JP6046389B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescence element.

In recent years, organic electroluminescence displays (hereinafter referred to as “organic EL displays”) using organic electroluminescence elements (hereinafter referred to as “organic EL elements”) have attracted attention as next-generation displays. This organic EL element includes organic layers such as a light emitting layer and a charge transport layer. The organic EL element may be obtained using a low molecular organic material or may be obtained using a high molecular organic material.
When using a polymer organic material as the main material, a film having a uniform film quality and thickness can be easily formed when a coating method such as an ink jet printing method or a spin coating method is used. This is particularly advantageous when manufacturing an organic EL display. Therefore, it has been proposed to use a polymer organic material for an organic EL element (see Patent Document 1). Furthermore, when a polymer organic material is used in an organic EL device, it has been proposed to use a hole transport layer and a light emitting layer made of a polymer organic material for the purpose of improving the characteristics of the device (see Patent Document 2). ).

International Publication No. 99/054385 International Publication No. 2005/052027

  However, when a conventional polymer organic material is used for an organic EL element, it cannot be said that the luminance life of the organic EL element is sufficient.

  Then, an object of this invention is to provide the organic EL element which is excellent in a brightness | luminance lifetime.

（式（Ａ）、（Ｂ）及び（Ｃ）中、
Ａｒ^１及びＡｒ^５は、それぞれ独立に、アリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を表す。
Ａｒ^２、Ａｒ^３及びＡｒ^４は、それぞれ独立に、アリーレン基又は２価の複素環基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、アルキル基、アリール基又は１価の複素環基を表す。
Ｘ^１は、−ＣＲ^３＝ＣＲ^４−で表される基又は−Ｃ≡Ｃ−で表される基を表す。Ｒ^３及びＲ^４は、それぞれ独立に、水素原子、カルボキシル基、置換カルボキシル基、シアノ基、アルキル基、アリール基又は１価の複素環基を表す。
ａは、０又は１を表す。）
−［−（Ｙ）_ｎ−Ｚ−］_ｍ− （１）

（式（１）中、
Ｙは、下記式（Ｙ−１）又は下記式（Ｙ−２）で表される構造から、水素原子を２個除いた２価の基を表す。
Ｚは、下記式（Ｚ−１）、（Ｚ−２）、（Ｚ−３）、（Ｚ−４）、（Ｚ−５）、（Ｚ−６）、（Ｚ−７）又は（Ｚ−８）で表される構造から水素原子を２個除いた２価の基を表す。
ｍは４〜１００００の整数を表す。ｎは１〜３の整数を表す。
複数個あるＹ、Ｚ及びｎは、各々、同一であっても異なっていてもよい。
Ｙ及びＺが有する水素原子は、Ｒ’で置換されていてもよく、Ｒ’は、カルボキシル基、ニトロ基、シアノ基、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、アシル基、アシルオキシ基、イミン残基、アミド化合物残基、酸イミド残基、１価の複素環基及び１価の複素環チオ基からなる群より選ばれる官能基、又は、ハロゲン原子を表す。Ｒ’が複数個ある場合、それらは同一であっても異なっていてもよく、複数個のＲ’は互いに結合して、それぞれが結合する炭素原子又は窒素原子とともに、環構造を形成していてもよい。前記官能基は置換基を有していてもよい。）

（式（Ｚ−１）〜式（Ｚ−８）中、
Ｘは、−ＣＨ＝で表される基又はＮ＝で表される基を表す。複数個あるＸは、同一であっても異なっていてもよい。但し、Ｘとしての−Ｎ＝で表される基の数は、０〜２である。
Ｒ^Ｘは、カルボキシル基、ニトロ基、シアノ基、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、アシル基、アシルオキシ基、イミン残基、アミド化合物残基、酸イミド残基、１価の複素環基及び１価の複素環チオ基からなる群より選ばれる官能基、又は、水素原子若しくはハロゲン原子を表す。複数個あるＲ^Ｘは、同一であっても異なっていてもよく、複数個のＲ^Ｘは互いに結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。前記官能基は置換基を有していてもよい。）

（式（２）中、
Ｒ^Ｚは、アルキル基、アルコキシ基、アリール基、アルケニル基、アルキニル基、アミノ基、シリル基、ハロゲン原子、アシル基、１価の複素環基、カルボキシル基、ニトロ基及びシアノ基からなる群より選ばれる官能基、又は、水素原子を表す。前記官能基は置換基を有していてもよい。複数個あるＲ^Ｚは、同一であっても異なっていてもよい。）

（式（３）中、
Ｒ^ｎは、水素原子、アルキル基、アルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数個あるＲ^ｎは、同一であっても異なっていてもよい。
Ａｒ^６及びＡｒ^７は、それぞれ独立に、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^６及びＡｒ^７はそれぞれ、隣り合うＲ^ｎと直接結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。）
［２］ 前記Ｙが、下記式（Ｙ−３）、（Ｙ−４）、（Ｙ−５）又は（Ｙ−６）で表される２価の基である、［１］に記載の有機エレクトロルミネッセンス素子。

（式（Ｙ−３）〜（Ｙ−６）中、
Ｒ”は、水素原子、アルキル基、アリール基又は１価の複素環基を表す。複数個あるＲ”は、同一であっても異なっていてもよい。複数個あるＲ”は互いに結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。）
［３］ 前記Ｚが、下記式（Ｚ−９）、（Ｚ−１０）、（Ｚ−１１）、（Ｚ−１２）、（Ｚ−１３）、（Ｚ−１４）、（Ｚ−１５）、（Ｚ−１６）、（Ｚ−１７）、（Ｚ−１８）、（Ｚ−１９）又は（Ｚ−２０）で表される２価の基である、［１］又は［２］に記載の有機エレクトロルミネッセンス素子。

（式（Ｚ−９）〜（Ｚ−２０）中、
Ｒ”は、水素原子、アルキル基、アリール基又は１価の複素環基を表す。複数個あるＲ”は、同一であっても異なっていてもよく、複数個あるＲ”は互いに結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。
Ｒ^Ｘは、カルボキシル基、ニトロ基、シアノ基、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、アシル基、アシルオキシ基、イミン残基、アミド化合物残基、酸イミド残基、１価の複素環基及び１価の複素環チオ基からなる群より選ばれる官能基、又は水素原子若しくはハロゲン原子を表す。複数個あるＲ^Ｘは、同一であっても異なっていてもよい。複数個あるＲ^Ｘは互いに結合して環構造を形成していてもよい。前記官能基は置換基を有していてもよい。）
［４］ 前記Ｚが、前記式（Ｚ−１１）、（Ｚ−１５）又は（Ｚ−１７）で表される２価の基である、［３］に記載の有機エレクトロルミネッセンス素子。
［５］ 前記式（Ａ）で表される構成単位が、それぞれ独立に、下記式（１ａ）、（１ｂ）、（１ｃ）、（１ｄ）、又は（１ｅ）で表される構成単位である、［１］〜［４］のいずれか１つに記載の有機エレクトロルミネッセンス素子。

（式（１ａ）〜（１ｅ）中、
Ｒ”は、水素原子、アルキル基、アリール基又は１価の複素環基を表す。複数個あるＲ”は、同一であっても異なっていてもよく、複数個あるＲ”は互いに結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。
Ｒ^Ｘは、カルボキシル基、ニトロ基、シアノ基、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アルケニル基、アルキニル基、アミノ基、シリル基、アシル基、アシルオキシ基、イミン残基、アミド化合物残基、酸イミド残基、１価の複素環基及び１価の複素環チオ基からなる群より選ばれる官能基、又は、水素原子若しくはハロゲン原子を表す。複数個あるＲ^Ｘは、同一であっても異なっていてもよく、複数個あるＲ^Ｘは互いに結合して、それぞれが結合する炭素原子とともに、環構造を形成していてもよい。前記官能基は置換基を有していてもよい。）
［６］ 前記高分子化合物ＩＶ、高分子化合物Ｖ又は高分子化合物ＶＩが、架橋基を有する構成単位を含む、［１］〜［５］のいずれか１つに記載の有機エレクトロルミネッセンス素子。 That is, the present invention provides the following [1] to [6].
[1] An organic electroluminescence device comprising an anode, a cathode, a light emitting layer provided between the anode and the cathode, and a hole injection layer or a hole transport layer provided between the anode and the light emitting layer. There,
The light emitting layer is represented by the polymer compound I having at least one structural unit selected from the group consisting of structural units represented by the following formulas (A), (B) and (C), and the following formula (1). Or at least one selected from the group consisting of structural units represented by the following formulas (A), (B) and (C) A polymer compound III which is a block copolymer having a structural unit represented by the following formula (1):
The hole injection layer or the hole transport layer is represented by the following formula (2), which is a structural unit containing a polymer compound IV having 10 mol% or more of a structural unit represented by the following formula (B) and fullerene or a fullerene derivative. And a polymer compound V containing at least one constituent unit selected from the group consisting of a constituent unit containing azulene or an azulene derivative and a constituent unit containing a stilbene or stilbene derivative represented by the following formula (3): Or a structural unit containing 10 mol% or more of a structural unit represented by the following formula (B), a structural unit containing a fullerene or a fullerene derivative, or a structural unit containing an azulene or an azulene derivative represented by the following formula (2) And at least selected from the group consisting of structural units containing a stilbene or stilbene derivative represented by the following formula (3): It includes one constituent unit, a polymer compound VI having the organic electroluminescent element.

(In the formulas (A), (B) and (C),
Ar ¹ and Ar ⁵ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure.
Ar ² , Ar ³ and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group.
X ¹ represents a group represented by —CR ³ ═CR ⁴ — or a group represented by —C≡C—. R ³ and R ⁴ each independently represents a hydrogen atom, a carboxyl group, a substituted carboxyl group, a cyano group, an alkyl group, an aryl group, or a monovalent heterocyclic group.
a represents 0 or 1. )
-[-(Y) _n -Z-] _m- (1)

(In the formula (1),
Y represents a divalent group obtained by removing two hydrogen atoms from the structure represented by the following formula (Y-1) or the following formula (Y-2).
Z represents the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z- And a divalent group obtained by removing two hydrogen atoms from the structure represented by 8).
m represents an integer of 4 to 10,000. n represents an integer of 1 to 3.
A plurality of Y, Z and n may be the same or different.
The hydrogen atom of Y and Z may be substituted with R ′, and R ′ is a carboxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. , Alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, imine residue, amide compound residue, acid imide residue, monovalent heterocyclic group and monovalent heterocyclic thio group It represents a functional group selected from the above or a halogen atom. When there are a plurality of R ′, they may be the same or different, and the plurality of R ′ are bonded to each other to form a ring structure together with the carbon atom or nitrogen atom to which each R ′ is bonded. Also good. The functional group may have a substituent. )

(In the formula (Z-1) to the formula (Z-8),
X represents a group represented by —CH═ or a group represented by N═. A plurality of X may be the same or different. However, the number of groups represented by -N = as X is 0-2.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent. )

(In the formula (2),
^RZ is selected from the group consisting of alkyl groups, alkoxy groups, aryl groups, alkenyl groups, alkynyl groups, amino groups, silyl groups, halogen atoms, acyl groups, monovalent heterocyclic groups, carboxyl groups, nitro groups, and cyano groups. Represents a functional group selected or a hydrogen atom. The functional group may have a substituent. A plurality of R ^Z may be the same or different. )

(In formula (3),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ⁿ may be the same or different.
Ar ⁶ and Ar ⁷ each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ^n, and may form a ring structure together with the carbon atom to which each is bonded. )
[2] The organic material according to [1], wherein Y is a divalent group represented by the following formula (Y-3), (Y-4), (Y-5), or (Y-6). Electroluminescence element.

(In the formulas (Y-3) to (Y-6),
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different. A plurality of R ″ may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded.
[3] The Z is represented by the following formulas (Z-9), (Z-10), (Z-11), (Z-12), (Z-13), (Z-14), (Z-15). , (Z-16), (Z-17), (Z-18), (Z-19) or (Z-20), which is a divalent group represented by [1] or [2] Organic electroluminescence element.

(In the formulas (Z-9) to (Z-20),
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different, and a plurality of R ″ are bonded to each other. A ring structure may be formed together with the carbon atoms to which each is bonded.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. A plurality of R ^X may be the same or different. A plurality of R ^X may be bonded to each other to form a ring structure. The functional group may have a substituent. )
[4] The organic electroluminescence element according to [3], wherein Z is a divalent group represented by the formula (Z-11), (Z-15), or (Z-17).
[5] The structural unit represented by the formula (A) is independently a structural unit represented by the following formula (1a), (1b), (1c), (1d), or (1e). , [1] to [4] The organic electroluminescence device according to any one of [1] to [4].

(In the formulas (1a) to (1e),
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different, and a plurality of R ″ are bonded to each other. A ring structure may be formed together with the carbon atoms to which each is bonded.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent. )
[6] The organic electroluminescence device according to any one of [1] to [5], wherein the polymer compound IV, the polymer compound V, or the polymer compound VI includes a structural unit having a crosslinking group.

  ADVANTAGE OF THE INVENTION According to this invention, the organic EL element which is excellent in the brightness lifetime can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, a tert-butyl group may be expressed as “t-Bu” and a phenyl group as “Ph”.

[Explanation of terms]
Hereinafter, terms commonly used in this specification will be described with specific examples as necessary.

  The term “structural unit” represents an atom or atomic group present in the molecular chain of a polymer compound, and the term “constituent chain” is linked so as to include one or more structural units in a predetermined order. Represents a molecular chain.

  The term “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The term “C _p -C _q ” (p, q is a positive number satisfying p <q) indicates that the number of carbon atoms in the partial structure corresponding to the functional group name described immediately after this term is p— It means q. That is, when the organic group described immediately after “C _p -C _q ” is an organic group named by combining a plurality of functional group names (for example, C _p -C _q alkoxyphenyl group), It means that the number of carbon atoms of the partial structure corresponding to the functional group name (for example, alkoxy) described immediately after “C _{p to} C _q ” among the functional group names is _p to _q . For example, “C ₁ -C ₁₂ alkyl group” means an alkyl group having 1 to 12 carbon atoms, and “C ₁ -C ₁₂ alkoxyphenyl group” means “alkoxy group having 1 to 12 carbon atoms”. Means a phenyl group having "group".

  The term “alkyl group” means any one of a linear alkyl group, a branched alkyl group and a cyclic alkyl group (cycloalkyl group) which may have a substituent. As the alkyl group, a linear alkyl group or a cyclic alkyl group is preferable, and an alkyl group which may be substituted with a halogen atom or the like is preferable.

Here, the term “substituent” includes carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, It means an acyl group, an acyloxy group, an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group, a monovalent heterocyclic thio group, a halogen atom, and the like.
Some or all of the hydrogen atoms that may be contained in these substituents may be substituted with fluorine atoms. Moreover, it is preferable that the carbon atom number of a substituent in case a substituent has a carbon chain is 1-20.

  The number of carbon atoms of the alkyl group is preferably 1 to 20 (preferably 3 to 20 in the case of a branched alkyl group and a cyclic alkyl group), more preferably 1 to 15 (of a branched alkyl group and a cyclic alkyl group). In this case, it is preferably 3 to 15), more preferably 1 to 12 (in the case of a branched alkyl group and a cyclic alkyl group, preferably 3 to 12). Examples of the alkyl group which may have 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, Hexyl, cyclohexyl, 2-ethylhexyl, heptyl, octyl, 3,7-dimethyloctyl, nonyl, decyl, dodecyl, arylalkyl, trifluoromethyl, pentafluoroethyl, perfluoro Examples thereof include a butyl group, a perfluorohexyl group, and a perfluorooctyl group.

The term “arylalkyl group” means an arylalkyl group which may have a substituent and may be substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylalkyl group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30.
Have a substituent Examples of even an arylalkyl group, a phenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl _-C 1 _{-C 12} alkyl group and 2-naphthyl _-C 1 _{-C 12} alkyl group, and the like.

  The term “alkoxy group” means any of a linear alkoxy group, a branched alkoxy group or a cyclic alkoxy group (cycloalkoxy group) which may have a substituent. As the alkoxy group, a linear alkoxy group or a cyclic alkoxy group is preferable, and an alkoxy group which may be substituted with a halogen atom or an alkoxy group is preferable.

The number of carbon atoms of the alkoxy group is preferably 1-20 (in the case of a branched alkoxyl group and a cyclic alkoxy group, preferably 3-20), more preferably 1-15 (of the branched alkoxyl group and cyclic alkoxy group). In this case, preferably 3 to 15), more preferably 1 to 12 (in the case of a branched alkoxyl group and a cyclic alkoxy group, preferably 3 to 12).
Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, Hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, arylalkoxy group, trifluoromethoxy group, Examples include a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

The term “arylalkoxy group” means an arylalkoxy group which may have a substituent. The arylalkoxy group is preferably an arylalkoxy group which may be substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylalkoxy group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30.
Have a substituent Examples of which may arylalkoxy group, phenyl _-C 1 _{-C 12} alkoxy _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _group, C 1 _{-C 12} alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl _-C 1 _{-C 12} alkoxy group and 2-naphthyl _-C 1 _{-C 12} alkoxy groups and the like.

  The term “alkylthio group” means any one of a linear alkylthio group, a branched alkylthio group and a cyclic alkylthio group (cycloalkylthio group) which may have a substituent. As the alkylthio group, a linear alkylthio group or a cyclic alkylthio group is preferable, and an alkylthio group which may be substituted with a halogen atom or the like is preferable.

  The number of carbon atoms of the alkylthio group is preferably 1 to 20 (preferably 3 to 20 in the case of a branched alkylthio group and a cyclic alkylthio group), more preferably 1 to 15 (of a branched alkylthio group and a cyclic alkylthio group). In this case, it is preferably 3 to 15), more preferably 1 to 12 (in the case of a branched alkylthio group and a cyclic alkylthio group, preferably 3 to 12). Examples of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group. Group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, arylalkylthio group, 3,7-dimethyloctylthio group, dodecylthio group and trifluoromethylthio group.

The term “arylalkylthio group” means an arylalkylthio group which may have a substituent. The arylalkylthio group is preferably an arylalkylthio group substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylalkylthio group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30. Have a substituent Examples of which may arylalkylthio group, phenyl _-C 1 _{-C 12} alkylthio _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylthio _group, C 1 _{-C 12} alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl _-C 1 _{-C 12} alkylthio group and a 2-naphthyl _-C 1 _{-C 12} alkylthio groups and the like.

  The term “aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The aryl group may have a substituent. As the aryl group, an aryl group consisting only of an aromatic ring, an aryl group which may be substituted with a halogen atom, an alkoxy group or the like is preferable. Examples of the aryl group include a group having a benzene ring, a group having a condensed ring, two or more benzene rings and / or condensed rings, a single bond or a divalent organic group (for example, an alkylene group such as a vinylene group). And a group bonded via each other.

The number of carbon atoms of the aryl group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30. Examples of the aryl group which may have a substituent, a phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, C 1 _{-C 12} alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthryl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, pentafluorophenyl group, biphenyl _group, C 1 _{-C 12} alkoxy biphenylyl group and _C 1 _{-C 12} alkyl biphenylyl group, and among them , phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, C 1 _{-C 12} alkylphenyl group, biphenyl _group, C 1 _{-C 12} alkoxy biphenylyl group or a _C 1 _{-C 12} alkyl biphenylyl group are preferred.

Examples of C ₁ -C ₁₂ alkoxyphenyl groups include methoxyphenyl, ethoxyphenyl, propyloxyphenyl, isopropyloxyphenyl, butyloxyphenyl, isobutyloxyphenyl, tert-butyloxyphenyl, pentyloxy A phenyl group, a hexyloxyphenyl group, an octyloxyphenyl group, etc. are mentioned.

Examples of C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, a mesityl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, tert- butylphenyl group, Examples include pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, and dodecylphenyl group.

  The term “aryloxy group” means an aryloxy group which may have a substituent. The aryloxy group is preferably an aryloxy group which may be substituted with a halogen atom or an alkoxy group.

The number of carbon atoms of the aryloxy group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30. Examples of aryloxy group which may have a substituent, a phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and Examples thereof include a pentafluorophenyloxy group, and among them, a C _{1 to} C ₁₂ alkoxyphenoxy group or a C _{1 to} C ₁₂ alkylphenoxy group is preferable.

Examples of C ₁ -C ₁₂ alkoxyphenoxy groups include methoxyphenoxy group, ethoxyphenoxy group, propyloxyphenoxy group, isopropyloxyphenoxy group, butyloxyphenoxy group, isobutyloxyphenoxy group, tert-butyloxyphenoxy group, pentyloxy Examples thereof include a phenoxy group, a hexyloxyphenoxy group, and an octyloxyphenoxy group.

Examples of C ₁ -C ₁₂ alkylphenoxy groups include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butylphenoxy group. Group, isobutylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc. Is mentioned.

The term “arylthio group” means an arylthio group which may have a substituent. The arylthio group is preferably an arylthio group which may be substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylthio group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30. As good arylthio group which may have a substituent group, phenylthio _group, C 1 _{-C 12} alkoxyphenyl-thio _group, C 1 _{-C 12} alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group and pentafluorophenyl A thio group etc. are mentioned.

  The term “alkenyl group” means any one of a linear alkenyl group, a branched alkenyl group and a cyclic alkenyl group which may have a substituent. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 15, and further preferably 2 to 10. Examples of the alkenyl group which may have a substituent include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group and 1-hexenyl. Group, 2-hexenyl group, 1-octenyl group, arylalkenyl group and the like.

The term “arylalkenyl group” is an arylalkenyl group which may have a substituent, preferably an arylalkenyl group which may be substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylalkenyl group is preferably 8 to 60, more preferably 8 to 48, and still more preferably 8 to 30. The aryl alkenyl group which may have a substituent, a phenyl _-C 2 _{-C 12} alkenyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkenyl _group, C 1 _{-C 12} alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl _-C 2 _{-C 12} alkenyl group and 2-naphthyl _-C 2 _{-C 12} alkenyl group, and among them _C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkenyl groups or _C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkenyl groups are preferred.

  The term “alkynyl group” means any one of a linear alkynyl group, a branched alkynyl group and a cyclic alkynyl group, which may have a substituent. The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 15, and further preferably 2 to 10. Examples of the alkynyl group which may have a substituent include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1 -A hexynyl group, 2-hexynyl group, 1-octynyl group, arylalkynyl group, etc. are mentioned.

The term “arylalkynyl group” means an arylalkynyl group which may have a substituent. The arylalkynyl group is an arylalkynyl group which may be substituted with a halogen atom or an alkoxy group. The number of carbon atoms of the arylalkynyl group is preferably 8 to 60, more preferably 8 to 48, and still more preferably 8 to 30. Examples of aryl alkynyl group which may have a substituent, a phenyl _-C 2 _{-C 12} alkynyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkynyl _group, C 1 _{-C 12} alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl _-C 2 _{-C 12} alkynyl and 2-naphthyl _-C 2 _{-C 12} alkynyl group, and among them _C 1 _{-C 12} alkoxyphenyl _-C 2 -C ₁₂ alkynyl or _C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkynyl group are preferable.

The term “monovalent heterocyclic group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. The monovalent heterocyclic group may have a substituent. As the monovalent heterocyclic group, an unsubstituted monovalent heterocyclic group or a monovalent heterocyclic group substituted with a substituent such as an alkyl group is preferable, and a monovalent heterocyclic group is preferable. The number of carbon atoms of the monovalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30 and even more preferably 4 to 20 without including the number of carbon atoms of the substituent. Heterocyclic compounds are not only carbon atoms but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms as elements constituting the ring among organic compounds having a cyclic structure. , A compound containing a heteroatom such as a tellurium atom or an arsenic atom. Examples of the monovalent heterocyclic group which may have a substituent, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group and isoquinolyl group, and among them a thienyl _group, C 1 _{-C 12} alkyl thienyl group, a pyridyl group or a _C 1 _{-C 12} alkyl A pyridyl group is preferred.

  The term “monovalent heterocyclic thio group” is a group in which a hydrogen atom of a sulfanyl group is substituted with a monovalent heterocyclic group, and may have a substituent. Examples of the monovalent heterocyclic thio group include a pyridylthio group, a pyridazinylthio group, a pyrimidinylthio group, a pyrazinylthio group, and a triazinylthio group.

  The term “amino group” means an amino group which may have a substituent. The amino group is preferably an unsubstituted amino group, or an amino group substituted with one or two substituents selected from an alkyl group, an aryl group, and a monovalent heterocyclic group (hereinafter referred to as “substituted amino group”). It is said.) The substituent may further have a substituent (hereinafter, the substituent that the functional group further has may be referred to as “secondary substituent”).

The number of carbon atoms of the substituted amino group is preferably 1 to 60, more preferably 2 to 48, and further preferably 2 to 40, not including the number of carbon atoms of the secondary substituent. Examples of the substituted amino group which may have a secondary substituent include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group Butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3 , 3,7-dimethyl octyl group, a dodecyl group, a cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxy Phenylamino group, bis _(C 1 _{-C 12} alkoxyphenyl) amino _groups, C 1 _{-C 12} alkylphenyl group, bis _(C 1 _{-C 12} alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenyl group, pyridylamino group, pyridazinylamino group, pyrimidinyl group, pyrazinylamino group, triazinylamino group, phenyl _-C 1 _{-C 12} alkylamino _group, C 1 _{-C 12} alkoxyphenyl - C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkyl) amino groups, 1-naphthyl - ₁ -C ₁₂ alkylamino group, and a 2-naphthyl _-C 1 _{-C 12} alkylamino groups and the like.

  The term “silyl group” means a silyl group which may have a substituent. The silyl group is preferably an unsubstituted silyl group, or a silyl group substituted with 1 to 3 substituents selected from an alkyl group, an aryl group and a monovalent heterocyclic group (hereinafter referred to as “substituted silyl group”). It is said.) The substituent may have a secondary substituent.

The number of carbon atoms of the substituted silyl group does not include the number of carbon atoms of the secondary substituent, and is preferably 1 to 60, more preferably 3 to 48, and further preferably 3 to 40. Examples of the substituted silyl group which may have a secondary substituent include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, tert -Butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl - dimethylsilyl group, dodecyl dimethyl silyl group, a phenyl _-C 1 _{-C 12} alkylsilyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylsilyl _group, C 1 _{-C 12} alkylphenyl _-C 1 -C ₁₂ Arukirushi Group, 1-naphthyl _-C 1 _{-C 12} alkylsilyl group, 2-naphthyl _-C 1 _{-C 12} alkylsilyl group, a phenyl _-C 1 _{-C 12} alkyldimethylsilyl group, triphenylsilyl group, tri -p- Examples include xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, and dimethylphenylsilyl group.

  The term “acyl group” means an acyl group which may have a substituent. The acyl group is preferably an acyl group which may be substituted with a halogen atom or the like. The number of carbon atoms in the acyl group is preferably 2-20, more preferably 2-18, and even more preferably 2-16. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The term “acyloxy group” means an acyloxy group which may have a substituent. The acyloxy group is preferably an acyloxy group which may be substituted with a halogen atom or the like. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 18, and further preferably 2 to 16. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The term “imine residue” refers to an imine compound having at least one of the structures represented by the general formula: H—CR ^X1 = N—R ^Y1 or the general formula: H— ^N═C (R ^Y1 ) ₂ Means a residue in which the hydrogen atom in the above general formula is removed. In the above general formula, R ^X1 represents a hydrogen atom, an alkyl group, an aryl group, an arylalkenyl group or an arylalkynyl group, and R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group, an arylalkenyl group or an arylalkynyl group. When two R ^Y1 are present, they may be the same or different, and the two R ^Y1 are bonded to each other to form a divalent group such as an ethylene group or a trimethylene group. A ring may be formed as an alkylene group having 2 to 18 carbon atoms such as a tetramethylene group, a pentamethylene group or a hexamethylene group. Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, or aldimine is substituted with an alkyl group, aryl group, arylalkenyl group, or arylalkynyl group. The number of carbon atoms of the imine residue is preferably 2-20, more preferably 2-18, and even more preferably 2-16. Specific examples of the imine residue include groups represented by the following structural formulas.

The term “amide compound residue” is derived from an amide compound having at least one of structures represented by the general formula: H—NR ^X2 —COR ^Y2 or the general formula: H—CO—N (R ^Y2 ) ₂ . It means a residue obtained by removing a hydrogen atom in the above general formula. In the general formula, R ^X2 and R ^Y2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The number of carbon atoms in the amide compound residue is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16. Examples of amide compound residues include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide Group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

The term “acid imide residue” means a residue obtained by removing a hydrogen atom in the above general formula from an acid imide having a structure represented by the general formula: R ^X3 —CO—NH—CO—R ^Y3. . In the above general formula, R ^X3 and R ^Y3 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or R ^X3 and R ^Y3. Represents a ring structure formed by bonding to each other. The number of carbon atoms of the acid imide residue is preferably 4 to 20, more preferably 4 to 18, and still more preferably 4 to 16. Examples of the acid imide residue include the following groups.

  The term “arylene group” means an atomic group formed by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon, and includes those having an independent benzene ring or condensed ring, It may have a substituent. The number of carbon atoms of the arylene group does not include the number of carbon atoms of the substituent, and is preferably 6 to 60, more preferably 6 to 48, still more preferably 6 to 30, and particularly preferably 6 to 18. Examples of the arylene group include a phenylene group such as a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group; a biphenylylene group such as a 2,7-biphenylylene group and a 3,6-biphenylylene group; 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group and the like; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracene Anthracene diyl group such as diyl group and 9,10-anthracenediyl group; Phenanthrene diyl group such as 2,7-phenanthrene diyl group; 1,7-naphthacene diyl group, 2,8-naphthacene diyl group, 5,12-naphthacene diyl group and the like Naphthacenediyl group; fluorene such as 2,7-fluorenediyl group and 3,6-fluorenediyl group 1,6-pyrenediyl group, 1,8-pyrenediyl group, 2,7-pyrenediyl group, pyrenediyl group such as 4,9-pyrenediyl group; 3,9-perylenediyl group, 3,10-perylenediyl group, etc. Perylenediyl group and the like. Of these, a phenylene group which may have a substituent and a fluorenediyl group which may have a substituent are preferable.

  The term “divalent heterocyclic group” means a remaining atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound, and having a substituent. It may be. The divalent heterocyclic group is preferably a divalent heterocyclic group which may be substituted with an alkyl group or the like.

  The number of carbon atoms of the divalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30 and even more preferably 4 to 12 without including the number of carbon atoms of the substituent. Examples of the divalent heterocyclic group include pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; thiophenediyl groups such as 2,5-thiophendiyl group; Flangedyl groups such as yl groups; quinoline diyl groups such as 2,6-quinolinediyl groups; isoquinoline diyl groups such as 1,4-isoquinolinediyl groups and 1,5-isoquinolinediyl groups; quinoxalines such as 5,8-quinoxalinediyl groups Diyl group; 2,1,3-benzothiadiazole diyl group such as 2,1,3-benzothiadiazole-4,7-diyl group; benzothiazole diyl group such as 4,7-benzothiazol diyl group; Carbazole diyl groups such as carbazole diyl group and 3,6-carbazole diyl group; Phenoxazines such as 3,7-phenoxazine diyl group Yl group; phenothiazine-diyl group such as 3,7-phenothiazine-diyl group; 2,7 dibenzosilole dibenzosilole-diyl group such as a roll-diyl group and the like. Of these, preferably 2,1,3-benzothiadiazole-4,7-diyl group which may have a substituent, phenoxazinediyl group which may have a substituent, and a substituent It may be a phenothiazinediyl group. The divalent heterocyclic group is preferably a divalent heterocyclic group.

The term “substituted carboxy group” means a group in which a hydrogen atom of a carboxyl group is substituted with a substituent.
The number of carbon atoms of the substituted carboxyl group is preferably 1 to 60, more preferably 2 to 20, and further preferably 3 to 15. Examples of the substituted carboxyl group include the groups shown below.

The organic EL device of the present invention includes an anode, a cathode, a light emitting layer provided between the anode and the cathode, and a hole injection layer or a hole transport layer provided between the anode and the light emitting layer. The light emitting layer includes a polymer compound I having at least one structural unit selected from the group consisting of structural units represented by the following formulas (A), (B) and (C), and the following formula (1): Or at least one selected from the group consisting of structural units represented by the following formulas (A), (B) and (C): A polymer compound III which is a block copolymer having a structural unit of a seed and a structural unit represented by the following formula (1),
The hole injection layer or the hole transport layer is represented by the following formula (2), which is a structural unit containing a polymer compound IV having 10 mol% or more of a structural unit represented by the following formula (B) and fullerene or a fullerene derivative. And a polymer compound V comprising at least one structural unit selected from the group consisting of a structural unit comprising azulene or an azulene derivative and a structural unit comprising a stilbene or stilbene derivative represented by the following formula (3): Or a structural unit containing 10 mol% or more of a structural unit represented by the following formula (B), a fullerene or a fullerene derivative, a structural unit containing an azulene or an azulene derivative represented by the following formula (2), and At least 1 selected from the group consisting of structural units containing a stilbene or stilbene derivative represented by the following formula (3) Comprising a constituent unit, a polymer compound VI with.

In formulas (A), (B) and (C),
Ar ¹ and Ar ⁵ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure.
Ar ² , Ar ³ and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group.
X ¹ represents a group represented by —CR ³ ═CR ⁴ — or a group represented by C≡C—. R ³ and R ⁴ each independently represents a hydrogen atom, a carboxyl group, a substituted carboxyl group, a cyano group, an alkyl group, an aryl group, or a monovalent heterocyclic group.
a represents 0 or 1.
-[-(Y) _n -Z-] _m- (1)

In formula (1),
Y represents a divalent group obtained by removing two hydrogen atoms from the structure represented by the following formula (Y-1) or the following formula (Y-2).
Z represents the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z- And a divalent group obtained by removing two hydrogen atoms from the structure represented by 8).
m represents an integer of 4 to 10,000. n represents an integer of 1 to 3.
A plurality of Y, Z and n may be the same or different.
The hydrogen atom of Y and Z may be substituted with R ′, and R ′ is a carboxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. , Alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, imine residue, amide compound residue, acid imide residue, monovalent heterocyclic group and monovalent heterocyclic thio group It represents a functional group selected from the above or a halogen atom. When there are a plurality of R ′, they may be the same or different, and the plurality of R ′ are bonded to each other to form a ring structure together with the carbon atom or nitrogen atom to which each R ′ is bonded. Also good. The functional group may have a substituent.

In formula (Z-1) to formula (Z-8),
X represents a group represented by —CH═ or a group represented by N═. A plurality of X may be the same or different. However, the number of groups represented by -N = as X is 0-2.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent.

In formula (2),
^RZ is selected from the group consisting of alkyl groups, alkoxy groups, aryl groups, alkenyl groups, alkynyl groups, amino groups, silyl groups, halogen atoms, acyl groups, monovalent heterocyclic groups, carboxyl groups, nitro groups, and cyano groups. Represents a functional group selected or a hydrogen atom. The functional group may have a substituent. A plurality of R ^Z may be the same or different.

In formula (3),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ⁿ may be the same or different.
Ar ⁶ and Ar ⁷ each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ^n, and may form a ring structure together with the carbon atom to which each is bonded.

  Hereinafter, materials and components used for the organic EL element will be specifically described.

<Polymer Compound I>
As a light emitting material generally used for an organic EL element, for example, “Organic EL display” (Shitoki Tokito, Chiba Adachi, Hideyuki Murata, Ohm Co., Ltd., August 20, 2004, first edition, first edition) (1 printing issuance) The fluorescent material or triplet light-emitting material described on pages 17 to 48, pages 83 to 99, or pages 101 to 120 can be used. Examples of low-molecular fluorescent materials include perylene and its derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes and other dyes, 8-hydroxyquinoline metal complexes, 8-hydroxyquinoline derivative metal complexes, and aromatics. Examples include amines, tetraphenylcyclopentadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof. More specifically, the light emitting materials described in JP-A-57-51781 and JP-A-59-194393 can be used. Other examples of the light emitting material include, for example, International Publication No. 99/13692, International Publication No. 99/48160, German Patent Application Publication No. 2340304, International Publication No. 00/53656, International Publication No. 01/19834, International Publication No. 00/55927, German Patent Application Publication No. 2348316, International Publication No. 00/46321, International Publication No. 00/06665, International Publication No. 99/54943, International Publication No. 99/54385, US Pat. No. 5,777,070, WO 98/06773, WO 97/05184, WO 00/35987, WO 00/53655, WO 01 / 34722, International Publication No. 99/24526, International Publication No. 00/22027, International Publication No. 00/22026 , WO 98/27136, US Pat. No. 5,736,636, WO 98/21262, US Pat. No. 5,741,921, WO 97/09394, WO 96/29356, International Publication No. 96/10617, European Patent Application No. 0707020, International Publication No. 95/07955, JP 2001-181618 A, JP 2001-123156 A, JP 2001-3045 A, Special JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000. No.-80167, JP-A-10-324870, JP-A-1 -114891, JP-A-9-111233, JP-A-9-45478, etc., polyfluorene, copolymers of derivatives thereof, polyarylene, copolymers of derivatives thereof, polyarylene vinylene, Examples thereof include a copolymer of the derivative, an aromatic amine or a (co) polymer of the derivative.

  The high molecular compound I used for the light emitting layer in this embodiment has at least 1 type of the structural units represented by the following general formula (A), (B) and (C). In addition, although it has at least 1 sort (s) of the structural unit represented by the following general formula (A), (B) and (C), the high molecular compound which consists of a structural chain represented by the said general formula (1) (Luminescent material) is classified into polymer compound II described later or polymer compound III which is a block copolymer.

In the formulas (A), (B) and (C), Ar ¹ and Ar ⁵ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. Ar ² , Ar ³ and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, and X ¹ is a group represented by —CR ³ ═CR ⁴ — or —C≡C— Represents a group represented by R ³ and R ⁴ each independently represents a hydrogen atom, a carboxyl group, a substituted carboxyl group, a cyano group, an alkyl group, an aryl group, or a monovalent heterocyclic group. a is 0 or 1.

  The polymer compound I preferably has a structural unit represented by the general formula (B) because hole transportability is improved.

  In addition, since the charge (which means holes and electrons; hereinafter the same) is improved in injection property and charge transport property, and excitation energy is efficiently formed by the combination of holes and electrons, Polymer light-emitting material having a structural unit represented by formula (A) and a structural unit represented by general formula (B), a structural unit represented by general formula (B) and general formula (C) A polymer light-emitting material having a structural unit represented by: or a structural unit represented by the general formula (A); a structural unit represented by the general formula (B); and the general formula (C). A polymer light-emitting material having a structural unit is preferable. Among these, the polymer compound I having the structural unit represented by the general formula (A) and the structural unit represented by the general formula (B) has a charge injection property, a charge transport property, a hole, and It is more preferable from the viewpoint of formation of excitation energy by electron bonding.

  The polymer compound I comprises a structural unit represented by the general formula (B), a structural unit represented by the general formula (A) and / or a structural unit represented by the general formula (C). In this case, a preferable content ratio (molar ratio) between the structural unit represented by the general formula (B) and other structural units is 1:99 to 40:60, more preferably 3:97 to 30:70. More preferably, it is 5: 95-20: 80.

The number average molecular weight in terms of polystyrene of the polymer compound I is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ . The weight average molecular weight in terms of polystyrene, preferably ^{1 × 10 4 ~5 × 10 7} , more preferably from ^{5 × 10 4 ~1 × 10 7} . When the number average molecular weight and the weight average molecular weight exceed the above lower limit, the resistance to charge transfer tends to be small and the film formability by the coating method tends to improve. There is a tendency for film properties to be good.

In General Formula (A), Ar ¹ represents an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure, and may have a substituent. Here, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl group, an acyloxy group, 1 And a valent heterocyclic group, a carboxyl group, a nitro group, a cyano group, and the like. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a substituted amino group, or a monovalent heterocyclic group is preferable, and an alkyl group or an alkoxy group. Or an aryl group is more preferable.

In the general formula (A), the arylene group represented by Ar ¹ includes 1,4-phenylene group, 1,3-phenylene group, 2,7-biphenylylene group, 1,4-naphthalenediyl group, 1, Examples include 5-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-fluorenediyl group, 3,6-fluorenediyl group, 2,7-phenanthenediyl group, and the like.

  When two or more structural units represented by the general formula (A) are included, these are structural units composed of a fluorenediyl group which may have a substituent, and phenylene groups which may have a substituent. A structural unit, a naphthalenediyl group which may have a substituent, a 2,7-biphenylylene group which may have a substituent, and a 2,7-phenanthrenediyl group which may have a substituent Is preferably selected from the group consisting of

  Preferable examples of the structural unit represented by the general formula (A) include structural units represented by the following formula (1a), (1b), (1c), (1d), or (1e).

In formulas (1a) to (1e),
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different, and a plurality of R ″ are bonded to each other. A ring structure may be formed together with the carbon atoms to which each is bonded.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent.

  As the structural units represented by the general formulas (1a) to (1e), structural units represented by the following general formula (2b), (3b), or (5b) are more preferable.

In formula (2b), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group. These groups may have a substituent. R ⁵⁰ and R ⁵¹ are preferably a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and more preferably an alkyl group or an aryl group.

In Formula (3b), R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. R ⁶⁰ and R ⁶¹ may be bonded to each other to form a ring structure.

R ⁶⁰ and R ⁶¹ are preferably an alkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group. The combination of R ⁶⁰ and R ⁶¹ is preferably such that R ⁶⁰ is an alkyl group, R ⁶¹ is an aryl group or a monovalent heterocyclic group, more preferably R ⁶⁰ is an alkyl group, and R ⁶¹ is An aryl group.

In formula (5b), R ⁷⁰ , R ⁷¹ , R ⁷² and R ⁷³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. These groups may have a substituent. R ⁷⁰ , R ⁷¹ , R ⁷² and R ⁷³ may be bonded to each other to form a ring structure.
R ⁷⁰ , R ⁷¹ , R ⁷² and R ⁷³ are preferably a hydrogen atom, an alkyl group or an aryl group or a monovalent group, and more preferably an alkyl group or an aryl group.

In General Formula (B), Ar ² , Ar ^3, and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Here, examples of the substituent that Ar ² , Ar ³ and Ar ⁴ may have include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, and a halogen atom. , Acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group or halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, substituted amino group, acyl group or cyano group Group is preferable, and an alkyl group, an alkoxy group, or an aryl group is more preferable.

In the general formula (B), examples of the arylene group which is Ar ² , Ar ³ and Ar ⁴ include 1,3-phenylene group, 1,4-phenylene group, 2,7-biphenylylene group and 1,4-naphthalene. Examples thereof include a diyl group, a 2,6-naphthalenediyl group, and a 2,7-fluorenediyl group.

In the general formula (B), examples of the divalent heterocyclic group which is Ar ² , Ar ³ and Ar ⁴ include 2,5-thiophenediyl group, N-methyl-2,5-pyrrolediyl group, 2,5 -Flangiyl group, 4,7-benzo [2,1,3] thiadiazolediyl group, 2,5-pyridinediyl group, 2,5-pyrimidinediyl group and the like.

Ar ² and Ar ⁴ are preferably an arylene group, and are a 1,3-phenylene group, a 1,4-phenylene group, a 2,7-biphenylylene group, a 1,4-naphthalenediyl group, or a 2,6-naphthalenediyl group. Group, more preferably 1,4-phenylene group, 2,7-biphenylylene group or 1,4-naphthalenediyl group, particularly preferably 1,4-phenylene group, This group may have a substituent.

Ar ³ represents 1,3-phenylene group, 1,4-phenylene group, 2,7-biphenylylene group, 1,4-naphthalenediyl group, 2,7-fluorenediyl group, or 4,7-benzo [2, 1,3] thiadiazolediyl group, more preferably 1,4-phenylene group, 2,7-biphenylylene group, 1,4-naphthalenediyl group or 2,7-fluorenediyl group, A 1,4-phenylene group or a 2,7-biphenylylene group is particularly preferable. Moreover, these groups may have a substituent.

R ¹ and R ² are each independently preferably an alkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and even more preferably an aryl group.

Examples of the structural unit represented by the general formula (B) include the following general formulas (B-0), (B-1), (B-2), (B-3), (B-4) and ( And a structural unit represented by B-5).
In the following general formulas (B-0), (B-1), (B-2), (B-3), (B-4) and (B-5), ^Ra represents a hydrogen atom, an alkyl group, Alkoxy group, aryl group, aryloxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group or cyano group Represent. A plurality of R ^a may be the same or different, and may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded.
In the following general formulas (B-0), (B-1), (B-2), (B-3), (B-4) and (B-5), R ^b is a hydrogen atom, an alkyl group, an alkoxy group. Represents a group, aryl group, aryloxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group or cyano group . The plurality of R ^b may be the same or different, and the plurality of R ^b may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The ring structure formed by bonding R ^{b to} each other is preferably a 5-membered ring.

In the general formula (B), when a is 1, Ar ² and Ar ³ or Ar ³ and Ar ⁴ may be bonded to each other to form a ring. When a is 0, Ar ² and Ar ⁴ may be bonded to each other to form a ring. Here, Ar ² and Ar ³ , Ar ³ and Ar ⁴ or Ar ² and Ar ⁴ may be bonded via a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom, or directly. It may be bonded.
More specifically, examples of the structural unit represented by the general formula (B) include the following general formulas (B-6), (B-7), (B-8), (B-9) or The structural unit represented by (B-10) is preferred.

In formulas (B-6), (B-7), (B-8), (B-9) and (B-10), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group represented by — (CR ¹⁷ R ¹⁸ ) _d —. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are preferably an alkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group. Or it is an aryl group, More preferably, it is an aryl group. R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. d represents an integer of 0-2. d is preferably 0 or 1, and more preferably 1. When d is 2, a plurality of R ¹⁷ may be the same or different, and a plurality of R ¹⁸ may be the same or different.

Examples of Ar ⁵ in the general formula (C) include the same divalent groups as Ar ¹ described above. X ¹ is a group represented by —CR ³ ═CR ⁴ — or a group represented by —C≡C—. R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.

  Examples of the structural unit represented by the general formula (C) include the following formulas (C-1), (C-2), (C-3), (C-4), (C-5), (C -6), (C-7), (C-8) or the structural unit represented by (C-9) is mentioned.

<Polymer Compound II>
The polymer compound II is a polymer compound composed of a structural unit represented by the following general formula (1).
-[-(Y) _n -Z-] _m- (1)

  In formula (1), Y represents a divalent group obtained by removing two hydrogen atoms from the structure represented by the following general formula (Y-1) or (Y-2). Z represents the following general formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z And a divalent group obtained by removing two hydrogen atoms from the structure represented by -8). m represents an integer of 4 to 10,000. n represents an integer of 1 to 3. A plurality of Y, Z and n may be the same or different.

  In addition, the hydrogen atom which Y and Z have may be substituted by R '. R ′ is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a halogen atom. When there are a plurality of R ′, they may be the same or different, and a plurality of R ′ are bonded to each other to form a ring structure together with the carbon atom or nitrogen atom to which each is bonded. Also good. However, the hydrogen atom of the functional group may be further substituted with a substituent.

  In formulas (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) and (Z-8), X represents a group represented by —CH═ or a group represented by —N═. A plurality of X may be the same or different. However, the number of groups represented by -N = as X is 0-2.

R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. However, the hydrogen atom of the functional group may be further substituted with a substituent.

  In the structural unit represented by the general formula (1), when n is 2 or more (n ≧ 2), a plurality of Ys represent hydrogen atoms from the structure represented by the general formula (Y-1). In the case of divalent groups excluding two, the structures represented by the plurality of general formulas (Y-1) may be the same or different, and are preferably the same.

  In the structural unit represented by the general formula (1), when n is 2 or more (n ≧ 2), a plurality of Ys represent hydrogen atoms from the structure represented by the general formula (Y-1). In the case of a divalent group excluding two, the structure represented by a plurality of general formulas (Y-1) may consist of only a structure in which all X are represented by -CH =. , A structure in which all Xs are represented by —CH═ and a group in which one or two of X are represented by —N═, and the remaining X is a group represented by —CH═. Or a structure in which one or two of X is a group represented by —N═, and the remaining X consists of only a structure represented by —CH═. It is preferable that all Xs consist only of a structure represented by —CH═.

  When the hydrogen atom of Y and Z is substituted with R ′, R ′ is preferably a functional group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an amino group, and a monovalent heterocyclic group. A group or a halogen atom. R ′ is more preferably a functional group or a halogen atom selected from the group consisting of an alkyl group, an aryl group and a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and particularly preferably an alkyl group. is there. When there are a plurality of R ′, they may be the same or different, and a plurality of R ′ are bonded to each other to form a ring structure together with the carbon atom or nitrogen atom to which each R ′ is bonded. It may be. When R ′ forms a ring structure, it is preferably a ring structure having no unsaturated bond, and examples of R ′ that can form such a structure include an alkyl group, an alkoxy group, an alkylthio group, and an amino group. And a silyl group.

In the structural unit represented by the general formula (1), when n is 2 or more (n ≧ 2), a plurality of Ys represent hydrogen atoms from the structure represented by the general formula (Y-2). In the case of a divalent group excluding two, the structures represented by the plurality of general formulas (Y-2) may be the same or different, and are preferably the same.
In the structural unit represented by the general formula (1), when n is 2 or more (n ≧ 2), a plurality of Y are hydrogen atoms from the structure represented by the general formula (Y-2). In the case of a divalent group in which two are removed, the structure represented by a plurality of general formulas (Y-2) may be composed only of groups in which all Xs are represented by -CH =. Well, both X is a group represented by -CH = and one or two of X are groups represented by -N =, and the remaining X is a group represented by -CH = Or one or two of X may be a group represented by -N =, and the remaining X may consist only of a group represented by -CH =, all It is preferable that X in the group consists only of a group represented by —CH═.

In the structural unit represented by the general formula (1), m structures represented by [— (Y) _n —Z—] may be the same as or different from each other. For example, when m = 4 and n is four, n = 1 in order from the structure located on one end side of the array of the four connected structures toward the structure located on the other end side. If a 2,1,2 a structural unit represented by the general formula ^{(1), - [- Y} 01 -Z 01 -] - [- Y 02 -Y 03 -Z 02 -] - [- Y 04 ^{-Z 03 -] - [- Y} 05 -Y 06 -Z 04 -] - denoted. Here, Y ⁰¹ , Y ⁰² , Y ⁰³ , Y ⁰⁴ , Y ⁰⁵ and Y ⁰⁶ may be the same or different, and Z ⁰¹ , Z ⁰² , Z ⁰³ and Z ⁰⁴ are the same. May be different. The same applies even if m and n are other integer combinations.

In the structural unit represented by the general formula (1), included in the divalent group represented by the formulas (Z-1) to (Z-8) and the following formulas (Z-9) to (Z-20). R ^X is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and an aryl group. Is more preferable. Further, the formula (Z-4), (Z -6), (Z-8), in the divalent groups represented by (Z-15) and (Z-16), one of the two ^{R X,} It is preferable that one is an alkyl group and the other is an aryl group. In the divalent groups represented by the formulas (Z-5), (Z-17), and (Z-18), a plurality of R ^X are bonded to each other, and a ring is formed together with the carbon atom to which each is bonded. It is preferable to form a structure. The ring structure may be a ring having no unsaturated bond or a ring having an unsaturated bond.

  In general formula (1), m represents an integer of 4 to 10,000. m is preferably an integer of 10 to 10000, more preferably an integer of 30 to 10000, and particularly preferably an integer of 50 to 5000. In general formula (1), a plurality of n's each independently represents an integer of 1 to 3. A plurality of n is preferably the same, and it is more preferable that all of the plurality of n are 1 or all 2.

  In the general formula (1), a plurality of Y's are divalent independently represented by the following general formula (Y-3), (Y-4), (Y-5) or (Y-6). It is preferably a group, more preferably a divalent group represented by the following general formula (Y-3), (Y-4) or (Y-5), and the following general formula (Y-3) Or it is more preferable that it is a bivalent group represented by (Y-5), and it is especially preferable that it is a bivalent group represented by the following general formula (Y-3).

  In formulas (Y-3), (Y-4), (Y-5) and (Y-6), R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. Certain R ″ may be the same or different.

  R ″ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

  Specific preferred structures of Y in the general formula (1) include the following divalent groups.

  In the structural unit represented by the general formula (1), Z represents the general formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z- 6) represents a divalent group obtained by removing two hydrogen atoms from the structure represented by (Z-7) or (Z-8). A plurality of Z are represented by the general formulas (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) and (Z Z-8) may be composed of only one group of divalent groups obtained by removing two hydrogen atoms from the structure represented by Z-8), and may be composed of a plurality of types of groups. It preferably consists of only one group.

  In the structural unit represented by the general formula (1), two or more of a plurality of Z are represented by the general formulas (Z-1), (Z-2), (Z-3), (Z-4), When it is any one of divalent groups obtained by removing two hydrogen atoms from the structure represented by (Z-5), (Z-6), (Z-7) and (Z-8) , General formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z-8) The structures represented by may be the same or different. In general formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z-8) The structures represented are preferably identical. Two or more of a plurality of Z are represented by the general formulas (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), ( When the divalent group is obtained by removing two hydrogen atoms from the structure represented by Z-7) or (Z-8), a plurality of general formulas (Z-1), (Z-2), (Z -3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z-8), all Xs are represented by -CH =. All X is a group represented by —CH═ and one or two of X are groups represented by —N═, and the remaining X is —CH═. Or one or two of X may be a group represented by -N = and the remaining X may be composed only of a group represented by -CH =. All X's are only groups represented by -CH = It made it is preferable.

  In the general formula (1), Z represents the following general formulas (Z-9), (Z-10), (Z-11), (Z-12), (Z-13), (Z-14), ( It is preferably a divalent group represented by Z-15), (Z-16), (Z-17), (Z-18), (Z-19) or (Z-20). A plurality of Z may be the same or different.

In formulas (Z-9) to (Z-20), R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different. May be. However, ^RX is as described above.

  Among these, Z is represented by the general formula (Z-9), (Z-11), (Z-13), (Z-15), (Z-16), (Z-17) or (Z-19). It is preferable that it is a divalent group represented by general formula (Z-9), (Z-11), (Z-15), (Z-16), (Z-17) or (Z-19). Is more preferably a divalent group represented by general formula (Z-11), (Z-15) or (Z-17), A divalent group represented by formula (Z-15) is particularly preferable.

In the general formula (1), specific examples of the structure of Z include the following structures (divalent groups).

  Examples of the combination of Y and Z in the general formula (1) include a combination of a divalent group represented by the formula (Y-3) and a divalent group represented by the formula (Z-9) ( Hereinafter, “(Y-3) and (Z-9)” may be mentioned), and the above (Y-3) and (Z-9) are (Y-3) and (Z-11). , (Y-3) and (Z-13), (Y-3) and (Z-15), (Y-3) and (Z-16), (Y-3) and (Z-17), ( Y-3) and (Z-19), (Y-4) and (Z-9), (Y-4) and (Z-11), (Y-4) and (Z-13), (Y- 4) and (Z-15), (Y-4) and (Z-16), (Y-4) and (Z-17), (Y-4) and (Z-19), (Y-5) And (Z-9), (Y-5) and (Z-11), (Y-5) and (Z-13), (Y-5) and (Z-15) , (Y-5) and (Z-16), (Y-5) and (Z-17), (Y-5) and (Z-19), (Y-6) and (Z-9), ( Y-6) and (Z-11), (Y-6) and (Z-13), (Y-6) and (Z-15), (Y-6) and (Z-16), (Y- 6) and (Z-17) or (Y-6) and (Z-19), preferably (Y-3) and (Z-9), (Y-3) and (Z- 11), (Y-3) and (Z-13), (Y-3) and (Z-15), (Y-3) and (Z-16), (Y-3) and (Z-17) , (Y-3) and (Z-19), (Y-4) and (Z-9), (Y-4) and (Z-11), (Y-4) and (Z-13), ( Y-4) and (Z-15), (Y-4) and (Z-16), (Y-4) and (Z-17), (Y-4) and (Z-19), (Y- 5) and (Z 9), (Y-5) and (Z-11), (Y-5) and (Z-13), (Y-5) and (Z-15), (Y-5) and (Z-16) , (Y-5) and (Z-17) or (Y-5) and (Z-19), more preferably (Y-3) and (Z-9), (Y-3) and ( Z-11), (Y-3) and (Z-15), (Y-3) and (Z-16), (Y-3) and (Z-17), (Y-3) and (Z- 19), (Y-4) and (Z-9), (Y-4) and (Z-11), (Y-4) and (Z-15), (Y-4) and (Z-16) , (Y-4) and (Z-17), (Y-4) and (Z-19), (Y-5) and (Z-9), (Y-5) and (Z-11), ( Y-5) and (Z-15), (Y-5) and (Z-16), (Y-5) and (Z-17) or (Y-5) and (Z-19), Like Alternatively, (Y-3) and (Z-11), (Y-3) and (Z-15), (Y-3) and (Z-16), (Y-3) and (Z-17) , (Y-4) and (Z-11), (Y-4) and (Z-15), (Y-4) and (Z-16), (Y-4) and (Z-17), ( Y-5) and (Z-11), (Y-5) and (Z-15), (Y-5) and (Z-16) or (Y-5) and (Z-17), especially Preferably, (Y-3) and (Z-11), (Y-3) and (Z-15), (Y-3) and (Z-17), (Y-4) and (Z-11) , (Y-4) and (Z-15), (Y-4) and (Z-17), (Y-5) and (Z-11), (Y-5) and (Z-15) or ( Y-5) and (Z-17).

In the structural unit represented by the general formula (1), preferred specific examples of the structure represented by [— (Y) _n —Z—] are shown below.

  In the formula, x and y represent a copolymerization ratio, and x + y = 1.

The number average molecular weight in terms of polystyrene of the polymer compound having the constituent chain represented by the general formula (1) in the main chain is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ⁴ to. 5 × 10 ⁶ . Moreover, the weight average molecular weight in terms of polystyrene is preferably 1 × 10 ^{4 to} 5 × 10 ⁷ , and more preferably 5 × 10 ⁴ to 1 × 10 ⁷ .
When the number average molecular weight and the weight average molecular weight exceed the above lower limit, the resistance to charge transfer tends to be small, and the film formability in the coating method tends to improve, and the number average molecular weight and the weight average molecular weight are above the above upper limits. If it is less than 1, the film formability by the coating method tends to be good.

The composition containing the polymer compound I and the polymer compound II (hereinafter, also referred to as “composition X”) may be a composition composed only of the polymer compound I and the polymer compound II. Although preferred, it may contain other compounds. Here, when the weight of the polymer compound I is W _I , the weight of the polymer compound II is W _II , and the weight of other compounds other than the polymer compounds I and II is W _III , Although there is no limitation, it is preferable to satisfy | fill following formula (W1).
0.5 ≦ W _II × 100 / (W _I + W _II + W _III ) ≦ 37.5 (W1)
More preferably, the following formula (W2) is preferably satisfied.
1.0 ≦ W _II × 100 / (W _I + W _II + W _III ) ≦ 30 (W2)
More preferably, the following formula (W3) is preferably satisfied.
1.0 ≦ W _II × 100 / (W _I + W _II + W _III ) ≦ 20 (W3)
It is particularly preferable that the following formula (W4) is satisfied.
2.0 ≦ W _II × 100 / (W _I + W _II + W _III ) ≦ 15 (W4)

  Below, the preferable manufacturing method of the high molecular compound I of this embodiment and the high molecular compound II is demonstrated in detail. The polymer compound I and the polymer compound II of the present embodiment can be produced by, for example, condensation polymerization.

  Examples of the condensation polymerization include polymerization by Suzuki reaction (Chem. Rev., Vol. 95, p. 2457 (1995)), polymerization by Grignard reaction (Kyoritsu Shuppan, Polymer Functional Materials). Series Volume 2, Polymer Synthesis and Reaction (2), pages 432 to 433), or Method of Polymerization by Yamamoto Polymerization (Prog. Polym. Sci.), Volume 17, 1153-1205 Page, 1992).

  The polymer compound I and the polymer compound II are preferably polymer compounds synthesized by condensation polymerization, and more preferably polymer compounds synthesized by a method of polymerizing by a Suzuki reaction.

In particular, when polymerizing the polymer compound II composed of the structural unit represented by the general formula (1), a structure including the structure represented by [-(Y) _n -Z-] _m is synthesized in advance as one unit. Then, a method of polymerizing a polymer containing a structural unit by a polymerization method capable of controlling the sequence, such as a method of incorporating into a polymer main chain or a method of polymerizing by a Suzuki reaction, can be mentioned. Among these, the method of polymerizing by the Suzuki reaction is preferable, and the synthesis method is not particularly limited as long as it is a polymer composed of the structural unit represented by the formula (1).

Hereinafter, the method of polymerizing by the Suzuki reaction will be described.
In the polymer compound II, the group represented by Y and Z and the structural unit represented by the general formula (1) are represented by, for example, a compound represented by the following general formula (M1) and the following general formula (M2). Or a compound represented by the following general formula (M3) and a compound represented by the following general formula (M4) can be introduced by condensation polymerization.

  When the polymer compound I has a structural unit represented by the general formula (A), (B) or (C), the structure represented by the general formula (A), (B) or (C) The unit is introduced, for example, by condensation polymerization of a compound represented by the following general formula (M5), (M6) or (M7). In the polymer compound I, an arbitrary structure different from the structural unit represented by the general formula (A), (B) or (C) may be introduced by condensation polymerization.

A-Y-A (M1)

  In formula (M1), Y has the same meaning as described above. A represents a halogen atom. Two A may be the same or different.

B'-ZB '(M2)

In formula (M2), Z has the same meaning as described above. B ′ is a boric acid ester residue, a boric acid residue, a group represented by the following formula (a-1), a group represented by the following formula (a-2), or a group represented by the following formula (a-3). Or a group represented by the following formula (a-4). Two B's may be the same or different.

In formulas (a-1) to (a-4), R ^T represents an alkyl group or an aryl group which may have a substituent. X ^A represents a halogen atom.

A-ZA (M3)

In formula (M3), Z and A are as defined above. Two A may be the same or different.

B'-YB '(M4)

In formula (M4), Y and B ′ are as defined above. Two B's may be the same or different.

C′—Ar ¹ —C ′ (M5)

In the formula (M5), Ar ¹ has the same meaning as described above. C ′ represents a halogen atom, a boric acid ester residue, a boric acid residue, a group represented by the above formula (a-1), a group represented by the above formula (a-2), or the above formula (a-3). ) Or a group represented by the above formula (a-4). Two C's may be the same or different.

In the formula (M6), Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and C ′ are as defined above. a is 0 or 1.

C′—Ar ⁵ —X ¹ —C ′ (M7)

In the formula (M7), Ar ⁵ , X ¹ and C ′ are as defined above.

A, examples of the halogen atom represented by C 'and X ^A, a chlorine atom, a bromine atom, an iodine atom.

  Examples of boric acid ester residues represented by B 'and C' include groups represented by the following formulae.

In the above formula (a-1), examples of the alkyl group having no substituent represented by ^RT include a methyl group, an ethyl group, and an n-butyl group. Examples of the alkyl group having a substituent represented by ^RT include a trifluoromethyl group and a pentafluoroethyl group.

In the above formula (a-1), examples of the optionally substituted aryl group represented by ^RT include a phenyl group, a 4-methylphenyl group, and a 4-n-butylphenyl group. It is done.

  Examples of the group represented by the formula (a-1) include a methanesulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, and a 4-methylphenylsulfonate group.

In said formula (a-4), as an alkyl group which does not have a substituent represented by ^RT , a methyl group, an ethyl group, and n-butyl group are mentioned, for example. Examples of the alkyl group having a substituent represented by ^RT include a trifluoromethyl group and a pentafluoroethyl group.

In the above formula (a-1), examples of the aryl group represented by ^RT include a phenyl group, a 4-methylphenyl group, and a 4-n-butylphenyl group.

  Examples of the group represented by the above formula (a-4) include a trimethylstannanyl group, a triethylstannanyl group, and a tributylstannanyl group.

  The compound represented by the general formula (M1), (M2), (M3), (M4), (M5), (M6) or (M7) may be a compound synthesized and isolated in advance. It can also be prepared in a reaction system and used as it is.

  B ′ in the above general formulas (M2) and (M4), and C ′ in (M5), (M6) and (M7) are the above general formulas (M2), (M4), (M5) and (M6). ) And (M7) are simple and easy to handle, and are preferably boric acid ester residues or boric acid residues.

  As the method of the condensation polymerization, the compound represented by the general formula (M1), (M2), (M3), (M4), (M5), (M6) or (M7) is used as an appropriate catalyst or an appropriate one. The method of making it react using a simple base is mentioned.

  Examples of the catalyst include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium complexes such as palladium acetate, nickel [tetrakis (triphenylphosphine)], [1,3- Transition metal complexes such as nickel complexes such as bis (diphenylphosphino) propane] dichloronickel and [bis (1,4-cyclooctadiene)] nickel, and triphenylphosphine and tri (tert-butyl) as necessary. Phosphine), tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl and other catalysts. As the catalyst, a catalyst synthesized in advance can be used, or a catalyst prepared in a reaction system can be used as it is. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the catalyst is used, the catalyst with respect to the total number of moles of the compound represented by the general formula (M1), (M2), (M3), (M4), (M5), (M6) or (M7) The amount of the metal atom is preferably 0.00001 molar equivalent to 3 molar equivalent, more preferably 0.00005 molar equivalent to 0.5 molar equivalent, and 0.0001 molar equivalent to 0.2 molar. It is more preferable that it is equivalent, and it is especially preferable that it is 0.0001 molar equivalent-0.01 molar equivalent.

  Examples of the bases include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride or tripotassium phosphate, or tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide. Or organic bases, such as tetrabutylammonium hydroxide, are mentioned. These bases may be used alone or in combination of two or more.

  When the base is used, the amount used is the mole of the compound represented by the general formula (M1), (M2), (M3), (M4), (M5), (M6) or (M7). It is preferably 0.5 molar equivalents to 20 molar equivalents, more preferably 1 molar equivalents to 10 molar equivalents, based on the total number.

  The condensation polymerization is usually performed in the presence of a solvent such as an organic solvent.

  The organic solvent that can be used for the condensation polymerization is the type or reaction of the compound represented by the general formula (M1), (M2), (M3), (M4), (M5), (M6), or (M7). It depends on. Examples of the organic solvent include toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide or N, N-dimethylformamide. In order to suppress side reactions, it is desirable to deoxidize the solvent. A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the organic solvent used is such that the total concentration of the compounds represented by the general formulas (M1), (M2), (M3), (M4), (M5), (M6) or (M7) is usually The amount is 0.1 to 90% by mass, preferably 1 to 50% by mass, more preferably 2 to 30% by mass.

  The reaction temperature of the condensation polymerization is preferably −100 ° C. to 200 ° C., more preferably −80 ° C. to 150 ° C., and further preferably 0 ° C. to 120 ° C.

  Although the said reaction time is based on conditions, such as reaction temperature, it is 1 hour or more normally, Preferably it is 2 hours-500 hours.

When the polymer compound I and the polymer compound II are both synthesized by condensation polymerization, the total number of moles of the formulas (A), (B), and (C) in the polymer compound I is expressed as N _L , polymer When the number of Y and Z in the compound II is N _Y and _NZ , respectively, N _L , N _Y , and _NZ introduced by condensation polymerization preferably satisfy the following formula (2 ′).
0.5 ≦ N _Y × 100 / (N _Y + N _Z + N _L ) ≦ 37.5 (2 ′)

  The post-treatment of the condensation polymerization is a known method including steps of adding a reaction solution obtained by condensation polymerization to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying the obtained precipitate. Can be performed.

  The polymer compound and the light emitting material obtained as described above can be mixed by a known method to form a composition.

[Polymer Compound III (Block Copolymer)]
In this specification, the term “block copolymer” includes at least one chain structure (hereinafter sometimes referred to as a block) composed of a specific structural unit in a part of a polymer compound, and is included in the block. It means a polymer compound characterized in that the structural unit is not substantially present in any part other than the block in terms of constitution or arrangement.

  In addition, the block copolymer includes a plurality of blocks and blocks in which constituent units included in adjacent blocks are different. That is, adjacent blocks are composed of a chain structure of different structural units, or even a block composed of the same kind of structural units has a different structural ratio or chain structure.

  For example, a block-type copolymer is a polymer compound in which a specific block and a structure connecting two specific blocks may be different in terms of block configuration or block arrangement characteristics. . In addition, for example, a block copolymer is a polymer compound in which a specific block and other blocks may be different in characteristics in terms of block configuration or block arrangement.

  In the block copolymer, the constitution of the block only needs to be able to infer the content of the constitutional unit, the arrangement pattern of the constitutional unit, or the average chain length, and even if these cannot be completely calculated or specified for the constitution of the block. Good.

  The polymer compound III of the present embodiment has a block composed of a structural unit represented by the general formula (1) (hereinafter sometimes referred to as a block A) in the main chain, and further includes the general formula (A), The main chain has a block having at least one of the structural units represented by (B) and (C) (hereinafter sometimes referred to as block B). Light emission during driving of the organic EL element may be light emission from either block A or block B, and is preferably light emission from block B.

  The block A contained in the polymer compound III preferably has 1 to 30 structural units represented by the general formula (1). The structural unit represented by the general formula (1) is the same as the structural unit represented by the general formula (1) already described in the polymer compound II. However, the block B does not include the structural unit represented by the formula (1).

  More preferably, the block B includes a structural unit represented by the general formula (B). More preferably, it is preferable to include one or more structural units represented by the above formula (A) and one or more structural units represented by the above formula (B). The structural units represented by the general formulas (A), (B), and (C) are the same as the structural units represented by the general formulas (A), (B), and (C) described above in the polymer compound I. is there.

  In the block copolymer, the bond between the chemical structure constituting the light emitting material and the structural unit represented by the general formula (1) is, for example, a single bond, a conjugated bond via an aromatic ring, or an alkylene chain. Non-conjugated bond through the like. Among these, a single bond or a conjugated bond via an aromatic ring is preferable.

The number average molecular weight in terms of polystyrene of the block copolymer is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ . Moreover, the weight average molecular weight in terms of polystyrene is preferably 1 × 10 ^{4 to} 5 × 10 ⁷ , and more preferably 5 × 10 ⁴ to 1 × 10 ⁷ . When the number average molecular weight and the weight average molecular weight are above the lower limit, the resistance to charge transfer tends to be small and the film formability by the coating method is likely to be improved. Tend to be better.

A method for producing polymer compound III, which is a block copolymer, will be described. The polymer compound III is preferably synthesized by condensation polymerization, and more preferably synthesized by a method of polymerizing a polymer containing a structural unit by a polymerization method capable of controlling the sequence, such as a method of polymerizing by a Suzuki reaction. The synthesis method is not particularly limited as long as it is a polymer containing a structural unit and a chemical structure constituting the light emitting material. In addition, when synthesize | combining by the method of superposing | polymerizing a block type copolymer by a Suzuki reaction, a block type copolymer is compoundable similarly to the above-mentioned high molecular compound.
When the block copolymer is obtained by condensation polymerization, the groups represented by Y and Z and the chemical structure constituting the light emitting material are introduced into the block copolymer by condensation polymerization. Further, any structure different from the group and chemical structure may be introduced by condensation polymerization.

  Examples of the condensation polymerization method include the same methods as described above. For example, as a method for producing a block copolymer having a block having a structural chain represented by the general formula (1) and a block having a chemical structure constituting a light emitting material other than the block in the main chain, (Method 1), (Method 2) or (Method 3).

(Method 1)
A monomer necessary for forming a block having a structural unit represented by the general formula (1) is subjected to condensation polymerization to prepare a polymer having a structural unit represented by the general formula (1), and then the polymer. A monomer necessary for forming a block having a chemical structure constituting the light emitting material is added to the polymer and subjected to condensation polymerization.
(Method 2)
After preparing a polymer having a chemical structure constituting a light emitting material, which is obtained by condensation polymerization of monomers necessary for forming a block having a chemical structure constituting the light emitting material, the polymer is represented by the general formula (1). A monomer necessary for forming a block having the structural unit represented is added and subjected to condensation polymerization.
(Method 3)
A monomer necessary for forming a block having a structural unit represented by the general formula (1) is subjected to condensation polymerization, and a polymer (a) having a structural unit represented by the general formula (1) is prepared. Then, a polymer (b) obtained by condensation polymerization of monomers necessary for forming a block having a chemical structure constituting the light emitting material is prepared, and the polymer (a) and the polymer (b) are subjected to condensation polymerization.

  Examples of the monomer used in (Method 1) to (Method 3) include the same general formulas (M1), (M2), (M3), (M4), (M5) as those of the above-described polymer compound or luminescent material. ), (M6) or (M7). For example, in the above (Method 1), in the polymer having the structural unit represented by the general formula (1), the structural unit represented by the general formula (1) is a compound represented by the general formula (M1). And a compound represented by the above general formula (M2), or a compound represented by the above general formula (M3) and a compound represented by the above general formula (M4) are introduced by condensation polymerization. . Furthermore, the chemical structure constituting the luminescent material is introduced by adding a compound represented by the general formula (M5), (M6) or (M7) to the polymer and subjecting it to condensation polymerization. As described above, the chemical structure constituting the structural chain represented by the general formula (1) and the light emitting material is introduced into the block copolymer. Also in (Method 2) and (Method 3), in the same manner as in (Method 1), the structural structure represented by the general formula (1) and the chemical structure constituting the light emitting material are introduced into the block copolymer. The

  Conditions such as the type and amount of the catalyst, base and organic solvent used in the condensation polymerization, and the reaction temperature are the same as described above.

In the block copolymer, the number of moles of Y, the number of moles of Z, and the total number of moles of the structural units represented by formulas (A), (B), and (C) are represented by N _Y , N _Z , and When N _K is satisfied, N _Y , N _Z , N _M and N _K preferably satisfy the following formula (4 ′), and more preferably satisfy the following formula (4′-1).
2 ≦ N _Y × 100 / (N _Y + N _Z + N _K ) <40 (4 ′)
3 ≦ N _Y × 100 / (N _Y + N _Z + N _K ) ≦ 30 (4′−1)

[Polymer IV]
The polymer compound IV is a polymer compound having a hole transporting ability having 10 mol% or more of the structural unit represented by the formula (B). The structural unit represented by the formula (B) is as described above. The content of the structural unit represented by the formula (B) in the polymer compound IV is preferably 10 mol% to 99 mol%, more preferably 10 mol% to 90 mol%, more preferably 10 mol% to 50 mol%. Especially preferably, it is 10 mol% -45 mol%.

  The structural unit other than the formula (B) constituting the polymer compound IV is not particularly limited, and is preferably a structural unit capable of forming a conjugated polymer from the viewpoint of hole injecting property and hole transporting property. More preferably, it is a structural unit represented by the formula (A) and / or the formula (C). The structural units represented by formula (A) and formula (C) are as already described.

  The organic EL device according to this embodiment includes a hole injection layer and / or a hole transport layer and a light emitting layer. From the viewpoint of ease of production and device lifetime, a structure in which a light emitting layer is laminated on a hole injection layer or a hole transport layer is preferable. In order to realize such a laminated structure, the polymer compound IV preferably includes a structural unit having a crosslinking group.

  As the structural unit having a crosslinking group that may be contained in the polymer compound IV, for example, one or more selected from the group consisting of a structural unit represented by the following formula (3A) and a structural unit represented by the following formula (4A) These structural units are listed.

In formula (3A),
b represents an integer of 1 to 4;
Ar ¹⁰ represents a (2 + b) -valent aromatic hydrocarbon group or a (2 + b) -valent heterocyclic group, and these groups optionally have a substituent. R ²⁰ represents a single bond, an alkylene group, a phenylene group or a divalent group obtained by combining these groups, and these groups optionally have a substituent. When a plurality of R ²⁰ are present, they may be the same or different.
Q ¹ represents a monovalent crosslinkable group. When a plurality of Q ¹ are present, they may be the same or different.

  In the structural unit represented by the formula (3A), as described above, b is an integer of 1 to 4, but from the viewpoint of producing the structural unit represented by the formula (3A), an integer of 1 to 3. It is preferable that it is, and it is more preferable that it is 1-2.

In the structural unit represented by the formula (3A), the number of carbon atoms of the (2 + b) -valent aromatic hydrocarbon group which may be substituted and which is Ar ¹⁰ is usually 6 to 60, Preferably it is 6-48, More preferably, it is 6-20, More preferably, it is 6-14. The (2 + b) -valent aromatic hydrocarbon group is preferably a divalent, trivalent, tetravalent or pentavalent aromatic hydrocarbon group, and is a trivalent or tetravalent aromatic hydrocarbon group. Is more preferable. Here, the “(2 + b) -valent aromatic hydrocarbon group” means the remaining atomic group obtained by removing (2 + b) hydrogen atoms bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. , A group having a benzene ring, and a group having a condensed ring. The number of carbon atoms does not include the number of carbon atoms of the substituent that Ar ¹⁰ may have.
Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 1-tetracene, pyrene, perylene, fluorene, benzofluorene, phenanthrene, dihydrophenanthrene, chrysene, coronene and the like. As the aromatic hydrocarbon, the stability of the polymer compound of the present embodiment can be further improved, and the hole injection property and / or the light emitting device produced using the polymer compound can be used. Since the hole transport property can be further improved, benzene, naphthalene, anthracene, pyrene, fluorene, benzofluorene, phenanthrene, and dihydrophenanthrene are preferable, and benzene, naphthalene, and fluorene are more preferable.

In the structural unit represented by the formula (3A), the number of carbon atoms of the (2 + b) -valent heterocyclic group which may be substituted and which is Ar ¹⁰ is usually 3 to 60, preferably 3-20. The (2 + b) -valent heterocyclic group is preferably a divalent, trivalent, tetravalent or pentavalent heterocyclic group, more preferably a divalent, trivalent or tetravalent heterocyclic group. . Here, the “(2 + b) -valent heterocyclic group” means a remaining atomic group obtained by removing (2 + b) hydrogen atoms bonded to a carbon atom constituting a ring from a heterocyclic compound. A group having a ring or a condensed ring is included. The number of carbon atoms of the (2 + b) -valent heterocyclic group does not include the number of carbon atoms of the substituent that the (2 + b) -valent heterocyclic group may have.
Examples of the heterocyclic compound include pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, dibenzofuran, dibenzothiophene, carbazole, phenoxazine, phenothiazine, benzothiadiazole, dibenzosilole, and the like.

In the structural unit represented by the formula (3A), when the group represented by Ar ¹⁰ has a substituent, the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, An arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, more preferably alkyl Group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group and cyano group, more preferably alkyl group, alkoxy group and aryl group.

In the structural unit represented by the formula (3A), in addition to improving the hole injecting property and hole transporting property of the organic EL device of this embodiment, the durability of the organic EL device can be improved. ¹⁰ is preferably an aromatic hydrocarbon group which may have a substituent.

In the formula (3A), the alkylene group represented by R ²⁰ may be linear, branched or cyclic, and may have a substituent. In order to easily synthesize a monomer as a raw material, the alkylene group represented by R ²⁰ is preferably a linear alkylene group. The number of carbon atoms of the linear alkylene group and the branched alkylene group is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6. The number of carbon atoms of the cyclic alkylene group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 6.
Examples of the alkylene group include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,3-butylene group, 1,3-pentylene group, 1,4-pentylene group, 1,5-pentylene group, Examples include 1,4-hexylene group, 1,6-hexylene group, 1,7-heptylene group, 1,6-octylene group, 1,8-octylene group and the like.

In the structural unit represented by the formula (3A), the phenylene group represented by R ²⁰ may have a substituent. Examples of the phenylene group include an o-phenylene group, an m-phenylene group, and a p-phenylene group. Examples of the substituent that these phenylene groups may have include an alkyl group, an alkoxy group, a halogen atom, and a cyano group.

In the structural unit represented by the formula (3A), examples of Q ¹ that is a crosslinkable group include the following formulas (Q-1), (Q-2), and (Q-01) to (Q-19). The crosslinkable group represented is mentioned. Since the synthesis of the monomer as a raw material becomes easy, the crosslinkable group has the formulas (Q-1), (Q-2), (Q-01), (Q-03), (Q-04), (Q −06) to (Q-19) are preferable, and the crosslinkable groups are represented by formulas (Q-1), (Q-2), and (Q-09) to (Q-19). A crosslinkable group is more preferable, and a crosslinkable group represented by formulas (Q-1) and (Q-2) is more preferable.

  In formula (Q-1), benzocyclobutene may have a substituent. Examples of the substituent in the crosslinkable group represented by the formula (Q-1) include a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a substituent It may have an amino group that may have, a silyl group that may have a substituent, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, and a substituent. Examples thereof include a monovalent heterocyclic group, a carboxyl group optionally having a substituent, a cyano group, and a nitro group.

In formula (Q-2), nf represents 0 or 1.
R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, amino Represents a group, a silyl group, an acyl group, an acyloxy group, a halogen atom, a cyano group or a nitro group, and these groups optionally have a substituent.

  In addition, in the crosslinkable group represented by the formula (Q-2), the group having a double bond with a wavy line is an E-form, a Z-form, or an E-form and a Z-form are mixed. Means good.

In formulas (Q-01) to (Q-19),
R ^s is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an amino group, a silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group It represents a monovalent heterocyclic group, carboxyl group, cyano group or nitro group, and these groups may have a substituent. Plural present R ^s may be be the same or different.
^Rw represents a hydrogen atom, an alkyl group, an acyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
As R ^s , synthesis of a monomer as a raw material becomes easy, so that a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent may be used. A preferable aryl group, an aryloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent is preferable, a hydrogen atom, an alkyl group which may have a substituent, An alkoxy group which may have a substituent and an aryl group which may have a substituent are more preferable.

R ^w is an alkyl group substituted with an aryl group, an acyl group which may have a substituent, and a monovalent heterocyclic group which may have a substituent, because synthesis of the monomer as a raw material becomes easy Is preferred.
In formulas (Q-01) to (Q-19), “*” represents a bond.

  Examples of the crosslinkable group represented by the formula (Q-1) include a crosslinkable group represented by the following formula (Q-1-1) or (Q-1-2), and a monomer as a raw material Since synthesis is facilitated, a crosslinkable group represented by formula (Q-1-1) is preferable.

In formulas (Q-1-1) and (Q-1-2),
^Rt is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, amino group, silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group It represents a monovalent heterocyclic group, carboxyl group, cyano group or nitro group, and these groups may have a substituent. A plurality of R ^t may be the same or different.

R ^t has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent because synthesis of a monomer as a raw material becomes easy. The aryl group may be an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent, and may have a hydrogen atom or a substituent. A preferable alkyl group, an optionally substituted alkoxy group, and an optionally substituted aryl group, more preferably a hydrogen atom or an optionally substituted alkyl group. More preferably.
In formulas (Q-1-1) and (Q-1-2), “*” represents a bond.

  In the crosslinkable group represented by the formula (Q-2), nf represents 0 or 1, and is preferably 0 because it facilitates the synthesis of the raw material monomer.

In the crosslinkable group represented by the formula (Q-2), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each a hydrogen atom, from the viewpoint of hole injection property, hole transport property and durability, It is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a halogen atom or a cyano group, more preferably a hydrogen atom, an alkyl group or a fluorine atom, and further a hydrogen atom. preferable.

  The structural unit represented by the formula (3A) is preferably a structural unit represented by the following formula (3a) from the viewpoints of hole injecting property, hole transporting property, and durability.

In the formula (3a), d is 1 or 2.
R ²⁰ represents the same meaning as R ²⁰ in the structural unit represented by the above formula (3A), and the same applies to examples and preferred ranges. When there are a plurality of structural units represented by the formula (3a), they may be the same or different.

Q ¹ represents the same meaning as described above. When a plurality of Q ¹ are present, they may be the same or different.
R ³⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a heterocyclic oxy group, and these groups may have a substituent.

  In the structural unit represented by the formula (3a), d is a hole injecting property, a hole transporting property, and a durability of the organic EL device manufactured using the composition containing the polymer compound (A) of the present embodiment. From the viewpoint of more excellent properties and converting an organic thin film containing the composition into an insolubilized organic thin film, it is more preferably 2.

In the structural unit represented by the formula (3a), R ³⁰ represents a hole injecting property, a hole transporting property, and an organic EL device manufactured using the composition containing the polymer compound (A) of the present embodiment. Since durability is more excellent, an alkyl group which may have a substituent or an aryl group which may have a substituent is preferable, and an aryl group which may have a substituent. Is more preferable, and an aryl group substituted with an alkyl group is more preferable.

  In the structural unit represented by the formula (3a), the fluorene ring may have a substituent, and the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an aryl group. Alkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group or cyano group, more preferably alkyl group , An alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group, and a cyano group, and more preferably an alkyl group, an alkoxy group, and an aryl group.

  As the structural unit represented by the formula (3A), for example, the following formulas (3-101) to (3-136) are preferable, and the formulas (3-101) to (3-111), (3-113) to (3-116), (3-119) and (3-125) to (3-136) are more preferable, and the formulas (3-101) to (3-105), (3-107), (3-108) ), (3-111), (3-114) to (3-116), (3-125), (3-127), (3-129), (3-130), (3-133) to (3-136) is more preferable, and the formulas (3-103), (3-105), (3-111), (3-115), (3-125), (3-131), (3-133) Is particularly preferred.

  The polymer compound IV may have only one type of structural unit represented by the above formula (3A) as a structural unit containing a crosslinkable group, or may be represented by the above formula (3A). A plurality of different structural units may be included. From the viewpoint of converting an organic thin film containing the polymer compound IV into an insolubilized organic thin film, it contains at least one monovalent crosslinkable group represented by the formula (Q-1), and the formula (Q-2). At least one kind of monovalent crosslinkable group represented by the formula (Q-1) and at least one kind of monovalent crosslinkable group represented by the formula (Q-2). It is preferable to include it, and it is more preferable to include at least one monovalent crosslinkable group represented by the above formula (Q-1) and the above formula (Q-2).

  The structural unit represented by the following formula (4A) having a crosslinking group, which can be contained in the polymer compound IV, will be described.

In formula (4A), t represents 0 or 1.
Ar ¹¹ and Ar ¹³ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. Ar ¹² represents an arylene group, a divalent heterocyclic group, or a divalent group in which two or more different groups selected from an arylene group and a divalent heterocyclic group are connected to each other. This group may have a substituent.
Q ² represents a monovalent crosslinkable group, and Q ³ has a monovalent crosslinkable group, an alkyl group which may have a substituent, an arylene group which may have a substituent, or a substituent. Represents a divalent heterocyclic group which may be substituted.

  In the structural unit represented by the formula (4A), t is an organic EL produced by using a composition containing the polymer compound (A) according to the present embodiment, which is easy to synthesize a monomer as a raw material. Since the hole injection property, hole transport property and durability of the device can be further improved, 0 is preferable.

In the structural unit represented by the formula (4A), the groups represented by Ar ¹¹ , Ar ¹² and Ar ¹³ are preferably arylene groups which may have a substituent.

In the structural unit represented by the formula (4A), examples of the arylene group in Ar ¹¹ , Ar ¹² and Ar ¹³ include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, 1 , 4-Naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12 A naphthacenediyl group, 2,7-fluorenediyl group, 3,6-fluorenediyl group, 1,6-pyrenediyl group, 2,7-pyrenediyl group and 3,8-perylenediyl group can be selected; , 4-phenylene group, 2,7-fluorenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthre Ndiyl group and 1,6-pyrene diyl group are preferable, and 1,4-phenylene group is more preferable. These groups may have a substituent.

In the structural unit represented by the formula (4A), examples of the divalent heterocyclic group in Ar ¹¹ , Ar ¹² and Ar ¹³ include a 2,5-pyrroldiyl group, a dibenzofurandiyl group, a dibenzothiophenediyl group, and 2, 1,3-benzothiadiazole-4,7-diyl groups can be selected, and these groups may have a substituent.

In the structural unit represented by the formula (4A), as the divalent group in which two or more different groups selected from an arylene group and a divalent heterocyclic group in Ar ¹² may be linked, the above formula ( B-1), (B-2), (B-3), (B-4), (B-5), (B-6) or a group represented by (B-7) is preferable. And more preferably a group represented by the formula (B-1). In addition, these groups may have a substituent.

In the structural unit represented by the formula (4A), when the groups represented by Ar ¹¹ , Ar ¹² and Ar ¹³ have a substituent, the substituent includes an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. , Arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group Preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, more preferably an alkyl group, an alkoxy group or an aryl group. It is.

In the structural unit represented by the formula (4A), examples of the monovalent crosslinkable group represented by Q ² include the above formulas (Q-1), (Q-2), and (Q-01) to (Q-01)-( Q-19) is mentioned, and the organic EL device produced using the polymer compound of the present embodiment is more excellent in hole injecting property, hole transporting property and durability. Crosslinkable groups represented by (Q-1), (Q-2), (Q-01), (Q-03), (Q-04), and (Q-06) to (Q-18) are preferable. The crosslinkable groups represented by formulas (Q-1), (Q-2), and (Q-07) to (Q-18) are more preferable, and the crosslinkable groups represented by formula (Q-1) are more preferable. Further preferred.

In the structural unit represented by the formula (4A), examples of the monovalent crosslinkable group represented by Q ³ include the above formulas (Q-1), (Q-2), and (Q-01) to (Q-01)-( And a crosslinkable group represented by Q-19). Since the organic EL device manufactured using the polymer compound of the present embodiment is more excellent in hole injecting property, hole transporting property and durability, the formulas (Q-1), (Q-2), (Q- 01), (Q-03), (Q-04), and (Q-06) to (Q-18) are preferably crosslinkable groups represented by formulas (Q-1), (Q-2), ( The crosslinkable group represented by Q-07) to (Q-18) is more preferable, and the crosslinkable group represented by Formula (Q-1) is more preferable.

In the structural unit represented by the formula (4A), the alkyl group which may have a substituent represented by Q ³ is the same as the “alkyl group” described as the substituent, but preferably a C ₁ -C ₂₀ alkyl group.

In the structural unit represented by the formula (4A), the aryl group which may have a substituent represented by Q ³ is the same as the “aryl group” described as the substituent, but preferably A phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, or a 2-fluorenyl group.

In the structural unit represented by the formula (4A), the monovalent heterocyclic group optionally having a substituent represented by Q ³ is the “monovalent heterocyclic group” described as the substituent. The same, but preferably a pyridyl group, a pyrimidyl group, a triazyl group or a quinolyl group.

In the structural unit represented by the formula (4A), Q ³ is preferably the same monovalent crosslinkable group as Q ^{1 in} order to facilitate the synthesis of the raw material monomer.

In the structural unit represented by the formula (4A), when the group represented by Q ³ has a substituent, the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, An arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, more preferably alkyl Group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group and cyano group, more preferably alkyl group, alkoxy group and aryl group.

  Examples of the structural unit represented by the formula (4A) include structural units represented by the formulas (4-101) to (4-105), and the formulas (4-101), (4-102), The structural unit represented by (4-104) or (4-105) is preferred, the formula (4-101) or (4-102) is more preferred, and the structural unit represented by the formula (4-101) is further preferable.

  The content of the structural unit having a crosslinking group (total content) is more excellent in thermal crosslinkability when an organic EL device is produced using a composition containing the polymer compound IV. The content is preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 25 mol%, and still more preferably 3 mol% to 20 mol% with respect to all the constituent units contained.

[Polymer Compound V]
The polymer compound V includes a structural unit containing fullerene or a fullerene derivative, a structural unit containing azulene or an azulene derivative represented by the formula (3), and a stilbene or stilbene derivative represented by the formula (4). It is a polymer compound containing at least one structural unit selected from the group consisting of structural units (sometimes referred to as structural unit (c-1)). It is preferable that the high molecular compound V contains the structural unit represented by Formula (B) from a viewpoint of hole injection property and hole transport property besides the said structural unit.
A fullerene derivative refers to two monovalent groups or one two bonds each formed by breaking one bond constituting a carbon-carbon double bond of a skeleton constituting a fullerene. It is a compound substituted with a valent group. The number of carbon-carbon double bonds to be cut may be one or two or more.
The structural unit containing fullerene or a fullerene derivative is a structural unit containing a group containing an atomic group in which one bond constituting a carbon-carbon double bond of a skeleton constituting fullerene is cut from fullerene or a fullerene derivative. (The number of carbon-carbon double bonds to be cleaved may be one or two or more, but preferably one).
The structural unit containing fullerene or fullerene derivative that can be contained in the polymer compound V is not particularly limited as long as it is a structural unit containing fullerene or fullerene derivative. The structural unit containing fullerene or a fullerene derivative that can be contained in the polymer compound V is selected from the group consisting of a structural unit represented by the following formula (5-1) and a structural unit represented by the following formula (5-2). It is preferably at least one kind of structural unit.

In Formula (5-1), Ar ⁸ represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ¹⁴ represents an arylidine group or a trivalent heterocyclic group, and these groups optionally have a substituent.
R ⁷ is a single bond, an alkylene group which may have a substituent having 1 to 20 carbon atoms, an arylene group which may have a substituent having 6 to 20 carbon atoms, or The divalent group which combined these is represented.
R ⁵ and R ⁶ each independently have a hydrogen atom, an alkyl group optionally having a substituent having 1 to 20 carbon atoms, or a substituent having 1 to 20 carbon atoms. Represents an optionally substituted alkoxy group. When a plurality of R ¹ and R ² are present, they may be the same or different.
Ring F represents a fullerene ring.
q represents the integer of 1-4. p represents 0 or 1;
When there are a plurality of R ⁷ , Ar ¹⁴ , R ⁵ , R ⁶ , p and ring F, they may be the same or different. When p is 0, the carbon atom substituted with R ⁵ and the carbon atom substituted with R ⁶ are not directly bonded.

In the formula (5-1), as the arylene group represented by Ar ⁸ , a phenylene group (for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), naphthalenediyl group ( For example, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group), anthracenediyl group (for example, 2,6-anthracenediyl group, 9,10-anthracenediyl group), Phenanthrene diyl group (for example, 2,7-phenanthrene diyl group), dihydrophenanthrene diyl group (for example, 2,7-dihydrophenanthrene diyl group), naphthacene diyl group (for example, 5,12-naphthacene diyl group), fluorenediyl group ( For example, 2,7-fluorenediyl group, 3,6-fluorenediyl group) or perylenediyl group ( For example, 3,8-perylenediyl group) may be mentioned, and these groups may have a substituent.

In formula (5-1), examples of the divalent heterocyclic group represented by Ar ⁸ include pyrrole diyl groups such as N-methyl-2,5-pyrrolediyl group; Pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; quinolinediyl groups such as 2,4-quinolinediyl group and 2,6-quinolinediyl group; 1,4-isoquinolinediyl group, 1, Isoquinolinediyl groups such as 5-isoquinolinediyl group; carbazolediyl groups such as 3,6-carbazolediyl group, 2,5-pyrroldiyl group, 2,1,3-benzothiadiazole-4,7-diyl group, dibenzofurandiyl group , A dibenzothiophene diyl group and a dibenzosilol diyl group, and these groups optionally have a substituent.

In formula (5-1), Ar ⁸ is preferably an arylene group which may have a substituent, and more preferably a fluorenediyl group which may have a substituent.

In formula (5-1), the number of carbon atoms of the arylidine group which may have a substituent represented by Ar ¹⁴ does not include the number of carbon atoms of the substituent, and is usually 6 to 30, preferably Is 6-16. The number of carbon atoms of the trivalent heterocyclic group which may have a substituent represented by Ar ¹⁴ does not include the number of carbon atoms of the substituent and is usually 6 to 30, preferably 6 to 16. is there. The trivalent heterocyclic group may contain a nitrogen atom, an oxygen atom, a sulfur atom, etc. in addition to a carbon atom as an atom forming an aromatic ring.

In the formula (5-1), examples of the arylidine group having no substituent represented by Ar ¹⁴ include a phenidine group, a naphthalenetriyl group, an anthracentriyl group, a phenanthrenetriyl group, a naphthacentriyl group, and a fluorene. A triyl group, a perylene triyl group, a chrysantyl group, and the like can be given. Examples of the arylidine group having a substituent include the above-described groups having a substituent.

In the formula (5-1), examples of the trivalent heterocyclic group having no substituent represented by Ar ¹⁴ include a pyrroltriyl group, a furantriyl group, a pyridinetriyl group, a quinolinetriyl group, and an isoquinolinetri group. Yl group. Examples of the trivalent heterocyclic group having a substituent include the above-described groups having a substituent.

In formula (5-1), R ⁷ is preferably a single bond or an alkylene group having no substituent, more preferably a single bond, or 1 to 20 carbon atoms. An alkylene group having no substituent.

In formula (5-1), R ⁵ and R ⁶ are preferably hydrogen atoms.

In formula (5-1), ring F represents a fullerene ring. Ring _{F, C 60} fullerene _{ring, C 70} fullerene _{ring, C 76} fullerene _{ring, C 78} fullerene ring and _{C 84} fullerene rings and the like, _{preferably, C 60} fullerene _{ring, C 70} fullerene _{ring, C 84} fullerene ring And more preferably a C ₆₀ fullerene ring. Here, an alkyl group or a cyano group may be bonded to these fullerene rings.

  In formula (5-1), q is preferably an integer of 1 to 3, and more preferably 1 or 2.

  In formula (5-1), p is preferably 0.

In formula (5-2), Ar ⁸ represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
R ⁷ is a single bond, an alkylene group which may have a substituent having 1 to 20 carbon atoms, an arylene group which may have a substituent having 6 to 20 carbon atoms, or The divalent group which combined these is shown.
R ^a is a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, an alkoxy group which may have a substituent having 1 to 20 carbon atoms, or A single bond with R ⁷ is represented. A plurality of R ^a may be the same or different. Ring F represents a fullerene ring.
q represents the integer of 1-4. When there are a plurality of R ⁷ and ring F, they may be the same or different.

In formula (5-2), Ar ⁸ , R ⁷ , ring F and q are the same as the examples and preferred examples of the structural unit represented by formula (5-1).

In formula (5-2), R ^a is preferably a hydrogen atom.

  The structural unit represented by the formula (5-1) is more preferably a structural unit represented by the following general formula (6).

In formula (6), R ⁷ has a single bond, an alkylene group which may have a substituent having 1 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Or a divalent group obtained by combining these groups. When there are a plurality of R ⁷ , they may be the same or different.
R ^b represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
s is 1 or 2.

Wherein (6), ^{R 7} is already synonymous with ^{R 7} in the formula (5) and the formula (9) in which described.

In formula (6), R ⁷ is preferably an alkylene group having no single bond or a substituent, and more preferably an alkylene group having no single bond or a substituent having 1 to 6 carbon atoms.

In the formula (6), the alkyl group, alkoxy group, aryl group and monovalent heterocyclic group represented by R ^b are the same as those described in the above “Explanation of terms” and examples.

In the formula (6), R ^b is preferably an alkyl group which may have a substituent, or an aryl group which may have a substituent, more preferably an alkyl group having no substituent or An aryl group having a substituent.

  Examples of the structural unit represented by the general formula (6) include the following formulas (6A-1), (6A-2), (6A-3), (6A-4), (6A-5), (6A -6), (6A-7), (6A-8), (6A-9), (6A-10), and structural units represented by (6A-11).

  A structural unit containing azulene or an azulene derivative represented by the following formula (2) will be described.

In the formula (2), R ^Z represents an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, a monovalent heterocyclic group, a carboxyl group, a nitro group, and A functional group selected from the group consisting of a cyano group or a hydrogen atom.
However, the hydrogen atom of the functional group may be substituted with a substituent. A plurality of R ^Z may be the same or different.
As the structural unit containing azulene or an azulene derivative represented by the formula (2), a structural unit containing a group consisting of an atomic group excluding one R ^Z of the formula (2), or the R of the formula (2) ^Z a include two except comprising structural units, preferably, 2 except comprising constituent units R ^Z azulene or azulene derivative represented by the formula (2).

The two except comprising constituent units ^{R Z} azulene or azulene derivative represented by the formula (2) is preferably a structural unit represented by the following formula (12-1) to (12-6), more Preferably it is a structural unit represented by the following formula (12-1), formula (12-2), formula (12-4), formula (12-5) or formula (12-6), and particularly preferably It is a structural unit represented by Formula (12-1).

In formulas (12-1) to (12-6), R ^Z represents the same meaning as R ^Z in formula (2), and is the same as the examples and preferred ranges in formula (2).

  Specific examples of the structural units represented by the above formulas (12-1) to (12-6) include structural units represented by the following formulas (12-01) to (12-013), preferably , Structural units represented by formulas (12-01) to (12-06), more preferably structural units represented by formulas (12-01) to (12-03), particularly preferably It is a structural unit represented by (12-01).

  The structural unit containing the stilbene or stilbene derivative represented by the following formula (3) will be described.

In formula (3),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ⁿ may be the same or different.
Ar ⁶ and Ar ⁷ each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Ar ⁶ and Ar ⁷ may each be directly bonded to adjacent R ⁿ to form a ring structure.
The structural unit containing the stilbene or stilbene derivative represented by the formula (3) is one selected from the group consisting of R ⁿ , Ar ⁶ and Ar ⁷ from the stilbene or stilbene derivative represented by the formula (3). From the structural unit containing a group consisting of an atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring in the above group, or from the stilbene or stilbene derivative represented by the formula (3), R ⁿ , Examples include a structural unit obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring in one or more groups selected from the group consisting of Ar ⁶ and Ar ⁷ , and preferably represented by the formula (3). It is a structural unit obtained by removing two hydrogen atoms from the stilbene or stilbene derivative.

Two hydrogen atoms directly bonded to the carbon atoms constituting the ring in one or more groups selected from the group consisting of R ⁿ , Ar ⁶ and Ar ⁷ are removed from the stilbene or stilbene derivative represented by the formula (3). The structural unit is at least one selected from the group consisting of a structural unit represented by the following formula (7a), a structural unit represented by the following formula (7b), and a structural unit represented by the following formula (7c). The structural unit is preferably.

In formula (7a),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. R ⁿ of two present, may be the same or different.
Ar ⁷ represents an aryl group or a monovalent heterocyclic group. Ar ⁷ may be directly bonded to adjacent R ⁿ to form a ring structure.
Ar ⁹ represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.

Wherein (7b), R ⁿ is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. R ⁿ of two present, may be the same or different.
Ar ⁹ represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. Two Ar ⁹ may be the same or different. Ar ⁹ may be directly bonded to adjacent R ⁿ to form a ring structure.

In formula (7c),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
R ^{n ′} represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ⁷ represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Ar ⁷ may be directly bonded to R ⁿ to form a ring structure.
Ar ⁹ represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. Ar ⁹ may be directly bonded to R ^{n ′} to form a ring structure.

In formula (7a), formula (7b), and formula (7c), R ⁿ represents the same meaning as R ⁿ in formula (3), and is the same as the examples and preferred ranges in formula (3).

In formula (7a) and formula (7c), Ar ⁷ represents the same meaning as R ⁷ in formula (3), and is the same as the examples and preferred ranges in formula (3).

In the formula (7a), the formula (7b) and the formula (7c), the “arylene group” and the “divalent heterocyclic group” represented by Ar ⁹ are as described in the “Terminology” above.

In formula (7a), formula (7b) and formula (7c), Ar ⁹ is preferably an arylene group which may have a substituent, and more preferably an arylene group. A phenylene group, a naphthalenediyl group and a fluorenediyl group which may have a substituent, and more preferably a phenylene group which may have a substituent.

In the formula (7c), the “arylene group” and the “divalent heterocyclic group” represented by R ^{n ′} are as described in the above “Explanation of terms”.

In formula (7c), R ^{n ′} is preferably an arylene group which may have a substituent, more preferably a phenylene group which may have a substituent, or a substituent. They may be a naphthalenediyl group and a fluorenediyl group, and more preferably a phenylene group which may have a substituent.

  As specific examples of the structural unit represented by the formula (7a), structural units represented by the following formulas (7a-1) to (7a-11) are preferable from the viewpoint of luminance life, and the formula (7a- 1) The structural unit represented by Formula (7a-7)-Formula (7a-10) is more preferable.

In formula (7a-1) to formula (7a-11), R ^X is the same as described above and examples.
In formulas (7a-1) to (7a-11), R ^y has a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. And an optionally substituted aryl group or a monovalent heterocyclic group which may have a substituent. Each R ^y may be the same as or different from each other.

From the viewpoint of luminance lifetime, R ^y is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, more preferably a hydrogen atom or a substituent. An aryl group optionally having a hydrogen atom, and more preferably a hydrogen atom or a phenyl group optionally having a substituent.

  In formula (7a-1) to formula (7a-11), c represents an integer of 0 to 3. c is preferably 0 or 1, more preferably 0.

  The structural unit represented by the formula (7a) is represented by the formula (7a-20) or the formula (7a-1) which is a preferred form of the structural unit represented by the formula (7a-10). The structural unit represented by the formula (7a-30) which is a preferred form of the structural unit is preferable.

  As specific examples of the structural unit represented by the formula (7b), structural units represented by the following formulas (7b-1) to (7b-9) are preferable from the viewpoint of luminance life, and the formula (7b- The structural unit represented by 1) is more preferable.

In formula (7b-1) to formula (7b-9), R ^y is the same as described above and examples.
In formulas (7b-1) to (7b-9), R ⁸ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, An alkylthio group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a substitution An alkenyl group which may have a group, an alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, An acyl group which may have a substituent, an acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, and a monovalent complex which may have a substituent; A cyclic group, a heterocyclic oxy group which may have a substituent, and a substituent. Optionally substituted heterocyclic thio group, optionally substituted imine residue, optionally substituted amide compound residue, optionally substituted acid imide residue , An optionally substituted carboxyl group, hydroxyl group, nitro group or cyano group. Each R ⁸ may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atom to which each R ⁸ is bonded.

R ⁸ is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group.

In formula (7b-4), R ^X is the same as described above and in the examples.

  As the structural unit represented by the formula (7b), a structural unit represented by the formula (7c-20) which is a preferred form of the following formula (7c-1) is preferable.

  As specific examples of the structural unit represented by the formula (7b), structural units represented by the formula (7c-1) to the formula (7c-3) are preferable from the viewpoint of luminance life.

  As the structural unit represented by the formula (3), the formula (7b-20) which is a preferred form of the formula (7b-1) and the formula (7b-30) which is a preferred form of the formula (7b-2). ) Is preferred.

The organic EL device of the present embodiment has a hole injection layer and / or a hole transport layer and a light emitting layer, but on the hole injection layer or the hole transport layer from the viewpoint of ease of production and device lifetime. It is preferable that a light emitting layer is laminated. In order to realize this laminated structure, the polymer compound V preferably includes a structural unit having a crosslinkable group.
The structural unit having a crosslinkable group and the content thereof are as described above. The crosslinkable group is a structural unit represented by formula (B), a structural unit containing fullerene or a fullerene derivative, a structural unit containing azulene or an azulene derivative represented by the above formula (2), and the above formula (3). It may be contained in the structural unit containing the stilbene or stilbene derivative represented.

  The composition ratio of polymer compound IV and polymer compound V in a composition containing polymer compound IV and polymer compound V (hereinafter sometimes referred to as “composition Y”) is particularly limited. However, the structural unit represented by the formula (B) is preferably 10 mol% to 99 mol% with respect to the total number of moles of the structural units constituting the polymer compound IV and the polymer compound IV. More preferably, it is 10 mol%-90 mol%, More preferably, it is 10 mol%-50 mol%, Especially preferably, it is 10 mol%-45 mol%. The structural unit (c-1) is preferably 0.001 mol% to 50 mol% with respect to the total number of moles of the structural units constituting the polymer compound IV and the polymer compound IV, and 0.01 mol % To 20 mol% is more preferable, and 0.01 mol% to 10 mol% is more preferable.

[Polymer Compound VI]
The polymer compound VI will be described. The polymer compound VI contains 10 mol% or more of the structural unit represented by the formula (B) and includes a fullerene or a fullerene derivative, and a structural unit that includes an azulene or an azulene derivative represented by the formula (2). And a polymer compound containing the structural unit (c-1), which is at least one structural unit selected from the group consisting of structural units containing the stilbene or stilbene derivative represented by the formula (3).
The structural unit containing a fullerene or a fullerene derivative, the structural unit containing an azulene or an azulene derivative represented by the formula (2), and the structural unit containing a stilbene or a stilbene derivative represented by the formula (3) are as defined above. is there.

  The organic EL device of the present embodiment has a hole injection layer and / or a hole transport layer and a light emitting layer, but on the hole injection layer or the hole transport layer from the viewpoint of ease of production and device lifetime. It is preferable that a light emitting layer is laminated. In order to realize this laminated structure, the polymer compound VI preferably includes a structural unit having a crosslinkable group. The structural unit having a crosslinkable group and the content thereof are as described above. The crosslinkable group is a structural unit represented by formula (B), a structural unit containing fullerene or a fullerene derivative, a structural unit containing azulene or an azulene derivative represented by the above formula (2), and the above formula (3). It may be contained in the structural unit containing the stilbene or stilbene derivative represented.

  The structural unit represented by the formula (B) in the polymer compound VI of the present embodiment is preferably 10 mol% to 99 mol% with respect to the total number of moles of the structural units constituting the polymer compound VI. More preferably, it is 10 mol% -90 mol%, More preferably, it is 10 mol% -50 mol%, Most preferably, it is 10 mol% -45 mol%. In addition, the structural unit (c-1) is preferably 0.001 mol% to 50 mol%, and 0.01 mol% to 20 mol% with respect to the total number of moles of the structural units constituting the polymer compound VI. More preferably, it is more preferably 0.01 mol% to 10 mol%.

The composition X forming the light emitting layer of this embodiment may contain at least one material selected from the group consisting of a hole transport material and an electron transport material. In addition, the polymer compound III, which is a block copolymer forming the light emitting layer of the present embodiment, is at least one selected from the group consisting of a hole injection material and an electron injection material, and a hole transport material and an electron transport material. It is good also as a composition with a seed material.
The composition Y for forming the hole injection layer and the hole transport layer of the present embodiment may contain a hole injection material and a hole transport material. Further, the polymer compound VI forming the hole injection layer and the hole transport layer of the present embodiment may contain a hole injection material and a hole transport material.
The hole injection material and the electron injection material, and the hole transport material and the electron transport material mainly play a role of adjusting the charge (hole and electron) balance in the organic EL element.

Examples of hole injection materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, starburst amines, Phthalocyanine derivatives, amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, Examples thereof include poly (N-vinylcarbazole) derivatives, organosilane derivatives, and polymers containing these. In addition, conductive metal oxides such as vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, conductive polymers and oligomers such as polyaniline, aniline-based copolymers, thiophene oligomers, and polythiophenes, poly ( 3,4-ethylenedioxythiophene) / polystyrene sulfonic acid, polypyrrole, and other organic conductive materials, polymers containing them, polymer compounds having the structural unit represented by the above formula (1), amorphous carbon, octadecyltri Examples include silane coupling agents such as methoxysilane. Further, tetracyanoquinodimethane derivatives (for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), 1,4-naphthoquinone derivatives, diphenoquinone derivatives, The composition which added acceptor organic compounds, such as a polynitro compound, is mentioned. Among these, aromatic tertiary amine compounds, poly (N-vinylcarbazole) derivatives, vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other conductive metal oxides, polyaniline, aniline series Copolymers, conductive polymers and oligomers such as thiophene oligomers and polythiophenes, organic conductive materials such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid and polypyrrole, and polymers containing them, the above formula ( A polymer compound having the structural unit represented by 1) and a composition obtained by adding an acceptor organic compound to the organic material are preferable.
A method for producing the hole injection layer is not particularly limited, and a known method can be used. Examples of inorganic compound materials include vacuum deposition, sputtering, and ion plating, and examples of low molecular organic materials include vacuum deposition, transfer methods such as laser transfer and thermal transfer, and formation from solutions. And a method using a membrane (a mixed solution with a polymer binder may be used). In the case of a polymer organic material, for example, a method by film formation from a solution can be mentioned.

  The content ratio of the hole injection material in the composition is preferably 0.1 to 100 parts by weight, more preferably 1 to 70 parts by weight with respect to 100 parts by weight of the composition, since the charge balance becomes good. More preferably, it is 5 to 50 parts by weight.

As the electron injection material, known electron injection materials can be used. Examples of the electron injection material include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, Anthraquinone or its derivative, tetracyanoanthraquinodimethane or its derivative, fluorenone derivative, diphenyldicyanoethylene or its derivative, diphenoquinone derivative, anthraquinodimethane derivative, anthrone derivative, thiopyrandioxide derivative, carbodiimide derivative, fluorenylidenemethane Derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivatives Metal complexes, metal phthalocyanines, various metal complexes represented by metal complexes having benzoxazole or benzothiazole as a ligand, organic silane derivatives, polymer compounds having a structural unit represented by formula (1), etc. Can be mentioned. Among these, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, aromatic rings such as naphthalene and perylene. A tetracarboxylic acid anhydride, a metal complex of 8-quinolinol derivative, a metal phthalocyanine, and a polymer compound having a structural unit represented by the formula (1) are preferable.
A method for producing the electron injection layer is not particularly limited, and a known method can be used. Examples of the method for producing the electron injection layer include a vacuum deposition method, a sputtering method, an ion plating method and the like in the case of an inorganic compound material, and a vacuum deposition method, laser transfer and thermal transfer in the case of a low molecular organic material. And a transfer method such as a method of forming a film from a solution (a mixed solution with a polymer binder may be used). In the case of a polymer organic material, an example of a method for producing an electron injection layer is a method by film formation from a solution.

The content ratio of the electron injecting material in the composition is preferably 0.1 to 100 parts by weight, more preferably 1 to 70 parts by weight with respect to 100 parts by weight of the composition because the charge balance becomes good. Yes, more preferably 5 to 50 parts by weight.
The content ratio of the electron injecting material is preferably 0.1 to 100 parts by weight, more preferably 1 to 70 parts by weight with respect to 100 parts by weight of the block copolymer because the charge balance becomes good. More preferably, it is 5 to 50 parts by weight.

Examples of hole transport materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, Examples thereof include polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, and poly (2,5-thienylene vinylene) and derivatives thereof. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Also included are hole transport materials described in JP-A-379992 and JP-A-3-152184. Among these, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives are preferable.
A method for producing the hole transport layer is not particularly limited, and a known method can be used. In the case of inorganic compound materials, vacuum deposition, sputtering, ion plating, and the like can be mentioned. In the case of low molecular organic materials, vacuum deposition, 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 addition, as an example of a method for forming the hole transport layer, in the case of a polymer organic material, a method by film formation from a solution can be given.

The content ratio of the hole transport material in the composition is preferably 3 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the composition because the charge balance becomes good. Especially preferably, it is 3-10 mass parts.
In addition, since the hole transport material has a good charge balance, it is preferably 3 to 30 parts by weight, more preferably 3 to 20 parts by weight, and particularly preferably 3 to 30 parts by weight with respect to 100 parts by weight of the block copolymer. 10 parts by weight are added.

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene And derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Examples thereof include electron transport materials described in JP-A-379992 and JP-A-3-152184. Of these, oxadiazole derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene are preferable.
The method for producing the electron transport layer is not particularly limited, and a known method can be used. Examples of methods for producing the electron transport layer include vacuum deposition, sputtering, ion plating, etc. for inorganic compound materials, and vacuum deposition, laser transfer and thermal transfer for low molecular organic materials. And a transfer method such as a method of forming a film from a solution (a mixed solution with a polymer binder may be used). In addition, as an example of a method for producing an electron transport layer, in the case of a polymer organic material, a method by film formation from a solution can be given.

The content ratio of the electron transport material in the composition is preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the composition because the charge balance is good. Especially preferably, it is 5-20 mass parts.
Further, the content ratio of the electron transport material is preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, particularly preferably 100 parts by mass with respect to 100 parts by mass of the block copolymer, since the charge balance becomes good. 5-20 parts by weight are added.

[Solution (liquid composition)]
When the composition of this embodiment contains an organic solvent, and the block copolymer and polymer compound of this embodiment are mixed with an organic solvent, a solution or dispersion (hereinafter simply referred to as “solution”). It can be said.) By using a solution, film formation by coating can be performed. This solution is generally called an ink composition, a liquid composition, or the like. The solution may contain the above-described hole injection material, electron injection material, hole transport material, and / or electron transport material.

  Examples of organic solvents include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorine solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, trimethyl Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane, acetone, Ketone solvents such as methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Ter, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, polyhydric alcohols such as glycerin and 1,2-hexanediol and derivatives thereof, methanol, ethanol, propanol, isopropanol and cyclo Examples thereof include alcohol solvents such as hexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. In addition, these solvents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these organic solvents, when an organic solvent having a structure containing a benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher is included, the viscosity of the solution falls within an appropriate range. Since there exists a tendency for property to become favorable, it is preferable.

The content ratio of the organic solvent is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 with respect to 1 part by mass of the composition because the film formability is improved. -100 mass parts.
Moreover, since the film forming property becomes favorable, the content ratio of the organic solvent is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 1 part by mass of the block copolymer. Particularly preferred is 30 to 100 parts by mass.

When the composition and / or block copolymer of the present embodiment is in the form of a solution containing an organic solvent, a thin film made of the composition and / or block copolymer is formed (on the other layer). For example, after the solution is applied to a target (another layer, substrate, etc.), the organic film is simply removed by drying the obtained coating film, that is, the film is formed in a simple process. This is very advantageous in manufacturing. The coating film formed by applying the solution may be dried by heating to about 50 ° C. to 150 ° C., and the coating film may be dried by reducing the pressure to about 10 ⁻³ Pa. Also good.

  For the above lamination or film formation process, 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, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, ink jet printing, and nozzle coating can be used.

  When the composition and / or block copolymer of this embodiment contains an organic solvent, the preferred viscosity of the solution varies depending on the coating method applied. The viscosity of the solution is preferably in the range of 0.5 mPa · s to 500 mPa · s at 25 ° C. In addition, when the solution is applied via an ejection device, such as an inkjet printing method, the viscosity of the solution is in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent clogging and flight bending during ejection. It is preferable that

[Thin film]
The composition and / or block copolymer is a thin film that is an organic layer. Such a thin film can be manufactured by a simple process by the above-described method by a coating method using the above solution as a coating solution. And since such a thin film contains the said composition and / or a block type copolymer, it is suitable as functional layers, such as a light emitting layer of an organic EL element, and an organic EL element provided with the said thin film as a light emitting layer is Has an excellent luminance life.

[Organic EL device]
The organic EL element includes a pair of electrodes composed of an anode and a cathode, and the organic layer provided between the pair of electrodes. Here, the organic layer is generally a functional layer such as a light emitting layer. The organic EL element preferably includes a light emitting layer made of the above thin film.

Examples of the configuration of the organic EL element include the following configurations a) to l).
a) Anode / hole injection layer / light emitting layer / cathode b) Anode / hole injection layer / light emitting layer / electron injection layer / cathode c) Anode / hole injection layer / light emitting layer / electron transport layer / cathode d) Anode / Hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode e) anode / hole transport layer / light emitting layer / cathode f) anode / hole transport layer / light emitting layer / electron injection layer / cathode g) Anode / hole transport layer / light emitting layer / electron transport layer / cathode h) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode i) anode / hole injection layer / hole transport layer / Emissive layer / cathode j) anode / hole injection layer / hole transport layer / emission layer / electron injection layer / cathode k) anode / hole injection layer / hole transport layer / emission layer / electron transport layer / cathode l) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode Here, “/” indicates that the layers sandwiching the layer are adjacent to each other. Represents. The same applies hereinafter.

  Note that the light-emitting layer is a layer having a function of emitting light. The hole injection layer is a layer having a function of injecting holes, and the electron injection layer is a layer having a function of injecting electrons. The hole injection layer and the electron injection layer are collectively referred to as a charge injection layer. The hole transport layer is a layer having a function of transporting holes, and the electron transport layer is a layer having a function of transporting electrons. The hole transport layer and the electron transport layer are collectively referred to as a charge transport layer.

  The lamination / film formation of each layer is preferably performed by a coating method using a solution. For lamination / film formation from solution, 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, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, ink jet printing, and nozzle coating can be used.

  What is necessary is just to select the thickness of a light emitting layer so that a drive voltage and luminous efficiency may become an appropriate value. The thickness of the light emitting layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The hole transport layer may be formed by any method, but when the hole transport material is a low molecular compound, it is preferable to form a film using a mixed solution with a polymer binder. When the hole transport material is a polymer compound, it is preferable to form a film using a solution.

  The polymer binder that can be mixed is preferably a polymer binder that does not extremely inhibit charge transport and does not strongly absorb visible light. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The thickness of the hole transport layer may be selected so that the driving voltage and the light emission efficiency are appropriate values, but at least a thickness that does not cause pinholes is required. The driving voltage becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the organic EL element has an electron transport layer, the electron transport material used is as described above. The electron transport layer may be formed by any method, but when the electron transport material is a low-molecular compound, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is preferable. When the electron transport material is a polymer compound, a method of forming a film from a solution or a molten state is preferable. For film formation from a solution or a molten state, a polymer binder may be used in combination. For film formation using a solution, a method already exemplified as a coating method can be used.

  The polymer binder that can be mixed is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. Examples of polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The thickness of the electron transport layer may be selected so that the drive voltage and the light emission efficiency are appropriate values, but at least a thickness that does not cause pinholes is required. Is undesirably high. Therefore, the thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Further, among the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the drive voltage of the element are particularly charge injection layers (hole injection layers). , Sometimes referred to as an electron injection layer). Furthermore, in order to improve the adhesion with the electrode and the charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode. Therefore, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. Note that the order and number of layers to be stacked, and the thickness of each layer may be selected in consideration of light emission efficiency and element lifetime.

  The charge injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and has an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer. Examples thereof include a layer including a material having a material, a layer including a material provided between the cathode and the electron transport layer, and having a material having an intermediate electron affinity between the cathode material and the electron transport material included in the electron transport layer.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm to 10 ³ S / cm, and a leakage current between the light emitting pixels. for the smaller ^is more preferably ^{10 -5 S / cm~10 2 S /} cm, further preferably ^{10 -5 S / cm~10 1 S /} cm. In order to satisfy this range, the conductive polymer may be doped with an appropriate amount of ions.

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

  The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be selected in relation to the electrode and the material of the adjacent layer, and examples thereof include the above-described hole injection material and electron injection material.

The insulating layer is a layer having a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 nm to 10 nm, more preferably 1 nm to 5 nm.
Examples of materials used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the configuration of the organic EL element provided with an insulating layer include organic EL elements having the following structures m) to r).
m) Anode / insulating layer / hole transporting layer / light emitting layer / cathode n) Anode / hole transporting layer / light emitting layer / insulating layer / cathode o) Anode / insulating layer / hole transporting layer / light emitting layer / insulating layer / Cathode p) Anode / insulating layer / hole transport layer / light emitting layer / electron transport layer / cathode q) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode r) Anode / insulating layer / hole Transport layer / light emitting layer / electron transport layer / insulating layer / cathode

[substrate]
The substrate on which the organic EL element is formed may be a substrate that does not change chemically when a functional layer such as an electrode or an organic layer is formed. Examples of the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the electrode on the opposite side to the electrode closer to the substrate is preferably transparent or translucent.

  In the present embodiment, it is usually preferable that at least one of the anode and cathode electrodes is transparent or translucent, and the anode side is transparent or translucent.

[anode]
As a material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium tin oxide (indium oxide, zinc oxide, tin oxide, or a composite thereof) A film made of a conductive inorganic compound such as ITO) or indium zinc oxide (IZO), or a film formed of NESA, gold, platinum, silver, copper, or the like is used. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode. In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, or carbon, or a layer made of a metal oxide, a metal fluoride, or an organic insulating material may be provided on the anode. .

  Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  The thickness of the anode can be selected in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 40 nm to 500 nm. .

[cathode]
As a material for the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Metals such as europium, terbium or ytterbium, two or more of them, or one or more of them, and one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin An alloy with a seed or more, graphite, a graphite intercalation compound, or the like is used.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.

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

  Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the light emitting layer or between the cathode and the electron transport layer. A protective layer for protecting the organic EL element may be attached. In order to stably use the organic EL 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 organic EL element from the outside.

  As the protective layer, resin, metal oxide, metal fluoride, metal boride, or the like can be used. Further, as the protective cover, a glass plate or a plastic plate having a low water permeability treatment on the surface can be used, and the protective cover is sealed by sticking it to the element substrate with a thermosetting resin or a photocurable resin. Are preferably used. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and the moisture adsorbed in the manufacturing process can be prevented by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element.

  An organic EL element having an organic layer containing the composition and / or block copolymer of the present embodiment includes a curved light source and a planar light source such as a planar light source (for example, illumination); a segment display device, a dot It is useful for display devices such as matrix display devices (for example, dot matrix flat displays) and liquid crystal display devices (for example, liquid crystal display devices, backlights of liquid crystal displays). Further, the composition and / or block copolymer of the present embodiment is suitable as a material used for the production thereof, in addition to a laser dye, an organic solar cell material, an organic semiconductor for an organic transistor, It is also useful as a conductive thin film and a material for conductive thin films such as an organic semiconductor thin film, a light emitting thin film material that emits fluorescence, and a field effect transistor material.

  When the light emitting layer containing the composition and / or block copolymer of this embodiment is used as white illumination, a light emitting material other than blue may be included in the light emitting layer in order to obtain white color purity. Alternatively, a second light emitting layer having a light emitting material other than blue may be included.

  In order to obtain planar light emission using an organic EL device having an organic layer containing the composition and / or block copolymer of the present embodiment, the planar anode and cathode are arranged so as to overlap each other. Just do it. Further, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar organic EL element, either one of the anode and the cathode, or both electrodes in a pattern-like manner There is a method of forming. A segment display device capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Furthermore, in order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes and arranged orthogonally. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively or may be driven actively in combination with a TFT or the like. These display devices can be used for computers, televisions, portable terminals, cellular phones, car navigation systems, video camera viewfinders, and the like.

  EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Number average molecular weight and weight average molecular weight)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were analyzed by gel permeation chromatography (GPC), and the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated from the analysis results. .
<Analysis conditions>
Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: PLgel MIXED-B (manufactured by Polymer Laboratories)
Column temperature: 40 ° C
Moving bed: Tetrahydrofuran Flow rate: 2.0 mL / min
Detection wavelength: 228 nm

(NMR measurement)
Unless otherwise specified, NMR measurement is 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: MERCURY 300, manufactured by Varian, Inc.). went.

(Measurement of LC-MS)
The measurement of LC-MS was performed by the following method. The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). For the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran and a mixed solution thereof were 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: 2.1 mm, length: 100 mm, particle size: 3 μm) was used.

(Synthesis of compounds used for polymerization)
<Synthesis Example 1: Synthesis of Compound 1A>
Compound 1A was prepared according to Eur. J. et al. Org. Chem. 2005, pp. Synthesized according to the method described in 2207.
Under a nitrogen atmosphere, azulene (3.0 parts by mass) was charged into a three-necked eggplant flask, and hexane was added and stirred. It cooled to 0 degreeC using the ice bath, and NBS (N-bromosuccinimide) (10.4 mass parts) was added little by little, keeping reaction temperature there. After completion of the reaction, the resulting mixture was stirred at room temperature for 2 hours, after which the solvent was removed. The obtained solid was purified by silica gel column chromatography and recrystallization using hexane. The target compound 1A is 3.75 parts by mass (HPLC purity 100%) as a recovery from recrystallization, and 2.83 parts by mass (HPLC purity 99.6%) as a recovery from the filtrate. It was. The overall yield was 99.1%. The structure of Compound 1A was confirmed by NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.32 (d, 12 Hz, 2H), 7.81 (s, 1H), 7.68 (t, 12 Hz, 1H), 7.27 (M, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm) = 140.36, 138.50, 137.01, 136.07, 124.33, 102.99.

<Synthesis Example 2: Synthesis of Compound 3B>
Compound 1B was synthesized according to the following scheme.
Under a stream of argon, 1-bromo-3,5-di-n-hexylbenzene (20.0 parts by mass) and tetrahydrofuran were added to the reaction vessel to prepare a uniform solution, and the solution was cooled to -69 ° C. . To the solution, a 2.76 M n-butyllithium / hexane solution (1 molar equivalent to 1-bromo-3,5-di-n-hexylbenzene) was added dropwise at −68 ° C. over 1.5 hours, The solution was further stirred at -70 ° C for 1.5 hours. Subsequently, the solution which consists of compound 1B-1 (9.0 mass parts) and tetrahydrofuran was dripped at -70 degreeC over 1 hour, and it stirred at -70 degreeC for 2 hours. Next, methanol and distilled water were added to the solution and stirred at -70 ° C, and then the mixture was warmed to room temperature and stirred overnight at room temperature. Subsequently, the reaction mixture was filtered, the filtrate was concentrated, heptane and water were added and stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and liquid-separated. A saturated saline solution was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated to obtain 23.4 parts by mass of Compound 1B.

  Under a stream of argon, Compound 1B (48.0 parts by mass) and dichloromethane were added to the reaction vessel to prepare a uniform solution and cooled to −30 ° C. Boron trifluoride diethyl ether complex (1 molar equivalent with respect to compound 1B) was added dropwise to the solution over 30 minutes, and the mixture was stirred overnight at room temperature. Next, the reaction mixture was cooled to −20 ° C., distilled water was added, and the mixture was stirred for 1 hour and then allowed to stand to remove the separated aqueous layer from the organic layer. Subsequently, water was added and stirred, and the aqueous layer which was allowed to stand and separated was removed from the organic layer. A 10% by mass aqueous sodium hydrogen carbonate solution was added to the obtained organic layer and stirred, and the aqueous layer separated and allowed to stand was removed from the organic layer. The organic layer was concentrated to remove the solvent. Subsequently, the residue was purified by silica gel column chromatography using toluene and heptane as developing solvents, and concentrated to remove the solvent. Subsequently, recrystallization was performed using butyl acetate and methanol to obtain 23.2 parts by mass of the target compound 2B.

Compound 3B was obtained according to the following scheme.
Under a stream of argon, a 2 L 4-necked flask was charged with compound 2B (9.5 parts by mass), compound 3B-1 (6.6 parts by mass), 1,4-dioxane, potassium acetate (7.05 parts by mass), 1, 1′-bis (diphenylphosphino) ferrocene (dppf, 0.1 part by mass) and 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (PdCl ₂ (dppf) · CH ₂ Cl ₂ , 0.15 parts by mass), and the mixture was stirred at 100 ° C. to 102 ° C. for 5 hours. Subsequently, after cooling the obtained reaction mixture to room temperature, it filtered with the filter which spread Celite and the silica gel, and the obtained filtrate was concentrated and the solvent was removed. Subsequently, activated carbon was added to the solution prepared by adding hexane, and the mixture was stirred at a temperature at which hexane was refluxed for 1 hour. The resulting mixture was cooled to room temperature, filtered through a filter packed with celite, and concentrated to remove the solvent. Subsequently, 10.1 mass parts of target compound 3B was obtained by recrystallizing with toluene and acetonitrile.

<Synthesis Example 3: Synthesis of Compound 3C>
Compound 1C was obtained according to the following scheme.
Under an inert gas atmosphere, 3-n-hexyl-5-methylbromobenzene (26.2 parts by mass) and anhydrous tetrahydrofuran were added to a three-necked flask to form a homogeneous solution, and the mixture was cooled to -70 ° C. To the resulting solution, a 2.5M n-butyllithium / hexane solution (0.93 molar equivalent to 3-n-hexyl-5-methylbromobenzene) was kept at a solution temperature of -70 ° C. And stirred at the same temperature for 4 hours to prepare a solution (hereinafter referred to as “solution A”).
Separately, 2-methoxycarbonyl-4,4′-dibromobiphenyl (16.0 parts by mass) and anhydrous tetrahydrofuran were added to a two-necked flask to prepare a solution (hereinafter referred to as “solution B”).
Solution B was added dropwise to solution A so that the temperature of solution A was maintained at -70 ° C, and stirred. The reaction was then stirred at room temperature for 15 hours. Next, water was added to the reaction solution at 0 ° C. and stirred. Subsequently, the solvent was distilled off by concentrating the obtained mixed liquid under reduced pressure, hexane and water were added to the residue, and the mixture was stirred and allowed to stand to remove the generated aqueous layer to obtain an organic layer. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain Compound 1C represented by the following formula as a white solid.

  Under an inert gas atmosphere, Compound 1C (30.0 parts by mass) and anhydrous dichloromethane were added to a three-necked flask and cooled to 5 ° C. Boron trifluoride diethyl ether complex (4.2 molar equivalents relative to compound 1C) was added dropwise to the resulting mixture so that the temperature was kept within the range of 0 ° C to 5 ° C, and then at room temperature. Stir overnight. The reaction solution was carefully poured into ice water, stirred for 30 minutes, allowed to stand, and the separated aqueous layer was removed from the organic layer. A 10% by mass aqueous potassium phosphate solution was added to the organic layer, and the mixture was stirred for 2 hours. Then, the aqueous layer formed by standing was removed from the organic layer. The obtained organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated to distill off the solvent to obtain an oily liquid. Methanol was added to this oily liquid to obtain a solid. By recrystallizing this solid from n-butyl acetate and methanol, 24.0 parts by mass of Compound 2C represented by the following formula was obtained.

In a three-necked flask, compound 2C synthesized in Synthesis Example 3 (8.0 parts by mass), bis (pinacolato) diboron (6.6 parts by mass), 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) Methylene chloride complex (Pd (dppf) .CH ₂ Cl ₂ , 0.15 parts by mass), 1,1′-bis (diphenylphosphino) ferrocene (0.099 parts by mass), anhydrous 1,4-dioxane and potassium acetate (7.0 parts by mass) was added and stirred at 100 ° C. for 20 hours. After cooling the reaction solution to room temperature, the solution was passed through silica gel, the silica gel was washed with toluene, and the resulting solution was concentrated to distill off the solvent to obtain a brown liquid. This liquid was purified by silica gel column chromatography using hexane as a developing solvent. Acetonitrile was added to the liquid obtained by concentrating the eluate to obtain a solid. This solid was recrystallized once using acetonitrile and toluene, recrystallized once using dichloromethane and methanol, and dried under reduced pressure to obtain 2.9 masses of compound 3C represented by the following formula. I got a part.

<Synthesis Example 4: Synthesis of Compound 4F>
In a three-necked flask, 9.6 parts by mass of 3,5-dibromophenol, 30.9 parts by mass of 3,5-bis (4-tert-butylphenyl) phenylboronic acid (the method described in JP-A-2005-82730) And 95.0 parts by mass (20% by mass aqueous solution) of tetraethylammonium hydroxide were added, and the gas in the flask was replaced with nitrogen gas. Thereto were added 0.15 parts by mass of toluene and dichlorobis (triphenylphosphine) palladium, and the mixture was heated at 100 ° C. for 8 hours. Then, when the obtained liquid mixture was allowed to cool, crystals were precipitated. The crystals were dissolved by adding chloroform, and the resulting solution was acidified with 1N hydrochloric acid and separated. The obtained aqueous layer was extracted with chloroform, and the extracted chloroform was combined with the organic layer and washed with water and saturated brine in this order. The washed organic layer was filtered through a glass filter covered with silica gel and the solvent was distilled off to obtain 41.8 parts by mass of a crude product. Hexane was added thereto, and after raising the temperature to the reflux temperature, the mixture was slowly cooled to room temperature, filtered, and washed with hexane to obtain 28.0 parts by mass of Compound 1F represented by the following formula.

LC-MS (APPI-MS, posi) 775 ([M + H] ⁺ , exact mass = 774)
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.35 (36H, s), 5.19 (1H, s), 7.15 (s, 2H), 7.47 (d, 8H) ), 7.59 (s, 1H), 7.60 (d, 8H), 7.78 (s, 6H).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.8, 34.9, 113.9, 119.6, 125.2, 125.7, 126.2, 127.4, 138. 6, 142.1, 142.6, 144.0, 150.9, 156.6.

  The gas in the 4-necked flask was replaced with nitrogen gas, and 28.0 parts by mass of Compound 1F and 13.0 parts by mass of N, N-dimethyl-4-aminopyridine were dissolved in dehydrated dichloromethane in the 4-necked flask. Cooled to. There, 25.0 mass parts of trifluoromethanesulfonic anhydride was dripped over 30 minutes. And after stirring for 20 minutes, the cold bath was removed and stirring was continued for 1.5 hours. The obtained mixed solution was passed through a glass filter covered with silica gel, filtered, and washed with toluene. When the solvent was distilled off from the obtained mixed liquid, 28.9 parts by mass of Compound 2F represented by the following formula was obtained.

LC-MS (ESI-MS, positive) 945 ([M + K] ⁺ , exact mass = 906)
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.38 (36H, s), 7.52 (8H, d), 7.57 (2H, s), 7.64 (8H, d ), 7.77 (4H, s), 7.85 (2H, s), 7.97 (1H, s).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 119.3.

  The gas in the four-neck flask was replaced with nitrogen gas, and 6.1 parts by mass of phenoxazine was added and dissolved in dehydrated toluene. Thereto, 0.71 part by mass of tris (dibenzylideneacetone) dipalladium, 0.86 part by mass of 1,1′-bis (diphenylphosphino) ferrocene and 15.2 parts by mass of cesium carbonate were added and heated to 110 ° C. . A solution prepared by dissolving 28.9 parts by mass of Compound 2F in dehydrated toluene with nitrogen bubbling was added dropwise over 1 hour. Then, after stirring for 20 hours, the obtained mixture was filtered with a glass filter with silica gel while hot, and washed with toluene. When the solvent was distilled off from the obtained mixed liquid, 33.0 parts by mass of a crude product was obtained. This crude product was dissolved in toluene, and the obtained solution was dropped into 1 L of methanol to cause reprecipitation. The obtained solution was filtered and washed with methanol to obtain 50.0 parts by mass of a crude product. Toluene was added and dissolved by heating, ethanol was added dropwise and recrystallized. Furthermore, when the obtained product was filtered and washed with ethanol, 24.8 parts by mass of the product was obtained. When this product was recrystallized using a mixed solvent of toluene and ethanol, 16.6 parts by mass of Compound 3F represented by the following formula was obtained.

LC-MS (APCI, positive) 940 ([M + H] ⁺ , exact mass = 939)
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.37 (36H, s), 6.13-6.16 (2H, m), 6.62-6.71 (6H, m) , 7.50 (8H, d), 7.64 (8H, d), 7.72 (2H, s), 7.83 (6H, s), 8.11 (1H, s).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 113.7, 115.8, 121.7, 123.7, 125.0, 126.0, 126. 1, 126.3, 127.4, 128.8, 134.6, 138.4, 140.4, 141.1, 142.8, 144.3, 145.3, 151.0.

  The gas in the four-necked flask was replaced with nitrogen gas, and 16.6 parts by mass of Compound 3F was added and dissolved in chloroform. The obtained solution was cooled to 0 ° C., and a solution obtained by dissolving 6.3 parts by mass of NBS (N-bromosuccinimide) in DMF was added dropwise thereto over 50 minutes. And after stirring for 10 minutes, the cold bath was removed and stirring was continued for 3 hours. The obtained mixed solution was cooled again to 0 ° C., and a solution in which 0.1 part by mass of NBS was dissolved in DMF was added dropwise thereto. And after stirring for 1.5 hours at room temperature, water was dripped there and liquid-separated. The obtained aqueous layer was extracted twice with toluene, the extracted toluene was combined with the organic layer, and toluene was added. The resulting mixture was washed with water and saturated brine. The washed mixture was filtered through a glass filter with silica gel and washed with toluene. When the solvent was distilled off from the obtained mixed liquid, 25.1 parts by mass of Compound 4F represented by the following formula was obtained.

LC-MS (APCI, positive) 1096 ([M + H] ⁺ , exact mass = 1095)
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.37 (36H, s), 5.99 (2H, d), 6.75 (2H, d), 6.85 (2H, brs) ), 7.50 (8H, d), 7.61-7.65 (10H, m), 7.82 (6H, d), 8.11 (1H, s).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 113.3, 114.9, 119.0, 125.0, 126.2, 126.7, 127. 3, 128.2, 129.3, 133.5, 138.3, 139.6, 140.7, 142.9, 144.5, 145.6, 151.1.

<Synthesis Example 5: Synthesis of Compound 4I>
Under an argon gas atmosphere, 1-bromo-3,5-di-n-hexylbenzene (58.4 g) and tetrahydrofuran were added to the reaction vessel to prepare a homogeneous solution and cooled to -75 ° C. To this 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 for 1.5 hours. The solution was added dropwise, and the solution was further stirred at -70 ° C for 1.5 hours. Next, a solution consisting of 2,7-dibromofluorenone (55.2 g) and tetrahydrofuran was added dropwise thereto at −75 ° C. over 1 hour, and the reaction solution was warmed to room temperature and stirred for 4 hours. Next, the solution was cooled to 0 ° C., slowly added with acetone and a 2 mol% aqueous hydrochloric acid solution, stirred, then warmed to room temperature and allowed to stand at room temperature. Next, the reaction mixture was filtered, the filtrate was concentrated, hexane and water were added and stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and liquid-separated. A saturated saline solution was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated to obtain Compound 1I (30.2 g) represented by the following formula.

  The reaction vessel was placed under an argon stream, and Compound 1I (27.7 g) and trifluoroacetic acid (36 mL) were added. A mixed solution of trimethylsilane (8.4 mL) and hexane (25 mL) was added dropwise to the solution over 30 minutes, and the mixture was stirred overnight at room temperature. Next, the reaction solution was cooled to 10 ° C., hexane and distilled water were added, and the mixture was stirred for 1 hour. Then, the aqueous layer which was allowed to stand and separated was removed from the organic layer. Subsequently, water was added and stirred, and the aqueous layer which was allowed to stand and separated was removed from the organic layer. A saturated saline solution was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated. Subsequently, the mixture was purified by silica gel column chromatography using hexane and dichloromethane as developing solvents, and concentrated to remove the solvent. Then, the compound 2I (12.1 g) represented by the following formula was obtained by washing with methanol.

  Under a stream of argon, Compound 2I (12.0 g), dimethyl sulfoxide (60 mL), water (2 mL) and potassium hydroxide (4.85 g) were added to the reaction vessel. Methyl iodide (4.1 mL) was added dropwise to the solution, and the mixture was stirred overnight at room temperature. Next, hexane and distilled water were added to the reaction solution at room temperature, and the mixture was stirred for 1 hour. Then, the aqueous layer which was allowed to stand and separated was removed from the organic layer. Next, water was added thereto and stirred, and the aqueous layer obtained by allowing the reaction solution to stand and separating was removed from the organic layer. A saturated saline solution was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated. Subsequently, recrystallization was performed using methanol and butyl acetate to obtain a target compound 3I (4.3 g) represented by the following formula.

Under an argon gas atmosphere, in a reaction vessel, compound 3I (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) 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (PdCl ₂ (dppf) · CH ₂ Cl ₂ , 88 mg) was added, and the mixture was stirred at 100 ° C. for 20 hours. Subsequently, after cooling the obtained reaction mixture to room temperature, it filtered with the filter which spread Celite and the silica gel, and the obtained filtrate was concentrated and the solvent was removed. Subsequently, activated carbon was added to the solution prepared by adding hexane, and the mixture was stirred at a temperature at which hexane was refluxed for 1 hour. The resulting mixture was cooled to room temperature, filtered through a filter packed with celite, and concentrated to remove the solvent. Subsequently, recrystallization was performed with toluene and methanol to obtain a target compound 4I (3.9 g) represented by the following formula.

<Synthesis Example 6: Synthesis of Compound 1T>
The gas inside the 100 mL three-necked flask was replaced with nitrogen gas, and 2-ethylhexyl magnesium bromide (1.0 M diethyl ether solution, 25 mL, 25 mmol) was added and refluxed. A suspension of 2-bromoanthracene (5.34 g, 20.8 mmol) and PdCl ₂ (dppf) · CH ₂ Cl ₂ (33 mg, 0.04 mmol) suspended in 50 mL of dehydrated cyclopentyl methyl ether in this solution Was added dropwise over 35 minutes. After refluxing for 1 hour, the reaction mixture was cooled in an ice bath and 2M hydrochloric acid (5 mL) was added dropwise. Thereto, 50 mL of toluene was added, and washing was performed by sequentially separating with 50 mL and 30 mL of water. The aqueous layers were combined and re-extracted with toluene. The organic layers were combined and washed with 30 mL of saturated brine. The mixture was filtered through a glass filter with 20 g of silica gel and washed with toluene. When the solvent of the filtrate was distilled off, 7.45 g of a crude product was obtained.

  5.40 g of the crude product was recrystallized from isopropyl alcohol (54 mL). Here, after confirming the dissolution of the crude product by heating, crystallization was observed at an internal temperature of 65 ° C., and the mixture was kept at this temperature for 2 hours. Thereafter, the resulting solution was slowly cooled, allowed to cool to room temperature, filtered, and washed with isopropyl alcohol. Recrystallization with isopropyl alcohol was further repeated twice to obtain 3.81 g of 2- (2-ethylhexyl) anthracene (yield 67.2%) as a white solid.

LC-MS (APPI positive) 291 ([M + H] ⁺ , exact mass = 290)
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 0.87 to 0.94 (6H, m), 1.27 to 1.48 (8H, m), 1.68 to 1.75 ( 1H, m), 2.71 (2H, d), 7.29 (1H, d), 7.40-7.46 (2H, m), 7.71 (s, 1H), 7.91 (1H) D), 7.95-7.98 (2H, m), 8.32 (1H, s), 8.36 (1H, s).
¹³ C-NMR (CDCl ₃ , 75 MHz): δ (ppm) = 11.1, 14.4, 23.4, 25.9, 29.2, 32.8, 40.9, 41.0, 125. 2, 125.5, 125.6, 126.2, 127.2, 128.2, 128.3, 128.4, 128.5, 131.0, 131.8, 132.2, 139.2.

The gas inside the 300 mL four-necked flask was replaced with nitrogen gas, and 2- (2-ethylhexyl) anthracene (3.50 g, 12.1 mmol) was taken and dissolved in 105 mL of dehydrated dichloromethane. The resulting solution was cooled in an ice bath and bromine (4.17 g, 26.1 mmol) was added dropwise over 20 minutes over 20 minutes. Subsequently, after stirring for 45 minutes, 1 mass% sodium thiosulfate aqueous solution was dripped in 5 minutes, and reaction was stopped. The layers were separated, and the organic layer was extracted with 100 mL of chloroform. The organic layers were combined and washed with water. The mixture was filtered through a glass filter with 20 g of silica gel and washed with hexane. The filtrate was concentrated to give 5.47 g of crude product as a yellow viscous oil.
This yellow viscous oil was purified by silica gel column chromatography (silica 120 g, developing solvent hexane only) to obtain 4.26 g of a yellow viscous oil. Next, 1 L of methanol was added and heated to dissolve, and left overnight to obtain crystals. The obtained slurry was concentrated to about 150 mL and then filtered to obtain 3.91 g of a pale yellow solid.

  The obtained solid was dissolved in hexane (50 mL), activated carbon 1.00 g was added, and the mixture was stirred for 1 hour. The solution was filtered through a glass filter with 13 g of celite, washed with hexane, and the filtrate was concentrated. To this was added isopropyl alcohol (100 mL) and heated, then allowed to cool to 35 ° C., and seed crystals were added. After stirring, the mixture was filtered and washed with isopropyl alcohol to obtain 2.76 g (yield 51%) of 9,10-dibromo-2- (2-ethylhexyl) anthracene (Compound 1T) as a pale yellow solid.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 0.86 to 0.97 (6H, m), 1.20 to 1.40 (8H, m), 1.72 to 1.77 ( 1H, m), 2.78 (2H, d), 7.43 (1H, d), 7.55 to 7.59 (2H, m), 8.28 (1H, s), 8.46 (1H D), 8.51 to 8.54 (2H, m).
¹³ C-NMR (CDCl ₃ , 75 MHz): δ (ppm) = 11.2, 14.5, 23.3, 25.9, 29.1, 32.7, 40.7, 40.9, 122. 8, 123.6, 127.2, 127.3, 127.6, 128.3, 128.4, 128.5, 130.3, 130.8, 131.4, 141.7.

<Synthesis Example 7: Synthesis of Compound 2D>
The gas in the three-neck flask was replaced with nitrogen gas, and 22.6 parts by mass of 1-bromo-3-n-hexylbenzene was dissolved in anhydrous tetrahydrofuran in the three-neck flask. The obtained solution was cooled to −75 ° C. or lower, and a 2.5M n-butyllithium / hexane solution (0.96 molar equivalent with respect to 1-bromo-3-n-hexylbenzene) was dropped, and −75 ° C. It stirred for 5 hours, keeping below. A solution prepared by dissolving 15.0 parts by mass of 2-methoxycarbonyl-4,4′-dibromobiphenyl in anhydrous tetrahydrofuran was added dropwise thereto while maintaining at −70 ° C. or lower. The resulting solution was slowly warmed to room temperature and stirred overnight. While the reaction solution was stirred at 0 ° C., water was added dropwise. After the solvent was distilled off from the reaction solution, water was added to the residue and the mixture was extracted 3 times with hexane. The obtained organic layers were combined, washed with saturated brine, and the aqueous layer was re-extracted with hexane. The obtained organic layers were combined and dried over magnesium sulfate. When the solvent was distilled off from the dried organic layer, 26.4 parts by mass of a crude product of compound 1D represented by the following formula was obtained.

  In a three-necked flask, 26.4 parts by mass of the compound 1D synthesized above was dissolved in dichloromethane, and the gas in the flask was replaced with nitrogen gas. The resulting solution was cooled to 0 ° C. or lower, and boron trifluoride diethyl ether complex (5 molar equivalents relative to compound 1D) was added dropwise while maintaining the temperature at 5 ° C. or lower. The mixture was slowly warmed to room temperature and stirred overnight. The reaction solution was poured into ice water with stirring and stirred for 30 minutes. The reaction solution was separated, and the aqueous layer was extracted with dichloromethane. The organic layers were combined, a 10% by mass potassium phosphate aqueous solution was added for liquid separation, and the organic layer was washed twice with water. The organic layer was dried with magnesium sulfate. The oil obtained by distilling off the solvent from the dried organic layer was dissolved in toluene, passed through a glass filter covered with silica gel, and filtered. After the solvent was distilled off from the filtrate, methanol was added and stirred vigorously. The obtained crystals were filtered and washed with methanol. The washed crystal was recrystallized with a mixed solvent of hexane and butyl acetate to obtain 12.1 parts by mass of Compound 2D represented by the following formula.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.86 (6H, t), 1.26 (12H, m), 1.52 (4H, m), 2.51 (4H, t ), 6.87 (2H, d), 7.00 (2H, s), 7.04 (2H, d), 7.12 (2H, t), 7.46 (2H, dd), 7.48. (2H, d), 7.55 (2H, d).

で表される化合物１Ｋ（１．６４０ｇ、１．８０ｍｍｏｌ）、下記式：

で表される化合物Ｆ８ＢＲ（０．４１１ｇ、０．７５ｍｍｏｌ）、下記式：

で表される化合物１Ｌ（０．２３８ｇ、０．４５ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）及びトルエン（６２ｍＬ）を混合し、１０５℃に加熱した。反応液に２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍＬ）を滴下し、３時間２０分還流させた。反応後、そこに、フェニルボロン酸（３６．８ｍｇ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）及び２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍＬ）を加え、さらに１６時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、水で２回、３質量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、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、重合体１を３．１２ｇを得た。重合体１のポリスチレン換算の数平均分子量は８．０×１０^４であり、ポリスチレン換算の重量平均分子量は２．６×１０^５であった。
化合物１ＫはＷＯ２００５／０４９５４６号記載の合成法に従い合成した。化合物Ｆ８ＢＲはＷＯ２００２／０４５１８４号記載の合成法に従い合成した。化合物１Ｌは特開２０１０−２１５８８６号記載の合成法に従い合成した。 (Manufacture of polymer)
<Polymerization Example 1: Synthesis of Polymer 1>
Under an inert gas atmosphere, compound 3B (2.688 g, 2.96 mmol), the following formula:

Compound 1K (1.640 g, 1.80 mmol) represented by the following formula:

Compound F8BR (0.411 g, 0.75 mmol) represented by the following formula:

Embedded image 1L (0.238 g, 0.45 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (62 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3 hours and 20 minutes. After the reaction, phenylboronic acid (36.8 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (10 mL) were added thereto, and the mixture was further refluxed for 16 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, twice with a 3% by mass aqueous acetic acid solution and twice with water, and the resulting solution was dropped into methanol and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 3.12 g of polymer 1. The polystyrene equivalent number average molecular weight of the polymer 1 was 8.0 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 2.6 × 10 ⁵ .
Compound 1K was synthesized according to the synthesis method described in WO2005 / 049546. Compound F8BR was synthesized according to the synthesis method described in WO2002 / 045184. Compound 1L was synthesized according to the synthesis method described in JP 2010-215886 A.

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位とを、５０：３０：１２．５：７．５のモル比で有するランダム共重合体であった。 The theoretical value obtained from the amount ratio of the raw materials used for the polymer 1 is the following formula:

And the following formula:

And the following formula:

And the following formula:

And a random copolymer having a molar ratio of 50: 30: 12.5: 7.5.

<Polymerization Example 2: Synthesis of Polymer 2>:
Under an inert gas atmosphere, Compound 1A (0.0108 g, 0.04 mmol), Compound 3B (2.77072 g, 2.98 mmol), Compound 1K (1.6397 g, 1.80 mmol), Compound F8BR (0.3907 g, 0 .71 mmol), compound 1L (0.2378 g, 0.45 mmol), dichlorobis (triphenylphosphine) palladium (2.2 mg) and toluene (71 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3.5 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.2 mg), and a 20 wt% tetraethylammonium hydroxide aqueous solution (10 mL) were added thereto, and the mixture was refluxed for 17.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and when the resulting solution was added dropwise to methanol, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate.

This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 2.95 g of Polymer 2. The polystyrene equivalent number average molecular weight of the polymer 2 was 7.9 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 3.3 × 10 ⁵ .

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位とを、５０：３０：１１．８７：７．５：０．６３のモル比で有するランダム共重合体であった。 The theoretical value obtained from the amount ratio of the raw materials used for the polymer 2 is the following formula:

And the following formula:

And the following formula:

And the following formula:

And the following formula:

And a random copolymer having a molar ratio of 50: 30: 11.87: 7.5: 0.63.

で表される化合物１Ｚ（国際公開第２０１１／１６１４１７号記載の合成法に従って合成した。）（０．２４４１ｇ、０．５０ｍｍｏｌ）、化合物１Ｋ（１．０９３０ｇ、１．２０ｍｍｏｌ）、化合物１Ｌ（０．１５８４ｇ、０．３０ｍｍｏｌ）、ジクロロビス（トリス−ｏ−メトキシフェニルホスフィン）（１．８ｍｇ）、及び、トルエン（４７ｍＬ）を混合し、１０５℃に加熱した。 <Polymerization Example 3: Synthesis of Polymer 3>:
Under an inert gas atmosphere, compound 3B (1.8032 g, 1.99 mmol), the following formula:

1Z (synthesized according to the synthesis method described in International Publication No. 2011/161417) (0.2441 g, 0.50 mmol), Compound 1K (1.0930 g, 1.20 mmol), Compound 1L (0. 1584 g, 0.30 mmol), dichlorobis (tris-o-methoxyphenylphosphine) (1.8 mg), and toluene (47 mL) were mixed and heated to 105 ° C.

  A 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 5 hours. After the reaction, phenylboronic acid (26 mg), dichlorobis (triphenylphosphine) palladium (1.8 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 mL) were added thereto, and the mixture was refluxed for 16 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and when the resulting solution was added dropwise to methanol, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate.

This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 2.42 g of Polymer 3. The polystyrene equivalent number average molecular weight of the polymer 3 was 3.9 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 1.9 × 10 ⁵ .

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位とを、５０：３０：７．５：１２．５のモル比で有するランダム共重合体であった。 The theoretical value obtained from the amount ratio of the raw materials used for the polymer 3 is the following formula:

And the following formula:

And the following formula:

And the following formula:

And a random copolymer having a molar ratio of 50: 30: 7.5: 12.5.

<Polymerization Example 4: Synthesis of Polymer 4>:
Under an inert atmosphere, Polymer 1 (1.5000 g, 2.24 mmol), fullerene: C ₆₀ fullerene (manufactured by Sigma-Aldrich) (0.4848 g, 0.67 mmol), and 110 mL of orthodichlorobenzene were mixed. After bubbling with argon for 30 minutes, it was heated to 190 ° C. and stirred for 24 hours. Thereafter, the reaction solution was reprecipitated in methanol, filtered and dried under reduced pressure.
After drying, 80 mL of THF was added to the obtained crude polymer to dissolve it, and celite filtration was performed. Thereafter, Celite was laminated on the lower layer of the Kiriyama funnel, and a mixture of activated carbon and silica gel was laminated on the upper layer, and the polymer solution was passed through. After repeating this operation twice, THF was distilled off and redissolved in toluene. The polymer solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 0.86 g of polymer 4. The polystyrene equivalent number average molecular weight of the polymer 4 was 1.6 × 10 ⁵ , and the polystyrene equivalent weight average molecular weight was 4.8 × 10 ⁵ .
Moreover, the fullerene carrying amount with respect to all the structural units of the obtained polymer 4 was 6.3 mol%. In addition, it is estimated that the structural unit containing fullerene in the polymer 4 is a structural unit represented by the said Formula (6A-1).

<Polymerization Example 5: Synthesis of Polymer 5>
Under an inert gas atmosphere, Compound 3C (2.2749 g, 2.97 mmol), Compound F8BR (0.3290 g, 0.60 mmol), Compound 2D (1.2375 g, 1.92 mmol), the following formula:

で表される化合物３Ｇ（０．１３３０ｇ、０．１８ｍｍｏｌ）、化合物４Ｆ（０．３２９５ｇ、０．３０ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）及びトルエン（７６ｍＬ）を混合し、１０５℃に加熱した。反応液に２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍＬ）を滴下し、２時間還流させた。反応後、そこに、フェニルボロン酸（３７ｍｇ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）、トルエン（６ｍＬ）及び２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍｌ）を加え、さらに１４．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、有機層を、水で２回、３質量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、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、重合体５ ２．４２ｇを得た。重合体５のポリスチレン換算の数平均分子量は１．０×１０^５であり、ポリスチレン換算の重量平均分子量は２．９×１０^５であった。化合物３Ｇは特開２００６−１６９２６５号記載の合成法に従い合成した。

Compound 3G (0.1330 g, 0.18 mmol), Compound 4F (0.3295 g, 0.30 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (76 mL) represented by Heated to ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (6 mL) and 20% by mass tetraethylammonium hydroxide aqueous solution (10 ml) were added thereto, and further 14.5 hours. Refluxed. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the obtained mixture, the organic layer was washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water, and the resulting solution was dropped into methanol and collected by filtration. Obtained. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 2.42 g of polymer 5. The number average molecular weight in terms of polystyrene of the polymer 5 was 1.0 × 10 ⁵ , and the weight average molecular weight in terms of polystyrene was 2.9 × 10 ⁵ . Compound 3G was synthesized according to the synthesis method described in JP-A No. 2006-169265.

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位と、下記式：

で表される構成単位とを、５０：１０：３２：３：５のモル比で有するランダム共重合体であった。 The theoretical value obtained from the amount ratio of the raw materials used for the polymer 5 is the following formula:

And the following formula:

And the following formula:

And the following formula:

And the following formula:

And a random copolymer having a molar ratio of 50: 10: 32: 3: 5.

<Polymerization Example 6: Synthesis of Polymer 6>
Under an inert gas atmosphere, compound 4I (1.725 g, 2.55 mmol), compound 1T (0.8401 g, 2.50 mmol), dichlorobis (tris-o-methoxyphenylphosphine) palladium (2.2 mg) and toluene (39 mL) ) And heated to 100 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (8.3 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2.5 hours. After the reaction, phenylboronic acid (30.5 mg), dichlorobis (tris-o-methoxyphenylphosphine) palladium (2.2 mg) and 20% by mass tetraethylammonium hydroxide aqueous solution (8.3 mL) were added thereto, and further 12 Reflux for 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 (18 mL), twice with a 3% by mass aqueous acetic acid solution (18 mL) and twice with water (18 mL), and the obtained solution was added dropwise to methanol (253 mL). A precipitate was obtained by filtration. This precipitate was dissolved in toluene (52 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 (253 mL) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 6.4 g of polymer 6 (polymer compound). The polystyrene equivalent number average molecular weight of the polymer 6 was 1.2 × 10 ⁵ , and the polystyrene equivalent weight average molecular weight was 4.8 × 10 ⁵ .

で表される式（１）中のＺに該当する構成単位と、下記式：

で表される式（１）中のＹに該当する構成単位とを、５０：５０のモル比で有し、式（１）で表される構成単位からなる交互共重合体であった。 The theoretical value obtained from the amount ratio of the raw materials used for the polymer 6 is the following formula:

A structural unit corresponding to Z in the formula (1) represented by the formula:

It is an alternating copolymer which has a structural unit corresponding to Y in the formula (1) represented by the formula (1) and has a molar ratio of 50:50 and is composed of the structural unit represented by the formula (1).

(Manufacture and evaluation of organic EL elements)
<Example 1: Production and evaluation of organic EL element 1>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injection material, is formed to a thickness of 50 nm by spin coating on a glass substrate with an ITO film having a thickness of 45 nm formed by sputtering. And it dried for 15 minutes at 170 degreeC using the hotplate, and produced the base material for organic EL.

[Preparation of hole transport layer]
Next, a solution of polymer 2 dissolved in a xylene solvent at a concentration of 0.7% by mass was spin-coated to form a film having a thickness of about 20 nm. Thereafter, heat treatment was performed on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere.

[Production of light emitting layer]
Next, the polymer 5 solution dissolved in the chlorobenzene solvent at a concentration of 1.0% by mass and the polymer 6 solution dissolved in the chlorobenzene solvent at the concentration of 1.0% by mass in a mass ratio. , Polymer 5: Polymer 6 = 90: 10 were mixed to prepare Composition 1.
The composition 1 was formed into a film on the organic EL substrate by a spin coating method at a rotational speed of 2000 rpm. The thickness was about 60 nm.

After drying this at 130 ° C. for 10 minutes under a nitrogen atmosphere, about 3 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the organic EL device 1 was produced. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

  When voltage was applied to the obtained organic EL device 1, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from this device. The device started to emit light at 2.7 V, and the maximum light emission efficiency was 9.3 cd / A.

The organic EL element 1 obtained as described above was driven at a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, the time required to reach 60% of the initial luminance (hereinafter referred to as LT60) was 134 hours.

<Example 2: Production and evaluation of organic EL element 2>
Instead of the polymer 2 used for the hole transport layer in Example 1, a solution of the polymer 1 dissolved in a xylene solvent at a concentration of 0.7% by mass, and 0.7% by mass in the xylene solvent The solution of the polymer 3 dissolved in the concentration was mixed in a mass ratio so that the polymer 1: polymer 3 = 90: 10, and the same procedure as in Example 1 was performed except that the composition 2 was prepared. Thus, an organic EL element 2 was produced. When voltage was applied to the obtained organic EL element 2, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from the organic EL element. The organic EL device started to emit light from 2.7 V, and the maximum luminous efficiency was 9.4 cd / A.

The organic EL element 2 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, LT60 was 163 hours.

<Example 3: Production and evaluation of organic EL element 3>
Instead of the polymer 2 used for the hole transport layer in Example 1, a solution of the polymer 1 dissolved in a xylene solvent at a concentration of 0.7% by mass, and 0.7% by mass in the xylene solvent The solution of the polymer 4 dissolved in the concentration was mixed in a mass ratio such that polymer 1: polymer 4 = 87: 13, and the same procedure as in Example 1 was performed except that the composition 3 was prepared. Thus, an organic EL element 3 was produced. When voltage was applied to the obtained organic EL device 3, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from this device. The device started to emit light at 2.6 V, and the maximum light emission efficiency was 9.0 cd / A.

The organic EL element 3 obtained as described above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, LT60 was 137 hours.

<Comparative Example 1: Production and evaluation of organic EL element 4>
An organic EL element 4 was produced in the same manner as in Example 1 except that the polymer 1 was used instead of the polymer 2 used in the hole transport layer in Example 1. When voltage was applied to the obtained organic EL element 4, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from this organic EL element. The organic EL device started to emit light at 2.6 V, and the maximum luminous efficiency was 11.2 cd / A.

The organic EL element 4 obtained as described above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, LT60 was 100 hours.

<Comparative Example 2: Production and evaluation of organic EL element 5>
Instead of the composition 1 used in the light emitting layer in Example 1, a solution of the polymer 5 dissolved at a concentration of 1.0% by mass in a chlorobenzene solvent was prepared and used as the light emitting layer. In the same manner as in Example 1, an organic EL element 5 was produced. When voltage was applied to the obtained organic EL element 5, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from the organic EL element. The organic EL device started to emit light at 2.6 V, and the maximum luminous efficiency was 6.9 cd / A.

The organic EL element 5 obtained as described above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, LT60 was 87 hours.

<Comparative Example 3: Production and evaluation of organic EL element 6>
Instead of the composition 1 used for the light emitting layer in Example 2, a solution of the polymer 5 dissolved at a concentration of 1.0% by mass in a chlorobenzene solvent was prepared and used as the light emitting layer. In the same manner as in Example 1, an organic EL element 6 was produced. When voltage was applied to the obtained organic EL element 6, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from the organic EL element. The organic EL device started to emit light at 2.6 V, and the maximum luminous efficiency was 7.8 cd / A.

The organic EL element 6 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, LT60 was 82 hours.

<Comparative Example 4: Production and evaluation of organic EL element 7>
Instead of the composition 1 used for the light emitting layer in Example 3, a solution of the polymer 5 dissolved at a concentration of 1.0% by mass in a chlorobenzene solvent was prepared and used as the light emitting layer. In the same manner as in Example 1, an organic EL element 7 was produced. When voltage was applied to the obtained organic EL device 7, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from this device. The device started to emit light at 2.6 V, and the maximum light emission efficiency was 7.3 cd / A.

The organic EL element 7 obtained as described above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, LT60 was 114 hours.

<Comparative Example 5: Production and Evaluation of Organic EL Element 8>
Instead of the polymer 2 used for the hole transport layer in Example 1, the polymer 1 was used, and instead of the composition 1 used for the light emitting layer, it was dissolved in a chlorobenzene solvent at a concentration of 1.0% by mass. An organic EL element 8 was produced in the same manner as in Example 1 except that the polymer 5 solution was prepared and used as the light emitting layer. When voltage was applied to the obtained organic EL device 8, EL light emission having a peak at 460 nm mainly derived from the polymer 5 was obtained from this device. The organic EL device started to emit light at 2.6 V, and the maximum luminous efficiency was 10.6 cd / A.

The organic EL element 8 obtained as described above was driven at a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, LT60 was 36 hours.

  The results of Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 1 below.

Claims (3)

An organic electroluminescence device comprising an anode, a cathode, a light emitting layer provided between the anode and the cathode, and a hole injection layer or a hole transport layer provided between the anode and the light emitting layer,
The light emitting layer includes a polymer compound I having at least one structural unit selected from the group consisting of structural units represented by the following formulas (A) and (B ), and a structural unit represented by the following formula (1). wherein becomes a polymer compound II, wherein the composition comprising from
The hole injection layer or a hole transport layer, one of R ^Z of structural units containing a 10 mol% or more of the structural unit represented by the following formula (B), the fullerene or fullerene derivative, the following formula (2) 2 except comprising constituent units R ^Z of structural units or the following formula (2) including a group consisting of excluding chemical moiety, and R ⁿ stilbene or a stilbene derivative represented by the following formula ^(3), Ar ⁶ and A structural unit containing a group consisting of an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring in one or more groups selected from the group consisting of Ar ⁷ or represented by the following formula (3) A group consisting of structural units obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring in one or more groups selected from the group consisting of R ⁿ , Ar ⁶ and Ar ⁷ from a stilbene or stilbene derivative. An organic electroluminescence device comprising a polymer compound VI having at least one structural unit selected from:

(In the formulas (A) and (B ) ,
Ar ¹ each independently represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure.
Ar ² , Ar ³ and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group.
a represents 0 or 1. )
-[-(Y) _n -Z-] _m- (1)

(In the formula (1),
Y represents a divalent group you express the following formula (Y- 3) or the following formula (Y- 5).
Z is represented by the following formula (Z- 13), represents a divalent group you express by (Z- 15) or (Z- 17).
m represents an integer of 4 to 10,000. n represents an integer of 1 to 3.
A plurality of Y, Z and n may be the same or different.
The hydrogen atom of Y and Z may be substituted with R ′, and R ′ is a carboxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. , Alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, imine residue, amide compound residue, acid imide residue, monovalent heterocyclic group and monovalent heterocyclic thio group It represents a functional group selected from the above or a halogen atom. When there are a plurality of R ′, they may be the same or different, and the plurality of R ′ are bonded to each other to form a ring structure together with the carbon atom or nitrogen atom to which each R ′ is bonded. Also good. The functional group may have a substituent. )

(In the formula (Y-3), the formula (Y-5), the formula (Z- 13 ) , the formula (Z- 15 ) and the formula (Z-17) ,
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different. A plurality of R ″ may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent. )

(In the formula (2),
^RZ is selected from the group consisting of alkyl groups, alkoxy groups, aryl groups, alkenyl groups, alkynyl groups, amino groups, silyl groups, halogen atoms, acyl groups, monovalent heterocyclic groups, carboxyl groups, nitro groups, and cyano groups. Represents a functional group selected or a hydrogen atom. The functional group may have a substituent. A plurality of R ^Z may be the same or different. )

(In formula (3),
R ⁿ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ⁿ may be the same or different.
Ar ⁶ and Ar ⁷ each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ^n, and may form a ring structure together with the carbon atom to which each is bonded. ) The structural unit represented by the formula (A) is independently a structural unit represented by the following formula (1a), (1b), (1c), (1d), or (1e). 2. The organic electroluminescence device according to 1.

(In the formulas (1a) to (1e),
R ″ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R ″ may be the same or different, and a plurality of R ″ are bonded to each other. A ring structure may be formed together with the carbon atoms to which each is bonded.
R ^X is a carboxyl group, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, acyl group, acyloxy group, It represents a functional group selected from the group consisting of an imine residue, an amide compound residue, an acid imide residue, a monovalent heterocyclic group and a monovalent heterocyclic thio group, or a hydrogen atom or a halogen atom. The plurality of R ^X may be the same or different, and the plurality of R ^X may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. The functional group may have a substituent. ) Before Symbol high molecular compound VI comprises a structural unit having a bridging group, the organic electroluminescent device according to claim 1 or 2.