like, and may be a layer having a function of blocking electrons injected from the cathode. The electron blocking layer mainly has a function of blocking electrons injected from the cathode and cathode, and further has a function of injecting holes from the anode as needed, or a function of transporting holes. Refers to the layer.

  On the other hand, an electron injection layer can be arbitrarily provided between the cathode and the light emitting layer, and further, the light emitting layer and the electron injection layer (when the electron injection layer is present) or the cathode (when the electron injection layer is not present). ) Between the electron transport layer and the hole blocking layer.

  Here, the anode is an electrode that supplies holes to a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, etc., and the cathode is an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer. An electrode for supplying electrons to a layer or the like.

  In the light emitting device of the present invention, at least one of the anode and the cathode is usually transparent or translucent, but the anode is preferably transparent or translucent.

  The light emitting layer is a function that allows holes to be injected from the layer adjacent to the anode side when an electric field is applied, and a function that allows electrons to be injected from the layer adjacent to the cathode side. A layer having a function of moving electric charges (electrons and holes) by the force of an electric field, a function of providing a bonding field of electrons and holes, and connecting this to light emission.

  The electron injection layer is a layer having a function of injecting electrons from the cathode. The electron transport layer is a layer having a function of transporting electrons and a function of supplying electrons to the light emitting layer and the like, and may be a layer having a function of blocking holes injected from the anode. The hole blocking layer mainly has a function of blocking holes injected from the anode, and further has a function of injecting electrons from the cathode as needed or a function of transporting electrons. Refers to the layer.

  The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer.

  The light-emitting device of this embodiment usually further includes a substrate as an optional component, and the cathode, anode, and light-emitting layer, and, if necessary, a hole transport layer, an electron transport layer, and a hole on the surface of the substrate. An injection layer, an electron injection layer, and other arbitrary constituent layers can be provided.

  In one embodiment of the light emitting device of this embodiment, an anode is usually provided on a substrate, a hole transport layer and a light emitting layer are laminated as an upper layer, and a cathode is further laminated as an upper layer. As a modification, a cathode is provided on a substrate, a light emitting layer and a hole transport layer are stacked as an upper layer, and an anode is further stacked as an upper layer.

  As another modification, a so-called bottom emission type in which light is taken from the substrate side, a so-called top emission type in which light is taken from the side opposite to the substrate, or a double-sided light emitting element may be used. As yet another modification, a layer having other functions such as an arbitrary protective film, buffer film, and reflective layer may be provided. The light emitting element may be further covered with a sealing film or a sealing substrate to form a light emitting device in which the light emitting element is blocked from outside air.

  Specific examples of the layer configuration of the light emitting device of the present invention include the layer configurations represented by the following (a-1) to (a-24), and (a-13) to (a-24). Is preferable, and the layer configuration represented by (a-19) to (a-24) is more preferable. In addition, “/” indicates that the layers before and after that are stacked adjacent to each other (for example, “hole transport layer / light emitting layer” means that the hole transport layer and the light emitting layer are stacked adjacent to each other). ).

(A-1) Anode / light emitting layer / cathode (a-2) Anode / light emitting layer / electron transport layer / cathode (a-3) Anode / light emitting layer / electron injection layer / cathode (a-4) Anode / light emitting layer / Hole blocking layer / electron injection layer / cathode (a-5) anode / light emitting layer / electron transport layer / electron injection layer / cathode (a-6) anode / light emitting layer / hole blocking layer / electron transport layer / electron Injection layer / cathode (a-7) anode / hole injection layer / light emitting layer / cathode (a-8) anode / hole injection layer / light emitting layer / electron injection layer / cathode (a-9) anode / hole injection Layer / light emitting layer / hole blocking layer / electron injection layer / cathode (a-10) anode / hole injection layer / light emitting layer / electron transport layer / cathode (a-11) anode / hole injection layer / light emitting layer / Electron transport layer / electron injection layer / cathode (a-12) anode / hole injection layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (a-13) anode / hole transport layer / Luminescent layer Cathode (a-14) anode / hole transport layer / light emitting layer / electron injection layer / cathode (a-15) anode / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode (a-16) ) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (a-17) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (a-18) anode / hole transport Layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (a-19) anode / hole injection layer / hole transport layer / light emitting layer / cathode (a-20) anode / hole injection Layer / hole transport layer / light emitting layer / electron injection layer / cathode (a-21) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode (a-22) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (a-23) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode a-24) anode / hole injection layer / hole transport layer / luminescent layer / hole blocking layer / electron transport layer / electron injection layer / cathode

  In the light-emitting element of the present invention, the order and number of layers to be stacked and the thickness of each layer can be appropriately used in consideration of the light-emitting efficiency and luminance life of the light-emitting element.

<Material constituting each layer of light emitting element>
Next, the material of each layer constituting the light emitting element of the present invention (that is, the material constituting the light emitting element of the present invention) and the forming method will be described in detail.

[substrate]
The substrate constituting the light-emitting element of the present invention may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed, such as a glass substrate, a plastic substrate, a polymer film, a metal film, a silicon substrate, A laminate of these is used. A commercially available substrate is available as the substrate, but it can also be manufactured by a known method.

  When the light-emitting element of the present invention constitutes a pixel of a display device, a pixel driving circuit may be provided on the substrate, or a planarization film may be provided on the driving circuit. . When a planarization film is provided, it is preferable that the centerline average roughness (Ra) of the planarization film satisfies Ra <10 nm. Ra can be measured with reference to JIS-B0651-JIS-B0656 and JIS-B0671-1 based on JIS-B0601-2001 of Japanese Industrial Standard JIS.

[anode]
In the anode constituting the light emitting device of the present invention, the hole injection property to the material used in the hole injection layer, the hole transport layer, the light emitting layer, etc. is improved, so that the work on the surface of the anode on the light emitting layer side is improved. The function is preferably 4.0 eV or more.
The material of the anode is not particularly limited as long as it is a material that plays a role of injecting holes into the layer on the light emitting layer side. Usually, the work function is 3.0 eV or more, and preferably 4.0 eV or more.

  As a material for the anode, a known material such as an electrically conductive compound such as a metal, an alloy, a metal oxide or a metal sulfide, a conductive polymer material, or a mixture thereof can be used. Specifically, indium oxide, zinc oxide, tin oxide, molybdenum oxide, indium tin oxide (ITO), indium zinc oxide (IZO), conductive metal oxides such as NESA, gold, platinum, silver, Examples include metals such as chromium and nickel, conductive inorganic materials such as copper iodide, conductive polymer materials such as polyaniline and derivatives thereof, polythiophene and derivatives thereof, and mixtures thereof. ITO, IZO, tin oxide Is preferred.

  The anode may have a single layer structure composed of one or more of these materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In the case of a multilayer structure, it is more preferable to use a material having a work function of 4.0 eV or more for the outermost surface layer on the light emitting layer side.

As a method for producing the anode, a known method can be used, and examples thereof include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
When a conductive polymer material is used as the anode material, the anode is preferably prepared by a film formation from a solution described later.

  The thickness of the anode can be selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 40 to 100 nm. . Moreover, since poor electrical connection such as a short circuit can be more effectively prevented, the center line average roughness (Ra) of the light emitting layer side surface of the anode preferably satisfies Ra <10 nm, and satisfies Ra <5 nm. Is more preferable.

  Further, after the anode is fabricated by the above method, electron acceptance such as UV ozone, silane coupling agent, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, etc. The surface treatment may be performed with a solution containing a functional compound. The electrical connection with the organic layer in contact with the anode is improved by the surface treatment.

  In the light emitting device of this embodiment, when the anode is used as the light reflecting electrode, the anode includes a light reflecting layer made of a highly light reflecting metal and a material having a work function of 4.0 eV or higher. A multilayer structure in which is combined is preferable.

As a configuration of such an anode,
(I) Ag-MoO ₃
(Ii) (Ag—Pd—Cu alloy) — (ITO and / or IZO)
(Iii) (Al—Nd alloy) — (ITO and / or IZO)
(Iv) (Mo—Cr alloy) — (ITO and / or IZO)
(V) (Ag—Pd—Cu alloy) — (ITO and / or IZO) —MoO ₃
Is exemplified. In order to obtain a sufficient light reflectance, the thickness of the highly light-reflective metal layer such as Al, Ag, Al alloy, Ag alloy, or Cr alloy is preferably 50 nm or more, and more preferably 80 nm or more. The thickness of the high work function material layer is usually in the range of 5 nm to 500 nm.

[Hole injection layer]
In the light emitting device of the present invention, the material of the hole injection layer is not particularly limited as long as it has a function of improving the hole injection efficiency from the anode to the layer on the light emitting layer side.

  The material of the hole injection layer may have a crosslinking group described later.

  The material of the hole injection layer is preferably a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer described later, specifically 4.5 eV or more. A compound having an ionization potential of 0 eV or less is more preferable.

  Examples of the material for the hole injection layer include phthalocyanine materials, metal oxide materials, amorphous carbon materials, low molecular organic materials, and high molecular organic materials. Metal oxide materials and high molecular organic materials are preferable, and high molecular organic materials are preferable. A material is more preferred.

  Examples of the phthalocyanine material in the hole injection layer include copper phthalocyanine and zinc phthalocyanine.

  Examples of the metal oxide material in the hole injection layer include vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, silicon oxide, and germanium oxide.

  Low molecular organic materials in the hole injection layer include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, starburst amines, phthalocyanine derivatives. Amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, triarylamine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, and organic silane derivatives.

  Examples of the high molecular organic material in the hole injection layer include a high molecular compound containing the compound exemplified in the low molecular organic material as a constituent unit, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, and an aromatic amine in the side chain or main chain. Polysiloxane derivatives having a compound group, polyaniline and derivatives thereof, aniline-based copolymers, polypyrrole and derivatives thereof, thiophene oligomers and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2, 5-thienylene vinylene) and its derivatives are exemplified.

  The material for the hole injection layer may be used alone or in combination of two or more. That is, the material of the hole injection layer may be a single component or a composition composed of a plurality of components.

  The material of the hole injection layer may further contain an acceptor.

  Acceptors include organic sulfonic acid compounds such as polystyrene sulfonic acid (PSS), alkylbenzene sulfonic acid, camphor sulfonic acid, tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8- Tetracyanoquinodimethane compounds such as tetracyanoquinodimethane, trifluoromethyl-tetracyanoquinodimethane, 2,3-dicyano-p-benzoquinone, 2,3-dicyano-5-nitro-1,4-naphthoquinone, Quinone compounds such as 3,3,5,5-tetrabromo-diphenoquinone, halogens such as chlorine, bromine and iodine, Lewis acids such as phosphorus pentafluoride, arsenic pentafluoride and antimony pentafluoride, ferric chloride, chloride Transition metal compounds such as ferric iron, titanium tetrachloride, palladium, chloride ions, bromide ions, iodide ions, perchloric acid ON, electrolyte anions such as hexafluoroantimonate ion, sulfonate anion, nitro compounds such as 2,4,7-trinitro-9H-fluoren-9-one (TNF), tris (4-bromophenyl) aminium hexachloro A salt of a triarylamine compound such as antimonate (TBAHA) and a Lewis acid.

  As a material of the hole injection layer doped with the acceptor, the following formula:

で表されるα−ＮＰＤに塩化第三鉄または五フッ化アンチモンをドープした組成物、亜鉛フタロシアニンに２，３，５，６−テトラフルオロ−７，７，８，８−テトラシアノキノジメタンをドープした組成物、ポリ（３，４−エチレンジオキシチオフェン）（ＰＥＤＯＴ）にＰＳＳをドープしたＰＥＤＯＴ／ＰＳＳ、ポリアニリンに樟脳スルホン酸をドープした組成物、下記式：

A composition in which ferric chloride or antimony pentafluoride is doped to α-NPD represented by the formula: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane in zinc phthalocyanine A composition doped with PSS, PEDOT / PSS doped with PSS in poly (3,4-ethylenedioxythiophene) (PEDOT), a composition doped with camphorsulfonic acid in polyaniline, the following formula:

で表されるＰＴＰＤＥＫにＴＢＡＨＡをドープした組成物、ポリピロールにパラジウムをドープした下記式：

A composition obtained by doping TPDHA into PTPDK represented by the following formula: Polypyrrole doped with palladium:

で表されるＰＨＰｙ−Ｐｄ等、が例示される。

And PHPy-Pd, etc. represented by

  The hole injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  A known method can be used as a method for forming the hole injection layer. In the case of inorganic compound materials, vacuum evaporation, sputtering, ion plating, etc. can be mentioned. In the case of low molecular organic materials, vacuum evaporation, transfer methods such as laser transfer and thermal transfer, and film formation from solution And a method (a mixed solution with a polymer binder may be used). In the case of a polymer organic material, a method of forming a film from a solution is exemplified.

  When forming a hole injection layer using a mixed solution in which a polymer compound binder and a low molecular weight organic material are dispersed, the polymer compound binder to be mixed is preferably one that does not extremely inhibit charge transport and is visible. Those that do not strongly absorb light are preferably used. . Specifically, poly (N-vinylcarbazole) or a derivative thereof, polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof And polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the material of the hole injection layer is preferable. Solvents include water, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and other chlorinated solvents, tetrahydrofuran, dioxane and other ether solvents, toluene, xylene, Aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene, anisole, 4-methylanisole, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n -Aliphatic hydrocarbon solvents such as nonane and n-decane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol Polybutyl alcohol such as monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, methanol, Examples include alcohol solvents such as ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary Coating methods such as coating methods, spray coating methods, nozzle coating methods, gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reversal printing methods, inkjet printing methods, etc. may be used. it can. From the viewpoint of easy pattern formation, a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, an ink jet printing method, or a nozzle coating method is preferable.

  The viscosity of the solution used for film formation from the solution may be adjusted according to the type of coating method. However, when the solution such as the ink jet printing method passes through a discharge device, clogging and flight bending at the time of discharge are prevented. In order to do so, it is preferably in the range of 1-20 mPa · s at 25 ° C.

  When an organic compound layer such as a hole transport layer and a light emitting layer is formed following the hole injection layer, particularly when both layers are formed by a coating method, the previously applied layer is applied later. A layered structure may not be formed by dissolving in a solvent contained in the layer solution. In this case, a method of making the lower layer insoluble in the solvent can be used. As a method for making it insoluble in a solvent, a method in which a polymer compound itself is crosslinked with a crosslinking group, a low molecular compound having a crosslinking group having an aromatic ring represented by aromatic bisazide is mixed as a crosslinking agent. Cross-linking method, a method of cross-linking by mixing a low molecular weight compound having a cross-linking group represented by an acrylate group as a cross-linking agent, and exposing the lower layer to ultraviolet light to an organic solvent used for the upper layer preparation For example, a method of insolubilizing, a method of heating the lower layer and insolubilizing in an organic solvent used for forming the upper layer, and the like. When heating the lower layer, the heating temperature is usually 100 to 300 ° C., and the time is usually 1 minute to 1 hour.

  In addition, as another method of laminating without dissolving the lower layer by a method other than crosslinking, there is a method of using solutions of different polarities in adjacent layers. For example, a water-soluble polymer compound is used for the lower layer and the upper layer is used. There is a method of using an oil-soluble polymer compound so that the lower layer does not dissolve even when applied.

  The optimum value of the thickness of the hole injection layer varies depending on the material to be used, but at least a thickness that does not generate pinholes is required. If the thickness is too large, the driving voltage of the device becomes high, which is not preferable. Therefore, the thickness of the hole injection layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 10 nm to 100 nm.

[Hole transport layer]
In the light emitting device of the present invention, a known material can be used as a material for the hole transport layer, and it is preferable to use a low molecular organic material or a polymer organic material in the hole injection layer, More preferably, it is used. Moreover, it is more preferable that these materials have a crosslinking group described later.
That is, in the light emitting device of the present invention, it is more preferable to use a crosslinkable compound for the hole transport layer.

  The material which comprises a positive hole transport layer may be used individually by 1 type, or may use 2 or more types together.

  In the present specification, the “crosslinkable compound” is a compound having one or more crosslinking groups. The crosslinkable compound may be either a high molecular organic material or a low molecular organic material. When the crosslinkable compound is a compound having two or more crosslinkable groups, the plural crosslinkable groups may be the same or different.

  The “crosslinking group” means a group capable of generating a new chemical bond by heat or light irradiation.

  The bridging group is not particularly limited, but is preferably a group containing an unsaturated double bond, cyclic ether, or benzocyclobutane, more preferably a group containing a structure selected from the following substituent group T. A group including a structure represented by the formula (15A-T1), (15A-T3) or (15A-T5) to (15A-T9) is more preferable, and the following formula (15A-T1) or (15A- A group including a structure represented by T6) is particularly preferable, and a group including a structure represented by Formula (15A-T6) is particularly preferable. In the following, * represents the same meaning as described above.

  <Substituent group T>

In the above, R ^XX2 represents a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group or a monovalent aromatic heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or It is a monovalent aromatic heterocyclic group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, and these groups may have a substituent. ^When there are a plurality of R ^{XX2 s} , they may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded. R ^A represents the same meaning as described above.
The definitions and examples of the alkyl group, aryl group, and monovalent aromatic heterocyclic group represented by R ^XX2 are the definitions of the alkyl group, aryl group, and monovalent aromatic heterocyclic group that are the above-described substituents. And similar to the examples.

  Examples of the crosslinking group include groups represented by the following formulas (15A-1) to (15A-34), and the formulas (15A-1), (15A-2), and (15A-6) to (15A-9). ), (15A-12) to (15A-14) or (15A-29) to (15A-32) are preferred, and the groups represented by formulas (15A-6) to (15A-9) or (15A-12) are preferred. ) To (15A-14) are more preferred, groups represented by the formulas (15A-6) to (15A-9) are more preferred, and these groups may have a substituent. In the following, * represents the same meaning as described above.

  The crosslinkable compound is preferably a compound having a hole transporting property, and more preferably a compound having a triarylamine skeleton. Specifically, Journal of Material Chemistry (J. Mater. Chem.), Vol. 18, pages 4485-4592 (2008), Chemistry of Materials (Chem. Mater.), Vol. 23, pages 658-681. (2011), International Publication No. 2011/049241, JP 2011-149013 A, JP 2011-149012 A, JP 2010-215886 A, JP 2010-53349 A, JP 2008-248241 A. The crosslinkable compound described in the publication is exemplified.

  As a compound having a triarylamine skeleton, a triarylamine compound, a polymer compound containing a structural unit represented by formula (2-3), or a polymer compound containing a structural unit represented by formula (1) Preferably, it is a polymer compound containing a structural unit represented by the formula (2-3) or a polymer compound containing a structural unit represented by the formula (1), more preferably a formula (2-3) The polymer compound containing the structural unit represented by this.

Examples of the triarylamine compound in the crosslinkable compound include compounds in which at least one of the groups represented by R ^1BB and R ^2BB in the formula (1B-B) is a crosslinking group, and the formula (1B-B) Among the groups represented by R ^1BB , R ^2BB, and Ar ^1BB , a compound in which at least one group has a crosslinking group as a substituent can be given.

  In the triarylamine compound in the crosslinkable compound, the number of crosslinking groups is usually 10 or less, preferably 5 or less, more preferably 3 or less, and still more preferably 1 or 2.

  As a triarylamine compound in a crosslinkable compound, the compound represented by the following is mentioned, for example, These groups may have a substituent.

［式中、Ｔ^１Ａは、架橋基を表す。Ｔ^１Ａが複数ある場合、それらは同一でも異なっていてもよい。Ｒ^Ｂは前記と同じ意味を表す。］

[Wherein, T ^1A represents a crosslinking group. When there are a plurality of T ^{1A s} , they may be the same or different. R ^B are as defined above. ]

  The polymer compound containing the structural unit represented by the formula (2-3) in the crosslinkable compound means a polymer compound containing the structural unit represented by the formula (2-3) and the structural unit having a crosslinking group. To do.

The “structural unit having a crosslinkable group” is not particularly limited as long as it is a structural unit having a crosslinkable group. Among the constituent units and ^{RC in} the constituent unit represented by the formula (2-3), at least one of the constituent units is a crosslinking group, preferably the formula (2-1) or (2-3). structural unit represented by structural units having a crosslinking group as the substituent in), or of R ^C in the structural unit represented by the formula (2-3), a structural unit in which at least one bridging group, More preferably, at least one of the structural units represented by the formula (2-1) has a crosslinking group as a substituent or R ^{C in} the structural unit represented by the formula (2-3) is a crosslinked group. A structural unit that is a group.

  In the structural unit having a crosslinking group, the number of crosslinking groups is usually 10 or less, preferably 5 or less, more preferably 3 or less, and still more preferably 1 or 2.

  The structural unit having a crosslinking group is preferably a structural unit represented by the following formulas (T1-A1) to (T1-A9), more preferably the following formulas (T1-A2), (T1-A4) to ( A structural unit represented by T1-A6) or (T1-A8), and more preferably a structural unit represented by the following formula (T1-A4) or (T1-A5).

［式中、Ｒ^Ｙ１、Ｔ^１Ａ、Ｒ^Ｂ、Ｒ^ＣおよびＢ^３〜Ｂ^５は前記と同じ意味を表す。］

[Wherein, R ^Y1 , T ^1A , R ^B , R ^C and B ^{3 to} B ⁵ represent the same meaning as described above. ]

  The high molecular compound containing the structural unit represented by Formula (2-3) in the crosslinkable compound further comprises structural units represented by Formulas (2-1), (2-2), and (2-4). It is preferable to include one or more structural units selected from the group, and it is more preferable to include one or more structural units represented by the formula (2-1).

  In the polymer compound containing the structural unit represented by Formula (2-3) in the crosslinkable compound, the structural unit having a crosslinking group may contain only one type, or may contain two or more types.

  In the polymer compound containing the structural unit represented by Formula (2-3) in the crosslinkable compound, the ratio of the total number of moles of the structural unit having a crosslinking group to the total number of moles of all the structural units is the polymer compound. Since the luminance life of the light emitting device obtained by using this is excellent, 0.01 to 50% is preferable, 0.1% to 30% is more preferable, 1% to 20% is further preferable, and 5% to 10% is particularly preferable. preferable.

  In the polymer compound containing the structural unit represented by the formula (2-3) in the crosslinkable compound, the structural unit represented by the formula (2-3) may contain only one type, or two or more types. May be.

  In the polymer compound containing the structural unit represented by the formula (2-3) in the crosslinkable compound, the ratio of the total number of moles of the structural unit represented by the formula (2-3) to the total number of moles of all the structural units. Is preferably 1 to 99%, more preferably 10 to 70%, and still more preferably 20 to 50%, from the viewpoint of hole transport properties of the polymer compound.

  In the polymer compound containing the structural unit represented by the formula (2-3) in the crosslinkable compound, the structural unit having the crosslinking group and the formulas (2-1) to (2-4) with respect to the total number of moles of all the structural units. ) Is preferably 50% to 100%, more preferably 80% to 100%, since the luminance life of a light emitting device obtained using the polymer compound is excellent.

  The polymer compound containing the structural unit represented by the formula (1) in the crosslinkable compound means a polymer compound containing the structural unit represented by the formula (1) and a structural unit having a crosslinking group.

  Definitions and examples of the structural unit having a crosslinking group are the same as the definitions and examples of the “polymer compound including the structural unit represented by the formula (2-3) in the crosslinkable compound” described above.

  The polymer compound containing the structural unit represented by Formula (1) in the crosslinkable compound is further one or more selected from the group consisting of structural units represented by Formulas (2-1) to (2-4). It is preferable that the structural unit is included, and it is more preferable that at least one structural unit represented by the formula (2-1) is included.

  In the polymer compound containing the structural unit represented by the formula (1) in the crosslinkable compound, the structural unit having a crosslinking group may include only one type, or may include two or more types.

  In the polymer compound containing the structural unit represented by the formula (1) in the crosslinkable compound, the ratio of the total number of moles of the structural unit having a crosslinking group to the total number of moles of all the structural units is the polymer compound of the present invention. Since the luminance life of the light-emitting element obtained by using is more excellent, 0.01 to 50% is preferable, 0.1% to 30% is more preferable, 1% to 20% is further preferable, and 5% to 10% is more preferable. Particularly preferred.

  In the polymer compound containing the structural unit represented by the formula (1) in the crosslinkable compound, the structural unit represented by the formula (1) may contain only one type or two or more types.

  In the polymer compound containing the structural unit represented by Formula (1) in the crosslinkable compound, the ratio of the total number of moles of the structural unit represented by Formula (1) to the total number of moles of all structural units is the present invention. Since the high molecular compound has excellent hole transport properties, it is preferably 1 to 99%, more preferably 10 to 70%, and still more preferably 20 to 50%.

  In the polymer compound containing the structural unit represented by Formula (1) in the crosslinkable compound, the structural unit represented by Formula (1), the structural unit having a crosslinking group, and the formula (with respect to the total number of moles of all structural units) The ratio of the total number of moles of (2-1) to (2-4) is preferably 50 to 100% and more preferably 80 to 100% because the luminance life of the light-emitting device obtained using the polymer compound of the present invention is more excellent. % Is more preferable.

  Although the optimum value of the thickness of the hole transport layer varies depending on the material used, it is usually 1 nm to 1 μm, preferably 2 to 500 nm, more preferably 5 to 200 nm.

  As a method for forming the hole transport layer, a known method can be used. In the case of a low molecular organic material, a vacuum deposition method, a transfer method such as laser transfer or thermal transfer, a method by film formation from a solution (a mixed solution with a polymer binder may be used), and the like. In the case of a polymer organic material, a method of forming a film from a solution is exemplified.

  When forming a hole injection layer using a mixed solution in which a polymer binder and a low molecular weight organic material are dispersed, the polymer binder to be mixed is preferably one that does not extremely inhibit charge transport, Those that do not absorb strongly are preferably used. . Specifically, poly (N-vinylcarbazole) or a derivative thereof, polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof And polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the material of the hole transport layer is preferable. Solvents include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, mesitylene, Aromatic hydrocarbon solvents such as ethylbenzene, n-hexylbenzene, cyclohexylbenzene, anisole, 4-methylanisole, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane Aliphatic hydrocarbon solvents such as n-decane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol Polyhydric alcohols such as butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, methanol, ethanol And alcohol solvents such as propanol, isopropanol and cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary Coating methods such as coating methods, spray coating methods, nozzle coating methods, gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reversal printing methods, inkjet printing methods, etc. may be used. it can. From the viewpoint of easy pattern formation, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, a printing method such as an inkjet printing method, and a nozzle coating method are preferable.

  The viscosity of the solution used for film formation from the solution may be adjusted according to the type of coating method. However, when the solution such as the ink jet printing method passes through a discharge device, clogging and flight bending at the time of discharge are prevented. In order to do so, it is preferably in the range of 1-20 mPa · s at 25 ° C.

When the hole transport layer is provided adjacent to the light-emitting layer, particularly when both layers are formed by a coating method, the two layers of materials may be mixed to adversely affect the characteristics of the device. is there. In the case of forming the light emitting layer by the coating method after forming the hole transporting layer, as a method for reducing the mixing of the two layers of materials, the hole transporting layer is formed by the coating method, and this hole transporting is performed. The method of forming a light emitting layer after heating a layer and insolubilizing with respect to the organic solvent used for light emitting layer preparation is mentioned.
The heating temperature is usually 150 to 300 ° C. The heating time is usually 1 minute to 1 hour.
In this case, in order to remove components that have not been insolubilized by heating, the hole transport layer may be rinsed with a solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When the solvent is insolubilized sufficiently by heating, rinsing can be omitted. In order to sufficiently insolubilize the solvent by heating, it is preferable to use a polymer organic material containing a polymerizable group in the molecule as the polymer organic material used for the hole transport layer. Furthermore, the number of moles of the polymerizable group is preferably 5% or more based on the number of moles of the structural units in the molecule.
In addition, the molar ratio is calculated using the structure of the polymer organic material estimated from the charged ratio of the raw material monomer during the synthesis of the polymer organic material and the number average molecular weight of the polymer organic material in terms of polystyrene. can do.

[Light emitting layer]
In the light emitting device of the present invention, the material of the light emitting layer is not particularly limited as long as it is a material having a light emitting property (light emitting material), but the above light emitting material, the polymer compound of the present invention or the composition of the present invention is used. Preferably, the polymer compound of the present invention or the composition of the present invention is more preferably included. That is, the organic thin film of the present invention is preferably used as a light emitting layer.

  The material which comprises a light emitting layer may be used individually by 1 type, or may use 2 or more types together.

  The light emitting layer is formed by the method described in the explanation of the organic thin film of the present invention.

  Although the optimum value of the thickness of the light emitting layer varies depending on the material used, it is usually 1 nm to 10 μm, preferably 5 nm to 1 μm, more preferably 10 nm to 500 nm, still more preferably 10 nm to 200 nm.

[Electron transport layer and hole blocking layer]
In the light emitting device of the present embodiment, as the material constituting the electron transport layer and the hole blocking layer, known materials can be used, and triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorene derivatives, benzoquinone or its Derivatives, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives , 8-quinolinol derivative metal complexes, metal phthalocyanines, metal complexes represented by metal complexes having benzoxazole or benzothiazole as a ligand, organosilane derivatives, silole derivatives, and polymers containing these as structural units Organic materials are mentioned.

  Among these, triazole derivative, oxadiazole derivative, benzoquinone or derivative thereof, anthraquinone or derivative thereof, metal complex of 8-hydroxyquinoline or derivative thereof, polyquinoline or derivative thereof, polyquinoxaline or derivative thereof, polyfluorene or derivative thereof Preferably, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  The material of the electron transport layer and the hole blocking layer may have the above-described crosslinking group.

  The materials for the electron transport layer and the hole blocking layer may be used alone or in combination of two or more.

When the material constituting the electron transport layer and the hole blocking layer is a polymer organic material, the weight average molecular weight of the material in terms of standard polystyrene is preferably 1.0 × 10 ^{4 to} 1.0 × 10 ^6. .

  The material constituting the electron transport layer and the hole blocking layer may be a single component or a composition composed of a plurality of components. In addition, the electron transport layer and the hole blocking layer may have a single layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

  Examples of the method for forming the electron transport layer and the hole blocking layer include the same methods as those for forming the hole injection layer. Examples of the film formation method from the solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the method include a coating method and a printing method. When a sublimable compound material is used, a vacuum deposition method, a transfer method, and the like can be given.

  Examples of the solvent used for film formation from a solution include the solvents listed in the method for forming a hole injection layer.

  When an organic layer such as an electron injection layer is formed by a coating method following the electron transport layer and the hole blocking layer, if the lower layer dissolves in the solvent contained in the solution of the layer to be applied later, The lower layer can be made insoluble in the solvent by the same method as exemplified in the method for forming the injection layer.

  The thickness of the electron transport layer varies depending on the material used, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 100 nm.

[Electron injection layer]
In the light emitting device of this embodiment, the material of the electron injection layer is not particularly limited as long as it has a function of improving the electron injection efficiency from the cathode to the layer on the light emitting layer side.

  As a material constituting the electron injection layer, a known material can be used, and an optimum material is appropriately selected according to the type of the light emitting layer, and among the alkali metal, alkaline earth metal, alkali metal and alkaline earth metal. An alloy including one or more kinds, an oxide of an alkali metal or an alkaline earth metal, a halide, a carbonate, or a mixture of these substances can be given. Examples of alkali metals, alkali metal oxides, halides and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, Examples thereof include rubidium oxide, rubidium fluoride, cesium oxide, cesium fluoride, and lithium carbonate. Examples of alkaline earth metals, alkaline earth metal oxides, halides and carbonates include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, Examples thereof include barium fluoride, strontium oxide, strontium fluoride, and magnesium carbonate. The electron injection layer may be composed of a laminate in which two or more layers are laminated, and examples thereof include LiF / Ca. The electron injection layer is formed by vapor deposition, sputtering, printing, or the like.

  The material for the electron injection layer may be used alone or in combination of two or more.

  The thickness of the electron injection layer is preferably about 1 nm to 1 μm.

[Insulation layer]
The insulating layer having a thickness of 5 nm or less that the light-emitting element of this embodiment can optionally have functions such as improving adhesion with the electrode, improving charge injection from the electrode, and preventing mixing with the adjacent layer. Examples of the material for the insulating layer include metal fluorides, metal oxides, organic insulating materials (polymethyl methacrylate, etc.), and the like. Examples of the light emitting element provided with an insulating layer having a thickness of 5 nm or less include an element having an insulating layer having a thickness of 5 nm or less adjacent to the cathode, and an element having an insulating layer having a thickness of 5 nm or less adjacent to the anode. It is done.

[cathode]
In the light emitting device of the present invention, the material of the cathode is not particularly limited as long as it is a material that plays a role of electron injection into the layer on the light emitting layer side, but usually has a work function of 5.0 eV or less, preferably 4 .5 eV or less.

  As the material of the cathode, a known material can be used. Specifically, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And an alloy of two or more of them, or an alloy of one or more of them with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite Or a graphite intercalation compound etc. are illustrated. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like. The

  The cathode may have a laminated structure of two or more layers. Examples of the laminated structure include a laminated structure of the metal, metal oxide, fluoride, or an alloy thereof and a metal such as aluminum, silver, or chromium.

  The thickness of the cathode may be adjusted in consideration of electric conductivity and durability, and is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 to 500 nm.

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

[Protective layer]
As the protective layer, for example, a high molecular weight compound, metal oxide, metal fluoride, or metal boride can be used. As the protective cover, for example, a metal plate, a glass plate, or a plastic plate having a surface subjected to low water permeability treatment can be used. For example, a method in which the protective cover is bonded to the substrate with a thermosetting resin or a photocurable resin and sealed is preferably used. If the space is maintained using a spacer, it is easy to prevent damage to the light emitting element. If an inert gas such as nitrogen gas or argon gas is sealed in this space, the oxidation of the cathode can be prevented. Furthermore, by installing a desiccant such as barium oxide in this space, it becomes easy to suppress the moisture absorbed in the manufacturing process or the minute amount of moisture entering through the cured resin from damaging the device. .

(Manufacturing method of light emitting element)
The manufacturing method of the light emitting element of the present invention is not particularly limited, and can be manufactured by sequentially laminating each layer on a substrate. Specifically, an anode is provided on a substrate, a layer such as a hole injection layer, an electronic element layer, or a hole transport layer is provided thereon, a light emitting layer is provided thereon, and an electron transport layer, a positive electrode is provided thereon. It can be produced by providing layers such as a hole blocking layer and an electron injection layer as needed, and further laminating a cathode thereon.

(Use of light-emitting elements)
In order to obtain planar light emission using the light emitting element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain patterned light emission, a method of installing a mask having a patterned window on the surface of a planar light emitting element, a layer that is desired to be a non-light emitting portion is formed extremely thick and substantially non-light emitting And an anode or cathode, or a method of forming both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display device capable of displaying numbers, letters, simple symbols, and the like can be obtained. Furthermore, 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 multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter.
The dot matrix display device can be driven passively or may be driven actively in combination with a TFT or the like. These display devices can be used in computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like. The planar light-emitting element is thin and self-luminous, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

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

  The polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound were determined under the following measurement conditions using gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.05% by mass, and 10 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC and was allowed to flow at a flow rate of 2.0 mL / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

  The measurement of NMR was performed by dissolving 5 to 20 mg of a measurement sample in about 0.5 mL of an organic solvent, and using NMR (trade name: INOVA300, manufactured by Varian, Inc.).

  The measurement of LC-MS was performed by the following method. A measurement sample is dissolved in an appropriate organic solvent (chloroform, tetrahydrofuran, ethyl acetate, toluene, etc.) so as to have a concentration of 1 to 10 mg / mL, and LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD) is used. Measured and analyzed. For the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran or a mixture thereof was used, and acetic acid was added as necessary. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 4.6 mm, length: 250 mm, particle diameter: 3 μm) was used.

<Synthesis Example 1: Synthesis of Compound 2>

  After making the inside of the reaction vessel a nitrogen gas atmosphere, 1,5-bis (trifluoromethanesulfonate) naphthyl (compound 1,25.0 g), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium ( II) Dichloromethylene adduct (0.24 g) and tert-butyl methyl ether (410 ml) were added, and 2-ethylhexylmagnesium bromide (173 ml of 1 mol / L diethyl ether solution) was added dropwise at 10 ° C. or lower. Stir for hours. After completion of the reaction, the reaction solution obtained above was poured into a mixed solution consisting of water (500 ml) and 2N hydrochloric acid (100 ml), extracted with ethyl acetate, washed with aqueous sodium chloride solution, and the resulting organic layer Was dried over magnesium sulfate and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain 21.3 g of Compound 2 as a pale yellow oil.

LC-MS (ESI, positive): [M ⁺ ] 353
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.75-1.00 (12H, m), 1.10-1.50 (16H, m), 1.69-1.85 ( 2H, m), 2.90-3.05 (4H, m), 7.24-7.38 (3H, m), 7.35-7.44 (3H, m), 7.90-7. 95 (3H, m).

<Synthesis Example 2: Synthesis of Compound 3>

The reaction vessel was filled with a nitrogen gas atmosphere, and then compound 3 (21.3 g), bis (pinacolato) diboron (4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2 '-Bi-1,3,2-dioxaborolane) (46.0 g), bis (1,5-cyclooctadiene) di-μ-methoxydiiridium (I) (0.24 g) (manufactured by Aldrich), 4 , 4′-Di-tert-butyl-2,2′-dipyridyl (0.19 g) and dioxane (140 ml) were added, and the mixture was stirred at 100 ° C. for 3 hours. After cooling, dioxane was distilled off under reduced pressure, methanol (200 ml) was added to the resulting residue, and the precipitated solid was collected by filtration and dried.
The obtained solid was dissolved in toluene (250 ml), activated clay (20 g) was added, and the mixture was stirred at 60 ° C. for 30 minutes, followed by hot filtration with a filter pre-coated with silica gel. Concentrated. Methanol (250 ml) was added to the obtained concentrated residue, and the precipitated solid was collected by filtration and dried to obtain 28.0 g of Compound 4 as a white powder solid.

LC-MS (ESI, positive): [M ⁺ ] 605
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 0.85-0.95 (12H, m), 1.24-1.50 (16H, m), 1.66-1.85 (2H) M), 2.90-3.18 (4H, m), 7.60 (2H, s), 8.47 (2H, s).

<Synthesis Example 3: Synthesis of Compound 4>

  After the reaction vessel was filled with a nitrogen gas atmosphere, Compound 3 (28.0 g), dioxane (420 ml), N, N-dimethylformamide (hereinafter sometimes referred to as “DMF”) (420 ml) and water (210 ml) Then, copper (II) bromide (62.7 g) was further added, and the mixture was stirred at 95 ° C. for 2 hours. Thereafter, copper (II) bromide (31.4 g) was further added at the same temperature, and after stirring for 1.5 hours, copper (II) bromide (31.4 g) was further added at the same temperature. Stir for hours. After cooling, hexane (300 ml) was added to the resulting reaction solution and stirred, and then the resulting organic layer was separated and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) and concentrated to obtain a solid (21.0 g). The obtained solid was dissolved in toluene (150 ml), activated carbon (5 g) was added, and the mixture was stirred at 60 ° C. for 30 minutes, and then filtered hot with a filter pre-coated with Celite, and the obtained filtrate was concentrated under reduced pressure. . The resulting concentrated residue was recrystallized with a mixed solution of toluene and methanol to obtain 13.2 g of Compound 4 as a white solid.

MS (ESI, positive) [M ⁺ ] 511
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.80-0.98 (12H, m), 1.20-1.44 (16H, m), 1.64-1.80 ( 2H, m), 2.77-2.95 (4H, m), 7.37 (2H, s), 8.00 (2H, s).

<Synthesis Example 4: Synthesis of Compound 5>

  The reaction vessel was filled with a nitrogen gas atmosphere, then compound 4 (5.0 g), N-phenyl-N- (4-tert-butyl) -2,6-dimethylphenylamine (7.4 g), tris (dibenzylidene) Acetone) dipalladium (0) (0.45 g), tri-tert-butylphosphonium tetrafluoroborate (0.57 g) and sodium tert-butoxide (3.8 g) were added, and toluene (64 g) and tert-butanol ( 1.9 g) was added. Then, it heated up to 55 degreeC and stirred, keeping heat for 3 hours. The obtained reaction solution was cooled to room temperature, water was added, and the mixture was filtered through a filter pre-coated with Celite, the resulting residue was washed with toluene, and the aqueous layer was separated from the obtained filtrate. The layer was washed with water. The obtained organic layer was concentrated to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: a mixture consisting of hexane and toluene), the resulting solution was concentrated, recrystallized with a mixture consisting of ethanol and hexane, and pale yellow 7.0 g of compound 5 was obtained as a solid.

<Synthesis Example 5: Synthesis of Compound 6>

  After making the inside of the reaction vessel a nitrogen gas atmosphere, Compound 5 (5.8 g), N, N-dimethylformamide (24 mL), chlorobenzene (360 mL) and chlorobenzene (74 mL) were added and cooled to 20 ° C. Thereafter, the entire flask was shielded from light, and N-bromosuccinimide (NBS) (2.4 g) was added in multiple portions at 20 ° C. After stirring for 2 hours while keeping the temperature at the same temperature, water was added, and then a 5 mass% aqueous sodium sulfite solution (0.4 g) and water (22 g) were added. After raising the temperature to room temperature, toluene was added to the resulting solution, and the aqueous layer was separated. The obtained organic layer was washed twice with water and concentrated to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: a mixture consisting of hexane and toluene), the resulting solution was concentrated, recrystallized with a mixture consisting of toluene and isopropanol, and pale yellow 5.1 g of compound 6 was obtained as a solid.

LC-MS (APPI, positive): [M + H ⁺ ] 1010

<Synthesis Example 6: Synthesis of Compound 8>

  After making the inside of the reaction vessel an argon gas atmosphere, 1-bromo-3,5-di-n-hexylbenzene (58.4 g) and tetrahydrofuran were added to prepare a homogeneous solution and cooled to -75 ° C. To the resulting solution was added 2.5M n-butyllithium / hexane solution (1 molar equivalent to 1-bromo-3,5-di-n-hexylbenzene) (71.2 ml) at -75 ° C. The solution was added dropwise over 5 hours, and the resulting solution was further stirred at -70 ° C for 1.5 hours. Thereafter, a solution consisting of 2,7-dibromofluorenone (compound 7, 55.2 g) and tetrahydrofuran was added dropwise at -75 ° C over 1 hour, and the resulting reaction solution was allowed to warm to room temperature and stirred for 4 hours. did. Thereafter, the resulting solution was cooled to 0 ° C., slowly added with acetone and 2 mol% aqueous hydrochloric acid and stirred, then warmed to room temperature and allowed to stand at room temperature. Then, the obtained reaction mixture was filtered, the obtained filtrate was concentrated, hexane and water were added and stirred, and liquid separation was performed. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated to obtain 30.2 g of Compound 8.

<Synthesis Example 7: Synthesis of Compound 9>

  The inside of the reaction vessel was under an argon gas stream, and compound 8 (27.7 g) and trifluoroacetic acid (36 ml) were added. To the resulting solution, a mixed solution of trimethylsilane (8.4 ml) and hexane (25 ml) was added dropwise over 30 minutes and stirred overnight at room temperature. Thereafter, the obtained reaction solution was cooled to 10 ° C., hexane and distilled water were added, and the mixture was stirred for 1 hour, followed by liquid separation. Then, water was added and stirred, and liquid separation was performed again. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated. Thereafter, the mixture was purified by silica gel column chromatography using a mixed solvent consisting of hexane and dichloromethane as a developing solvent, and concentrated to remove the solvent. Thereafter, the obtained residue was washed with methanol to obtain 12.1 g of the intended compound 9.

<Synthesis Example 8: Synthesis of Compound 10>

  The reaction vessel was placed under an argon gas stream, and compound 9 (12.0 g), dimethyl sulfoxide (60 ml), water (2 ml) and potassium hydroxide (4.85 g) were added. Methyl iodide (4.1 ml) was added dropwise to the resulting solution and stirred overnight at room temperature. Thereafter, hexane and distilled water were added to the obtained reaction solution at room temperature, and the mixture was stirred for 1 hour, followed by liquid separation. Then, water was added to the obtained oil layer and stirred, and liquid separation was performed again. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated. Then, the obtained residue was recrystallized with a mixed solution composed of methanol and butyl acetate to obtain 4.3 g of the intended compound 10.

<Synthesis Example 9: Synthesis of Compound 11>

The reaction vessel was filled with an argon gas atmosphere, compound 10 (4.2 g), bis (pinacolato) diboron (4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′- Bi-1,3,2-dioxaborolane (4.0 g), 1,4-dioxane (45 ml), potassium acetate (4.2 g), 1,1′-bis (diphenylphosphino) ferrocene (dppf) (59 mg) ) And 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (PdCl ₂ (dppf) CH ₂ Cl ₂ , 88 mg) were added and stirred at 100 ° C. for 20 hours. Then, after cooling the obtained reaction liquid to room temperature, it filtered with the filter which spread celite and the silica gel, and the obtained filtrate was concentrated and the dioxane was removed. Thereafter, activated carbon was added to the solution prepared by adding hexane, and the mixture was stirred at a temperature at which hexane was refluxed for 1 hour. The obtained reaction solution was cooled to room temperature, filtered through a filter packed with celite, and the obtained filtrate was concentrated to remove hexane. Then, the obtained residue was recrystallized with a mixed solution composed of toluene and methanol to obtain 3.9 g of the intended compound 11.

<Synthesis Example 10: Synthesis of Compound 12>

  The reaction vessel was filled with an argon gas atmosphere, and 3-n-hexyl bromobenzene (111.1 g) and tetrahydrofuran were added to prepare a homogeneous solution and cooled to -75 ° C. To the resulting solution was added 2.5M n-butyllithium / hexane solution (1 molar equivalent to 1-bromo-3,5-di-n-hexylbenzene) (176 ml) at -75 ° C for 1.5 hours. The resulting solution was further stirred at -70 ° C for 1.5 hours. Thereafter, a solution consisting of 2,7-dibromofluorenone (142 g) and tetrahydrofuran was added dropwise at −75 ° C. over 1 hour, and the resulting reaction solution was warmed to room temperature and stirred for 4 hours. Thereafter, the resulting solution was cooled to 0 ° C., slowly added with acetone and 2 mol% aqueous hydrochloric acid and stirred, then warmed to room temperature and allowed to stand at room temperature. Then, the obtained reaction liquid was filtered, the obtained filtrate was concentrated, hexane and water were added and stirred, and liquid separation was performed. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated. Then, it refine | purified by the silica gel column chromatography using the mixed solvent which consists of hexane and a dichloromethane as a developing solvent, and 162g of compounds 12 were obtained.

<Synthesis Example 11: Synthesis of Compound 13>

  The inside of the reaction vessel was under an argon gas stream, and Compound 12 (162 g) and trifluoroacetic acid (245 ml) were added. Trimethylsilane (115 ml) was added dropwise to the resulting solution over 30 minutes and stirred overnight at room temperature. Thereafter, the obtained reaction solution was cooled to 10 ° C., hexane and distilled water were added, and the mixture was stirred for 1 hour, followed by liquid separation. Then, water was added to the obtained oil layer and stirred, and liquid separation was performed again. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated. Thereafter, the mixture was purified by silica gel column chromatography using a mixed solvent consisting of hexane and dichloromethane as a developing solvent, and concentrated to remove the solvent. The obtained residue was washed with methanol to obtain 138 g of the intended compound 13.

<Synthesis Example 12: Synthesis of Compound 14>

  The reaction vessel was placed under an argon gas stream, and compound 13 (138 g), 1-bromooctane (75.4 ml), methyl trioctyl ammonium chloride (trade name: Aliquat (registered trademark) 336, manufactured by Aldrich) (1.2 g) ) And 40% potassium hydroxide (60 ml) were added and stirred at 85 ° C. overnight. Then, the obtained reaction solution was cooled to room temperature, dichloromethane and distilled water were added, and after stirring for 1 hour, liquid separation was performed. Then, water was added to the obtained oil layer and stirred, and liquid separation was performed again. Saturated saline was added to the obtained oil layer and the mixture was stirred and separated again. Magnesium sulfate was added to the obtained oil layer, stirred and filtered, and the obtained filtrate was concentrated. Thereafter, the mixture was purified by silica gel column chromatography using a mixed solvent consisting of hexane and dichloromethane as a developing solvent, and concentrated to remove the solvent. Thereafter, the obtained residue was reprecipitated with a mixed solution of methanol and dichloromethane to obtain 145 g of the intended compound 14.

<Synthesis Example 13: Synthesis of Compound 16>

The atmosphere in the reaction vessel was an argon gas atmosphere, and 2,6-dibromonaphthalene (compound 15, 15.0 g), 2,6-dimethyl-4-tert-butylaniline (27.9 g), tris (dibenzylideneacetone) dipalladium (0) (2.40 g), tri-tert-butylphosphonium tetrafluoroborate (3.04 g) and sodium tert-butoxide (20.2 g) were added, and toluene (300 g) and tert-butanol (6.00 g) were added. ) Was added. Then, it heated up to 90 degreeC and stirred, keeping heat for 3 hours.
The obtained reaction liquid was cooled to 60 ° C., water (300 g) and ethyl acetate (450 g) were sequentially added, and the mixture was cooled to 0 ° C. at a cooling rate of about 10 ° C./hour, whereby a solid was precipitated. The obtained solid was collected by filtration and dried to obtain 24.8 g of Compound 16 as a white solid.

LC-MS (APPI, positive): [M + H ⁺ ] 479

<Synthesis Example 14: Synthesis of Compound 17>

  The reaction vessel was filled with an argon gas atmosphere, and compound 16 (8.00 g), tris (dibenzylideneacetone) dipalladium (0) (0.765 g), 1,1′-bis (diphenylphosphino) ferrocene (1.85 g) ) And sodium tert-butoxide (6.42 g) were added, followed by xylene (160 g). Thereafter, the temperature was raised to 90 ° C., 1,4-dibromobenzene (15.8 g) was added, and the mixture was stirred at 130 ° C. for 4 hours. Then, it is cooled to 45 ° C., added with water (240 g), stirred, then subjected to celite precoat treatment, liquid separation, and purification by silica gel column chromatography (developing solvent: a mixture of hexane and ethyl acetate). Then, the target solution was concentrated. The obtained residue was dissolved in a mixed solvent consisting of toluene and hexane, activated carbon (6.5 g) was added, and the mixture was stirred at 60 ° C. for 1 hour. The resulting mixture was then filtered and concentrated. The obtained residue was recrystallized with a mixed solvent consisting of toluene and isopropanol, and then recrystallized with a mixed solvent consisting of toluene and acetonitrile. Further, the obtained solid was recrystallized twice with a mixed solvent composed of tetrahydrofuran and methanol, and then recrystallized twice with a mixed solvent composed of tetrahydrofuran and acetonitrile. 14 g was obtained.

LC-MS (APPI, positive): [M + H ⁺ ] 789

<Synthesis Example 15: Synthesis of Compound 18>
Compound 18 was synthesized according to the method described in WO2002 / 045184.

<Synthesis Example 16: Synthesis of Compound 19>
Compound 19 was synthesized according to the method described in WO2002 / 045184.

<Synthesis Example 17: Synthesis of Compound 20>
Compound 20 was synthesized according to the method described in International Publication No. 2011/049241.

<Synthesis Example 18: Synthesis of Compound 21>
Compound 21 was synthesized according to the method described in WO2002 / 045184.

<Synthesis Example 19: Synthesis of Compound 22>
Compound 22 was synthesized according to the method described in International Publication No. 2005/074329.

<Synthesis Example 20: Synthesis of polymer compound HT1>
The polymer compound HT1 was synthesized according to the method described in International Publication No. 2011/049241. The number average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound HT1 were Mn = 8.9 × 10 ⁴ and Mw = 4.2 × 10 ⁵ , respectively.

  The polymer compound HT1 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４２．５：７．５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 42.5: 7.5.

<Example 1: Synthesis of polymer compound EP-1>
After the inside of the reaction vessel was filled with an inert gas atmosphere, Compound 11 (1.3360 g, 1.97 mmol), Compound 14 (1.0772 g, 1.80 mmol), Compound 6 (0.2033 g, 0.200 mmol) and toluene ( 50 mL) and heated to about 80 ° C. Thereafter, a 20% by mass aqueous tetraethylammonium hydroxide solution (7.5 mL) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.77 mg) were sequentially added, and the mixture was stirred at 110 ° C. under reflux for 5.5 hours. Thereafter, phenylboronic acid (24.4 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (7.5 mL) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.77 mg) were sequentially added, and the mixture was refluxed at 110 ° C. Stir below for 16 hours. Then, 5 mass% sodium N, N-diethyldithiocarbamate aqueous solution (23.1 g) was added, and the mixture was stirred at about 85 ° C. for 2 hours. The obtained mixture was cooled, then washed twice with water (30 mL), twice with a 3% by mass acetic acid aqueous solution (30 mL), and twice with water (30 mL). The resulting organic layer was added dropwise to methanol (330 mL), and the resulting precipitate was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in order.
The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.37 g of polymer compound EP-1.

The number average molecular weight in terms of polystyrene of the polymer compound EP-1 was 4.2 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 2.09 × 10 ⁵ . .

  The polymer compound EP-1 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Example 2: Synthesis of polymer compound EP-2>
After the inside of the reaction vessel was filled with an inert gas atmosphere, Compound 3 (1.1963 g, 1.97 mmol), Compound 14 (1.0772 g, 1.80 mmol), Compound 6 (0.2033 g, 0.200 mmol) and toluene ( 50 mL) and heated to about 80 ° C. Then, 20 mass% tetraethylammonium hydroxide aqueous solution (7.5 mL) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.78 mg) were sequentially added, and the mixture was stirred at 110 ° C. under reflux for 3.5 hours. Thereafter, phenylboronic acid (26.0 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (7.5 mL) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.77 mg) were sequentially added, and the mixture was refluxed at 110 ° C. Stir below for 16 hours. Then, 5 mass% sodium N, N-diethyldithiocarbamate aqueous solution (23.1 g) was added, and the mixture was stirred at about 85 ° C. for 2 hours. The obtained mixture was cooled, then washed twice with water (30 mL), twice with a 3% by mass acetic acid aqueous solution (30 mL), and twice with water (30 mL). The resulting organic layer was added dropwise to methanol (330 mL), and the resulting precipitate was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.14 g of polymer compound EP-2.

The number average molecular weight in terms of polystyrene of the polymer compound EP-2 was 9.1 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 2.70 × 10 ⁵ . .

  The polymer compound EP-2 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Example 3: Synthesis of polymer compound EP-3>
After the inside of the reaction vessel was filled with an inert gas atmosphere, Compound 3 (1.1656 g, 1.96 mmol), Compound 14 (1.0772 g, 1.80 mmol), Compound 17 (0.1583 g, 0.200 mmol) and toluene ( 50 mL) and heated to about 80 ° C. Then, 20 mass% tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.78 mg) were sequentially added, and the mixture was stirred at 110 ° C. under reflux for 4.5 hours. Thereafter, compound 3 (9.56 mg) was added, and the mixture was stirred at 110 ° C. under reflux for 2 hours. Thereafter, compound 3 (15.4 mg) was added, and the mixture was stirred at 110 ° C. under reflux for 1 hour. Thereafter, phenylboronic acid (24.3 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.78 mg) were sequentially added, and the mixture was refluxed at 110 ° C. Stir below for 16 hours. Then, 5 mass% sodium N, N-diethyldithiocarbamate aqueous solution (20.1 g) was added, and the mixture was stirred at about 85 ° C. for 2 hours. The obtained mixture was cooled, then washed twice with water (20 mL), twice with a 3% by mass acetic acid aqueous solution (20 mL), and twice with water (20 mL). The resulting organic layer was added dropwise to methanol (300 mL), and the resulting precipitate was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.19 g of polymer compound EP-3.

The polymer compound EP-3 had a polystyrene-equivalent number average molecular weight of 4.2 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.60 × 10 ⁵ . .

  The polymer compound EP-3 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Example 4: Synthesis of polymer compound EP-4>
After making the inside of the reaction vessel an inert gas atmosphere, the following formula:

で表される化合物２３（１．２６８４ｇ、１．９７ｍｍｏｌ）、化合物１８（１．０２２１ｇ、１．８０ｍｍｏｌ）、化合物６（０．２０３３ｇ、０．２００ｍｍｏｌ）およびトルエン（５０ｍＬ）を混合し、約８０℃に加熱した。その後、２０質量％水酸化テトラエチルアンモニウム水溶液（６．９ｇ）およびジクロロビス（トリス（ｏ−メトキシフェニル））ホスフィンパラジウム（１．７５ｍｇ）を順次加え、１１０℃の還流下において３．５時間攪拌した。その後、フェニルボロン酸（２４．４ｍｇ）、２０質量％水酸化テトラエチルアンモニウム水溶液（６．９ｇ）およびジクロロビス（トリス（ｏ−メトキシフェニル））ホスフィンパラジウム（１．７９ｍｇ）を順次加え、１１０℃の還流下において１６時間攪拌した。その後、５質量％Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム水溶液（２０．１ｇ）を加え、約８５℃で２時間攪拌した。得られた混合物を冷却後、水（２０ｍＬ）で２回、３質量％酢酸水溶液（２０ｍＬ）で２回、水（２０ｍＬ）で２回洗浄した。得られた有機層をメタノール（３００ｍＬ）に滴下することで生じた沈殿を濾取し、乾燥して固体を得た。得られた固体をトルエンに溶解させ、アルミナカラムおよびシリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物ＥＰ−４を１．１９ｇ得た。

Compound 23 (1.2684 g, 1.97 mmol), Compound 18 (1.0221 g, 1.80 mmol), Compound 6 (0.2033 g, 0.200 mmol) and toluene (50 mL) represented by Heated to ° C. Thereafter, a 20% by mass tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.75 mg) were sequentially added, and the mixture was stirred at 110 ° C. under reflux for 3.5 hours. Thereafter, phenylboronic acid (24.4 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris (o-methoxyphenyl)) phosphine palladium (1.79 mg) were sequentially added, and the mixture was refluxed at 110 ° C. Stir below for 16 hours. Then, 5 mass% sodium N, N-diethyldithiocarbamate aqueous solution (20.1 g) was added, and the mixture was stirred at about 85 ° C. for 2 hours. The obtained mixture was cooled, then washed twice with water (20 mL), twice with a 3% by mass acetic acid aqueous solution (20 mL), and twice with water (20 mL). The resulting organic layer was added dropwise to methanol (300 mL), and the resulting precipitate was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.19 g of polymer compound EP-4.

The polymer compound EP-4 had a polystyrene-equivalent number average molecular weight of 9.7 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 3.66 × 10 ⁵ . .

  The polymer compound EP-4 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、９５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 95: 5.

<Comparative Example 1: Synthesis of polymer compound CP-1>
After making the inside of the reaction vessel an inert gas atmosphere, Compound 3 (1.1963 g, 1.97 mmol), Compound 14 (1.0769 g, 1.80 mmol), Compound 22 (0.1631 g, 0.20 mmol), dichlorobis ( Triphenylphosphine) palladium (1.4 mg) and toluene (47 ml) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (7.5 ml) was added dropwise to the resulting reaction solution, and the mixture was refluxed for 3 hours. After the reaction, phenylboronic acid (25 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (7.5 ml) and dichlorobis (triphenylphosphine) palladium (1.5 mg) were added thereto, and the mixture was further refluxed for 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. The obtained solution was cooled to room temperature, washed twice with water (26 ml), twice with a 3% by mass acetic acid aqueous solution (26 ml) and twice with water (26 ml), and the resulting solution was dissolved in methanol (310 mL). A precipitate was obtained by dropping and filtering. This precipitate was dissolved in toluene (63 mL) and purified by passing through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol (310 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.23 g of polymer compound CP-1.

The number average molecular weight in terms of polystyrene of the polymer compound CP-1 was 6.0 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 2.1 × 10 ⁵ .

  Polymer compound CP-1 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Comparative Example 2: Synthesis of polymer compound CP-2>
The reaction vessel was placed under an inert gas atmosphere, and Compound 11 (1.3359 g, 1.97 mmol), Compound 14 (1.0772 g, 1.80 mmol), Compound 22 (0.1631 g, 0.20 mmol), dichlorobis (triphenyl) Phosphine) palladium (1.4 mg) and toluene (47 ml) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (7.5 ml) was added dropwise to the resulting reaction solution, and the mixture was refluxed for 3 hours. After the reaction, phenylboronic acid (25 mg), 20 mass% tetraethylammonium hydroxide aqueous solution (7.5 ml) and dichlorobis (triphenylphosphine) palladium (1.5 mg) were added thereto, and the mixture was further refluxed for 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. The obtained mixture was cooled, then washed twice with water (26 ml), twice with a 3% by mass aqueous acetic acid solution (26 ml) and twice with water (26 ml), and the resulting solution was added dropwise to methanol (310 mL). A precipitate was obtained by filtration. This precipitate was dissolved in toluene (63 mL) and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (310 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.29 g of polymer compound CP-2.

The polymer compound CP-2 had a polystyrene-equivalent number average molecular weight of 6.3 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.1 × 10 ⁵ .

  The high molecular compound CP-2 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Example 5: Synthesis of light-emitting element E-1>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, is formed on a glass substrate with an ITO film having a thickness of 45 nm by sputtering to a thickness of 35 nm by spin coating. The substrate was heat-treated at 170 ° C. for 15 minutes to produce a light-emitting element substrate.

  Next, a solution ES-1 of polymer compound EP-1 dissolved in a chlorobenzene solvent at a concentration of 1.0 mass% was prepared.

The solution ES-1 was formed into a film having a thickness of 60 nm on the light-emitting element substrate by spin coating, and this was heat-treated on a hot plate at 130 ° C. for 10 minutes in a nitrogen gas atmosphere, and then fluorinated as a cathode. Sodium was vapor-deposited about 5 nm and then aluminum was vapor-deposited about 120 nm, and the light emitting element E-1 was produced. It should be noted that metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

The light emitting element E-1 obtained above was set to a current value so that the initial luminance was 1000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 7.

<Example 6: Synthesis of light-emitting element E-2>
A light emitting device E-2 was produced in the same manner as in Example 5 except that the polymer compound EP-4 was used instead of the polymer compound EP-1 in Example 5.

The light emitting element E-2 obtained above was set to a current value so that the initial luminance was 1000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 7.

<Comparative Example 3: Synthesis of Light-Emitting Element C-1>
A light emitting device C-1 was produced in the same manner as in Example 5 except that the polymer compound CP-2 was used in place of the polymer compound EP-1 in Example 5.

The light emitting element C-1 obtained above was set to a current value so that the initial luminance was 1000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 7.

<Example 7: Synthesis of light-emitting element E-3>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, is formed on a glass substrate with an ITO film having a thickness of 45 nm by sputtering to a thickness of 35 nm by spin coating. The substrate was heat-treated at 170 ° C. for 15 minutes to produce a light-emitting element substrate.

  Next, a solution of the polymer compound HT1 dissolved in a xylene solvent at a concentration of 0.7% by mass was spin-coated to form a film having a thickness of 20 nm on the light-emitting element substrate. Then, the base material for light emitting elements with a positive hole transport layer was produced by heat-processing this for 180 minutes at 180 degreeC on a hotplate in nitrogen gas atmosphere.

  Next, a solution ES-2 of a polymer compound EP-2 dissolved in a chlorobenzene solvent at a concentration of 1.0% by mass was prepared.

The solution ES-2 was formed into a film having a thickness of 60 nm on the substrate for a light-emitting element with a hole transport layer by spin coating, and this was heat-treated in a nitrogen gas atmosphere at 130 ° C. for 10 minutes, and then fluorinated as a cathode. Sodium was vapor-deposited about 5 nm and then aluminum was vapor-deposited about 120 nm, and the light emitting element E-3 was produced. It should be noted that metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

The light emitting element E-3 obtained above was set to a current value so that the initial luminance was 5000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 8.

<Example 8: Synthesis of light-emitting element E-4>
A light emitting device E-4 was produced in the same manner as in Example 7 except that the polymer compound EP-3 was used instead of the polymer compound EP-2 in Example 7.

The light emitting element E-4 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 8.

<Comparative Example 4: Synthesis of Light-Emitting Element C-2>
A light emitting device C-2 was produced in the same manner as in Example 7 except that the polymer compound CP-1 was used instead of the polymer compound EP-2 in Example 7.

The light emitting element C-2 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 8.

<Synthesis Example 21: Synthesis of Compound 23>
Compound 23 was synthesized according to the method described in WO2007 / 058368.

<Synthesis Example 22: Synthesis of Compound 24>
Compound 24 was synthesized according to the method described in JP2011-174062.

<Synthesis Example 23: Synthesis of Compound 25>
Compound 25 was synthesized according to the method described in WO2005 / 049546.

<Synthesis Example 24: Synthesis of Compound 26>
Compound 26 was synthesized according to the method described in JP-A-2008-106241.

<Synthesis Example 25: Synthesis of polymer compound HT2>
After the inside of the reaction vessel was filled with an inert gas atmosphere, Compound 24 (1.8163 g, 1.99 mmol), Compound 25 (1.5586 g, 1.70 mmol), Compound 26 (0.1587 g, 0.30 mmol), dichlorobis ( Triphenylphosphine) palladium (1.4 mg) and toluene (47 mL) were mixed and heated to 105 ° C. Thereafter, a 20% by mass tetraethylammonium hydroxide aqueous solution (6.6 mL) was added dropwise, and the mixture was stirred at 105 ° C. under reflux for 8 hours. Thereafter, phenylboronic acid (24.4 mg) and dichlorobis (triphenylphosphine) palladium (1.4 mg) were sequentially added, and the mixture was refluxed at 105 ° C. for 23 hours. Thereafter, a sodium diethyldithiocarbamate aqueous solution was added, and the mixture was stirred at 80 ° C. for 2 hours. The obtained mixture was cooled and then washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water. A precipitate formed by dropping the obtained organic layer into methanol was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.88 g of the polymer compound HT2.

The polymer compound HT2 had a polystyrene-equivalent number average molecular weight of 5.6 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.4 × 10 ⁵ .

  The polymer compound HT2 has the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位と、下記式：

And the following formula:

で示される構成単位とが、５０：４２．５：７．５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 42.5: 7.5.

<Synthesis Example 26: Synthesis of Compound COM-4>
Compound 26 was synthesized according to the method described in JP-A-2006-188673.

<Example 9: Production and evaluation of light-emitting element E-5>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, is formed on a glass substrate with an ITO film having a thickness of 45 nm by sputtering to a thickness of 35 nm by spin coating. The substrate was heat-treated at 170 ° C. for 15 minutes to produce a light-emitting element substrate.

  Next, a solution of a polymer compound HT2 dissolved in a xylene solvent at a concentration of 0.6% by mass was spin-coated to form a film with a thickness of 20 nm on the light-emitting element substrate. Then, the base material for light emitting elements with a positive hole transport layer was produced by heat-processing this for 180 minutes at 180 degreeC on a hotplate in nitrogen gas atmosphere.

  Next, a solution of compound 23 dissolved in a chlorobenzene solvent at a concentration of 1.0% by mass and a solution of polymer compound EP-3 dissolved in a chlorobenzene solvent at a concentration of 1.0% by mass, The solution ES-3 was prepared by mixing so that the compound 23: polymer compound EP-3 = 3: 97 in mass ratio.

The solution ES-3 was formed into a film having a thickness of 80 nm on the light-emitting element substrate with a hole transport layer by spin coating, and this was heat-treated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere, and then fluorinated as a cathode. Sodium was vapor-deposited about 5 nm and then aluminum was vapor-deposited about 120 nm, and the light emitting element E-5 was produced. It should be noted that metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

The light emitting element E-5 obtained above was driven at a constant current after setting the current value so that the initial luminance was 10,000 cd / m ^2, and the luminance half life was measured. The results are shown in Table 9.

<Comparative Example 5: Synthesis of Light-Emitting Element C-3>
A light emitting device C-3 was produced in the same manner as in Example 9 except that the polymer compound CP-1 was used instead of the polymer compound EP-3 in Example 9.

The light emitting element C-3 obtained above was set to a current value so that the initial luminance was 10,000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 9.

<Example 10: Production and evaluation of light-emitting element E-6>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, is formed on a glass substrate with an ITO film having a thickness of 45 nm by sputtering to a thickness of 35 nm by spin coating. The substrate was heat-treated at 170 ° C. for 15 minutes to produce a light-emitting element substrate.

  Next, a solution of a polymer compound HT2 dissolved in a xylene solvent at a concentration of 0.6% by mass was spin-coated to form a film with a thickness of 20 nm on the light-emitting element substrate. Then, the base material for light emitting elements with a positive hole transport layer was produced by heat-processing this for 180 minutes at 180 degreeC on a hotplate in nitrogen gas atmosphere.

  Next, a solution of compound COM-4 dissolved at a concentration of 1.0% by mass in a chlorobenzene solvent, and a solution of polymer compound EP-3 dissolved at a concentration of 1.0% by mass in a chlorobenzene solvent; Were mixed so that the mass ratio would be compound COM-4: polymer compound EP-1 = 7.5: 92.5 to prepare solution ES-4.

The solution ES-4 was formed into a film having a thickness of 80 nm on the substrate for a light-emitting element with a hole transport layer by spin coating, and this was heat-treated in a nitrogen gas atmosphere at 130 ° C. for 10 minutes, and then fluorinated as a cathode. Sodium was vapor-deposited about 5 nm and then aluminum was vapor-deposited about 120 nm, and the light emitting element E-6 was produced. It should be noted that metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

The light emitting element E-6 obtained above was driven at a constant current after setting the current value so that the initial luminance was 10,000 cd / m ^2, and the luminance half life was measured. The results are shown in Table 10.

<Comparative Example 6: Synthesis of Light-Emitting Element C-4>
A light emitting device C-4 was produced in the same manner as in Example 10 except that the polymer compound CP-2 was used instead of the polymer compound EP-1 in Example 10.

The light emitting element C-4 obtained above was set to have a current value so that the initial luminance was 10,000 cd / m ^2, and then was driven with a constant current, and the luminance half life was measured. The results are shown in Table 10.

  DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 11 ... Anode, 12 ... Hole injection layer, 13 ... Hole transport layer, 14 ... Light emitting layer, 15 ... Electron transport layer, 16 ... Electron injection layer, 17 ... Cathode, 20 ... Substrate, 21 ... Anode 22 ... hole injection layer, 23 ... light emitting layer, 24 ... cathode, 25 ... protective layer, 100 ... light emitting element, 110 ... light emitting element, 200 ... planar light source.

Claims (25)

A polymer compound comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (4) .

(1)
[Where:
Ar ¹ and Ar ² each independently represent an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent.
Ar ¹ and R ¹ may be bonded directly or via a divalent group to form a nitrogen-containing heterocycle. Ar ² and R ² may be bonded directly or via a divalent group to form a nitrogen-containing heterocyclic ring.
R ³ represents a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent aromatic heterocyclic group. These groups may have a substituent. When there are a plurality of R ³ , they may be the same or different. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RA , they may be the same or different and may be bonded to each other to form a ring.
n1 represents an integer of 0 or more and 6 or less. ]

(4)
[Where:
Ar ⁵ represents an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent.
R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A or a group represented by —N (R ^A ) ₂ , and these groups have a substituent. You may do it. R ^A represents the same meaning as described above.
Ring C1 and ring C2 each independently represent an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. ] The polymer compound according to claim 1 , wherein the formula (4) is a structural unit represented by the following formula (4-1).

(4-1)
[Where:
Ar ⁵ and R ⁴ represent the same meaning as described above.
R ⁵ and R ⁶ are each independently a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group or a monovalent group. Represents an aromatic heterocyclic group, and these groups optionally have a substituent. When there are a plurality of R ⁵ and R ⁶ , they may be the same or different. R ^A represents the same meaning as described above.
n5 and n6 each independently represents an integer of 0 or more and 3 or less. ] Wherein Ar ⁵ is also a phenyl group optionally having a substituent, the polymer compound according to claim 1 or 2. The polymer compound according to any one of claims 1 to 3 , wherein R ⁴ is an alkyl group which may have a substituent. The ring C1 and the ring C2 are each independently a benzene ring optionally having a substituent, and the Ar ⁵ Is a phenyl group which may have a substituent, and R ⁴ The polymer compound according to claim 1, wherein is an alkyl group which may have a substituent. The polymer compound according to any one of claims 1 to 5 , wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (1-1).

(1-1)
[Wherein, Ar ¹ , Ar ² , R ¹ , R ² , R ³ and n1 represent the same meaning as described above. ] Ar ¹ and Ar ² each independently form a ring from benzene, naphthalene, anthracene, tetracene, indene, fluorene, benzofluorene, spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, pyrene, perylene or chrysene. A divalent group formed by removing two hydrogen atoms directly bonded to a carbon atom to be bonded (the group may have a substituent), according to any one of claims 1 to 6 . The polymer compound described. The polymer compound according to any one of claims 1 to 7 ,
A composition comprising at least one material selected from the group consisting of a hole injection material, a hole transport material, a light emitting material, an electron transport material and an electron injection material. The composition according to claim 8 , wherein the light emitting material is a low molecular fluorescent material or a phosphorescent material. The composition according to claim 9 , wherein the low-molecular fluorescent material is a compound represented by the following formula (1B-B).

[Where:
n ^1BB represents an integer of 1 or more.
Ar ^1BB is an n ^1BB valent aromatic hydrocarbon group, an n ^1BB valent aromatic heterocyclic group, or two or more rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Or n ^1BB bonded via a group represented by —O—, —S—, —C (R ^3BB ) ₂ —, —C (R ^3BB ) = (R ^3BB ) — or —C≡C—. Represents a valent group, and these groups may have a substituent. R ^3BB represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. A plurality of R ^3BBs may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
R ^1BB and R ^2BB each independently represent a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When there are a plurality of R ^1BB and R ^2BB , they may be the same or different. ] The composition according to claim 10 , wherein the compound represented by the formula (1B-B) is a compound represented by the following formula (1B-B1), (1B-B2) or (1B-B3).

[Where:
R ^x4 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a group represented by —O—R ^A , a group represented by —N (R ^A ) ₂ , an aryl group, or a monovalent aromatic heterocyclic ring. Represents a group, and these groups may have a substituent. R ^A represents the same meaning as described above.
R ^1BB and R ^2BB represent the same meaning as described above. ] The composition according to claim 9 , wherein the phosphorescent material is an iridium complex or a platinum complex. The iridium complex is an iridium complex represented by the following formula Ir-1, Ir-2 or Ir-3, A composition according to claim 1 2.

[Where:
R ^D1 , R ^D2 , R ^D3 , R ^D4 , R ^D5 , R ^D6 , R ^D7 , R ^D8 , R ^D11 , R ¹² , R ¹³ , R ^D14 , R ¹⁵ , R ¹⁶ , R ^D17 , R ^D18 , R ^D19 And R ^D20 each independently represents a hydrogen atom, an alkyl group, a group represented by —O—R ^A , an aryl group, a monovalent aromatic heterocyclic group or a halogen atom, and these groups each represent a substituent. You may have. R ^A represents the same meaning as described above.
-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.
n _D1 represents 1, 2 or 3, and n _D2 represents 1 or 2. ] In the iridium complex represented by the formula Ir-1, at least one of R ^D1 , R ^D2 , R ^D3 , R ^D4 , R ^D5 , R ^D6 , R ^D7, and R ^D8 is represented by the formula (Dend-A) or (Dend is a group represented by -B), a composition according to claim 1 3.

[Where:
G ^DA1 represents a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent aromatic heterocyclic group.
T ^DA2 and T ^DA3 each independently represent an aryl group or a monovalent aromatic heterocyclic group.
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
* Represents a bond. ]

[Where:
G ^DA1 , G ^DA2 and G ^DA3 each independently represent a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent aromatic heterocyclic group.
T ^DA4 , T ^DA5 , T ^DA6 and T ^DA7 each independently represent an aryl group or a monovalent aromatic heterocyclic group.
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
* Represents a bond. ] In the iridium complex represented by the formula Ir-2, at least one of R ^D11 , R ¹² , R ¹³ , R ^D14 , R ¹⁵ , R ¹⁶ , R ^D17 , R ^D18 , R ^D19 and R ^D20 is the formula ( a group represented by Dend-a) or (Dend-B), a composition according to claim 1 3. In the iridium complex represented by the formula Ir-3, R ^D1 , R ^D2 , R ^D3 , R ^D4 , R ^D5 , R ^D6 , R ^D7 , R ^D8 , R ^D11 , R ¹² , R ¹³ , R ^D14 , R ^{15, R 16, R D17,} R D18, at least one of R ^D19 and R ^D20, but a group represented by the formula (Dend-a) or (Dend-B), the composition according to claim 1 3 object. A liquid composition comprising the polymer compound according to any one of claims 1 to 7 or the composition according to any one of claims 8 to 15 and a solvent. Containing a composition according to any one of claims 1 polymer compound according to any one of 7 or claim 8-1 5, the organic thin film. An anode, a cathode, and an organic layer provided between the anode and the cathode,
The light emitting element whose said organic layer is the organic thin film of Claim 18 . The light emitting device according to claim 19 , wherein the organic layer is a light emitting layer. A hole transport layer provided between the anode and the light emitting layer;
The light emitting device according to claim 19 or 20 , wherein a crosslinkable compound is used for the hole transport layer. Further comprising a hole injection layer provided between said anode hole transport layer, light-emitting device according to claim 2 1. The crosslinking compound is a compound having a triarylamine skeleton, the light emitting device according to claim 2 1, 2 2. The crosslinking compound is a crosslinked polymer compound, light emitting device according to any one of claims 2 1 to 2 3. Using a light-emitting element according to any one of claims 19 21 to 24, the planar light source or display device.

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