JP2019068061A - Light emitting element - Google Patents

Abstract

To provide a light emitting element with a low drive voltage.SOLUTION: A light emitting element includes: a first organic layer provided between an anode and a cathode; and at least one layer selected from a group composed of a second organic layer provided between the anode and the first organic layer and a third organic layer provided between the cathode and the first organic layer. The first organic layer contains a metal complex represented by Formula (1). The second organic layer contains a crosslinked product of a polymer compound containing a structural unit having a crosslinking group. The third organic layer contains a polymer compound including a structural unit having a predetermined ionic group or the like.SELECTED DRAWING: None

Description

  The present invention relates to a light emitting device.

  Light emitting devices such as organic electroluminescent devices can be suitably used for display and lighting applications. For example, Patent Document 1 discloses that a constitutional unit derived from a compound M1, a constitutional unit derived from a compound M2, and a constitutional unit having a crosslinking group derived from a compound M3 are 50: 42.5: 7. A light emitting device having a hole transporting layer containing a crosslinked product of a copolymer having a molar ratio of 0.5, a light emitting layer containing a metal complex BC1, and an electron transporting layer containing a polymer compound ET1 Is described.

International Publication No. 2015/156235

However, the above-described light emitting element does not necessarily have a sufficiently low driving voltage.
Then, an object of the present invention is to provide a light emitting element with low driving voltage.

The present invention provides the following [1] to [11].
[1]
An anode, a cathode, a first organic layer provided between the anode and the cathode, a second organic layer provided between the anode and the first organic layer, the cathode, and the cathode And at least one layer selected from the group consisting of a third organic layer provided between one organic layer;
The first organic layer contains a metal complex represented by Formula (1),
The second organic layer contains a crosslinked product of a polymer compound containing a structural unit having a crosslinking group,
A polymer compound including the at least one structural unit selected from the group consisting of the structural unit represented by the formula (ET-1) and the structural unit represented by the formula (ET-2) A light emitting element containing

［式中、
Ｍ¹はロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
ｎ¹は１以上の整数を表し、ｎ²は０以上の整数を表す。但し、Ｍ¹がロジウム原子又はイリジウム原子の場合、ｎ¹＋ｎ²は３であり、Ｍ¹がパラジウム原子又は白金原子の場合、ｎ¹＋ｎ²は２である。
環Ｒ^1Aは、ジアゾール環、トリアゾール環又はテトラゾール環を表す。
環Ｒ²は、芳香族炭化水素環又は芳香族複素環を表し、これらの環は置換基を有していてもよい。前記置換基が複数存在する場合、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。環Ｒ²が複数存在する場合、それらは同一でも異なっていてもよい。
Ｅ¹、Ｅ²、Ｅ^11A、Ｅ^12A及びＥ^13Aは、それぞれ独立に、窒素原子又は炭素原子を表す。Ｅ¹、Ｅ²、Ｅ^11A、Ｅ^12A及びＥ^13Aが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。但し、Ｅ¹及びＥ²の少なくとも一方は炭素原子である。
Ｒ^11A、Ｒ^12A及びＲ^13Aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、置換アミノ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^11A、Ｒ^12A及びＲ^13Aが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
但し、Ｅ^11A、Ｅ^12A及びＥ^13Aの少なくとも１つは窒素原子であり、且つ、該窒素原子に結合するＲ^11A、Ｒ^12A及びＲ^13Aの少なくとも１つは式（Ａｒ−１Ａ）で表される基である。
Ｒ^11AとＲ^12Aとは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。Ｒ^12AとＲ^13Aとは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。環Ｒ²が有していてもよい置換基とＲ^11Aとは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。
Ｅ^11Aが窒素原子の場合、Ｒ^11Aは存在しても存在しなくてもよい。Ｅ^12Aが窒素原子の場合、Ｒ^12Aは存在しても存在しなくてもよい。Ｅ^13Aが窒素原子の場合、Ｒ^13Aは存在しても存在しなくてもよい。
Ａ¹−Ｇ¹−Ａ²は、アニオン性の２座配位子を表す。Ａ¹及びＡ²は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。Ｇ¹は、単結合、又は、Ａ¹及びＡ²とともに２座配位子を構成する原子団を表す。Ａ¹−Ｇ¹−Ａ²が複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula,
M ¹ represents a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n ¹ represents an integer of 1 or more, and n ² represents an integer of 0 or more. However, if M ¹ is rhodium atom or an iridium atom, n ¹ + n ² is 3, when M ¹ is a palladium atom or a platinum atom, n ¹ + n ² is 2.
The ring R ^1A represents a diazole ring, a triazole ring or a tetrazole ring.
The ring R ² represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded. When a plurality of rings R ² exist, they may be the same or different.
E ¹ , E ² , E ^11A , E ^12A and E ^13A each independently represent a nitrogen atom or a carbon atom. When E ¹ , E ² , E ^11A , E ^12A and E ^13A are present in plurality, they may be the same or different. However, at least one of E ¹ and E ² is a carbon atom.
R ^11A , R ^12A and R ^13A are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen Represents an atom, and these groups may have a substituent. When there are a plurality of R ^11A , R ^12A and R ^13A , they may be the same or different.
However, at least one of E ^11A , E ^12A and E ^13A is a nitrogen atom, and at least one of R ^11A , R ^12A and R ^13A bonded to the nitrogen atom is represented by the formula (Ar-1A) Group.
R ^11A and R ^12A may be bonded to each other to form a ring with the atoms to which each is bonded. R ^12A and R ^13A may be bonded to each other to form a ring together with the atoms to which they are bonded. The substituent which the ring R ² may have and R ^11A may be bonded to each other to form a ring together with the atoms to which they are bonded.
When E ^11A is a nitrogen atom, R ^11A may be present or absent. When E ^12A is a nitrogen atom, R ^12A may be present or absent. When E ^13A is a nitrogen atom, R ^13A may be present or absent.
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. Each of A ¹ and A ² independently represents a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. G ¹ represents a single bond or an atomic group constituting a bidentate ligand with A ¹ and A ² . When ^two or more A ¹ -G ¹ -A ² are present, they may be the same or different. ]

［式中、
環Ａは、芳香族炭化水素環又は芳香族複素環を表し、これらの環は置換基を有していてもよい。前記置換基が複数存在する場合、それらは互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。
Ｒ²は、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、置換アミノ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。］

[In the formula,
Ring A represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded.
R ² represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, and these groups have a substituent It may be ]

［式中、
ｎＥ１は、１以上の整数を表す。
Ａｒ^E1は、芳香族炭化水素基又は複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^E1は、式（ＥＳ−１）で表される基を表す。Ｒ^E1が複数存在する場合、それらは同一でも異なっていてもよい。］

−Ｒ^E3−｛（Ｑ^E1）_nE3−Ｙ^E1（Ｍ^E1）_aE1（Ｚ^E1）_bE1｝_mE1 （ＥＳ−１）
［式中、
ｎＥ３及びｂＥ１は、それぞれ独立に、０以上の整数を表し、ａＥ１及びｍＥ１は、それぞれ独立に、１以上の整数を表す。ｎＥ３、ａＥ１及びｂＥ１が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。但し、Ｒ^E3が単結合である場合、ｍＥ１は１である。ａＥ１及びｂＥ１は、前記式（ＥＳ−１）で表される基の電荷が０となるように選択される。
Ｒ^E3は、単結合、炭化水素基、複素環基又はＯ−Ｒ^E3’を表し（Ｒ^E3’は、炭化水素基又は複素環基を表す。）、これらの基は置換基を有していてもよい。
Ｑ^E1は、アルキレン基、シクロアルキレン基、アリーレン基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。Ｑ^E1が複数存在する場合、それらは同一でも異なっていてもよい。
Ｙ^E1は、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−ＳＯ₂ ^-又は−ＰＯ₃ ^2-を表す。Ｙ^E1が複数存在する場合、それらは同一でも異なっていてもよい。
Ｍ^E1は、アルカリ金属カチオン、アルカリ土類金属カチオン又はアンモニウムカチオンを表し、前記アンモニウムカチオンは置換基を有していてもよい。Ｍ^E1が複数存在する場合、それらは同一でも異なっていてもよい。
Ｚ^E1は、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、ＯＨ^-、Ｂ（Ｒ^E4）₄ ^-、Ｒ^E4ＳＯ₃ ^-、Ｒ^E4ＣＯＯ^-、ＮＯ₃ ^-、ＳＯ₄ ^2-、ＨＳＯ₄ ^-、ＰＯ₄ ^3-、ＨＰＯ₄ ^2-、Ｈ₂ＰＯ₄ ^-、ＢＦ₄ ^-又はＰＦ₆ ^-を表す。Ｒ^E4は、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。Ｚ^E1が複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula,
nE1 represents an integer of 1 or more.
Ar ^E1 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
R ^E1 represents a group represented by the formula (ES-1). When a plurality of R ^E1 are present, they may be the same or different. ]

-R ^E3 -{(Q ^E1 ) _n ^E3- Y ^E1 (M ^E1 ) _aE1 (Z ^E1 ) _b ^E1 } _mE1 (ES-1)
[In the formula,
nE3 and bE1 each independently represent an integer of 0 or more, and aE1 and mE1 each independently represent an integer of 1 or more. When two or more nE3, aE1 and bE1 exist, they may be the same or different. However, mE1 is 1 when R ^E3 is a single bond. aE1 and bE1 are selected such that the charge of the group represented by the formula (ES-1) is zero.
R ^E3 represents a single bond, a hydrocarbon group, a heterocyclic group or O—R ^E3 ′ (R ^E3 ′ represents a hydrocarbon group or a heterocyclic group), and these groups have a substituent May be
Q ^E1 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups may have a substituent. When a plurality of Q ^E1 are present, they may be the same or different.
Y ^{E1 _{is, -CO 2 -, -SO 3 -}} , -SO 2 - represents a ^2- or -PO _3. When a plurality of Y ^E1 are present, they may be the same or different.
M ^E1 represents an alkali metal cation, an alkaline earth metal cation or an ammonium cation, and the ammonium cation may have a substituent. When a plurality of M ^E1 are present, they may be the same or different.
Z ^{E1 is, F -, Cl -, Br} -, I -, OH -, B (R E4) 4 -, R E4 SO 3 -, R E4 COO -, NO 3 -, SO 4 2-, HSO 4 - _{^{, PO 4 3-, HPO 4 2-}} , H 2 PO 4 -, BF 4 - or PF ₆ ^- represents a. R ^E4 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. When a plurality of Z ^E1 are present, they may be the same or different. ]

［式中、
ｎＥ２は、１以上の整数を表す。
Ａｒ^E2は、芳香族炭化水素基又は複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^E2は、式（ＥＳ−２）で表される基を表す。Ｒ^E2が複数存在する場合、それらは同一でも異なっていてもよい。］

−Ｒ^E5−｛（Ｑ^E2）_nE4−Ｙ^E2（Ｍ^E2）_aE2（Ｚ^E2）_bE2｝_mE2 （ＥＳ−２）
［式中、
ｎＥ４及びｂＥ２は、それぞれ独立に、０以上の整数を表し、ａＥ２及びｍＥ２は、それぞれ独立に、１以上の整数を表す。ｎＥ４、ａＥ２及びｂＥ２が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。但し、Ｒ^E5が単結合である場合、ｍＥ２は１である。ａＥ２及びｂＥ２は、前記式（ＥＳ−２）で表される基の電荷が０となるように選択される。
Ｒ^E5は、単結合、炭化水素基、複素環基又はＯ−Ｒ^E5’を表し（Ｒ^E5’は、炭化水素基又は複素環基を表す。）、これらの基は置換基を有していてもよい。
Ｑ^E2は、アルキレン基、シクロアルキレン基、アリーレン基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。Ｑ^E2が複数存在する場合、それらは同一でも異なっていてもよい。
Ｙ^E2は、−Ｃ⁺Ｒ^E6 ₂、−Ｎ⁺Ｒ^E6 ₃、−Ｐ⁺Ｒ^E6 ₃、−Ｓ⁺Ｒ^E6 ₂又は−Ｉ⁺Ｒ^E6 ₂を表す。Ｒ^E6は、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^E6は、同一でも異なっていてもよい。Ｙ^E2が複数存在する場合、それらは同一でも異なっていてもよい。
Ｍ^E2は、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、ＯＨ^-、Ｂ（Ｒ^E7）₄ ^-、Ｒ^E7ＳＯ₃ ^-、Ｒ^E7ＣＯＯ^-、ＢＦ₄ ^-、ＳｂＣｌ₆ ^-又はＳｂＦ₆ ^-を表す。Ｒ^E7は、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。
Ｍ^E2が複数存在する場合、それらは同一でも異なっていてもよい。
Ｚ^E2は、アルカリ金属カチオン又はアルカリ土類金属カチオンを表す。Ｚ^E2が複数存在する場合、それらは同一でも異なっていてもよい。］
［２］
前記第２の有機層を有し、かつ、前記架橋基が架橋基Ａ群から選ばれる架橋基である、［１］に記載の発光素子。
（架橋基Ａ群）

[In the formula,
nE2 represents an integer of 1 or more.
Ar ^E2 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
R ^E2 represents a group represented by the formula (ES-2). When two or more R ^E2 are present, they may be the same or different. ]

-R ^E5 -{(Q ^E2 ) _{n E4-} Y ^E2 (M ^E2 ) _aE2 (Z ^E2 ) _b ^E2 } _mE2 (ES-2)
[In the formula,
nE4 and bE2 each independently represent an integer of 0 or more, and aE2 and mE2 each independently represent an integer of 1 or more. When a plurality of nE4, aE2 and bE2 are present, they may be the same or different. However, mE2 is 1 when R ^E5 is a single bond. aE2 and bE2 are selected such that the charge of the group represented by the formula (ES-2) is zero.
R ^E5 represents a single bond, a hydrocarbon group, a heterocyclic group or O-R ^E5 '(R ^E5 ' represents a hydrocarbon group or a heterocyclic group), and these groups have a substituent May be
Q ^E2 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups may have a substituent. When two or more Q ^E2 are present, they may be the same or different.
Y ^E2 represents _{^{-C + R E6 2, -N +}} R E6 3, -P + R E6 3, -S + R E6 2 or -I ⁺ R ^E6 _2. R ^E6 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. Plural R ^E6 may be the same or different. When a plurality of Y ^E2 are present, they may be the same or different.
M ^E2 is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^E7 ) ₄ ⁻ , R ^E7 SO ₃ ⁻ , R ^E7 COO ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ or SbF ₆ ⁻ Represent. R ^E7 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.
When two or more M ^E2 are present, they may be the same or different.
Z ^E2 represents an alkali metal cation or an alkaline earth metal cation. When a plurality of Z ^E2 are present, they may be the same or different. ]
[2]
The light emitting device according to [1], which has the second organic layer, and the crosslinking group is a crosslinking group selected from the group of crosslinking groups A.
(Crosslinking group A group)

［式中、Ｒ^XLは、メチレン基、酸素原子又は硫黄原子を表し、ｎ^XLは、０〜５の整数を表す。Ｒ^XLが複数存在する場合、それらは同一でも異なっていてもよい。ｎ^XLが複数存在する場合、それらは同一でも異なっていてもよい。＊１は結合位置を表す。これらの架橋基は置換基を有していてもよく、該置換基が複数存在する場合、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。］
［３］
前記架橋基を有する構成単位が、式（３）又は式（４）で表される構成単位である、［２］に記載の発光素子。

[Wherein, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5]. When two or more R ^XL exist, they may be the same or different. When there are a plurality of n ^XL , they may be the same or different. * 1 represents a bonding position. These crosslinking groups may have a substituent, and when there are a plurality of such substituents, they may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]
[3]
The light emitting device according to [2], wherein the structural unit having a crosslinking group is a structural unit represented by Formula (3) or Formula (4).

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

[In the formula,
nA represents an integer of 0 to 5, and n represents 1 or 2. When a plurality of nA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
L ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent It is also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. If L ^A is plurally present, they may be the same or different.
X represents a crosslinking group selected from the aforementioned crosslinking group A group. When two or more X exist, they may be same or different. ]

［式中、
ｍＡは０〜５の整数を表し、ｍは１〜４の整数を表し、ｃは０又は１を表す。ｍＡが複数存在する場合、それらは同一でも異なっていてもよい。
Ａｒ⁵は、芳香族炭化水素基、複素環基、又は、少なくとも１種の芳香族炭化水素環と少なくとも１種の複素環とが直接結合した基を表し、これらの基は置換基を有していてもよい。
Ａｒ⁴及びＡｒ⁶は、それぞれ独立に、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ、該基が結合している窒素原子に結合している該基以外の基と、直接結合して、又は、酸素原子若しくは硫黄原子を介して結合して、環を形成していてもよい。
Ｋ^Aは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’は、前記と同じ意味を表す。Ｋ^Aが複数存在する場合、それらは同一でも異なっていてもよい。
Ｘ’は、前記架橋基Ａ群から選ばれる架橋基、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｘ’が複数存在する場合、それらは同一でも異なっていてもよい。但し、少なくとも１つのＸ’は、前記架橋基Ａ群から選ばれる架橋基である。］
［４］
前記式（１）で表される金属錯体が、式（１−Ａ１）又は式（１−Ａ２）で表される金属錯体である、［１］〜［３］のいずれかに記載の発光素子。

[In the formula,
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When there are a plurality of mAs, they may be the same or different.
Ar ⁵ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent It may be
Ar ⁴ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ⁴ , Ar ⁵ and Ar ⁶ are each directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, or bonded through an oxygen atom or a sulfur atom And may form a ring.
K ^A represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups each have a substituent It is also good. R 'represents the same meaning as described above. If K ^A there are a plurality, they may be the same or different.
X 'represents a bridging group selected from the above bridging group A, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent . When a plurality of X 'are present, they may be the same or different. However, at least one X ′ is a crosslinking group selected from the aforementioned crosslinking group A group. ]
[4]
The light emitting device according to any one of [1] to [3], wherein the metal complex represented by the formula (1) is a metal complex represented by the formula (1-A1) or the formula (1-A2) .

［式中、Ｍ¹、ｎ¹、ｎ²、Ｒ^11A、Ｒ^12A、Ｒ^13A、Ｅ^11A、Ｅ^12A、Ｅ^13A及びＡ¹−Ｇ¹−Ａ²は、前記と同じ意味を表す。
環Ｒ^2Aは、ベンゼン環、フルオレン環、スピロビフルオレン環、ジヒドロフェナントレン環、ピリジン環、ジアザベンゼン環、カルバゾール環、ジベンゾフラン環又はジベンゾチオフェン環を表し、これらの環は置換基を有していてもよい。前記置換基が複数存在する場合、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。環Ｒ^2Aが複数存在する場合、それらは同一でも異なっていてもよい。
環Ｒ^2Aが有していてもよい置換基とＲ^11Aとは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。
但し、式（１−Ａ１）中、Ｒ^11Aの少なくとも１つは前記式（Ａｒ−１Ａ）で表される基であり、式（１−Ａ２）中、Ｒ^12Aの少なくとも１つは前記式（Ａｒ−１Ａ）で表される基である。］
［５］
前記式（１）で表される金属錯体が、式（１−Ａ１）で表される金属錯体であり、かつ、前記式（１−Ａ１）で表される金属錯体が、式（１−Ａ１−１）、式（１−Ａ１−２）又は式（１−Ａ１−３）で表される金属錯体である、［４］に記載の発光素子。

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A , E ^11A , E ^12A , E ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
Ring R ^2A represents a benzene ring, a fluorene ring, a spirobifluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, and these rings may have a substituent Good. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded. When a plurality of rings R ^2A are present, they may be the same or different.
The substituent which ring R ^2A may have and R ^11A may be bonded to each other to form a ring together with the atoms to which they are bonded.
However, in Formula (1-A1), at least one of R ^11A is a group represented by Formula (Ar-1A), and in Formula (1-A2), at least one of R ^12A is It is a group represented by Ar-1A). ]
[5]
The metal complex represented by Formula (1) is a metal complex represented by Formula (1-A1), and the metal complex represented by Formula (1-A1) is a compound represented by Formula (1-A1) -1), a light emitting element given in [4] which is a metal complex denoted by a formula (1-A1-2), or a formula (1-A1-3).

［式中、Ｍ¹、ｎ¹、ｎ²、Ｒ^11A、Ｒ^12A、Ｒ^13A及びＡ¹−Ｇ¹−Ａ²は、前記と同じ意味を表す。
Ｒ^21A、Ｒ^22A、Ｒ^23A及びＲ^24Aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、置換アミノ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^21A、Ｒ^22A、Ｒ^23A及びＲ^24Aが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。Ｒ^21AとＲ^22A、Ｒ^22AとＲ^23A、Ｒ^23AとＲ^24A、及び、Ｒ^11AとＲ^21Aは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。］
［６］
前記式（１−Ａ２）で表される金属錯体が、式（１−Ａ２−１）又は式（１−Ａ２−２）で表される金属錯体である、［４］に記載の発光素子。

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
R ^21A , R ^22A , R ^23A and R ^24A are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, substituted amino A group or a halogen atom is represented, and these groups may have a substituent. When there are a plurality of R ^21A , R ^22A , R ^23A and R ^24A , they may be the same or different. R ^21A and R ^22A , R ^22A and R ^23A , R ^23A and R ^24A , and R ^11A and R ^21A may combine with each other to form a ring together with the atoms to which they are attached. ]
[6]
The light emitting element according to [4], wherein the metal complex represented by the formula (1-A2) is a metal complex represented by the formula (1-A2-1) or the formula (1-A2-2).

［式中、Ｍ¹、ｎ¹、ｎ²、Ｒ^11A、Ｒ^12A、Ｒ^13A及びＡ¹−Ｇ¹−Ａ²は、前記と同じ意味を表す。
Ｒ^21A、Ｒ^22A、Ｒ^23A及びＲ^24Aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、置換アミノ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^21A、Ｒ^22A、Ｒ^23A及びＲ^24Aが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。Ｒ^21AとＲ^22A、Ｒ^22AとＲ^23A、Ｒ^23AとＲ^24A、及び、Ｒ^11AとＲ^21Aは、互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。］
［７］
前記式（Ａｒ−１Ａ）で表される基が、式（Ａｒ−２Ａ）で表される基である、［１］〜［６］のいずれかに記載の発光素子。

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
R ^21A , R ^22A , R ^23A and R ^24A are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, substituted amino A group or a halogen atom is represented, and these groups may have a substituent. When there are a plurality of R ^21A , R ^22A , R ^23A and R ^24A , they may be the same or different. R ^21A and R ^22A , R ^22A and R ^23A , R ^23A and R ^24A , and R ^11A and R ^21A may combine with each other to form a ring together with the atoms to which they are attached. ]
[7]
The light emitting element in any one of [1]-[6] whose group represented by said Formula (Ar-1A) is group represented by Formula (Ar-2A).

［式中、Ｒ²は、前記と同じ意味を表す。
環Ａ¹は、ベンゼン環、ピリジン環又はジアザベンゼン環を表す。
Ｅ^1A、Ｅ^2A及びＥ^3Aは、それぞれ独立に、窒素原子又は炭素原子を表す。Ｅ^1Aが窒素原子の場合、Ｒ^1Aは存在しない。Ｅ^2Aが窒素原子の場合、Ｒ^2Aは存在しない。Ｅ^3Aが窒素原子の場合、Ｒ^3Aは存在しない。
Ｒ^1A、Ｒ^2A及びＲ^3Aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、置換アミノ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。
Ｒ^1AとＲ^2A、及び、Ｒ^2AとＲ^3Aは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。］
［８］
前記式（Ａｒ−２Ａ）で表される基が、式（Ａｒ−３Ａ）で表される基である、［７］に記載の発光素子。

[Wherein, R ² represents the same meaning as described above.
Ring A ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring.
E ^1A , E ^2A and E ^3A each independently represent a nitrogen atom or a carbon atom. When E ^1A is a nitrogen atom, R ^1A is absent. When E ^2A is a nitrogen atom, R ^2A is absent. When E ^3A is a nitrogen atom, R ^3A is absent.
R ^1A , R ^2A and R ^3A are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen Represents an atom, and these groups may have a substituent.
R ^1A and R ^2A , and R ^2A and R ^3A may be combined to form a ring together with the atoms to which they are attached. ]
[8]
The light emitting element according to [7], wherein the group represented by the formula (Ar-2A) is a group represented by the formula (Ar-3A).

［式中、Ｒ²、Ｒ^1A、Ｒ^2A及びＲ^3Aは、前記と同じ意味を表す。］
［９］
前記第１の有機層が、式（Ｈ−１）で表される化合物、若しくは、式（Ｙ）で表される構成単位を含む高分子化合物、又は、これらの組み合わせを更に含有する、［１］〜［８］のいずれかに記載の発光素子。

[Wherein, R ² , R ^1A , R ^2A and R ^3A represent the same meaning as described above. ]
[9]
The first organic layer further contains a compound represented by the formula (H-1), a polymer compound containing a constitutional unit represented by the formula (Y), or a combination thereof [1 ] The light emitting element in any one of-[8].

［式中、
Ａｒ^H1及びＡｒ^H2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。
ｎ^H1及びｎ^H2は、それぞれ独立に、０又は１を表す。ｎ^H1が複数存在する場合、それらは同一でも異なっていてもよい。複数存在するｎ^H2は、同一でも異なっていてもよい。
ｎ^H3は、０以上１０以下の整数を表す。
Ｌ^H1は、アリーレン基、２価の複素環基、又は、−［Ｃ（Ｒ^H11）₂］ｎ^H11−で表される基を表し、これらの基は置換基を有していてもよい。Ｌ^H1が複数存在する場合、それらは同一でも異なっていてもよい。ｎ^H11は、１以上１０以下の整数を表す。Ｒ^H11は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^H11は、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。
Ｌ^H2は、−Ｎ（−Ｌ^H21−Ｒ^H21）−で表される基を表す。Ｌ^H2が複数存在する場合、それらは同一でも異なっていてもよい。Ｌ^H21は、単結合、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^H21は、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[In the formula,
Ar ^H1 and Ar ^H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
n ^H1 and n ^H2 each independently represent 0 or 1. When there are a plurality of n ^H1 , they may be the same or different. Plural n ^H2 may be the same or different.
n ^H3 represents an integer of 0 or more and 10 or less.
L ^H1 represents an arylene group, a divalent heterocyclic group, or a group represented ^by- [C (R ^H11 ) ₂ ] n ^H11- , and these groups may have a substituent. When two or more L ^H1 are present, they may be the same or different. n ^H11 represents an integer of 1 or more and 10 or less. R ^H11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^H11 may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
L ^H2 represents a group represented by -N (-L ^H21 -R ^H21 )-. When two or more L ^H2 are present, they may be the same or different. L ^H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups may have a substituent. R ^H21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. ]

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、又は、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。］
［１０］
前記第２の有機層及び前記第３の有機層を有し、かつ、前記第１の有機層が第１の発光層であり、前記第２の有機層が正孔輸送層又は第２の発光層であり、前記第３の有機層が電子輸送層である、［１］〜［９］のいずれかに記載の発光素子。
［１１］
前記第２の有機層及び前記第３の有機層を有し、且つ、前記第１の有機層と前記第２の有機層と前記第３の有機層とが隣接している、［１］〜［１０］のいずれかに記載の発光素子。

[ ^Wherein , Ar ^{Y 1} represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one type of divalent heterocyclic group are directly bonded, Groups may have a substituent. ]
[10]
The light emitting layer includes the second organic layer and the third organic layer, and the first organic layer is a first light emitting layer, and the second organic layer is a hole transporting layer or a second light emitting layer. The light emitting device according to any one of [1] to [9], which is a layer, and the third organic layer is an electron transport layer.
[11]
[1] having the second organic layer and the third organic layer, wherein the first organic layer, the second organic layer, and the third organic layer are adjacent to each other [1] The light emitting element in any one of [10].

  According to the present invention, a light emitting element with low driving voltage can be provided.

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

<Description of common terms>
The terms commonly used in the present specification have the following meanings, unless otherwise specified.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.
The hydrogen atom may be a deuterium atom or a light hydrogen atom.
In the formula representing a metal complex, a solid line representing a bond to a metal means an ionic bond, a covalent bond or a coordinate bond.

The "polymer compound" means a polymer having a molecular weight distribution and having a number average molecular weight in terms of polystyrene of 1 × 10 ³ to 1 × 10 ⁸ .
The polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or may be another embodiment.
When the polymer compound is used for the preparation of a light emitting device, the terminal group of the polymer compound is preferably a stable group since the light emission characteristics or the brightness life may be reduced if the polymerization active group remains as it is. It is. The terminal group of the polymer compound is preferably a group conjugated with the main chain, and preferably, for example, an aryl group or a monovalent heterocyclic group bonded to the main chain of the polymer compound via a carbon-carbon bond. Can be mentioned.

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

  The "constituent unit" means a unit which is present one or more in the polymer compound.

The "alkyl group" may be linear or branched. The carbon atom number of the linear alkyl group is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent. The carbon atom number of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent.
The alkyl group may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group and an isoamyl group 2-ethylbutyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3-propylheptyl, decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-hexyldecyl, dodecyl And a group in which a hydrogen atom in these groups is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like (for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group , Perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5-di-hexyl group) Phenyl) propyl group, 6-ethyloxy-hexyl group).
The carbon atom number of the "cycloalkyl group" is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent.
The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group and a cyclohexylethyl group.

The “aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of the aryl group is usually 6 to 60, preferably 6 to 20, more preferably 6 to 10, not including the carbon atom number of the substituent.
The aryl group may have a substituent, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atom in these groups Are groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.

The "alkoxy group" may be linear or branched. The carbon atom number of the linear alkoxy group is usually 1 to 40, preferably 4 to 10, not including the carbon atom number of the substituent. The carbon atom number of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
The alkoxy group may have a substituent, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, And heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3, 7-dimethyloctyloxy group, lauryloxy group, and a hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, Examples thereof include groups substituted with a cycloalkoxy group, an aryl group, a fluorine atom and the like.
The carbon atom number of the "cycloalkoxy group" is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.

The carbon atom number of the "aryloxy group" is usually 6 to 60, preferably 6 to 48, not including the carbon atom number of the substituent.
The aryloxy group may have a substituent, and examples thereof include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Pyrenyloxy groups and groups in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like can be mentioned.

The “p-valent heterocyclic group” (p represents an integer of 1 or more) means p out of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from the heterocyclic compound. Means the remaining atomic groups excluding the hydrogen atom of Among p-valent heterocyclic groups, carbon atoms constituting the ring or the remaining atomic groups obtained by removing p hydrogen atoms from hydrogen atoms directly bonded to a hetero atom from an aromatic heterocyclic compound "P-valent aromatic heterocyclic group" is preferred.
The “aromatic heterocyclic compound” is a complex such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole etc. Compounds in which the ring itself exhibits aromaticity, and heterocycles such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, benzopyran and the like themselves do not exhibit aromaticity, but an aromatic ring is fused to the heterocycle. It means a compound.

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

  The "halogen atom" represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

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

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

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

The "arylene group" means an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The carbon atom number of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the carbon atom number of the substituent.
The arylene group may have a substituent, and examples thereof include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrendiyl group, dihydrophenanthrendiyl group, naphthacene diyl group, fluorenediyl group, pyrene diyl group, perylene diyl group, There may be mentioned a chrysendiyl group and a group in which these groups have a substituent, and preferably a group represented by the formula (A-1) to the formula (A-20). The arylene group includes a group in which a plurality of these groups are bonded.

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

[Wherein, R and R ^a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. Plural R and R ^a may be respectively the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which each is bonded. ]

The carbon atom number of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, and more preferably 4 to 15, not including the carbon atom number of the substituent.
The divalent heterocyclic group may have a substituent, and examples thereof include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, and the like. Preferred are dihydroacridines, furans, thiophenes, azoles, diazoles and triazoles, and divalent groups in which two hydrogen atoms of hydrogen atoms directly bonded to ring carbon atoms or hetero atoms are removed, preferably Are groups represented by formulas (AA-1) to (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

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

  The “crosslinking group” is a group capable of generating a new bond by being subjected to heat treatment, ultraviolet irradiation treatment, near ultraviolet irradiation treatment, visible light irradiation treatment, infrared irradiation treatment, radical reaction, etc. Preferred are crosslinking groups represented by formulas (XL-1) to (XL-19) of the crosslinking group A group.

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

<Light emitting element>
The light emitting device of the present invention comprises an anode, a cathode, a first organic layer provided between the anode and the cathode, and a second organic provided between the anode and the first organic layer. And at least one layer selected from the group consisting of a layer and a third organic layer provided between the cathode and the first organic layer, wherein the first organic layer is represented by formula (1) Wherein the second organic layer contains a crosslinked product of a polymer compound containing a structural unit having a crosslinking group, and the third organic layer contains a metal complex represented by the formula (ET-1): It contains a polymer compound containing at least one structural unit selected from the group consisting of the structural unit represented and the structural unit represented by the formula (ET-2).

(First organic layer)
The metal complex represented by Formula (1) may be contained individually by 1 type, and 2 or more types may be contained in the 1st organic layer.
The content of the metal complex represented by the formula (1) in the first organic layer may be in the range where the function as the first organic layer can be exhibited. For example, the content of the metal complex represented by the formula (1) may be 0.1 to 50% by mass, preferably 1 to 40% by mass, based on the total amount of the first organic layer, and 10 It is more preferable that it is -30 mass%.

[Metal Complex Represented by Formula (1)]
The metal complex represented by the formula (1) is usually a metal complex which exhibits phosphorescence at room temperature (25 ° C.), preferably a metal complex which emits light from a triplet excited state at room temperature.

M ¹ is preferably an iridium atom or a platinum atom, and more preferably an iridium atom, because the driving voltage of the light emitting device of the present invention is lower.
When M ¹ is a rhodium atom or an iridium atom, n ¹ is preferably 2 or 3, and more preferably 3.
When M ¹ is a palladium atom or a platinum atom, n ¹ is preferably 2.
E ¹ and E ² are preferably carbon atoms.

When ring R ^1A is a diazole ring, ring R ^1A is preferably an imidazole ring in which E ^11A is a nitrogen atom, or an imidazole ring in which E ^12A is a nitrogen atom, more preferably E ^11A is a nitrogen It is an imidazole ring which is an atom.
When ring R ^1A is a triazole ring, ring R ^1A is preferably a triazole ring in which E ^11A and E ^12A are nitrogen atoms, or a triazole ring in which E ^11A and E ^13A are nitrogen atoms, and more preferably Is a triazole ring in which E ^11A and E ^13A are nitrogen atoms.
When the ring R ^1A is a tetrazole ring, the ring R ^1A is preferably a tetrazole ring in which E ^{11A to} E ^13A is a nitrogen atom.
The ring R ^1A is preferably a diazole ring or a triazole ring, more preferably a triazole ring, because the driving voltage of the light emitting device of the present invention is lower.

When E ^11A is a nitrogen atom and R ^11A is present, R ^11A is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, preferably an aryl group or a monovalent heterocyclic ring. The group is more preferably a group, further preferably an aryl group, and these groups may have a substituent.
When E ^11A is a carbon atom, R ^11A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and a hydrogen atom, an alkyl group, a cycloalkyl group Or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and these groups may have a substituent.

When E ^12A is a nitrogen atom and R ^12A is present, R ^12A is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, preferably an aryl group or a monovalent heterocyclic ring. The group is more preferably a group, further preferably an aryl group, and these groups may have a substituent.
When E ^12A is a carbon atom, R ^12A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and a hydrogen atom, an alkyl group, a cycloalkyl group Or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and these groups may have a substituent.

When E ^13A is a nitrogen atom and R ^13A is present, R ^13A is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and an aryl group or a monovalent heterocyclic ring. The group is more preferably a group, further preferably an aryl group, and these groups may have a substituent.
When E ^13A is a carbon atom, R ^13A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and a hydrogen atom, an alkyl group, a cycloalkyl group Or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and these groups may have a substituent.

The aryl group in R ^{11A to} R ^13A is preferably a phenyl group, a naphthyl group, a phenanthrenyl group, a dihydrophenanthrenyl group, a fluorenyl group or a spirobifluorenyl group, and a phenyl group, a fluorenyl group or a spirobifluorenyl group. A group is more preferable, a phenyl group is still more preferable, and these groups may have a substituent.
The monovalent heterocyclic group represented by R ^{11A to} R ^13A is pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, azacarbazolyl, diazacarbazolyl Group, phenoxazinyl group or phenothiazinyl group is preferable, pyridyl group, pyrimidinyl group, triazinyl group, dibenzofuranyl group, dibenzothienyl group or carbazolyl group is more preferable, pyridyl group, pyrimidinyl group or triazinyl group is further preferable, and these groups May have a substituent.
In the substituted amino group in R ^{11A to} R ^{13A, as} a substituent that the amino group has, an aryl group or a monovalent heterocyclic group is preferable, and an aryl group is more preferable, and these groups further have a substituent It is also good. The examples and the preferred ranges of the aryl group and the monovalent heterocyclic group in the substituent which the amino group has are the same as the examples and the preferred ranges of the aryl group and the monovalent heterocyclic group in R ^{11A to} R ^13A .

The substituent that R ^{11A to} R ^13A may have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino A group or a halogen atom, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, still more preferably an alkyl group, a cycloalkyl group or an aryl group, Particularly preferred is an alkyl group, and these groups may further have a substituent.

As a substituent which the substituent which R ^{11A to} R ^13A may have may further have, preferably, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group is preferable A monovalent heterocyclic group, a substituted amino group or a halogen atom, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, still more preferably an alkyl group Or a cycloalkyl group. These groups may further have a substituent, but preferably have no substituent.

The aryl group, monovalent heterocyclic group or substituted amino group in R ^{11A to} R ^13A is preferably at least one of Formula (D-A) to Formula (D-C) because the drive voltage of the light emitting device of the present invention is lower. And more preferably a group represented by formula (D-A) or formula (D-C).

[Group Represented by Formula (D-A) to Formula (D-C)]
m ^{DA1 to} m ^DA7 are usually integers of 10 or less, preferably 5 or less, more preferably 2 or less, and further preferably 0 or 1. It is preferable that m ^{DA2 to} m ^DA7 be the same integer, and it is more preferable that m ^{DA1 to} m ^DA7 be the same integer.

G ^DA is preferably an aromatic hydrocarbon group or a heterocyclic group, more preferably a hydrogen directly bonded to a carbon atom or nitrogen atom constituting a ring from a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring or a carbazole ring It is a group formed by removing 3 atoms, and these groups may have a substituent.
The substituent that G ^DA may have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and more preferably an alkyl group, It is a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably an alkyl group or a cycloalkyl group, and these groups may have a substituent.
G ^DA is preferably a group represented by Formula (GDA-11) to Formula (GDA-15), more preferably a group represented by Formula (GDA-11) to Formula (GDA-14) And more preferably a group represented by the formula (GDA-11) or the formula (GDA-14), particularly a group represented by the formula (GDA-11).

［式中、
＊は、式（Ｄ−Ａ）におけるＡｒ^DA1、式（Ｄ−Ｂ）におけるＡｒ^DA1、式（Ｄ−Ｂ）におけるＡｒ^DA2、又は、式（Ｄ−Ｂ）におけるＡｒ^DA3との結合を表す。
＊＊は、式（Ｄ−Ａ）におけるＡｒ^DA2、式（Ｄ−Ｂ）におけるＡｒ^DA2、式（Ｄ−Ｂ）におけるＡｒ^DA4、又は、式（Ｄ−Ｂ）におけるＡｒ^DA6との結合を表す。
＊＊＊は、式（Ｄ−Ａ）におけるＡｒ^DA3、式（Ｄ−Ｂ）におけるＡｒ^DA3、式（Ｄ−Ｂ）におけるＡｒ^DA5、又は、式（Ｄ−Ｂ）におけるＡｒ^DA7との結合を表す。
Ｒ^DAは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は１価の複素環基を表し、これらの基は更に置換基を有していてもよい。Ｒ^DAが複数ある場合、それらは同一でも異なっていてもよい。］

[In the formula,
* Represents a bond to Ar ^DA1 in formula (D-A), Ar ^DA1 in formula (D-B), Ar ^DA2 in formula (D-B), or Ar ^DA3 in formula (D-B).
** represents a bond to Ar ^DA2 in formula (D-A), Ar ^DA2 in formula (D-B), Ar ^DA4 in formula (D-B), or Ar ^DA6 in formula (D-B) .
*** is, Ar ^DA3 in the formula (D-A), Ar ^DA3 in the formula (D-B), Ar ^DA5 in the formula (D-B), or, the bond between Ar ^DA7 in the formula (D-B) Represent.
R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may further have a substituent. When there are a plurality of ^RDAs , they may be the same or different. ]

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

Ar ^{DA1 to} Ar ^DA7 are preferably a phenylene group, a ^fluorenedyl group or a carbazole diyl group, more preferably a group represented by the formula (ArDA-1) to the formula (ArDA-6), and further preferably Is a group represented by the formula (ArDA-1) to the formula (ArDA-3), particularly preferably a group represented by the formula (ArDA-1), these groups each having a substituent It is also good.

［式中、
Ｒ^DAは前記と同じ意味を表す。
Ｒ^DBは、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^DBが複数ある場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。］

[In the formula,
R ^DA has the same meaning as described above.
R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of R ^{DB 's} , they may be the same or different, and may combine with each other to form a ring together with the carbon atoms to which they are attached. ]

R ^DB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, still more preferably an aryl group, The group may have a substituent.

Ar ^DA1 ~Ar ^DA7, R ^DA and examples and preferred ranges of the substituent which may be possessed by R ^DB are the same as examples and preferred ranges of the substituents which may be possessed by G ^DA.

T ^DA is preferably a group represented by Formula (TDA-1) to Formula (TDA-4), more preferably a group represented by Formula (TDA-1) or Formula (TDA-3) And more preferably a group represented by formula (TDA-1).

［式中、Ｒ^DA及びＲ^DBは、前記と同じ意味を表す。］

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

  The group represented by Formula (DA) is preferably a group represented by Formula (D-A1) to Formula (D-A5), more preferably Formula (D-A1), Formula (D-A3) Or a group represented by the formula (D-A5), more preferably a group represented by the formula (D-A1).

［式中、
Ｒ^p1〜Ｒ^p4は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基又はハロゲン原子を表す。Ｒ^p1、Ｒ^p2及びＲ^p4が複数ある場合、それらはそれぞれ同一であっても異なっていてもよい。
ｎｐ１は、０〜５の整数を表し、ｎｐ２は０〜３の整数を表し、ｎｐ３は０又は１を表し、ｎｐ４は０〜４の整数を表す。複数あるｎｐ１は、同一でも異なっていてもよい。］

[In the formula,
Each of R ^{p1 to} R ^p4 independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^p1 , R ^p2 and R ^p4 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, np3 represents 0 or 1, and np4 represents an integer of 0 to 4. The plurality of np1 may be the same or different. ]

  The group represented by formula (DB) is preferably a group represented by formula (D-B1) to formula (D-B3), more preferably a group represented by formula (D-B1) .

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

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

  The group represented by Formula (DC) is preferably a group represented by Formula (D-C1) to Formula (D-C4), and more preferably Formula (D-C1) to Formula (D-C3) And more preferably a group represented by the formula (D-C1) or the formula (D-C2), and particularly preferably a group represented by the formula (D-C1).

［式中、
Ｒ^p4〜Ｒ^p6は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基又はハロゲン原子を表す。Ｒ^p4〜Ｒ^p6が複数ある場合、それらはそれぞれ同一であっても異なっていてもよい。
ｎｐ４は、０〜４の整数を表し、ｎｐ５は０〜５の整数を表し、ｎｐ６は０〜５の整数を表す。］

[In the formula,
R ^{p4 to} R ^p6 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^{p4 to} R ^p6 , they may be the same or different.
np4 represents an integer of 0 to 4, np5 represents an integer of 0 to 5, and np6 represents an integer of 0 to 5. ]

  np1 is preferably 0 or 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0. np4 is preferably an integer of 0-2. np5 is preferably an integer of 1 to 3. np6 is preferably an integer of 0-2.

R ^{p1 to} R ^p6 are preferably an alkyl group or a cycloalkyl group, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a cyclohexyl group or a tert-octyl group And more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group or a tert-octyl group.

At least one of E ^11A and E ^12A is a nitrogen atom, and at least one of R ^11A and R ^12A bonded to the nitrogen atom is at least one of E ^11A and E ^{12A in} the ring R ^1A because the drive voltage of the light emitting device of the present invention is lower. is preferably a group represented by the formula (Ar-1A), E ^11A is a nitrogen atom, and it R ^11A binding to the nitrogen atom is a group represented by the formula (Ar-1A) Is more preferred.

When a plurality of rings R ^1A are present, at least one of E ^{11A to} E ^13A in at least one of the plurality of rings R ^1A is a nitrogen atom, and at least one of R ^{11A to} R ^13A bonded to the nitrogen atom One of them may be a group represented by the formula (Ar-1A), but the synthesis of the metal complex represented by the formula (1) is facilitated, so at least two of the plurality of rings R ^1A Preferably, at least one of ^{11A to} E ^13A is a nitrogen atom, and at least one of R ^{11A to} R ^13A bonded to the nitrogen atom is a group represented by formula (Ar-1A), and a plurality of them exist A group in which at least one of E ^{11A to} E ^13A is a nitrogen atom, and at least one of R ^{11A to} R ^13A bonded to the nitrogen atom is a group represented by formula (Ar-1A) in all the rings R ^1A It is more preferable that

The number of carbon atoms of the aromatic hydrocarbon ring in the ring R ² is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the number of carbon atoms of the substituent. The aromatic hydrocarbon ring in the ring R ² includes, for example, benzene ring, naphthalene ring, indene ring, fluorene ring, spirobifluorene ring, phenanthrene ring, dihydrophenanthrene ring, and one or more and five or less of these rings fused. The ring is preferably a benzene ring, a naphthalene ring, a fluorene ring, a spirobifluorene ring, a phenanthrene ring or a dihydrophenanthrene ring, since a fused ring is included and the driving voltage of the light emitting device of the present invention is lower. A benzene ring, a fluorene ring, a spirobifluorene ring or a dihydrophenanthrene ring, more preferably a benzene ring or a fluorene ring, particularly preferably a benzene ring, and these rings may have a substituent Good.
The carbon atom number of the aromatic heterocyclic ring in ring R ² is usually 2 to 60, preferably 3 to 30, and more preferably 4 to 15, not including the carbon atom number of the substituent. Examples of the aromatic heterocyclic ring in the ring R ² include pyrrole ring, diazole ring, furan ring, thiophene ring, pyridine ring, diazabenzene ring, and rings in which one to five aromatic rings are fused to these rings. Preferably, a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, an indole ring, a benzofuran ring, a benzothiophene ring, a carbazole ring, an azacarbazole ring, since the driving voltage of the light emitting device of the present invention is lower. A diazacarbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, still more preferably a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring Yes, especially preferred It is dibenzofuran ring, and these rings may have a substituent. When ring R ² is a 6-membered aromatic heterocycle, E ² is preferably a carbon atom.

The ring R ² is preferably a benzene ring, a fluorene ring, a spirobifluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzo, since the driving voltage of the light emitting device of the present invention is further lowered. It is a thiophene ring, more preferably a benzene ring, a fluorene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, still more preferably a benzene ring or a dibenzofuran ring, and these rings have a substituent It is also good.

The substituent which ring R ² may have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or It is a halogen atom, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, still more preferably an alkyl group or an aryl group, and these groups are further substituted It may have a group.

Examples and preferred ranges of the aryl group, the monovalent heterocyclic group and the substituted amino group in the substituent which the ring R ² may have are the aryl group in the R ^{11A to} R ^{13A and the} monovalent heterocyclic group, respectively. And the same as the examples and preferred ranges of the substituted amino group.

The example and the preferable range of the substituent which the substituent which ring R ² may have may further have are the same as the examples and the preferable range of the substituent which R ^{11A to} R ^13A may have It is.

Since the synthesis of the metal complex represented by the formula (1) is facilitated, R ^11A and R ^12A , R ^12A and R ^13A , and a substituent which the ring R ² may have and R ^11A are respectively Preferably, they do not form a ring with the atoms to which they are attached.

[Group Represented by Formula (Ar-1A)]
The examples and the preferred ranges of the aromatic hydrocarbon ring in the ring A are the same as the examples and the preferred ranges of the aromatic hydrocarbon ring in the ring R ² . The examples and the preferred ranges of the aromatic heterocycle in the ring A are the same as the examples and the preferred ranges of the aromatic heterocycle in the ring R ² .

  Ring A is preferably a benzene ring, a fluorene ring, a spirobifluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene because the driving voltage of the light emitting device of the present invention is lower. It is a ring, more preferably a benzene ring, a pyridine ring or a diazabenzene ring, further preferably a benzene ring, and these rings may have a substituent.

The example and the preferable range of the substituent which the ring A may have are the same as the examples and the preferable range of the substituent which the ring R ² may have.

  Since the synthesis of the metal complex represented by the formula (1) is facilitated, when there are a plurality of substituents which the ring A may have, they are bonded to each other to form a ring together with the atoms to which they are bonded. It is preferable not to form.

R ² is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably an alkyl group, because the driving voltage of the light emitting device of the present invention is lower. It is a cycloalkyl group or an aryl group, more preferably an alkyl group, and these groups may further have a substituent.
Examples and preferred ranges of the aryl group, monovalent heterocyclic group and substituted amino group in R ² are the same as the examples and preferred ranges of the aryl group, monovalent heterocyclic group and substituted amino group in R ^{11A to} R ^13A . is there.
The example and the preferable range of a substituent which R ² may have are the same as the examples and a preferable range of a substituent which R ^{11A to} R ^13A may have.

  The group represented by the formula (Ar-1A) is preferably a group represented by the formula (Ar-2A) because the drive voltage of the light emitting device of the present invention is lower.

E ^{1A to} E ^3A are preferably carbon atoms.

When ring A ¹ is a pyridine ring, pyridine rings in which E ^1A is a nitrogen atom are preferred.
When ring A ¹ is a diazabenzene ring, pyrimidine rings in which E ^1A and E ^3A are nitrogen atoms are preferred.
Ring A ¹ is preferably a benzene ring.

R ^{1A to} R ^3A are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, since the drive voltage of the light emitting device of the present invention is lower. More preferably, they are a hydrogen atom, an alkyl group or an aryl group, and these groups may have a substituent.
R ^1A and R ^3A are more preferably hydrogen atoms.
R ^2A is more preferably an alkyl group or an aryl group, and these groups may have a substituent.

Examples and preferred ranges of the aryl group, monovalent heterocyclic group and substituted amino group in R ^{1A to} R ^3A are the examples of aryl group, monovalent heterocyclic group and substituted amino group in R ^{11A to} R ^13A , respectively It is the same as the preferred range.
Examples of R ^1A to R ^3A substituent which may be possessed and preferred ranges are the same as examples of R ^11A to R ^13A substituent which may be possessed and preferred ranges.

Since the synthesis of the metal complex represented by the formula (1) is facilitated, R ^1A and R ^2A and R ^2A and R ^3A are respectively bonded to form a ring with the atoms to which each is bonded. Although it is preferable, it does not form a ring.

  The group represented by the formula (Ar-2A) is preferably a group represented by the formula (Ar-3A) because the drive voltage of the light emitting device of the present invention is lower.

[Anionic bidentate ligand]
Examples of the anionic bidentate ligand represented by A ¹ -G ¹ -A ² include a ligand represented by the following formula. However, the anionic bidentate ligand represented by A ¹ -G ¹ -A ² is different from the ligand whose number is defined by the index n ¹ .

［式中、
＊は、Ｍ¹と結合する部位を表す。
Ｒ^L1は、水素原子、アルキル基、シクロアルキル基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。複数存在するＲ^L1は、同一でも異なっていてもよい。
Ｒ^L2は、アルキル基、シクロアルキル基、アリール基、１価の複素環基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。］

[In the formula,
* Represents a site that binds to M ¹ .
R ^L1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a halogen atom, and these groups may have a substituent. Plural R ^L1 may be the same or different.
R ^L2 represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. ]

R ^L1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom, more preferably a hydrogen atom or an alkyl group, and these groups may have a substituent.
R ^L2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.

  The metal complex represented by the formula (1) is preferably a metal complex represented by the formula (1-A1) or the formula (1-A2) because the driving voltage of the light emitting device of the present invention is lower. And more preferably a metal complex represented by the formula (1-A1).

The ring R ^2A is preferably a benzene ring, a fluorene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a benzene ring or a dibenzofuran ring, and these rings may have a substituent.
The examples and the preferred ranges of the substituents which the ring R ^2A may have are the same as the examples and the preferred ranges of the substituents which the ring R ² may have.

Since the synthesis of the metal complex represented by Formula (1-A1) or Formula (1-A2) is facilitated, when there are a plurality of substituents that ring R ^2A may have, they are bonded to each other Preferably, they do not form a ring with the atoms to which they are attached.
Since the synthesis of the metal complex represented by the formula (1-A1) or the formula (1-A2) is facilitated, the substituent which the ring R ^2A may have and R ^11A are bonded to each other, It is preferred not to form a ring with the atoms to which each is attached.

Since the synthesis of the metal complex represented by the formula (1-A1) is facilitated, in the case of a plurality of R ^{11A in} the formula (1-A1), at least two of R ^11A are represented by the formula (Ar-1A) It is preferable that it is a group represented, and it is more preferable that all of R ^<11A> are groups represented by Formula (Ar-1A).
In formula (1-A1), E ^12A is preferably a carbon atom.
In formula (1-A1), E ^13A is preferably a nitrogen atom, and R ^13A is preferably absent.

Since the synthesis of the metal complex represented by the formula (1-A2) is facilitated, when there are a plurality of R ^{12A in} the formula (1-A2), at least two of R ^12A are represented by the formula (Ar-1A) It is preferable that it is a group represented, and it is more preferable that all of ^R12A is a group represented by Formula (Ar-1A).
In formula (1-A2), E ^13A is preferably a carbon atom.
In formula (1-A2), E ^11A is preferably a nitrogen atom, and R ^11A is preferably absent.

The metal complex represented by the formula (1-A1) has a lower driving voltage for the light emitting device of the present invention, and is preferably represented by the formula (1-A1-1) to the formula (1-A1-3). More preferably a metal complex represented by the formula (1-A1-1) or the formula (1-A1-2), and still more preferably a metal complex represented by the formula (1-A1-2) Metal complex.
The metal complex represented by the formula (1-A2) has a lower driving voltage for the light-emitting element of the present invention, and is preferably represented by the formula (1-A2-1) or the formula (1-A2-2). The metal complex is more preferably a metal complex represented by the formula (1-A2-2).

R ^{21A to} R ^24A are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and more preferably a hydrogen atom, an alkyl group or an aryl group These groups may have a substituent.

Examples and preferred ranges of the aryl group, monovalent heterocyclic group and substituted amino group in R ^{21A to} R ^24A are respectively an aryl group in a substituent which may be possessed by the ring R ² and a monovalent heterocyclic group And the same as the examples and preferred ranges of the substituted amino group.

In order to facilitate the synthesis of the metal complex represented by the formula (1), it is preferable that R ^11A and R ^21A be bonded to each other and not form a ring with the atoms to which each is bonded.

When R ^21A and R ^22A , R ^22A and R ^23A , or R ^23A and R ^24A combine with each other to form a ring with the atoms to which each is attached, examples of the ring formed include aromatic hydrocarbons A ring or an aromatic heterocycle is mentioned, preferably a benzene ring, an indene ring, a pyridine ring, a diazabenzene ring, a benzofuran ring, a benzothiophene ring or an indole ring, more preferably an indene ring, a benzofuran ring, It is a benzothiophene ring or an indole ring, more preferably a benzofuran ring or a benzothiophene ring, particularly preferably a benzofuran ring, and these rings may have a substituent.
When ^R21A and ^R22A , ^R22A and ^R23A , or ^R23A and ^R24A are bonded to each other to form a ring with the atoms to which they are attached, ^R21A and ^R22A , or ^R22A and R22 ^23A is preferably bonded to each other to form a ring with atoms to which each is bonded, and it is preferable that R ^22A and R ^23A be bonded to each other to form a ring with atoms to which each is bonded.

The example and the preferred range of the substituent which R ^{21A to} R ^24A may have are the same as the example and the preferred range of the substituent which the substituent which the ring R ² may have may further have. It is.

  As a metal complex represented by Formula (1), the metal complex represented by a following formula is mentioned, for example.

［式中、
Ｚ^Aは、−ＣＨ＝で表される基又は−Ｎ＝で表される基を表す。Ｚ^Aが複数存在する場合、それらは同一でも異なっていてもよい。
Ｚ^Bは、−Ｏ−で表される基又は−Ｓ−で表される基を表す。Ｚ^Bが複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula,
Z ^A represents a group represented by -CH = or a group represented by -N =. When a plurality of Z ^A are present, they may be the same or different.
Z ^B represents a group represented by -O- or a group represented by -S-. When two or more Z ^B exist, they may be the same or different. ]

Z ^A is preferably a group represented by -N =. Z ^B is preferably a group represented by -O-.

<Production Method of Metal Complex Represented by Formula (1)>
The metal complex represented by the formula (1) can be produced, for example, by a method of reacting a compound serving as a ligand with a metal compound. If necessary, functional group conversion reaction of the metal complex ligand may be performed.

  The metal complex represented by Formula (1) can be manufactured by the method including the process A with which the compound represented by Formula (M-1), and a metal compound or its hydrate is made to react, for example.

［式中、Ｍ¹、ｎ¹、ｎ²、環Ｒ^1A、環Ｒ²、Ｒ^11A〜Ｒ^13A、Ｅ¹、Ｅ²、Ｅ^11A〜Ｅ^13A及びＡ¹−Ｇ¹−Ａ²は、前記と同じ意味を表す。］

[Wherein, M ¹ , n ¹ , n ² , ring R ^1A , ring R ² , R ^{11A to} R ^13A , E ¹ , E ² , E ^{11A to} E ^13A and A ¹ -G ¹ -A ² are the above-mentioned Represents the same meaning as. ]

  In the step A, as a metal compound, for example, iridium compounds such as iridium chloride, tris (acetylacetonato) iridium (III), chloro (cyclooctadiene) iridium (I) dimer, iridium (III) acetate and the like; chloroplatinic acid And platinum compounds such as potassium; palladium compounds such as palladium chloride and palladium acetate; and rhodium compounds such as rhodium chloride. Examples of hydrates of metal compounds include iridium chloride trihydrate and rhodium chloride trihydrate.

  In step A, the amount of the compound represented by the formula (M-1) is generally 2 to 20 mol, per 1 mol of the metal compound or the hydrate thereof.

  Step A is usually performed in a solvent. As the solvent, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol and the like; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, diglyme and the like Halogen solvents such as methylene chloride and chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene and mesitylene; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as: acetone, dimethyl sulfoxide, water and the like.

  In step A, the reaction time is usually 30 minutes to 200 hours, and the reaction temperature is usually between the melting point and the boiling point of the solvent present in the reaction system.

  The compound, the catalyst and the solvent used in the reaction described in <Method of producing metal complex represented by Formula (1)> may be used alone or in combination of two or more.

[Host material]
Since the driving voltage of the light emitting device of the present invention is lower, the first organic layer is composed of the metal complex represented by the formula (1), hole injecting property, hole transporting property, electron injecting property and electron transporting property It is preferable that it is a layer containing a host material having at least one function selected from The first organic layer may contain one type of host material alone, or may contain two or more types.

  When the first organic layer is a layer containing the metal complex represented by the formula (1) and a host material, the content of the host material is the same as that of the metal complex represented by the formula (1) and the host material When the total is 100 parts by mass, it is usually 1 to 99 parts by mass, preferably 10 to 90 parts by mass, more preferably 30 to 85 parts by mass, and still more preferably 50 to 80 parts by mass. .

The lowest excited triplet state (T ₁ ) of the host material has a lower driving voltage for the light emitting element of the present invention, so the lowest excited triplet state (T ₁ ) of the metal complex represented by the formula ( ₁ ) Higher energy levels are preferred.

  As the host material, since the light-emitting element of the present invention can be manufactured by a wet method, it is preferable that the host material exhibits solubility in a solvent capable of dissolving the metal complex represented by Formula (1).

  Host materials are classified into low molecular weight compounds (low molecular weight host) and high molecular weight compounds (polymer host), and the first organic layer may contain any host material. As a host material which may be contained in the first organic layer, a low molecular weight compound is preferable.

[Small molecule host]
The low molecular weight host is preferably a compound represented by the formula (H-1).

Ar ^H1 and Ar ^{H2 each} represents a phenyl group, a fluorenyl group, a spirobifluorenyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a furyl group, a benzofuryl group Group, dibenzofuryl group, pyrrolyl group, indolyl group, azaindolyl group, carbazolyl group, azacarbazolyl group, diazacarbazolyl group, phenoxazinyl group or phenothiazinyl group, preferably phenyl group, fluorenyl group, spirobifluorene group. More preferably a sulfonyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group or an azacarbazolyl group, and a fluorenyl group, a spirobifluorenyl group, a dibenzothienyl group or a dibe More preferably from Zofuriru group or a carbazolyl group, especially preferably a group represented by the formula (TDA-3), these groups may have a substituent.

The substituent that Ar ^H1 and Ar ^H2 may have is preferably a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and an alkyl group and a cyclo An alkoxy group, an alkoxy group or a cycloalkoxy group is more preferable, an alkyl group or a cycloalkoxy group is more preferable, and these groups may further have a substituent.

n ^H1 is preferably 1. n ^H2 is preferably 0.
n ^H3 is usually an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1.
n ^H11 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and still more preferably 1.

R ^H11 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, a hydrogen atom or an alkyl group It is further preferable that these groups have one or more substituents.

L ^H1 is preferably an arylene group or a divalent heterocyclic group, and these groups may further have a substituent.

L ^H1 is a group represented by the formula (A-1) to the formula (A-3), the formula (A-8) to the formula (A-10), the formula (AA-1) to the formula (AA-6), the formula (AA-) 10) to a group represented by Formula (AA-21) or Formula (AA-24) to Formula (AA-34), preferably Formula (A-1), Formula (A-2) or Formula (A) A-8) Formula (A-9) Formula (AA-1) to Formula (AA-4) Formula (AA-10) to Formula (AA-15) Formula (AA-33) or Formula (AA) It is more preferable that it is a group represented by -34), Formula (A-1), Formula (A-2), Formula (A-8), Formula (AA-2), Formula (AA-4), More preferably, it is a group represented by formula (AA-10), formula (AA-12), formula (AA-14) or (AA-33), and formula (A-8) or formula (AA-10) A group represented by formula (AA-12) or formula (AA-14) Particularly preferably Rukoto, it is particularly preferably a group represented by the formula (AA-14).

The substituent which L ^H1 may have is preferably a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and an alkyl group, an alkoxy group, an aryl group The group or monovalent heterocyclic group is more preferable, the alkyl group, the aryl group or the monovalent heterocyclic group is more preferable, the monovalent heterocyclic group is particularly preferable, and these groups further have a substituent. It is also good.

L ^H21 is preferably a single bond or an arylene group, more preferably a single bond, and the arylene group may have a substituent.
The definition and examples of the arylene group or divalent heterocyclic group represented by L ^H21 are the same as the definitions and examples of the arylene group or divalent heterocyclic group represented by L ^H1 .

R ^H21 is preferably an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
The definitions and examples of the aryl group and monovalent heterocyclic group represented by R ^H21 are the same as the definitions and examples of the aryl group and monovalent heterocyclic group represented by Ar ^H1 and Ar ^H2 .
The definition and the example of the substituent which R ^H21 may have are the same as the definition and the example of the substituent which Ar ^H1 and Ar ^H2 may have.

  The compound represented by formula (H-1) is preferably a compound represented by formula (H-2).

［式中、Ａｒ^H1、Ａｒ^H2、ｎ^H3及びＬ^H1は、前記と同じ意味を表す。］

[Wherein, Ar ^H1 , Ar ^H2 , n ^H3 and L ^H1 represent the same meaning as described above. ]

  As a compound represented by Formula (H-1), the compound represented by a following formula and the below-mentioned compound HM-1 are illustrated.

  Examples of the polymer compound used for the host material include a polymer compound which is a hole transport material described later, and a polymer compound which is an electron transport material described later.

[Polymer host]
The polymer host is preferably a polymer compound containing a constitutional unit represented by the formula (Y).

The arylene group represented by Ar ^Y1 is more preferably a group represented by the formula (A-1), a formula (A-2), a formula (A-6) -the formula (A-10), a formula (A-19) or a formula (A-20), more preferably a group represented by the formula (A-1), a formula (A-2), a formula (A-7), a formula (A-9) or a formula (A-19) These groups may be substituted.

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

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

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

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

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

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

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

  Examples of the structural unit represented by formula (Y) include the structural units represented by formula (Y-1) -formula (Y-10), and from the viewpoint of the driving voltage of the light emitting device of the present invention, Preferably, it is a structural unit represented by formula (Y-1) -formula (Y-3), and from the viewpoint of the electron transportability of the light emitting device of the present invention, preferably it is a formula (Y-4) -formula ( It is a structural unit represented by Y-7), and from the viewpoint of the hole transportability of the light emitting device of the present invention, preferably a structural unit represented by the formula (Y-8) -the formula (Y-10) is there.

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

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

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

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

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

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

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

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

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

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

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

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

In R ^Y1 , four R ^Y2 in the group represented by —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — are preferably an alkyl group or a cycloalkyl group which may have a substituent. It is. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which each is attached, and in the case where R ^Y2 forms a ring, -C (R ^Y2 ) ₂ -C (R ^Y2 ) _2- The group represented is preferably a group represented by the formula (Y-B1)-(Y-B5), more preferably a group represented by the formula (Y-B3), and these groups are substituted It may have a group.

［式中、Ｒ^Y2は前記と同じ意味を表す。］

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

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

［式中、Ｒ^Y1及びＸ^Y1は前記と同じ意味を表す。］

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

［式中、Ｒ^Y1及びＸ^Y1は前記と同じ意味を表す。］

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

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

［式中、Ｒ^Y11及びＸ^Y1は前記と同じ意味を表す。］

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

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

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

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

  The constituent unit represented by the formula (Y-4) is preferably a constituent unit represented by the formula (Y-4 ′), and the constituent unit represented by the formula (Y-6) is a compound represented by the formula (Y It is preferable that it is a structural unit represented by -6 ').

［式中、Ｒ^Y1及びＲ^Y3は前記と同じ意味を表す。］

[Wherein, R ^Y1 and R ^Y3 represent the same meaning as described above. ]

［式中、
Ｒ^Y1は、前記を同じ意味を表す。
Ｒ^Y4は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は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。］

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

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

  As the constitutional unit represented by the formula (Y), for example, a constitutional unit comprising an arylene group represented by the formula (Y-101) -formula (Y-121), a formula (Y-201) -formula (Y-) Constituent unit comprising a divalent heterocyclic group represented by 206), at least one arylene group represented by the formula (Y-300) -formula (Y-304) and at least one divalent heterocyclic ring The structural unit which consists of bivalent group which group and directly couple | bonded is mentioned.

The structural unit represented by the formula (Y), in which Ar ^{Y 1} is an arylene group, has a lower driving voltage for the light emitting device of the present invention, and thus the total amount of structural units contained in the polymer host Preferably it is 0.5-90 mol%, More preferably, it is 30-80 mol%.

A constituent unit represented by the formula (Y), wherein Ar ^{Y 1} is a divalent heterocyclic group, or a bivalent in which at least one arylene group and at least one divalent heterocyclic group are directly bonded. The structural unit which is a group of the present invention is preferably 0.5 to 40 mol%, more preferably 3 to the total amount of the structural units contained in the polymer host, because the charge transportability of the light emitting device of the present invention is excellent. It is -30 mol%.

  The constituent unit represented by the formula (Y) may be contained alone in the polymer host, or two or more kinds may be contained.

  It is preferable that the polymer host further includes a structural unit represented by the following formula (X) because the polymer host is excellent in hole transportability.

［式中、
ａ^X1及びａ^X2は、それぞれ独立に、０以上の整数を表す。
Ａｒ^X1及びＡｒ^X3は、それぞれ独立に、アリーレン基又は２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^X2及びＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、又は、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。Ａｒ^X2及びＡｒ^X4が複数存在する場合、それらは同一でも異なっていてもよい。
Ｒ^X1、Ｒ^X2及びＲ^X3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^X2及びＲ^X3が複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula,
Each of a ^X1 and a ^X2 independently represents an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 are each independently an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded These groups may have a substituent. When a plurality of Ar ^X2 and Ar ^X4 exist, they may be the same or different.
Each of R ^X1 , R ^X2 and R ^X3 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of R ^X2 and R ^X3 exist, they may be the same or different. ]

a ^X1 is preferably 2 or less, more preferably 1, because the driving voltage of the light emitting device of the present invention is lower.
a ^X2 is preferably 2 or less, more preferably 0, because the drive voltage of the light emitting device of the present invention is lower.

R ^X1 , R ^X2 and R ^X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent It is also good.

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

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

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

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

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

More preferable range of an arylene group and a divalent heterocyclic group in a divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and at least one divalent heterocyclic group are directly bonded The more preferable range is the same as the more preferable range or the more preferable range of the arylene group and the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 respectively.

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

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

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

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

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

[Wherein, R ^X4 and R ^X5 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, halogen atom, monovalent heterocyclic group or cyano Represents a group, and these groups may have a substituent. A plurality of R ^X4 may be the same or different. Plural R ^{X5 s} may be the same or different, and adjacent R ^{X5 s} may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]

  The structural unit represented by the formula (X) is excellent in hole transportability, and is preferably 0.1 to 50 mol%, more preferably 1 to 50 mol%, based on the total amount of the structural units contained in the polymer host. It is 40 mol%, more preferably 5 to 30 mol%.

  Examples of the structural unit represented by the formula (X) include structural units represented by the formula (X1-1) -formula (X1-15), preferably a formula (X1-3) -formula (X1) It is a constitutional unit represented by -10).

  In the polymer host, the constitutional unit represented by the formula (X) may be contained alone or in combination of two or more.

  Examples of the polymer host include polymer compounds P-1 to P-6.

［表中、ｐ、ｑ、ｒ、ｓ及びｔは、各構成単位のモル比率を示す。ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝100であり、かつ、100≧ｐ＋ｑ＋ｒ＋ｓ≧70である。その他の構成単位とは、式(Ｙ)で表される構成単位及び式(Ｘ)で表される構成単位以外の構成単位を意味する。］

[In the table, p, q, r, s and t indicate the molar ratio of each constituent unit. p + q + r + s + t = 100, and 100 p p + q + r + s 70 70. The other structural unit means a structural unit other than the structural unit represented by Formula (Y) and the structural unit represented by Formula (X). ]

  The polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be other embodiments, but a plurality of raw material monomers may be used together. It is preferable that it is a polymerized copolymer.

The polystyrene equivalent number average molecular weight of the polymer host is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and more preferably 1.5 × 10 ^{4 to} 1.5 × 10 ⁵

[Method of producing polymer host]
The polymer host can be produced using a known polymerization method described in Chemical Review (Chem. Rev.), Vol. 109, p. 897-1091 (2009), etc., and the Suzuki reaction, Yamamoto reaction, Buchwald, etc. Examples thereof include a method of polymerization by a coupling reaction using a transition metal catalyst such as reaction, Stille reaction, Negishi reaction and Kumada reaction.

  In the above-mentioned polymerization method, as a method of charging the monomers, a method of charging the whole amount of the monomers at once into the reaction system, charging a part of the monomers and reacting them, then batching the remaining monomers, A method of charging continuously or in parts, a method of charging monomers continuously or in parts, etc. may be mentioned.

  Examples of transition metal catalysts include palladium catalysts and nickel catalysts.

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

[First composition]
The first organic layer includes a metal complex represented by the formula (1), the above-mentioned host material, a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material (however, In a layer containing a composition (hereinafter, also referred to as “first composition”) containing at least one material selected from the group consisting of (a) different from the metal complex represented by (a) and an antioxidant. It may be.

[Hole transport material]
The hole transport material is classified into a low molecular weight compound and a high molecular weight compound, and is preferably a high molecular weight compound having a crosslinking group.
As low molecular weight compounds, for example, triphenylamine and derivatives thereof, N, N′-di-1-naphthyl-N, N′-diphenylbenzidine (α-NPD), and N, N′-diphenyl-N, Aromatic amine compounds such as N'-di (m-tolyl) benzidine (TPD) can be mentioned.
Examples of the polymer compound include polyvinylcarbazole and derivatives thereof; polyarylenes having an aromatic amine structure in the side chain or main chain and derivatives thereof. The polymer compound may be a compound to which an electron accepting moiety such as fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene and trinitrofluorenone is bound.
In the first composition, the compounding amount of the hole transporting material is usually 1 to 400 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass.
The hole transport material may be used alone or in combination of two or more.

[Electron transport material]
Electron transport materials are classified into low molecular weight compounds and high molecular weight compounds. The electron transport material may have a crosslinking group.
As the low molecular weight compound, for example, metal complexes having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene and diphenoquinone And as well as their derivatives.
As a high molecular compound, polyphenylene, polyfluorene, and these derivatives are mentioned, for example. The polymer compound may be doped with metal.
In the first composition, the compounding amount of the electron transporting material is usually 1 to 400 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass.
The electron transporting material may be used alone or in combination of two or more.

[Hole Injection Material and Electron Injection Material]
The hole injecting material and the electron injecting material are classified into low molecular weight compounds and high molecular weight compounds, respectively. The hole injecting material and the electron injecting material may have a crosslinking group.
As a low molecular weight compound, metal phthalocyanines, such as copper phthalocyanine; Carbon; Metal oxides, such as molybdenum and tungsten; Metal fluorides, such as lithium fluoride, sodium fluoride, cesium fluoride, potassium fluoride, etc. are mentioned, for example.
As the polymer compound, for example, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; conductive materials such as polymers containing an aromatic amine structure in the main chain or side chain Polymers are included.
In the first composition, the compounding amount of the hole injecting material and the electron injecting material is usually 1 to 400 parts by mass when the metal complex represented by the formula (1) is 100 parts by mass.
The hole injecting material and the electron injecting material may be used alone or in combination of two or more.

[Ion doping]
When the hole injecting material or the electron injecting material contains a conductive polymer, the conductivity of the conductive polymer is preferably 1 × 10 ⁻⁵ S / cm to 1 × 10 ³ S / cm. The conductive polymer can be doped with an appropriate amount of ions in order to bring the conductivity of the conductive polymer into such a range. The type of ion to be doped is an anion if it is a hole injecting material, and a cation if it is an electron injecting material. Examples of the anion include polystyrene sulfonate ion, alkyl benzene sulfonate ion and camphor sulfonate ion. Examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutyl ammonium ion.
The ions to be doped may be used singly or in combination of two or more.

[Light emitting material]
Light emitting materials are classified into low molecular weight compounds and high molecular weight compounds. The light emitting material may have a crosslinking group.
The low molecular weight compounds include, for example, naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, and a triplet light emitting complex having iridium, platinum or europium as a central metal.
As a triplet light emission complex, the metal complex shown below is mentioned, for example.

  As the polymer compound, for example, arylene groups such as phenylene group, naphthalenediyl group, fluorenediyl group, phenanthrendiyl group, dihydrophenanthrendiyl group, anthracenediyl group, pyrendiyl group and the like; two hydrogen atoms from an aromatic amine Examples thereof include polymer compounds containing aromatic amine residues such as groups to be removed; and divalent heterocyclic groups such as carbazole diyl group, phenoxazine diyl group and phenothiazine diyl group.

  The light emitting material is preferably a triplet light emitting complex or a polymer compound, more preferably a triplet light emitting complex.

In the first composition, the content of the light emitting material is usually 0.01 to 400 parts by mass, preferably 0.1 to 0.1 parts by mass, based on 100 parts by mass of the metal complex represented by the formula (1). It is 100 parts by mass, more preferably 0.5 to 50 parts by mass, and still more preferably 1 to 10 parts by mass.
The light emitting materials may be used alone or in combination of two or more.

[Antioxidant]
The antioxidant may be a compound which is soluble in the same solvent as the metal complex represented by the formula (1) and does not inhibit light emission and charge transport, and examples thereof include phenolic antioxidants and phosphorus antioxidants. Can be mentioned.
In the first composition, the blending amount of the antioxidant is usually 0.001 to 10 parts by mass, based on 100 parts by mass of the metal complex represented by the formula (1).
The antioxidant may be used alone or in combination of two or more.

[First ink]
The composition containing the metal complex represented by the formula (1) and a solvent (hereinafter, also referred to as “first ink”) can be applied by spin coating, casting, microgravure coating, gravure coating, Suitable for wet methods such as bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, ink jet printing method, capillary coating method, nozzle coating method It can be used for

  The viscosity of the first ink may be adjusted according to the type of the wet method, but when the solution such as the ink jet printing method is applied to the printing method via the discharge device, clogging and flying bending at the discharge occur. As it is difficult, it is preferably 1 to 20 mPa · s at 25 ° C.

  The solvent contained in the first ink is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink. As a solvent, for example, chlorinated solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, etc .; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methylanisole, etc., toluene, Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetophenone; ethyl acetate, butyl acetate, ethyl cellsolve acetate, methyl benzoate, phenyl acetate and the like Ester solvents; polyhydric alcohol solvents such as ethylene glycol, glycerin and 1,2-hexanediol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone Amide solvents such as N, N-dimethylformamide may be mentioned. The solvents may be used alone or in combination of two or more.

  In the first ink, the content of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20 000 parts by mass, based on 100 parts by mass of the metal complex represented by the formula (1).

(Second organic layer)
The second organic layer is a layer containing a crosslinked body of a polymer compound containing a structural unit having a crosslinking group (hereinafter, referred to as “polymer compound of second organic layer”). In the second organic layer, the cross-linked body of the polymer compound of the second organic layer may be contained singly or in combination of two or more.

  The crosslinked product of the polymer compound of the second organic layer can be obtained by bringing the polymer compound of the second organic layer into a crosslinked state by the method, conditions, and the like described above.

[Polymer Compound of Second Organic Layer]
The polymer compound of the second organic layer is a polymer compound containing a structural unit having at least one type of crosslinking group selected from the group A of crosslinking groups since the driving voltage of the light emitting device of the present invention is lower. Is preferred.

  As the crosslinking group selected from the crosslinking group A group, since the driving voltage of the light emitting device of the present invention is lower, preferably, formula (XL-1) to formula (XL-4), formula (XL-7) to A crosslinking group represented by Formula (XL-10) or Formula (XL-16) to Formula (XL-19), and more preferably, Formula (XL-1), Formula (XL-3), Formula (XL) -9), a crosslinking group represented by the formula (XL-10), the formula (XL-16) or the formula (XL-17) to the formula (XL-19), more preferably the formula (XL-1) , A cross-linking group represented by the formula (XL-16) or the formula (XL-17) to the formula (XL-19), particularly preferably a group represented by the formula (XL-1) or the formula (XL-17) Cross-linking group.

  The structural unit having at least one crosslinking group selected from the crosslinking group A, which is contained in the polymer compound of the second organic layer, is represented by the structural unit represented by the formula (3) or the formula (4) Although it is preferable that it is a structural unit, it may be a structural unit represented by a following formula.

  When the polymer compound of the second organic layer contains two or more structural units having at least one crosslinking group selected from the crosslinking group A group, it has at least one crosslinking group selected from the crosslinking group A group It is preferred that at least two of the constituent units have mutually different crosslinking groups. Examples of the combination of crosslinking groups different from each other include formula (XL-1), formula (XL-2), formula (XL-5) to formula (XL-8) or formula (XL-14) to formula (XL-16) And a crosslinking group represented by Formula (XL-3), Formula (XL-4), Formula (XL-13) or Formula (XL-17) to Formula (XL-19) A combination is preferable, and a combination of a crosslinking group represented by Formula (XL-1) or Formula (XL-16) and a crosslinking group represented by Formula (XL-17) to Formula (XL-19) is more preferable Further preferred is a combination of a crosslinking group represented by the formula (XL-1) and a crosslinking group represented by the formula (XL-17).

  nA is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2 because the driving voltage of the light emitting device of the present invention is lower.

  n is preferably 2, because the drive voltage of the light emitting device of the present invention is lower.

Ar ³ is preferably an aromatic hydrocarbon group which may have a substituent, because the driving voltage of the light emitting device of the present invention is lower.

The carbon atom number of the aromatic hydrocarbon group represented by Ar ³ is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the carbon atom number of the substituent. is there.
Examples and preferred ranges of the arylene group moiety obtained by removing n substituent for the aromatic hydrocarbon group represented by Ar ³ are the same as examples and preferred ranges of the arylene group represented by Ar ^Y1.

The carbon atom number of the heterocyclic group represented by Ar ³ is usually 2 to 60, preferably 3 to 30, and more preferably 4 to 18, not including the carbon atom number of the substituent.
Examples and preferred ranges of the divalent heterocyclic group moiety excluding the n substituents of the heterocyclic group represented by Ar ³ are the examples and preferred ranges of the divalent heterocyclic group represented by Ar ^{Y 1} and It is the same.

Examples of substituents that may have a group represented by Ar ³ and preferred ranges are the same as examples and preferred ranges of substituent that may be possessed by the groups represented by Ar ^Y1.

The carbon atom number of the alkylene group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10, not including the carbon atom number of the substituent. The carbon atom number of the cycloalkylene group is usually 3 to 20, not including the carbon atom number of the substituent.
The alkylene group and the cycloalkylene group may have a substituent, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, an octylene group, and a hydrogen atom in these groups Are preferably a group substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a fluorine atom or the like.

Examples and preferred ranges of the arylene group represented by L ^A is the same as examples and preferred ranges of the arylene group represented by Ar ^Y1, the driving voltage of the light-emitting device of the present invention is lower, L ^A The arylene group represented by is preferably a phenylene group or a fluorenediyl group, and more preferably an m-phenylene group, a p-phenylene group, a fluorene-2,7-diyl group, a fluorene-9,9- It is a diyl group, and these groups may further have a substituent.
L Examples and preferred ranges of the divalent heterocyclic group represented by ^A are the same as examples and preferred ranges of the divalent heterocyclic group represented by later-described Ar ^Y1.

L ^A is preferably an arylene group or an alkylene group, and more preferably a phenylene group, a fluorenicyl group or an alkylene group, since L ^A facilitates the production of the polymer compound of the second organic layer, and further preferably Preferably, it is an alkylene group, and these groups may have a substituent.

L ^A substituent which may be possessed represented by, preferably, an alkyl group, a cycloalkyl group, an alkoxy group, cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group, a fluorine atom , A cyano group or a crosslinking group selected from the group A, more preferably selected from an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group or a crosslinked group A A bridging group, more preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, particularly preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups are further substituted It may have a group.

  Since X will lower the drive voltage of the light-emitting element of the present invention, preferably, X is preferably represented by Formula (XL-1) to Formula (XL-4), Formula (XL-7) to Formula (XL-10), or XL-16) a crosslinking group represented by formula (XL-19), and more preferably, formula (XL-1), formula (XL-3), formula (XL-9), formula (XL-10) A cross-linking group represented by formula (XL-16) or formula (XL-17) to formula (XL-19), and more preferably, a formula (XL-1), a formula (XL-16) or a formula It is a crosslinking group represented by (XL-17) to formula (XL-19), and particularly preferably a crosslinking group represented by formula (XL-1) or formula (XL-17).

The structural unit represented by the formula (3) is excellent in the stability and the crosslinkability of the polymer compound of the second organic layer, and therefore relative to the total amount of the structural units contained in the polymer compound of the second organic layer. Preferably, it is 0.5 to 80 mol%, more preferably 3 to 65 mol%, still more preferably 5 to 50 mol%.
The constituent unit represented by the formula (3) may be contained singly or in combination of two or more in the polymer compound of the second organic layer.
When the polymer compound of the second organic layer contains two or more structural units represented by the formula (3), at least two of the structural units represented by the formula (3) are cross-linked represented by X Preferably the groups are different from one another. The preferred range of the combination of crosslinking groups represented by different X's is the same as the preferred range of the aforementioned combination of different crosslinking groups.

[Constituent unit represented by equation (4)]
mA is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0, because the driving voltage of the light emitting device of the present invention is lower. It is 0.

  m is preferably 1 or 2, and more preferably 2, because the driving voltage of the light emitting device of the present invention is lower.

  c is preferably 0 because it facilitates the production of the polymer compound of the second organic layer and lowers the driving voltage of the light emitting device of the present invention.

Ar ⁵ is preferably an aromatic hydrocarbon group which may have a substituent, because the driving voltage of the light emitting device of the present invention is lower.
The definition and examples of the arylene group moiety of the aromatic hydrocarbon group represented by Ar ⁵ excluding the m substituents are the same as the definitions and examples of the arylene group represented by Ar ^{X 2} in formula (X) .
The definition and examples of the divalent heterocyclic group moiety excluding the m substituents of the heterocyclic group represented by Ar ⁵ are the same as those of the divalent heterocyclic group moiety represented by Ar ^X2 in formula (X) Same as definition and example.
The definition and examples of divalent groups other than m substituents of a group in which at least one aromatic hydrocarbon ring represented by Ar ⁵ and at least one hetero ring are directly bonded are represented by the formula (X) The definitions and examples of the divalent group in which at least one arylene group represented by Ar ^X2 and at least one divalent heterocyclic group are directly bonded to each other are the same as the definition and the example.

Ar ⁴ and Ar ⁶ are preferably arylene groups which may have a substituent, because the drive voltage of the light emitting device of the present invention is lower.
The definition and the example of the arylene group represented by Ar ⁴ and Ar ⁶ are the same as the definition and the example of the arylene group represented by Ar ^X1 and Ar ^X3 in the formula (X).
The definitions and examples of divalent heterocyclic groups represented by Ar ⁴ and Ar ⁶ are the same as the definitions and examples of divalent heterocyclic groups represented by Ar ^X1 and Ar ^X3 in Formula (X) described later. is there.

The example and the preferred range of the substituent which the group represented by Ar ^{4 to} Ar ⁶ may have is the same as the example and the preferred range of the substituent which the group represented by Ar ^{Y 1} described later may have. It is. The example and the preferable range of the substituent which the substituent which the group represented by Ar ^{4 to} Ar ⁶ may have may further have may be the substituent which the group represented by Ar ^{Y 1} may have Are the same as the examples and the preferred ranges of the substituents which may further have.

The definitions and examples of the alkylene group, cycloalkylene group, arylene group and divalent heterocyclic group represented by K ^A are respectively the alkylene group, cycloalkylene group, arylene group and divalent hetero group represented by L ^A The same as the definition and examples of the ring group.
K ^A is preferably an arylene group or an alkylene group, and more preferably a phenylene group, a fluorenedyl group or an alkylene group, since K ^A facilitates the production of the polymer compound of the second organic layer, and further preferably It is preferably a phenylene group or a methylene group, and these groups may have a substituent.
Examples and preferred ranges of the substituent which may be possessed by the groups represented by K ^A is the same as the example and preferred ranges of the substituents may have the group represented by L ^A.

  The definition and the example of the crosslinking group represented by X 'are the same as the definition and the example of X described above.

  The structural unit represented by the formula (4) is excellent in the stability of the polymer compound of the second organic layer, and the crosslinkability of the polymer compound of the second organic layer is excellent, so the second organic layer Preferably it is 0.5-50 mol%, More preferably, it is 3-30 mol%, More preferably, it is 5-20 mol% with respect to the total amount of the structural unit contained in these high molecular compounds.

  The constituent unit represented by the formula (4) may be contained singly or in combination of two or more in the polymer compound of the second organic layer.

  When the polymer compound of the second organic layer contains two or more structural units represented by Formula (4), at least two of the structural units represented by Formula (4) are represented by X ′ It is preferred that the bridging groups be different from one another. The preferred range of the combination of crosslinking groups represented by different X's is the same as the preferred range of the combination of different crosslinking groups described above.

  As a structural unit represented by Formula (3), the structural unit represented by Formula (3-1)-(3-30) is mentioned, for example, As a structural unit represented by Formula (4), For example, the structural unit represented by Formula (4-1)-(4-9) is mentioned. Among these, since the crosslinkability of the polymer compound of the second organic layer is excellent, it is preferably a structural unit represented by formulas (3-1) to (3-30), and more preferably 3-1) to (3-15), (3-19), (3-20), (3-23), (3-25) or (3-30), and is a structural unit further Preferably, they are structural units represented by formulas (3-1) to (3-13) or (3-30), and particularly preferably, they are represented by formulas (3-1) to (3-9) or (3- It is a structural unit represented by 30).

The polymer compound of the second organic layer preferably further includes a structural unit represented by the formula (Y) because the driving voltage of the light-emitting element of the present invention is lower.
The polymer compound of the second organic layer preferably has a structural unit represented by the formula (X) since it has excellent hole transportability.
The polymer compound of the second organic layer is excellent in the hole transportability, and the driving voltage of the light emitting device of the present invention is lower. Therefore, the structural unit represented by the formula (X) and the formula (Y It is preferable to include the structural unit represented by).

The definition, examples and preferred ranges of the constitutional units represented by the formula (X) which may be contained in the polymer compound of the second organic layer are represented by the formula (X) which may be contained in the polymer host. Are the same as the definition, examples and preferred ranges of the structural units.
When the polymer compound of the second organic layer contains a constituent unit represented by formula (X), the constituent unit represented by formula (X) contained in the polymer compound of the second organic layer is a hole Since the transportability is excellent, it is preferably 1 to 80 mol%, more preferably 10 to 70 mol%, further preferably to the total amount of the structural units contained in the polymer compound of the second organic layer. Is 30 to 60 mol%.
The structural unit represented by the formula (X) may be contained alone or in combination of two or more in the polymer compound of the second organic layer.

The definition, examples and preferred ranges of the constitutional units represented by the formula (Y) which may be contained in the polymer compound of the second organic layer are represented by the formula (Y) which may be contained in the polymer host. Are the same as the definition, examples and preferred ranges of the structural units.
When the polymer compound of the second organic layer contains a constitutional unit represented by the formula (Y) and Ar ^Y1 is an arylene group, it is represented by the formula (Y) contained in the polymer compound of the second organic layer The constituent unit is preferably 0.5 to 90% by mole based on the total amount of constituent units contained in the polymer compound of the second organic layer, since the drive voltage of the light emitting device of the present invention is lower. More preferably, it is 30-80 mol%.
The polymer compound of the second organic layer contains a constitutional unit represented by the formula (Y), and Ar ^Y1 is a divalent heterocyclic group, or at least one type of divalent complex with at least one arylene group. When the ring group is a divalent group directly bonded, the constitutional unit represented by the formula (Y) contained in the polymer compound of the second organic layer is the charge of the polymer compound of the second organic layer Since the transportability is excellent, it is preferably 0.5 to 40 mol%, more preferably 3 to 30 mol%, with respect to the total amount of the structural units contained in the polymer compound of the second organic layer.
The structural unit represented by the formula (Y) may be contained singly or in combination of two or more in the polymer compound of the second organic layer.

  As a high molecular compound of a 2nd organic layer, high molecular compound P-7-P-14 are mentioned, for example. Here, "others" means a structural unit other than the structural unit represented by Formula (3), Formula (4), Formula (X) and Formula (Y).

［表中、ｐ’、ｑ’、ｒ’、ｓ’及びｔ’は、各構成単位のモル比率（モル％）を表す。
ｐ’＋ｑ’＋ｒ’＋ｓ’＋ｔ’＝１００であり、且つ、７０≦ｐ’＋ｑ’＋ｒ’＋ｓ’≦１００である。］

[In the table, p ′, q ′, r ′, s ′ and t ′ represent the molar ratio (mol%) of each constituent unit.
p ′ + q ′ + r ′ + s ′ + t ′ = 100 and 70 ≦ p ′ + q ′ + r ′ + s ′ ≦ 100. ]

  The polymer compound of the second organic layer may be any of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and may be other embodiments, but plural It is preferable that it is a copolymer which copolymerized the raw material monomer of seed | species.

The polystyrene equivalent number average molecular weight of the polymer compound of the second organic layer is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and still more preferably It is 1.5 * 10 < ⁴ > -1 * 10 < ⁵ >.

[Method for producing polymer compound of second organic layer]
The polymer compound of the second organic layer can be produced by the same method as the method for producing the above-mentioned polymer host.

[Second composition]
The second organic layer is a crosslinked product of the polymer compound of the second organic layer, a hole transport material (but different from the crosslinked product of the polymer compound of the second organic layer), a hole injecting material, It is a layer containing a composition containing at least one material selected from the group consisting of an electron transport material, an electron injection material, a light emitting material, and an antioxidant (hereinafter, also referred to as a “second composition”). May be

  Examples and preferred ranges of the hole transporting material, the electron transporting material, the hole injecting material, the electron injecting material and the light emitting material contained in the second composition are the hole transporting material contained in the first composition, Examples and preferred ranges of the electron transport material, the hole injection material, the electron injection material and the light emitting material are the same. In the second composition, the compounding amounts of the hole transporting material, the electron transporting material, the hole injecting material, the electron injecting material and the light emitting material are each 100 parts by mass of the crosslinked product of the polymer compound of the second organic layer When it is set, it is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass.

  The example and the preferable range of the antioxidant contained in a 2nd composition are the same as the example and a preferable range of the antioxidant contained in a 1st composition. In the second composition, the blending amount of the antioxidant is usually 0.001 to 10 parts by mass, based on 100 parts by mass of the crosslinked product of the polymer compound of the second organic layer.

[Second ink]
A composition containing the polymer compound of the second organic layer and a solvent (hereinafter also referred to as “second ink”) is suitably used in the wet method described in the section of the first ink. Can. The preferred range of the viscosity of the second ink is the same as the preferred range of the viscosity of the first ink. Examples and preferred ranges of the solvent contained in the second ink are the same as examples and preferred ranges of the solvent contained in the first ink.
In the second ink, the compounding amount of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20 000 parts by mass, based on 100 parts by mass of the polymer compound of the second organic layer.

(Third organic layer)
The third organic layer is a polymer compound containing at least one structural unit selected from the group consisting of the structural unit represented by the formula (ET-1) and the structural unit represented by the formula (ET-2) Hereinafter, it is a layer containing “a polymer compound of the third organic layer”. In the third organic layer, the polymer compound of the third organic layer may be contained singly or in combination of two or more.

[Polymer Compound of Third Organic Layer]
nE1 is usually an integer of 1 to 4, preferably 1 or 2.

The example and the preferable range of the arylene group part except the nE1 substituent of the aromatic hydrocarbon group represented by Ar ^E1 are the same as the example and the preferable range of the arylene group represented by Ar ^Y1 .
Examples and preferred ranges of the divalent heterocyclic group moiety excluding nE1 substituents of the heterocyclic group represented by Ar ^E1 are the examples and preferred ranges of the divalent heterocyclic group represented by Ar ^Y1 and It is the same.
Ar ^E1 is preferably 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-naphthalenediyl, 1,4-naphthalenediyl, 2,7-fluorene A group obtained by removing one hydrogen atom nE directly bonded to an atom constituting a ring from an aryl group, a 3,6-fluorenedyl group, a 2,7-phenanthrendiyl group or a 2,7-carbazolediyl group; ^It may have a substituent other than ^E1 .

As a substituent other than R ^E1 which Ar ^E1 may have, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy A group, an amino group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, a carboxyl group and a group represented by the formula (ES-3) can be mentioned.

-O- (C _{n '} H _{2 n'} O) _nx- C _{m '} H _{2 m' + 1} (ES-3)
[Wherein, n ′, m ′ and nx each independently represent an integer of 1 or more. ]

nE3 is usually an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 2.
aE1 is usually an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1 or 2.
bE1 is usually an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably 0 or 1.
mE1 is usually an integer of 1 to 5, preferably 1 or 2, and more preferably 1.

When R ^E3 is —O—R ^E3 ′, the group represented by the formula (ES-1) is a group represented below.
^{-O-R E3 '- {(} Q E1) nE3 -Y E1 (M E1) aE1 (Z E1) bE1} mE1

R ^E3 is preferably a hydrocarbon group or a heterocyclic group, more preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, still more preferably an aromatic hydrocarbon group, and these groups each have a substituent It is also good.
^Examples of the substituent which R ^E3 may have include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group and a group represented by the formula (ES-3), and The group represented by 3) is preferable, and these groups may further have a substituent.

As Q ^E1 , an alkylene group, an arylene group or an oxygen atom is preferable, an alkylene group or an oxygen atom is more preferable, and these groups may have a substituent.

The _{^{Y E1, -CO 2 -, -SO}} 2 - or -PO ₃ ^2-is preferable, -CO ₂ ^- is more preferable.
Examples of the alkali metal cation represented by M ^E1, for ^{example, Li +, Na +, K} +, Rb +, Cs + are mentioned, K ^+, Rb ⁺ or Cs ⁺ is preferred, Cs ⁺ is more preferable.
Examples of the alkaline earth metal cation represented by M ^E1 include Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ , and Mg ²⁺ , Ca ²⁺ and Sr ^2+. Or Ba ²⁺ is preferred, and Ba ²⁺ is more preferred.
As M ^E1 , an alkali metal cation or an alkaline earth metal cation is preferable, and an alkali metal cation is more preferable.
As Z ^E1 , F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^E4 ) ₄ ⁻ , R ^E4 SO ₃ ⁻ , R ^E4 COO ⁻ or NO ₃ ⁻ is preferable, and F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^E4 SO ₃ ⁻ or R ^E4 COO ⁻ are preferable. As R ^E4 , an alkyl group is preferable.

  As a group represented by Formula (ES-1), the group represented by a following formula is mentioned, for example.

［式中、Ｍ⁺は、Ｌｉ⁺、Ｎａ⁺、Ｋ⁺、Ｃｓ⁺又はＮ（ＣＨ₃）₄ ⁺を表す。Ｍ⁺が複数存在する場合、それらは同一でも異なっていてもよい。］

[Wherein, M ⁺ represents Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ or N (CH ₃ ) ₄ ⁺ . When a plurality of M ⁺ are present, they may be the same or different. ]

  nE2 is usually an integer of 1 to 4, preferably 1 or 2.

The example and the preferable range of the arylene group part except the nE2 substituent of the aromatic hydrocarbon group represented by Ar ^E1 are the same as the example and the preferable range of the arylene group represented by Ar ^Y1 .
Examples and preferred ranges of the divalent heterocyclic group moiety excluding the nE2 substituents of the heterocyclic group represented by Ar ^E1 are the examples and preferred ranges of the divalent heterocyclic group represented by Ar ^Y1 and It is the same.
Ar ^E2 is preferably 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-naphthalenediyl, 1,4-naphthalenediyl, 2,7-fluorene A group in which two hydrogen atoms nE directly bonded to atoms constituting a ring are removed from an aryl group, a 3,6-fluorenedyl group, a 2,7-phenanthrendiyl group or a 2,7-carbazolediyl group, R ^It may have a substituent other than ^E2 .
The substituent other than R ^E2 which may be possessed by Ar ^E2 is the same as the substituent other than R ^E1 which may be possessed by Ar ^E1 .

nE 4 is usually an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 2.
aE2 is usually an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1 or 2.
bE2 is usually an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably 0 or 1.
mE2 is usually an integer of 1 to 5, preferably 1 or 2, and more preferably 1.

When R ^E5 is —O—R ^E5 ′, the group represented by Formula (ES-2) is a group represented below.
^{-O-R E5 '- {(} Q E1) nE3 -Y E1 (M E1) aE1 (Z E1) bE1} mE1

As R ^E5 , a hydrocarbon group or a heterocyclic group is preferable, an aromatic hydrocarbon group or an aromatic heterocyclic group is more preferable, an aromatic hydrocarbon group is more preferable, and these groups each have a substituent It is also good.

^Examples of the substituent which may be possessed by R ^E5 include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group and a group represented by the formula (ES-3). The group represented by 3) is preferable, and these groups may further have a substituent.

As Q ^E2 , an alkylene group, an arylene group or an oxygen atom is preferable, an alkylene group or an oxygen atom is more preferable, and these groups may have a substituent.

The _{^{Y E2, -C + R E6 2}} , -N + R E6 3, preferably -P ⁺ R ^E6 ₃ or ^{_{S + R E6 2, -N +}} R E6 3 is more preferable. As R ^E6 , a hydrogen atom, an alkyl group or an aryl group is preferable, a hydrogen atom or an alkyl group is more preferable, and these groups may have a substituent.
As M ^E2 , F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , B (R ^E7 ) ₄ ⁻ , R ^E7 SO ₃ ⁻ , R ^E7 COO ⁻ , BF ₄ ⁻ or SbF ^{6 −} is preferable, and Br ⁻ , I _{^{-, B (R E7) 4}} -, R E7 COO - or SbF ^6- is more preferable. As R ^E7 , an alkyl group which may have a substituent is preferable.
Examples of the alkali metal cation represented by Z ^E2 include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ , and Li ⁺ , Na ⁺ or K ⁺ is preferable.
Examples of the alkaline earth metal cation represented by Z ^E2 include Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ , with Mg ²⁺ or Ca ²⁺ being preferred.
As Z ^E2 , an alkali metal cation is preferable.

  As a group represented by Formula (ES-2), the group represented by a following formula is mentioned, for example.

［式中、Ｘ^-は、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｂ（Ｃ₆Ｈ₅）₄ ^-、ＣＨ₃ＣＯＯ^-又はＣＦ₃ＳＯ₃ ^-を表す。Ｘ^-が複数存在する場合、それらは同一でも異なっていてもよい。］

[Wherein, X ⁻ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , CH ₃ COO ⁻ or CF ₃ SO ₃ ⁻ . When a plurality of X ^- are present, they may be the same or different. ]

  As a structural unit represented by Formula (ET-1) or (ET-2), the structural unit represented by Formula (ET-31)-(ET-38) is mentioned, for example.

  The polymer compound of the third organic layer has a lower driving voltage for the light-emitting element of the present invention, and therefore, from the group consisting of the structural unit represented by the formula (Y) and the structural unit represented by the formula (X) It may further contain at least one selected structural unit, and preferably contains a structural unit represented by formula (Y).

The definition, examples and preferred ranges of the structural units represented by the formula (Y) which may be contained in the polymer compound of the third organic layer are represented by the formula (Y) which may be contained in the polymer host. Are the same as the definition, examples and preferred ranges of the structural units.
When the polymer compound of the third organic layer contains a constitutional unit represented by the formula (Y) and Ar ^Y1 is an arylene group, it is represented by the formula (Y) contained in the polymer compound of the third organic layer The constituent unit is preferably 0.5 to 90% by mole based on the total amount of constituent units contained in the polymer compound of the third organic layer, since the drive voltage of the light-emitting element of the present invention is lower. More preferably, it is 30-80 mol%.
The polymer compound of the third organic layer contains a constitutional unit represented by the formula (Y), and Ar ^Y1 is a divalent heterocyclic group, or at least one type of divalent complex with at least one arylene group. When the ring group is a divalent group directly bonded, the structural unit represented by the formula (Y) contained in the polymer compound of the third organic layer has a lower driving voltage of the light-emitting element of the present invention Therefore, it is preferably 0.5 to 40 mol%, more preferably 3 to 30 mol%, with respect to the total amount of the structural units contained in the polymer compound of the third organic layer.
The structural unit represented by the formula (Y) may be contained singly or in combination of two or more in the polymer compound of the third organic layer.

The definition, examples and preferred ranges of the constitutional units represented by the formula (X) which may be contained in the polymer compound of the third organic layer are represented by the formula (X) which may be contained in the polymer host. Are the same as the definition, examples and preferred ranges of the structural units.
When the polymer compound of the third organic layer contains a constituent unit represented by formula (X), the constituent unit represented by formula (X) contained in the polymer compound of the third organic layer is the third Preferably it is 0.1-30 mol% with respect to the total amount of the structural unit contained in the high molecular compound of the organic layer, More preferably, it is 0.5-10 mol%.
The structural unit represented by the formula (X) may be contained singly or in combination of two or more in the polymer compound of the third organic layer.

  As a high molecular compound of a 3rd organic layer, high molecular compound P-15-P-24 are mentioned, for example. Here, "others" means structural units other than the structural units represented by Formula (ET-1), Formula (ET-2), Formula (X), and Formula (Y).

［表中、ｐ”、ｑ”、ｒ”、ｓ”及びｔ’は、各構成単位のモル比率（モル％）を表す。
ｐ”＋ｑ”＋ｒ”＋ｓ”＋ｔ”＝１００であり、且つ、７０≦ｐ”＋ｑ”＋ｒ”＋ｓ”≦１００である。］

[In the table, p ′ ′, q ′ ′, r ′ ′, s ′ ′ and t ′ each represent a molar ratio (mol%) of each constituent unit.
It is p "+ q" + r "+ s" + t "= 100 and 70 <= p" + q "+ r" + s "<= 100.]

The polymer compound of the third organic layer may be any of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and may be other embodiments, but plural It is preferable that it is a copolymer which copolymerizes the raw material monomer of seed | species.
The polystyrene equivalent number average molecular weight of the polymer compound of the third organic layer is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and still more preferably It is 1.5 * 10 < ⁴ > -1 * 10 < ⁵ >.

[Method of producing polymer compound of third organic layer]
The polymer compound of the third organic layer is, for example, disclosed in JP-A-2009-239279, JP-A-2012-033845, JP-A-2012-216821, JP-A-2012-216822, JP-A-2012-216815. It can synthesize | combine according to the method as described in the gazette.

[Third composition]
The third organic layer is a polymer of the third organic layer, a hole transporting material, a hole injecting material, an electron transporting material (different from the polymer of the third organic layer), an electron injecting material, It may be a layer containing a composition containing at least one material selected from the group consisting of a light-emitting material and an antioxidant (hereinafter, also referred to as a “third composition”).

  Examples and preferred ranges of the hole transporting material, the electron transporting material, the hole injecting material, the electron injecting material and the light emitting material contained in the third composition are the hole transporting material contained in the first composition, Examples and preferred ranges of the electron transport material, the hole injection material, the electron injection material and the light emitting material are the same. In the third composition, the compounding amounts of the hole transporting material, the electron transporting material, the hole injecting material, the electron injecting material and the light emitting material are respectively 100 parts by mass of the polymer compound of the third organic layer Usually, it is 1 to 400 parts by mass, preferably 5 to 150 parts by mass.

  Examples and preferred ranges of the antioxidant contained in the third composition are the same as examples and preferred ranges of the antioxidant contained in the first composition. In the third organic layer, the blending amount of the antioxidant is usually 0.001 to 10 parts by mass, based on 100 parts by mass of the polymer compound of the third organic layer.

[Third ink]
A composition containing the polymer compound of the third organic layer and a solvent (hereinafter also referred to as “third ink”) is suitably used in the wet method described in the section of the first ink. Can. The preferred range of the viscosity of the third ink is the same as the preferred range of the viscosity of the first ink.

  Since the solvent contained in the third ink can be laminated on the organic layer (for example, the first organic layer) using the difference in solubility, the third organic layer can be formed. Ethers, esters, nitrile compounds, nitro compounds, fluorinated alcohols, thiols, sulfides, sulfoxides, thioketones, amides and carboxylic acids are preferred. Specific examples of the solvent include methanol, ethanol, 2-propanol, 1-butanol, tert-butyl alcohol, acetonitrile, 1,2-ethanediol, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, nitromethane, propylene carbonate , Pyridine, carbon disulfide, and mixed solvents of these solvents. When using a mixed solvent, one or more solvents selected from water, alcohols, ethers, esters, nitrile compounds, nitro compounds, fluorinated alcohols, thiols, sulfides, sulfoxides, thioketones, amides, carboxylic acids, and chlorinated solvents, It may be a mixed solvent with one or more solvents selected from aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and ketone solvents.

  In the third ink, the compounding amount of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20 000 parts by mass, based on 100 parts by mass of the polymer compound of the third organic layer.

<Layer configuration of light emitting element>
The light emitting device of the present invention may have layers other than the anode, the cathode, the first organic layer, the second organic layer, and the third organic layer.
In the light emitting device of the present invention, the first organic layer is usually a light emitting layer (hereinafter, referred to as “first light emitting layer”).

When the light emitting device of the present invention has the second organic layer, the second organic layer is preferably a hole transporting layer or a light emitting layer (that is, a light emitting layer separate from the first light emitting layer, , “The second light emitting layer”.
When the light emitting device of the present invention has the second organic layer, the driving voltage of the light emitting device of the present invention is lower, so it is preferable that the first organic layer and the second organic layer be adjacent to each other. .
When the light emitting device of the present invention has the second organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the second organic layer is provided between the anode and the first organic layer. It is preferably a hole transporting layer or a second light emitting layer.

When the light emitting device of the present invention has a second organic layer, and the second organic layer is a hole transport layer provided between the anode and the first organic layer, the light emitting device of the present invention It is preferable to further include a hole injection layer between the anode and the second organic layer because the drive voltage is lower. When the light emitting device of the present invention has a second organic layer, and the second organic layer is a hole transport layer provided between the anode and the first organic layer, the light emitting device of the present invention It is preferable to further include at least one of the electron injection layer and the electron transport layer between the cathode and the first organic layer because the drive voltage is lower.
When the light emitting device of the present invention has a second organic layer, and the second organic layer is a second light emitting layer provided between the anode and the first organic layer, the light emitting device of the present invention It is preferable to further include at least one layer of a hole injection layer and a hole transport layer between the anode and the second organic layer, since the driving voltage of When the light emitting device of the present invention has a second organic layer, and the second organic layer is a second light emitting layer provided between the anode and the first organic layer, the light emitting device of the present invention It is preferable to further include at least one of the electron injection layer and the electron transport layer between the cathode and the first organic layer, since the drive voltage of

  When the light emitting device of the present invention does not have the second organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the hole injecting layer and the holes are interposed between the anode and the first organic layer. It is preferred to have at least one of the transport layers.

When the light emitting device of the present invention has a third organic layer, the third organic layer is preferably an electron transporting layer.
When the light emitting device of the present invention has the third organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the first organic layer and the third organic layer are preferably adjacent to each other. .
When the light emitting device of the present invention has the third organic layer, the drive voltage of the light emitting device of the present invention is lower, so the third organic layer is an electron provided between the cathode and the first organic layer. It is preferably a transport layer.

  When the light emitting device of the present invention has a third organic layer, and the third organic layer is an electron transport layer provided between the cathode and the first organic layer, driving of the light emitting device of the present invention It is preferred to further include at least one layer of a hole injection layer and a hole transport layer between the anode and the first organic layer, as the voltage is lower. When the light emitting device of the present invention has a third organic layer, and the third organic layer is an electron transport layer provided between the cathode and the first organic layer, driving of the light emitting device of the present invention It is preferred to further include an electron injection layer between the cathode and the third organic layer, as the voltage is lower.

  When the light emitting device of the present invention does not have the third organic layer, the drive voltage of the light emitting device of the present invention is lower, so an electron injecting layer and an electron transporting layer are provided between the cathode and the first organic layer. It is preferred to have at least one layer of

When the light emitting device of the present invention has the second organic layer and the third organic layer, the driving voltage of the light emitting device of the present invention is lower, so the second organic layer is a hole transport layer or a second light emission. Preferably, the layer is a layer, and the third organic layer is an electron transport layer.
When the light emitting device of the present invention has the second organic layer and the third organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the first organic layer, the second organic layer, and the third organic layer. The organic layer is preferably adjacent to the organic layer.
When the light emitting device of the present invention has the second organic layer and the third organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the second organic layer is the anode and the first organic layer. It is preferable that the third organic layer be an electron transport layer provided between the cathode and the first organic layer, which is the hole transport layer or the second light emitting layer provided between the cathode and the first organic layer.

The light emitting device of the present invention has a second organic layer and a third organic layer, and the second organic layer is a hole transport layer provided between the anode and the first organic layer, and When the organic layer of No. 3 is an electron transport layer provided between the cathode and the first organic layer, the drive voltage of the light emitting device of the present invention is lower, so that it is between the anode and the second organic layer. It is preferable to further have a hole injection layer. The light emitting device of the present invention has a second organic layer and a third organic layer, and the second organic layer is a hole transport layer provided between the anode and the first organic layer, and When the organic layer of No. 3 is an electron transport layer provided between the cathode and the first organic layer, the drive voltage of the light emitting device of the present invention is lower, so that it is between the cathode and the first organic layer. It is preferable to further have an electron injection layer.
The light emitting device of the present invention has a second organic layer and a third organic layer, and the second organic layer is a second light emitting layer provided between the anode and the first organic layer, and In the case where the third organic layer is an electron transport layer provided between the cathode and the first organic layer, the drive voltage of the light emitting device of the present invention is lower, and thus, between the anode and the second organic layer. It is preferable to further include at least one of the hole injection layer and the hole transport layer. The light emitting device of the present invention has a second organic layer and a third organic layer, and the second organic layer is a second light emitting layer provided between the anode and the first organic layer, and When the third organic layer is an electron transport layer provided between the cathode and the first organic layer, the driving voltage of the light emitting device of the present invention is lower, so that the distance between the cathode and the first organic layer is It is preferable to further include an electron injection layer.

  Specific examples of the layer configuration of the light emitting device of the present invention include the layer configurations represented by (D1) to (D16). The light emitting device of the present invention generally has a substrate, but may be laminated from the anode on the substrate or may be laminated from the cathode on the substrate.

(D1) Anode / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / cathode (D2) anode / second light emitting layer (second organic layer) / second 1 light emitting layer (first organic layer) / cathode (D3) anode / first light emitting layer (first organic layer) / electron transport layer (third organic layer) / cathode (D4) anode / hole Injection layer / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / electron injection layer / cathode (D5) anode / hole injection layer / second light emitting layer (second Organic layer 2) / first light emitting layer (first organic layer) / electron injection layer / cathode (D6) anode / hole injection layer / hole transport layer (second organic layer) / first light emission Layer (first organic layer) / electron transport layer / electron injection layer / cathode (D7) anode / hole injection layer / second light emitting layer (second organic layer) / first light emitting layer (first Organic layer) / electron transport layer / electron injection layer / cathode (D8) Electrode / hole injection layer / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / second light emitting layer / electron transport layer / electron injection layer / cathode (D9) Anode / hole injection layer / first light emitting layer (first organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D10) anode / hole injection layer / hole transport layer / First light emitting layer (first organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D11) anode / hole injection layer / second light emitting layer / first light emission Layer (first organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D12) anode / hole injection layer / hole transport layer (second organic layer) / first Light emitting layer (first organic layer) / second light emitting layer / electron transport layer (third organic layer) / electron injection layer / cathode (D13) anode / hole injection layer / hole transport layer (second Organic layer) / first light emitting layer (first) Organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D14) anode / hole injection layer / second light emitting layer (second organic layer) / first light emitting layer (first example) 1 organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D15) anode / hole injection layer / hole transport layer / second light emitting layer (second organic layer) / First light emitting layer (first organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode (D16) anode / hole injection layer / hole transport layer (second organic layer) / Second light emitting layer / first light emitting layer (first organic layer) / electron transport layer (third organic layer) / electron injection layer / cathode

  In (D1) to (D16), "/" means that the layers before and after that are stacked adjacent to each other. Specifically, “second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / electron transport layer (third organic layer)” means the second light emission It means that the layer (second organic layer), the first light emitting layer (first organic layer), and the electron transport layer (third organic layer) are stacked adjacent to each other.

In the light emitting device of the present invention, the anode, the hole injection layer, the hole transport layer, the second light emitting layer, the electron transport layer, the electron injection layer and the cathode are each provided in two or more layers as necessary. It is also good.
When a plurality of anodes, hole injection layers, hole transport layers, second light emitting layers, electron transport layers, electron injection layers and cathodes are present, they may be the same or different.

  The thicknesses of the anode, the hole injection layer, the hole transport layer, the first light emitting layer, the second light emitting layer, the electron transport layer, the electron injection layer and the cathode are usually 1 nm to 1 μm, preferably 2 nm to It is 500 nm, more preferably 5 nm to 150 nm.

  In the light emitting element of the present invention, the order, the number, and the thickness of the layers to be stacked may be adjusted in consideration of the light emission efficiency, the driving voltage and the element life of the light emitting element.

[Second light emitting layer]
The second light emitting layer is usually a second organic layer or a layer containing a light emitting material. When the second light emitting layer is a layer containing a light emitting material, examples of the light emitting material contained in the second light emitting layer include a light emitting material which may be contained in the first composition described above. Be The light emitting materials contained in the second light emitting layer may be contained singly or in combination of two or more.
When the light emitting device of the present invention has the second light emitting layer and the hole transport layer described later is not the second organic layer, the second light emitting layer is preferably the second organic layer.

[Hole transport layer]
The hole transport layer is usually a second organic layer or a layer containing a hole transport material. When the hole transport layer is a layer containing a hole transport material, examples of the hole transport material include a hole transport material which may be contained in the first composition described above. The hole transport material contained in the hole transport layer may be contained singly or in combination of two or more.
When the light emitting device of the present invention has a hole transport layer and the above-mentioned second light emitting layer is not the second organic layer, the hole transport layer is preferably the second organic layer.

[Electron transport layer]
The electron transport layer is usually a third organic layer or a layer containing an electron transport material, preferably a third organic layer. When the electron transport layer is a layer containing an electron transport material, examples of the electron transport material contained in the electron transport layer include an electron transport material which may be contained in the above-mentioned first composition. . The electron transporting material contained in the electron transporting layer may be contained singly or in combination of two or more.

[Hole Injection Layer and Electron Injection Layer]
The hole injection layer is a layer containing a hole injection material. As a hole injection material contained in a hole injection layer, the hole injection material which the above-mentioned 1st composition may contain is mentioned, for example. The hole injection material contained in the hole injection layer may be contained singly or in combination of two or more.
The electron injection layer is a layer containing an electron injection material. As an electron injection material contained in an electron injection layer, the electron injection material which the above-mentioned 1st composition may contain is mentioned, for example. The electron injecting material contained in the electron injecting layer may be contained singly or in combination of two or more.

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

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

  The material of the cathode includes, for example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc and indium; alloys of two or more of them; one of them And alloys thereof with one or more species of silver, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; and graphite and graphite intercalation compounds. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

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

[Method of manufacturing light emitting device]
In the light emitting device of the present invention, examples of the method of forming the anode and the cathode include a vacuum evaporation method, a sputtering method, an ion plating method, a plating method and a laminating method.
In the case of using a low molecular weight compound as a method of forming the first organic layer, the second organic layer, the third organic layer, and the other layers in the light emitting device of the present embodiment, for example, vacuum from powder is used. A vapor deposition method, a method by film formation from a solution or molten state may be mentioned, and when using a polymer compound, for example, a method by film formation from a solution or molten state may be mentioned.

  The first organic layer, the second organic layer, the third organic layer, and the other layers use the various inks described above and the ink containing various materials (composition including various materials and a solvent) It can be formed by a wet method such as spin coating or ink jet printing. Note that the first organic layer, the second organic layer, the third organic layer, and the other layers may be formed by a dry method such as a vacuum evaporation method.

  When the first organic layer is formed by a wet method, it is preferable to use the first ink.

  When the second organic layer is formed by a wet method, it is preferable to use a second ink. After forming the second organic layer, the polymer compound in the second organic layer contained in the second organic layer can be crosslinked by heating or light irradiation. It is preferable to crosslink the polymer compound of the second organic layer contained in the second organic layer by heating after forming the second organic layer. Since the second organic layer is contained in a state in which the polymer compound of the second organic layer is crosslinked (crosslinked body of the polymer compound of the second organic layer), the second organic layer is used relative to the solvent It is substantially insolubilized. Therefore, the second organic layer can be suitably used for laminating light emitting elements.

The heating temperature for crosslinking is usually 25 ° C. to 300 ° C., preferably 50 ° C. to 260 ° C., more preferably 130 ° C. to 230 ° C., still more preferably 180 ° C. to 210 ° C. .
The heating time is usually 0.1 minutes to 1000 minutes, preferably 0.5 minutes to 500 minutes, more preferably 1 minute to 120 minutes, and still more preferably 10 minutes to 60 minutes.

  The type of light used for light irradiation is, for example, ultraviolet light, near ultraviolet light, or visible light.

  When the third organic layer is formed by a wet method, it is preferable to use a third ink. When laminating the third organic layer on the organic layer (for example, the first organic layer) using the difference in solubility with the organic layer, use a solution with low solubility in the organic layer Makes it easy to stack the electron transport layer.

  As an analysis method of the component contained in the first organic layer, the second organic layer or the third organic layer, for example, chemical separation analysis such as extraction, infrared spectroscopy, nuclear magnetic resonance spectroscopy, Instrumental analysis methods such as mass spectrometry, and analysis methods combining chemical separation analysis method and instrumental analysis method can be mentioned.

  By performing solid-liquid extraction using an organic solvent such as toluene, xylene, chloroform, or tetrahydrofuran on the first organic layer, the second organic layer, or the third organic layer, the organic solvent can be substantially reduced. It is possible to separate into an insoluble component (insoluble component) and a component soluble in an organic solvent (dissolved component). The insoluble component can be analyzed by infrared spectroscopy or nuclear magnetic resonance spectroscopy, and the dissolved component can be analyzed by nuclear magnetic resonance spectroscopy or mass spectrometry.

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

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

In Examples, the polystyrene equivalent number average molecular weight (Mn) of the polymer compound and the polystyrene equivalent weight average molecular weight (Mw) were determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase .
The polymer compound to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 μL was injected into SEC. The mobile phase flowed at a flow rate of 1.0 mL / min. PLgel MIXED-B (manufactured by Polymer Laboratories) was used as a column. As a detector, a UV-VIS detector (manufactured by Tosoh, trade name: UV-8320GPC) was used.

LC-MS was measured by the following method.
The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent, trade name: 1290 Infinity LC and 6230 TOF LC / MS). The mobile phase of LC-MS was used while changing the ratio of acetonitrile and tetrahydrofuran, and flowed at a flow rate of 1.0 mL / min. As a column, SUMIPAX ODS Z-CLUE (manufactured by Sumika Analysis Center, inner diameter: 4.6 mm, length: 250 mm, particle diameter 3 μm) was used.

TLC-MS was measured by the following method.
The measurement sample is dissolved in any solvent of toluene, tetrahydrofuran or chloroform at an arbitrary concentration, coated on a TLC plate for DART (manufactured by TechnoApplications, trade name: YSK5-100), and TLC-MS (manufactured by JEOL Ltd.) , Trade name: JMS-T100TD (The AccuTOF TLC)). The helium gas temperature at the time of measurement was adjusted in the range of 200 to 400.degree.

NMR was measured by the following method.
About 5 to 10 mg of a sample to be measured is about 0.5 mL of heavy chloroform (CDCl ₃ ), heavy tetrahydrofuran, heavy dimethyl sulfoxide, heavy acetone, heavy N, N-dimethylformamide, heavy toluene, heavy methanol, heavy ethanol, heavy 2-propanol Alternatively, they were dissolved in methylene dichloride and measured using an NMR apparatus (manufactured by JEOL RESONANCE, trade name: JNM-ECZ400S / L1, or Bruker, trade name: AVANCE 600).

  The value of high performance liquid chromatography (HPLC) area percentage was used as an index of compound purity. Unless otherwise indicated, this value is a value at UV = 254 nm in HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform so as to have a concentration of 0.01 to 0.2% by mass, and 1 to 10 μL was injected into HPLC according to the concentration. The mobile phase of HPLC was used at a flow rate of 1.0 mL / min, with the ratio of acetonitrile / tetrahydrofuran being changed from 100/0 to 0/100 (volume ratio). The column used was an ODS column having SUMIPAX ODS Z-CLUE (manufactured by Sumika Analysis Center, inner diameter: 4.6 mm, length: 250 mm, particle diameter 3 μm) or equivalent performance. As a detector, a photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used.

Synthesis Example M1 Synthesis of Compounds M1 to M8 and Metal Complex RM1 Compounds M1 and M2 were synthesized according to the method described in WO 2002/045184.
Compound M3 was synthesized according to the method described in WO 2011/049241.
Compound M4 was synthesized according to the method described in WO 2015/145871.
Compound M5, Compound M7 and Compound M8 were synthesized according to the method described in WO 2013/146806.
Compound M6 was synthesized according to the method described in WO 2005/049546.
The metal complex RM1 was synthesized according to the method described in WO 2009/157424.

Synthesis Example G1 Synthesis of Metal Complexes G1 and G2 The metal complex G1 was synthesized according to the method described in JP-A-2013-237789.
The metal complex G2 was synthesized according to the method described in WO 2009/131255.

<Synthesis Example R1 to R3> Synthesis of Metal Complex R1 to R3 The metal complex R1 was synthesized according to the method described in WO 2003/040256.
Metal complex R2 was synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2006-188673.
The metal complex R3 was purchased from Luminescence Technology.

<Compound HM-1, Compounds HTM-1 and BCP>
Compound HM-1, compound HTM-1 and BCP were purchased from Luminescence Technology.

<Synthesis Example HTL1> Synthesis of Polymer Compound HTL-1 A polymer compound HTL-1 was synthesized according to a method described in WO 2011/049241, using Compound M1, Compound M2 and Compound M3. The polystyrene equivalent number average molecular weight and weight average molecular weight of the polymer compound HTL-1 were Mn = 8.9 × 10 ⁴ and Mw = 4.2 × 10 ⁵ , respectively.
The polymer compound HTL-1 has a structural unit derived from the compound M1, a structural unit derived from the compound M2, and a structural unit derived from the compound M3 in the theoretical value determined from the amount of the raw materials charged. It is a copolymer comprised by the molar ratio of 50: 42.5: 7.5.

<Synthesis Example HTL2> Synthesis of Polymer Compound HTL-2 A polymer compound HTL-2 was synthesized according to a method described in WO 2015/145871 using a compound M4, a compound M5 and a compound M6. The polymer compound HTL-2 had Mn = 2.3 × 10 ⁴ and Mw = 1.2 × 10 ⁵ .
The polymer compound HTL-2 has a structural unit derived from the compound M4, a structural unit derived from the compound M5, and a structural unit derived from the compound M6 in the theoretical values determined from the amounts of the raw materials charged. It is a copolymer comprised by the molar ratio of 45: 5: 50.

<Synthesis Example HTL3> Synthesis of Polymer Compound HTL-3 After the inside of the reaction vessel was changed to an inert gas atmosphere, Compound M7 (2.52 g), Compound M5 (0.470 g), Compound M8 (4.90 g), Metal The complex RM1 (0.530 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (4.2 mg) and toluene (158 mL) were added and heated to 100.degree. To the reaction solution, 20% by mass tetraethylammonium hydroxide aqueous solution (16 mL) was dropped, and the mixture was refluxed for 8 hours. After the reaction, phenylboronic acid (116 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (4.2 mg) were added thereto and refluxed for 15 hours. Thereafter, an aqueous solution of sodium diethyldithiacarbamate was added thereto, and the mixture was stirred at 85 ° C. for 2 hours. After cooling, the reaction solution was washed with 3.6% by mass hydrochloric acid, 2.5% by mass aqueous ammonia, and water, and the obtained solution was added dropwise to methanol, whereby precipitation occurred. The precipitate was dissolved in toluene and purified by sequentially passing through an alumina column and a silica gel column. The obtained solution was added dropwise to methanol and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 6.02 g of a polymer compound HTL-3. The Mn of the polymer compound HTL-3 was 3.8 × 10 ⁴ , and the Mw was 4.5 × 10 ⁵ .
The polymer compound HTL-3 has a structural unit derived from the compound M7, a structural unit derived from the compound M5, a structural unit derived from the compound M8, and a metal in the theoretical value determined from the amount of the raw materials charged It is a copolymer in which the constituent unit derived from the complex RM1 is constituted at a molar ratio of 40: 10: 47: 3.

Synthesis Example Synthesis of Polymer Compound HTL-4 A polymer compound HTL-4 was synthesized according to the method described in JP 2012-36381 A using Compound M1 and Compound M2. The Mn of the polymer compound HTL-4 was 8.1 × 10 ⁴ , and the Mw was 3.4 × 10 ⁵ .
In the polymer compound HTL-4, in the theoretical value determined from the amount of the raw materials charged, the constituent unit derived from the compound M1 and the constituent unit derived from the compound M2 are constituted at a molar ratio of 50:50 It is a copolymer.

Synthesis Example Synthesis of Polymer Compound ET1 (Synthesis of Polymer Compound ET1a)
The compound ET1-1 and the compound ET1-2 were synthesized according to the method described in JP 2012-33845 A, and a polymer compound ET1a was synthesized using the compound ET1-1 and the compound ET1-2.

The Mn of the polymer compound ET1a was 5.2 × 10 ⁴ .

  In the polymer compound ET1a, in the theoretical value determined from the amount of the raw materials charged, the constituent unit derived from the compound ET1-1 and the constituent unit derived from the compound ET1-2 are constituted at a molar ratio of 50:50 Copolymer.

(Synthesis of Polymer Compound ET1)
The reaction vessel was changed to an inert gas atmosphere, and then the polymer compound ET1a (200 mg), tetrahydrofuran (20 mL) and ethanol (20 mL) were added, and the mixture was heated to 55 ° C. After that, cesium hydroxide (200 mg) dissolved in water (2 mL) was added thereto, and the mixture was stirred at 55 ° C. for 6 hours. Then, after cooling to room temperature, a solid was obtained by concentration under reduced pressure. The obtained solid was washed with water and then dried under reduced pressure to obtain Polymer Compound ET1 (150 mg, pale yellow solid). From the NMR spectrum of the obtained polymer compound ET1, it was confirmed that the signal derived from the ethyl group of the ethyl ester site of the polymer compound ET1a was completely disappeared.

<Synthesis Example BC1 to BC4> Synthesis of Metal Complexes BC1 to BC4 The metal complex BC1 was synthesized according to the method described in JP 2012-6914A.
Metal complexes BC2 to BC4 were synthesized according to the method described in WO 2016/185183.

  Synthesis Example B1 Synthesis of Metal Complex B1

  After the inside of the reaction vessel was changed to a nitrogen gas atmosphere, 2,4-dimethylaniline (200 g) and cyclopentyl methyl ether (400 mL) were added and stirred. Thereafter, the reaction vessel was cooled using an ice bath, and then a 16 mass% hydrogen chloride solution of cyclopentyl methyl ether (357 g) was dropped thereto. After the dropwise addition, stirring was continued at room temperature for 1 hour, the precipitated solid was collected by filtration, and the obtained solid was washed with hexane (150 mL). The obtained solid was crystallized using 2-propanol, and further dried at room temperature under reduced pressure to obtain compound 1a (220 g, pale red solid).

  The reaction vessel was changed to a nitrogen gas atmosphere, and then Compound 1a (140 g), chloroform (2100 mL) and triethylamine (267 mL) were added and stirred. Then, after cooling a reaction container using an ice bath, 2, 2- dimethyl butyryl chloride (113 mL) was dripped there. After the dropwise addition, stirring was continued at room temperature for 1 hour, and then a saturated aqueous solution of sodium carbonate (400 mL) was added thereto, and the mixture was stirred at room temperature. The reaction mixture obtained was separated, and the obtained organic layer was washed successively with saturated aqueous sodium carbonate solution and ion-exchanged water. Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. After concentration of the obtained filtrate, heptane was added thereto and stirred for 1 hour, and the obtained solid was collected by filtration. Thereafter, the obtained solid was dried under reduced pressure at 40 ° C. to obtain compound 1b (164 g, white solid). The HPLC area percentage value of compound 1b was 99.5% or more.

The NMR measurement results of compound 1b were as follows.
¹ H-NMR (CDCl ₃ , 400 MHz) δ (ppm): 0.94 (3H, t), 1.29 (6H, s), 1.67 (2H, q), 2.21 (3H, s) , 2.28 (3 H, s), 6.99 (1 H, s), 7.00 (1 H, d), 7.12 (1 H, br), 7. 65 (1 H, d).

  The reaction vessel was changed to an argon gas atmosphere, Compound 1b (60 g), monochlorobenzene (480 mL), 2-fluoropyridine (26 mL) and trifluoromethanesulfonic anhydride (50 mL) were added and stirred at room temperature for 30 minutes. . Thereafter, benzhydrazide (41 g) was added thereto, and the mixture was stirred at 90 ° C. for 3 hours. Then, after cooling the obtained reaction liquid to room temperature, sodium hydrogencarbonate aqueous solution (500 mL) was added there, and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water, and the obtained organic layer was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (mixed solvent of chloroform and tetrahydrofuran) and then crystallized using a mixed solvent of 2-propanol and heptane. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 1c (70 g, yield 80%) as a white solid. The HPLC area percentage value of compound 1c was 99.5% or more.

The measurement results of LC-MS and NMR of compound 1c were as follows.
LC-MS (APCI, positive): m / z = 320 [M + H] ^+
1 H-NMR (600 MHz, CD ₂ Cl ₂ ) δ (ppm): 7.42-7.37 (m, 2H), 7.35-7.31 (m, 2H), 7.29-7.25 (M, 2H), 7.19 (d, 1 H), 7.07 (s, 1 H), 2.40 (s, 3 H), 1.79 to 1.72 (m, 4 H), 1.57- 1.45 (m, 1 H), 1. 34 (s, 3 H), 1. 15 (s, 3 H), 0.89 (t, 3 H).

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (15.3 g), compound 1c (40.0 g) and pentadecane (40 mL) were added, and the mixture was stirred for 50 hours under heating and reflux. Thereafter, toluene was added thereto, followed by filtration with a filter covered with silica gel, and from the obtained silica gel, a mixed solvent of toluene and ethyl acetate was used to extract a yellow solution containing the metal complex B1. The resulting solution was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (toluene solvent), and then crystallized using a mixed solvent of toluene and methanol. Thereafter, the obtained solid was dried under reduced pressure at 50 ° C. to obtain metal complex B1 (30.5 g). The HPLC area percentage value of the metal complex B1 was 99.3%.

The measurement results of LC-MS of the metal complex B1 were as follows.
LC-MS (APCI, positive): m / z = 1149 [M + H] ⁺

  Synthesis Example B2 Synthesis of Metal Complex B2

The reaction vessel was changed to an argon gas atmosphere, and then 2,2′-dimethylhexanoic acid (40 g), chloroform (240 mL), N, N′-dimethylformamide (0.21 mL) and thionyl chloride (20 mL) were added, and 45 Stir at C for 3 hours. Thereafter, the reaction vessel was cooled using a water bath to obtain a reaction liquid containing 2,2′-dimethylhexanoyl chloride.
The inside of a reaction vessel prepared separately was changed to an argon gas atmosphere, Compound 1a (41.5 g), chloroform (400 mL) and triethylamine (75 mL) were added, and the reaction vessel was cooled using an ice bath. Then, the reaction liquid containing the 2,2'- dimethyl hexanoyl chloride obtained above was dripped there. After the dropwise addition, stirring was continued at room temperature for 1 hour, 2 mol / L aqueous sodium carbonate solution (280 mL) was added thereto, and the mixture was stirred at room temperature. The resulting reaction mixture was separated to obtain an organic layer. The obtained organic layer was washed with ion exchanged water (280 mL). Thereafter, the obtained organic layer was dried over anhydrous magnesium sulfate and filtered. The obtained filtrate was concentrated under reduced pressure to give compound 2b (60 g, yield 88%) as a pale yellow oil. The required amount of compound 2b was secured by repeating the above operation. The HPLC area percentage value of compound 2b was 99.5% or more.
The results of TLC-MS measurement of compound 2b were as follows.
TLC / MS (DART, positive): m / z = 248 [M + H] ⁺

  The reaction vessel was changed to an argon gas atmosphere, Compound 2b (40 g), monochlorobenzene (320 mL), 2-fluoropyridine (14 mL) and trifluoromethanesulfonic anhydride (27 mL) were added, and the mixture was stirred at room temperature for 30 minutes. . Thereafter, 3-bromobenzhydrazide (35 g) was added thereto, and the mixture was stirred at 90 ° C. for 7 hours. Then, after cooling the obtained reaction liquid to room temperature, 2 mol / L sodium hydrogencarbonate aqueous solution (160 mL) was added there, and after stirring, the organic layer was extracted. The obtained organic layer was washed with ion exchanged water. After that, the obtained organic layer was concentrated under reduced pressure to obtain an oil. The obtained oil was purified by silica gel column chromatography (mixed solvent of chloroform and ethanol) to obtain a solid. The obtained solid was crystallized using heptane and further dried under reduced pressure at 50 ° C. to give compound 2c (48 g, yield 77%) as a white solid. The HPLC area percentage value of compound 2c was 99.5% or more.

The measurement results of LC-MS and NMR of compound 2c were as follows.
LC / MS (APPI, positive): m / z = 426 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.60-7.55 (m, 1 H), 7.41 (d, 1 H), 7.25 (d, 1 H), 7. 21-7.13 (m, 2H), 7.09-7.03 (m, 2H), 2.36 (s, 3H), 1.76-1.59 (m, 4H), 1.43- 1.07 (m, 11 H), 0.84 (t, 3 H).

  The reaction vessel was changed to an argon gas atmosphere, then compound 2c (2.2 g), 4-tert-butylphenylboronic acid (1.0 g), toluene (22 mL) and (di-tert-butyl (4-dimethylaminophenyl) ) Phosphine) Dichloropalladium (II) (18 mg) was added, and the temperature was raised to 80 ° C. Then, after adding 20 mass% tetrabutyl ammonium hydroxide aqueous solution (16 mL) to there, it stirred under heating-refluxing for 18 hours. Then, after cooling the obtained reaction liquid to room temperature, toluene was added there and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water. Thereafter, the obtained organic layer was dried over anhydrous magnesium sulfate and then filtered through a filter covered with silica gel and celite. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (mixed solvent of chloroform and ethanol) and then crystallized using heptane. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 2d (2.2 g, yield 85%) as a white solid. The HPLC area percentage value of compound 2d was 99.5% or more.

The measurement results of LC-MS and NMR of compound 2d were as follows.
LC-MS (APPI, positive): m / z = 480 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.53 to 7.48 (m, 1 H), 7.46 to 7.39 (m, 2 H), 7.40 to 7.37 (M, 2H), 7.34-7. 29 (m, 2H), 7.26-7. 19 (m, 3H), 7.07 (s, 1H), 2.40 (s, 3H), 1.74 (s, 3 H), 1. 70 to 1.6 1 (m, 1 H), 1. 47 to 1. 36 (m, 1 H), 1. 34 to 1. 30 (m, 12 H), 1. 29-1.14 (m, 4 H), 1. 12 (s, 3 H), 0.86 (t, 3 H)

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (1.0 g), compound 2d (2.0 g) and pentadecane (3 mL) were added, and the mixture was stirred under heating reflux for 46 hours. Thereafter, toluene was added thereto, followed by filtration with a filter covered with silica gel, and from the obtained silica gel, a mixed solvent of toluene and ethyl acetate was used to extract a yellow solution containing metal complex B2. The obtained solution was concentrated under reduced pressure to obtain a solid, and the obtained solid was washed with acetonitrile and heptane, and further purified by silica gel column chromatography (mixed solvent of toluene and ethyl acetate). Thereafter, the obtained solid was crystallized using a mixed solvent of toluene and acetonitrile, and further dried under reduced pressure at 50 ° C. to obtain metal complex B2 (1.0 g) as a yellow solid. The HPLC area percentage value of metal complex B2 was 98.8%.

The measurement results of LC-MS and NMR of metal complex B2 were as follows.
LC-MS (APCI, positive): m / z = 1629 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.41 to 7.16 (m, 15 H), 7.10 to 6.64 (m, 12 H), 6.19 to 6.04 (M, 3 H), 2.54-2.43 (m, 9 H), 2.16-1.67 (m, 9 H), 1.62-1.03 (m, 63 H), 0.85-0 .63 (m, 9H).

  Synthesis Example B3 Synthesis of Metal Complex B3

  After the inside of the reaction vessel was changed to an argon gas atmosphere, 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50 g), 2-methyl-4-bromoaniline (46 g), tris (Dibenzylideneacetone) dipalladium (0) (3 g), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (4 g) and toluene (1 L) were added and stirred at room temperature. Thereafter, a 20% by mass tetraethylammonium hydroxide aqueous solution was dropped thereto at room temperature, and the mixture was stirred at 70 ° C. for 5 hours. The obtained reaction solution was cooled to room temperature, and the obtained reaction solution was separated to obtain an organic layer. The obtained organic layer was washed with ion exchanged water. Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. After the obtained filtrate was concentrated, tetrahydrofuran and activated clay were added thereto, and after stirring for 30 minutes at room temperature, the operation of filtering with a filter covered with Celite was repeated twice. The obtained filtrate was concentrated under reduced pressure, toluene and activated carbon were added thereto, and the mixture was stirred at room temperature for 30 minutes. Then, it filtered by the filter covered with celite and the obtained filtrate was concentrated. Compound 3a (92 g, reddish-brown oil) was obtained by repeating the above operation. The GC area percentage value of compound 3a was 99.5% or more.

  The reaction vessel was changed to a nitrogen gas atmosphere, then compound 3a (92 g) and cyclopentyl methyl ether (214 mL) were added and stirred. Thereafter, the reaction vessel was cooled using an ice bath, and thereto was added dropwise a 16 mass% hydrogen chloride solution of cyclopentyl methyl ether (114 g) and then heptane (649 mL). After dropwise addition, stirring was continued at room temperature for 1 hour, and the precipitated solid was collected by filtration, and the obtained solid was washed with heptane and acetone. The obtained solid was crystallized multiple times using 2-propanol, methanol, ethanol and heptane, and the obtained solid was dried under reduced pressure at room temperature to obtain compound 3b (37 g, light red solid). The necessary amount of compound 3b was secured by repeating the above operation.

The measurement results of NMR of compound 3b were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 7.33-7.65 (8 H, m), 4.85 (3 H, s), 2.46 (3 H, s).

After setting the inside of the reaction vessel to an argon atmosphere, 2,2′-dimethylhexanoic acid (29 g), chloroform (174 mL) and N, N′-dimethylformamide (0.14 g) were added and stirred at 50 ° C. After that, thionyl chloride (24 g) was added dropwise thereto, and the mixture was stirred at 50 ° C. for 4 hours. Thereafter, the reaction vessel was cooled using a water bath to prepare a reaction liquid containing 2,2′-dimethylhexanoyl chloride.
The inside of a separately prepared reaction vessel was changed to a nitrogen gas atmosphere, and then Compound 3b (39 g), chloroform (290 mL) and triethylamine (47 mL) were added and stirred. Thereafter, the reaction vessel was cooled using an ice bath, and then the reaction solution containing the 2,2'-dimethylhexanoyl chloride prepared above was dropped thereto. After the dropwise addition, stirring was continued at room temperature for 2 hours, to which saturated sodium carbonate aqueous solution (300 mL) was added, and the mixture was stirred at room temperature. The organic layer was obtained by separating the obtained reaction mixture. The obtained organic layer was washed successively with saturated aqueous sodium carbonate solution and ion exchange water. Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. The obtained filtrate was concentrated under reduced pressure, and then separated and purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate) to obtain an oil. Hexane was added to the obtained oil, and the resulting mixture was stirred for 1 hour while being cooled using an acetone bath to which dry ice was added, to precipitate a solid. Then, the obtained solid was collected by filtration, and the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 3c (40 g, white solid). The necessary amount of compound 3c was secured by repeating the above operation. The HPLC area percentage value of compound 3c was 99.5% or more.

The measurement results of NMR of compound 3c were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 7.98 (1 H, d), 7.55 (1 H, d), 7.42 (1 H, t), 7.41 (4 H, m) , 7.31 (1 H, t), 2. 32 (3 H, s), 1.62 (2 H, s), 1. 35 (10 H, s), 0.91 (3 H, s).

  The reaction vessel was changed to an argon gas atmosphere, and then compound 3c (30 g), monochlorobenzene (300 mL), 2-fluoropyridine (9 mL) and trifluoromethanesulfonic anhydride (18 mL) were added, and the mixture was stirred at room temperature for 30 minutes. . Thereafter, 2-bromobenzoylhydrazine (23 g) was added thereto, and the mixture was stirred at 90 ° C. for 3 hours. Then, after cooling the obtained reaction liquid to room temperature, sodium hydrogencarbonate aqueous solution (300 mL) was added there, and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water. After that, the obtained organic layer was concentrated under reduced pressure to obtain a solid. The obtained solid was washed with hexane and then crystallized multiple times using 2-propanol, heptane and acetonitrile. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 3d (31 g) as a white solid. The HPLC area percentage value of compound 3d was 99.5% or more.

The measurement results of LC-MS and NMR of compound 3d were as follows.
LC-MS (APCI, positive): m / z = 488 [M + H] ^+
1 H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 7.57-7.64 (m, 4 H), 7. 38-7. 49 (m, 6 H), 7. 28-7. 30 (d , 1H), 7.07 (t, 1 H), 1.85 (3 H, s), 1.67 to 1.74 (2 H, m), 1.42 to 1.50 (1 H, m), 39 (3H, s), 1.14-1.36 (3H, m), 1.17 (3H, s), 0.88 (3H, t).

  The reaction vessel was changed to an argon gas atmosphere, compound 3d (10 g), 4-tert-butylphenylboronic acid (4 g) and toluene were added, and the mixture was stirred at room temperature. Thereafter, bis (di-tert-butyl (4-dimethylaminobiphenyl) phosphine) dichloropalladium (72 mg) was added thereto, and the mixture was heated to 90 ° C. Then, after adding 20 mass% tetrabutyl ammonium hydroxide aqueous solution (64 g) dropwise there, it stirred at 90 degreeC for 3 hours. After cooling the reaction vessel to room temperature, the resulting reaction mixture was separated. The obtained organic layer was washed twice with ion exchanged water. Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. Activated carbon was added to the obtained filtrate, and after stirring for 30 minutes at room temperature, it was filtered by a filter covered with celite. The obtained filtrate was concentrated under reduced pressure, hexane was added thereto, and the solid was collected by filtration. The obtained solid was crystallized several times using hexane and 2-propanol, and the obtained solid was dried under reduced pressure at 50 ° C. to obtain compound 3e (9 g, white solid). The HPLC area percentage value of compound 3e was 99.5% or more.

The measurement results of LC-MS and NMR of compound 3e were as follows.
LC-MS (APCI, positive): m / z = 542 [M + H] ^+
1 H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 7.63 to 7.68 (m, 4H), 7.31 to 7.52 (m, 8H), 7.25 (d, 2H), 7.15-7.17 (d, 2H), 1.88 (s, 3H), 1.43 (s, 3H), 1.28 (s, 9H), 1.21 (s, 3H), 1 .45-1.78 (m, 1 H), 1.17-1. 39 (m, 5 H), 0.88 (3 H, t)

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (1.1 g), compound 3e (5.0 g) and pentadecane (13 mL) were added, and the mixture was stirred under heating reflux for 48 hours. Thereafter, toluene was added thereto, followed by filtration with a filter covered with silica gel, and from the obtained silica gel, a mixed solvent of toluene and ethyl acetate was used to extract a yellow solution containing metal complex B3. The obtained solution was concentrated under reduced pressure to obtain a solid, and the obtained solid was purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate) to obtain a solid. Crystallization of the obtained solid using a mixed solvent of toluene and acetonitrile, and crystallization using a mixed solvent of toluene and hexane were respectively repeated several times. Thereafter, the obtained solid was dried under reduced pressure at 50 ° C. to obtain metal complex B3 (1.7 g, yellow solid). The HPLC area percentage value of metal complex B3 was 98.3%.

The measurement results of NMR of metal complex B3 were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.42-7.73 (24 H, m), 6.97-7.11 (18 H, m), 6.13-6.26 (3H, m), 2.23-2.27 (4H, m), 2.01 (1H, s) 1.94 (1H, s), 0.97-1.89 (34H, m), 1 .88 (2 H, d), 1.56 (3 H, s), 1. 20 (27 H, s), 0.70-0.84 (9 H, m)

  Synthesis Example B4 Synthesis of Metal Complex B4

  The reaction vessel was changed to an argon gas atmosphere, then compound 2c (7.0 g), phenylboronic acid (2.1 g), toluene (70 mL) and (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloro palladium (II) (58 mg) was added, and the temperature was raised to 80 ° C. Then, after adding 20 mass% tetrabutyl ammonium hydroxide aqueous solution (51 g) to there, it stirred under heating-refluxing for 18 hours. Then, after cooling the obtained reaction liquid to room temperature, toluene was added there and the organic layer was extracted. The obtained organic layer was washed with ion-exchanged water, further dried over anhydrous magnesium sulfate, and filtered through a filter covered with silica gel and celite. Thereafter, the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product is purified by silica gel column chromatography (a mixed solvent of chloroform and ethanol), and then dried at 50 ° C. under reduced pressure to give compound 4d (4.7 g, yield 48%) as a colorless oil. I got it as a thing. The HPLC area percentage value of compound 4d was 99.5% or more.

The measurement results of LC-MS and NMR of compound 4d were as follows.
LC-MS (APPI, positive): m / z = 480 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ -d ₂ ) δ (ppm) = 7.54 to 7.46 (m, 2 H), 7.43 to 7.39 (m, 1 H), 7.39- 7.27 (m, 7 H), 7.21 (d, 1 H), 7.07 (s, 1 H), 2. 39 (s, 3 H), 1.75 (s, 3 H), 1.71-1 .62 (m, 1 H), 1.46 to 1.36 (m, 1 H), 1.33 (s, 3 H), 1.32 to 1.14 (m, 4 H), 1.13 (s, 3 H) ), 0.86 (t, 3H).

  The reaction vessel was changed to an argon gas atmosphere, and then trisacetylacetonatoiridium (1.5 g), compound 4d (4.5 g) and pentadecane (14 mL) were added, and the mixture was stirred under heating reflux for 46 hours. Thereafter, toluene was added thereto, followed by filtration with a filter covered with silica gel, and from the obtained silica gel, a mixed solvent of toluene and ethyl acetate was used to extract a yellow solution containing metal complex B4. The obtained solution was concentrated under reduced pressure to obtain a solid, and the obtained solid was washed with acetonitrile and heptane, and then purified by silica gel column chromatography (mixed solvent of toluene and ethyl acetate). Thereafter, the obtained solid was crystallized using a mixed solvent of toluene and acetonitrile, and then the obtained solid was dried under reduced pressure at 50 ° C. to obtain metal complex B4 (3.2 g) as a yellow solid. The HPLC area percentage value of metal complex B4 was 96.3%.

The measurement results of LC-MS and NMR of the metal complex B4 were as follows.
LC-MS (APCI, positive): m / z = 1629 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.41 to 7.17 (m, 15 H), 7.15 to 6.67 (m, 15 H), 6.21 to 6.06 (M, 3H), 2.53-2.43 (m, 9H), 2.16-2.05 (m, 5H), 1.90-1.67 (m, 4H), 1.62-0 .99 (m, 36 H), 0.83-0.62 (m, 9 H).

  Synthesis Example B5 Synthesis of Metal Complex B5

  The reaction vessel was changed to an argon gas atmosphere, and compound 2b (25.2 g), 2-fluoropyridine (10.8 g), chlorobenzene (202 mL) and trifluoroacetic anhydride (31.3 g) were added and stirred. Then, after cooling a reaction container using a water bath, 2-bromo 3- methyl benzoyl hydrazine (25.4 g) was added there, and it stirred at room temperature for 10 minutes. Thereafter, a small amount of the reaction solution is taken out and diluted with chloroform, and after performing HPLC measurement, it is confirmed that the remaining amount of compound 2b is less than 2% (HPLC area percentage value), Furthermore, it stirred at 90 degreeC for 7 hours. Then, after cooling a reaction container to room temperature, sodium hydrogencarbonate aqueous solution (100 mL) was added there, and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water. Thereafter, magnesium sulfate was added to the obtained organic layer and dried. Thereafter, 12.6 g of activated carbon was added to the dried organic layer, and the mixture was stirred, and then filtered with a filter covered with celite. The obtained filtrate was concentrated under reduced pressure to obtain a solid. After adding chloroform and tetrahydrofuran to the obtained solid, it filtered with the filter which covered silica gel and celite. After that, the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was crystallized using a mixed solvent of toluene and heptane. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 5c (36.2 g) as a white solid. The HPLC area percentage value of compound 5c was 99.5% or more.

The measurement results of NMR of compound 5c were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl _2- d ₂ ) δ (ppm) = 7.61-7.53 (m, 1 H), 7.28-7.21 (m, 1 H), 7.21- 7.12 (m, 1 H), 7.12-7.01 (m, 3 H), 2.34 (s, 3 H), 2.30 (s, 3 H), 1.75-1.60 (m, 5) 5H), 1.42-1.08 (m, 10H), 85 (t, 3H).

  After setting the inside of the reaction vessel to a nitrogen gas atmosphere, 3-bromospirofluorene (5.0 g), bispinacolato diboron (4.1 g), potassium acetate (4.9 g) and cyclopentyl methyl ether (125 mL) are added, It stirred. Thereafter, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane (0.3 g) was added thereto, and stirring was continued at 90 ° C. for 16 hours. Then, after cooling a reaction container to room temperature, the obtained reaction liquid was separated. The obtained organic layer was washed twice with ion exchanged water (50 mL). After that, the obtained organic layer was dried over magnesium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. Toluene and activated carbon (1.4 g) were added to the obtained solid, and the mixture was stirred at room temperature for 1 hour and then filtered with a filter covered with celite. The obtained filtrate was concentrated to obtain a white solid. The obtained white solid was crystallized using toluene and acetonitrile, and then the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 5d (4.5 g, white solid).

The ¹ H-NMR measurement results of the compound 5d are as follows.
¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 1.33 (12 H, m), 6.64 (4 H, m), 7.06-7.23 (3 H, m), 7 .35 (3 H, t), 7.51 (1 H, d), 7.86 (2 H, d), 7. 91 (1 H, d), 8.26 (1 H, s).

  The reaction vessel is changed to an argon gas atmosphere, and then compound 5c (1.7 g), compound 5d (2.0 g), 40% by mass tetrabutylammonium hydroxide aqueous solution (5.9 g), ion-exchanged water (5.9 g) And toluene (19.9 g) were added and stirred at room temperature. Thereafter, bis (di-tert-butyl (4-dimethylaminobiphenyl) phosphine) dichloropalladium (0.03 g) was added thereto, and the mixture was stirred at 80 ° C. for 19 hours. Then, after cooling a reaction container to room temperature, the obtained reaction liquid was separated. The obtained organic layer was washed twice with ion-exchanged water (27.0 g). Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. Activated carbon (0.5 g) was added to the obtained filtrate, and the mixture was stirred at room temperature for 1 hour, and then filtered with a filter covered with celite. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate) to obtain a solid. The obtained solid was crystallized multiple times using a mixed solvent of toluene and heptane, and a mixed solvent of toluene and acetonitrile. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure. Compound 5e (2.6 g, white solid) was obtained by repeating the above operation. The HPLC area percentage value of compound 5e was 99.5% or more.

The ¹ H-NMR measurement results of compound 5e were as follows.
¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.89-7.85 (m, 2H), 7.84-7.80 (m, 1 H), 7.60-7. 57 (m, 1 H), 7. 40-7. 35 (m, 3 H), 7. 30-7. 26 (m, 2 H), 7.2 3 (d, 1 H), 7. 18-7.08 ( m, 5H), 7.05 (br, 1H), 6.82 (dd, 1H), 6.74-6.63 (m, 4H), 2.32 (s, 3H), 2.27 (s) , 3H), 1.76 (s, 3H), 1.69-1.59 (m, 1H), 1.44-1.37 (m, 1H), 1.32 (s, 3H), 1. 29-1.15 (m, 4 H), 1.09 (s, 3 H), 0.85 (t, 3 H).

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (0.5 g), compound 5e (2.5 g) and pentadecane (7.2 g) were added, and the mixture was stirred under heating reflux for 46 hours. Thereafter, toluene (9.0 g) is added thereto, and the mixture is filtered by a filter covered with silica gel (22.6 g), and from the obtained silica gel, metal complex B5 is obtained using a mixed solvent of toluene and ethyl acetate. The yellow solution containing was extracted. The obtained solution was concentrated under reduced pressure to obtain a solid, and the obtained solid was purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate) to obtain a solid. The obtained solid was crystallized using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure at 50 ° C. to obtain a metal complex B5 (0.7 g, yellow solid). The HPLC area percentage value of metal complex B5 was 99.0%.

The LC / MS and ¹ H-NMR measurement results of the metal complex B5 were as follows.
LC / MS (APCI, positive): m / z = 2218 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.90-7.82 (m, 9 H), 7.51-7.34 (m, 15 H), 7.27-7. 09 (m, 15 H), 6.90-6.78 (m, 3 H), 6.75-6.59 (m, 12 H), 6.57-6.51 (m, 3 H), 5.88- 5.78 (m, 3H), 2.25 to 2.05 (m, 27H), 2.01 to 1.83 (m, 6H), 1.47 to 1.06 (m, 30H), 0.1. 89-0.72 (m, 9H).

  Synthesis Example B6 Synthesis of Metal Complex B6

Compound 2c (13.0 g), 5'-m-terphenylboronic acid (9.2 g), bis (di-t-butyl (4-dimethylaminobiphenyl) phosphine) after the inside of the reaction vessel is changed to an argon gas atmosphere Dichloropalladium (0.1 g) and toluene (100 mL) were added and stirred at room temperature. Then, after adding 40 mass% tetrabutyl ammonium hydroxide aqueous solution (49 mL) to there, it stirred at 90 degreeC for 21 hours. Then, after cooling a reaction container to room temperature, the obtained reaction liquid was separated. The obtained organic layer was washed with ion exchanged water. Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. Activated carbon (3.0 g) was added to the obtained filtrate, and the mixture was stirred at room temperature for 1 hour, and then filtered with a filter covered with celite. The resulting filtrate was concentrated under reduced pressure to give a crude product. The crude product obtained was purified by silica gel column chromatography (mixed solvent of chloroform and ethanol) to obtain an oil. Methanol and activated carbon were added to the obtained oil, and the mixture was stirred at room temperature for 1 hour, and then filtered through a filter with Celite. The obtained filtrate was concentrated under reduced pressure to obtain a white solid. The obtained solid was crystallized using a mixed solvent of heptane and 2-propanol, and the obtained solid was dried under reduced pressure at 50 ° C. to obtain compound 6a (11.3 g, white solid). The HPLC area percentage value of compound 6a was 99.5% or more.
The ¹ H-NMR measurement results of compound 6a were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.80-7.25 (m, 18 H), 7.20-7.07 (m, 1 H), 7.01 (t, 1 H) ), 2.19-2.09 (t, 3 H), 1.84-1.56 (m, 5 H), 1.45-1.06 (m, 10 H), 0.94-0.86 (m) , 3H).

The reaction vessel was changed to an argon gas atmosphere, and after adding trisacetylacetonatoiridium (2.1 g), compound 6a (10 g) and pentadecane (50 mL), the mixture was stirred for 63 hours under heating and reflux. Thereafter, the reaction vessel was cooled to room temperature, 2-propanol (100 mL) was added thereto, and the precipitated solid was collected by filtration. The obtained solid was washed with a mixed solvent of dichloromethane and acetonitrile to give a yellow solid (5.5 g). The obtained solid is separated and purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate), and then a mixed solvent of dichloromethane and ethanol, a mixed solvent of toluene and acetonitrile, and a mixed solvent of toluene and heptane Crystallized. Furthermore, the obtained solid was separated and purified by reverse phase silica gel column chromatography (mixed solvent of methylene chloride and acetonitrile), and then crystallized using a mixed solvent of toluene and ethanol. Thereafter, the obtained solid was dried under reduced pressure at 50 ° C. to obtain metal complex B6 (3.0 g, yellow solid). The HPLC area percentage value of metal complex B6 was 99.5% or more.
The results of ¹ H-NMR measurement of the metal complex B6 were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.66 to 7.56 (m, 15 H), 7.51 to 7.19 (m, 27 H), 7.17 to 6.80 (M, 12H), 6.41-6.26 (m, 3H), 2.34-2.49 (m, 6H), 1.96-1.80 (m, 12H), 1.63-1 .00 (m, 36 H), 0.89-0.65 (m, 9 H).

  Synthesis Example B7 Synthesis of Metal Complex B7

The reaction vessel was changed to an argon gas atmosphere, 2-dibenzofurancarboxylic acid (20.0 g), sulfuric acid (1.8 g) and ethanol (600 mL) were added, and after stirring at 80 ° C. for 45 hours, the obtained reaction liquid Was at room temperature. After repeating the above operation twice, the obtained two reaction solutions were combined. The combined reaction solution obtained was concentrated, and then ethyl acetate (400 mL) was added thereto and concentrated. Ethyl acetate (200 mL) and ion-exchanged water (200 mL) were added to the obtained concentrate to extract the organic layer. The obtained organic layer was washed with aqueous sodium carbonate solution (200 mL), and the obtained organic layer was washed with ion-exchanged water (200 mL). Then, after drying the obtained organic layer with magnesium sulfate, it filtered with the filter which covered celite and silica gel. The obtained filtrate was concentrated under reduced pressure to obtain an oil. Thereafter, the obtained oil was dried under reduced pressure at 50 ° C. to give compound 7a (39.4 g) as a pale yellow oil. The HPLC area percentage value of compound 7a was 99.0%.
The ¹ H-NMR measurement results of the compound 7a were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 1.40 (3 H, t), 4. 39 (2 H, q), 7. 38 (1 H, dt), 7. 50 (1 H, 1 H, dt), 7.59 (2H, d), 8.02 (1 H, dd), 8.16 (1 H, dd), 8.67 (1 H, d).

The reaction vessel is turned into an argon atmosphere, and compound 7a (40.0 g), ethanol (360 mL), ion-exchanged water (40 mL) and hydrazine monohydrate (125.0 g) are added, and the mixture is kept at 80 ° C. for 6 hours. It stirred. After cooling the reaction solution to room temperature, ion-exchanged water (300 mL) was added thereto, and the mixture was stirred at 0 ° C. for 1 hour to give a solid. The obtained solid was collected by filtration, and the obtained solid was washed twice with ion-exchanged water (200 mL), and further washed once with 50% aqueous ethanol (200 mL). After adding 2-propanol (565 mL) to the obtained solid, the suspension was stirred. Thereafter, the solid was collected by filtration, and the obtained solid was dried under reduced pressure at 50 ° C. to give compound 7b (34.5 g) as a white solid. The HPLC area percentage value of compound 7b was 97.1%.
The ¹ H-NMR measurement results of compound 7b were as follows.
¹ H-NMR (400 MHz, CD ₃ OD) δ (ppm) = 4.84 (2 H, s), 7. 39 (1 H, dt), 7.52 (1 H, dt), 7. 60 (1 H, dd) ), 7.64 (1 H, d), 7.93 (1 H, dd), 8.07 (1 H, dd), 8.48 (1 H, d).

After setting the reaction vessel under an argon atmosphere, compound 3c (22.0 g), monochlorobenzene (220 mL), 2-fluoropyridine (6.7 mL) and trifluoromethanesulfonic anhydride (12.8 mL) are added, and the mixture is stirred at room temperature. It stirred. Thereafter, Compound 7b (17.7 g) was added thereto, and the mixture was stirred at 85 ° C. for 3 hours. Then, after cooling the obtained reaction liquid to room temperature, sodium hydrogencarbonate aqueous solution (78 mL) was added there, and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water (88 mL). Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was washed with hexane. Thereafter, the obtained solid was crystallized using acetonitrile, and further dried under reduced pressure at 50 ° C. to obtain compound 7c (28.2 g) as a white solid. The HPLC area percentage value of compound 7c was 99.5% or more.
The ¹ H-NMR measurement results of the compound 7c were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 0.89 (3 H, t), 1. 18 (3 H, s), 1.20-1. 35 (3 H, m), 1. 39 (3H, m), 1.46 (1 H, dt), 1.63 (1 H, m), 1.66-1.75 (1 H, m), 1.83 (3 H, s), 7.29 (1 H, dt), 7.34-7. 66 (12 H, m), 7. 80 (1 H, dd), 8.02 (1 H, d).

The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (4.4 g), compound 7c (18.0 g) and pentadecane (90 mL) were added, and the mixture was stirred for 66 hours under heating to reflux. Then, after cooling the obtained reaction liquid to room temperature, when 2-propanol (90 mL) was added there, solid was produced. The obtained solid was collected by filtration, toluene (15 mL) was added to the obtained solid, and the mixture was filtered with a filter covered with silica gel (76 g). Thereafter, from the resulting silica gel, a mixed solvent of toluene and ethyl acetate was used to extract a yellow solution containing metal complex B7. The obtained solution was concentrated under reduced pressure, and the obtained solid was separated and purified by silica gel column chromatography (mixed solvent of toluene and ethyl acetate) to obtain a solid. The obtained solid was crystallized with a mixed solvent of toluene and ethanol, and further dried under reduced pressure at 50 ° C. to obtain metal complex B7 (7.0 g, yellow solid). The HPLC area percentage value of metal complex B7 was 98.3%.
The LC / MS and ¹ H-NMR measurement results of the metal complex B7 were as follows.
LC / MS (APCI, positive): m / z = 1688.8 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 0.49-0.86 (10 H, m), 0.94-1.70 (35 H, m), 1.81-1.91 (4H, m), 2.23-2.32 (5H, m), 6.51-6.59 (3H, m), 6.78-7.27 (15 H, m), 7.43-7 .81 (24H, m).

  Synthesis Example B8 Synthesis of Metal Complex B8

  The reaction vessel was changed to a nitrogen gas atmosphere, and then Compound 8a (27.5 g) and cyclopentyl methyl ether (55 g) were added and stirred. Thereafter, the reaction vessel was cooled using an ice bath, and then a 16 mass% hydrogen chloride solution of cyclopentyl methyl ether (27.8 g) was dropped thereto. Thereafter, heptane (110 g) was added dropwise thereto, and stirring was continued at room temperature for 1 hour, and the precipitated solid was collected by filtration. The obtained solid was washed with heptane and cyclopentyl methyl ether and further dried under reduced pressure to give compound 8b (29 g).

After the inside of the reaction vessel was changed to a nitrogen gas atmosphere, 2,2′-dimethylhexanoic acid (17.3 g), chloroform (114 g) and N, N′-dimethylformamide (0.04 g) were added and stirred at 50 ° C. . After that, thionyl chloride (15.0 g) was added dropwise thereto, and stirred at 40 ° C. for 3 hours to generate 2,2′-dimethylhexanoyl chloride. Thereafter, the reaction vessel was cooled using a water bath to obtain a reaction solution containing 2,2′-dimethylhexanoyl chloride.
The inside of a separately prepared reaction vessel was changed to a nitrogen gas atmosphere, and then Compound 8b (28.5 g), chloroform (114 g) and triethylamine (39.7 g) were added and stirred. Thereafter, the reaction vessel was cooled using an ice bath, and the reaction solution containing 2,2'-dimethylhexanoyl chloride prepared above was dropped there, and then stirred at 40 ° C for 5 hours. Then, after cooling the obtained reaction liquid to room temperature, ion-exchange water was dripped there. Thereafter, the aqueous layer was removed, and the obtained organic layer was washed with ion exchanged water, and further concentrated under reduced pressure to obtain a crude product. The obtained crude product was separated and purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate) and then crystallized using heptane. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to obtain compound 8c (26.4 g). The HPLC area percentage value of compound 8c was 99.5% or more.
The measurement results of NMR of compound 8c were as follows.
¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.64-7.60 (m, 2 H), 7.59-7.55 (m, 2 H), 7.44-7. 39 (m, 3 H), 7.36 (br, 1 H), 7.34-7. 29 (m, 1 H), 1.65 to 1.57 (m, 2 H), 1.43 (s, 9 H) , 1.36-1.27 (m, 10 H), 0.92-0.87 (m, 3 H).

The reaction vessel is filled with an argon gas atmosphere, and then compound 8c (5.5 g), monochlorobenzene (28 g), 2-fluoropyridine (1.7 g) and trifluoromethanesulfonic anhydride (4.9 g) are added, and room temperature is added. It stirred below for 1 hour. Thereafter, 3-bromobenzhydrazide (3.7 g) was added thereto, and the mixture was stirred at 110 ° C. for 17 hours. Then, after cooling the obtained reaction liquid to room temperature, 2 mol / L sodium hydrogencarbonate aqueous solution (30 g) was added there. Thereafter, the aqueous layer was removed, and the obtained organic layer was washed with ion exchanged water, and further concentrated under reduced pressure to obtain a crude product. The obtained crude product was separated and purified by silica gel column chromatography (a mixed solvent of hexane and ethyl acetate), and further dried under reduced pressure at 50 ° C. to obtain compound 8d (5.3 g). The HPLC area percentage value of compound 8d was 99.1%.
The measurement results of NMR of compound 8d were as follows.
¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.79 (d, 1 H), 7.69-7.64 (m, 2 H), 7.61 (dd, 1 H), 7 .55 (dd, 1 H), 7.53 to 7.47 (m, 2 H), 7.46 to 7.39 (m, 2 H), 7.35 (d, 1 H), 7.34 to 7.27 (M, 1 H), 7.12 (t, 1 H), 2.00-1. 86 (m, 1 H), 1.59-1.50 (m, 1 H), 1.44-1.26 (m , 6H), 1.25-1.13 (m, 4H), 0.99-0.88 (m, 12H).

The reaction vessel was changed to an argon gas atmosphere, and then compound 8d (5.2 g), 4-tert-butylphenylboronic acid (2.1 g), toluene (52 g) and (di-tert-butyl (4-dimethylaminophenyl) ) Phosphine) Dichloropalladium (II) (67 mg) was added, and the temperature was raised to 80 ° C. Then, after adding 20 mass% tetrabutyl ammonium hydroxide aqueous solution (30 mL) to there, it stirred for 70 hours, heating-refluxing. Then, after cooling the obtained reaction liquid to room temperature, toluene was added there and it filtered with the filter which covered silica gel and celite. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid is purified by silica gel column chromatography (a mixed solvent of hexane and chloroform), and further crystallized using a mixed solvent of toluene and heptane, and then dried at 50 ° C. under reduced pressure. Compound 8e (3.9 g) was obtained. The HPLC area percentage value of compound 8e was 99.5% or more.
The measurement results of NMR of compound 8e were as follows.
¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.82 (d, 1 H), 7.73-7.66 (m, 3 H), 7.64 (dd, 1 H), 7 .55-7.47 (m, 3H), 7.47-7.35 (m, 3H), 7.23-7.16 (m, 3H), 7.09-7.03 (m, 2H) , 2.01 to 1.90 (m, 1 H), 1.60 to 1.50 (m, 1 H), 1.44 to 1.16 (m, 19 H), 0.95 to 0.84 (m, 1) 12H).

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (0.86 g), compound 8e (3.6 g) and pentadecane (10 g) were added, and the mixture was stirred for 67 hours under heating to reflux. Then, after cooling the obtained reaction liquid to room temperature, toluene was added there and it filtered with the filter which covered silica gel. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The resulting solid is purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate), crystallized using a mixed solvent of toluene and acetonitrile, and then dried at 50 ° C. under reduced pressure to obtain a metal complex. B8 (1.0 g) was obtained. The HPLC area percentage value of metal complex B8 was 95.3%.

The measurement results of LC-MS and NMR of metal complex B8 were as follows.
LC-MS (APCI, positive): m / z = 1941 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 8.05-7.93 (m, 3H), 7.77-7.31 (m, 21H), 7.17-6. 81 (m, 18 H), 6.29-6. 16 (m, 3 H), 2.00-1. 77 (m, 2 H), 1.75-1.52 (m, 2 H), 1.50- 1.15 (m, 64H), 1.12 to 0.80 (m, 28H), 0.54 to 0.42 (m, 3H).

  Synthesis Example B9 Synthesis of Metal Complex B9

  The reaction vessel was changed to an argon gas atmosphere, then compound 3c (8.5 g), chlorobenzene (85 mL), 2-fluoropyridine (2.6 mL) and trifluoromethanesulfonic anhydride (5.1 mL) were added, and the mixture was cooled to room temperature. The mixture was stirred for 30 minutes. Thereafter, 3-methyl benzhydrazide (4.5 g) was added thereto, and the mixture was stirred at 90 ° C. for 2 hours. Then, after cooling the obtained reaction liquid to room temperature, sodium hydrogencarbonate aqueous solution was added and stirred there. Thereafter, the organic layer was extracted, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate and filtered. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was crystallized using a mixed solvent of heptane and 2-propanol, and further crystallized using acetonitrile. The obtained solid was dried under reduced pressure at 50 ° C. to give compound 9a (4.9 g). The HPLC area percentage value of compound 9a was 99.5% or more.

  The reaction vessel was changed to an argon gas atmosphere, trisacetylacetonatoiridium (1.3 g), compound 9a (1.3 g) and pentadecane (10 mL) were added, and the mixture was stirred for 50 hours under heating and reflux. Thereafter, toluene was added thereto, and the mixture was filtered by a filter covered with silica gel, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate) and then crystallized using a mixed solvent of heptane, toluene and 2-propanol. Thereafter, the obtained solid was dried under reduced pressure at 50 ° C. to obtain a metal complex B9 (1.2 g). The HPLC area percentage value of metal complex B9 was 99.5% or more.

The measurement results of LC-MS and NMR of metal complex B9 were as follows.
LC-MS (APCI, positive): m / z = 1460.8 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 0.69-0.91 (m, 9 H), 1.07-1.99 (m, 48 H), 2.14-2.36 (M, 6H), 5.73-5.81 (m, 3H), 6.40-6.81 (m, 6H), 7.28-7.75 (m, 24H).

  Synthesis Example B10 Synthesis of Metal Complex B10

  The reaction vessel is changed to an argon gas atmosphere, and then compound 5c (15.0 g), phenylboric acid (4.4 g), bis (di-tert-butyl (4-dimethylaminobiphenyl) phosphine) dichloropalladium (0.1 g) And toluene (75 mL) were added and stirred at 80.degree. Then, after adding 40 mass% tetrabutyl ammonium hydroxide aqueous solution (55 mL) to there, it stirred at 80 degreeC for 40 hours. Then, after cooling a reaction container to room temperature, the obtained reaction liquid was separated. The obtained organic layer was washed twice with ion exchanged water (75 mL), and the obtained organic layer was dried over magnesium sulfate. Thereafter, activated carbon (15.0 g) was added to the dried organic layer, and the mixture was stirred at room temperature for 1 hour, and then filtered with a filter covered with celite. The obtained filtrate was concentrated under reduced pressure to obtain an oil. The obtained oil was separated and purified by silica gel column chromatography (mixed solvent of chloroform and ethanol) to obtain a solid. The obtained solid was crystallized using a mixed solvent of heptane and 2-propanol, and further dried under reduced pressure at 50 ° C. to give compound 10a (4.0 g, white solid). The HPLC area percentage value of compound 10a was 99.5% or more.

The ¹ H-NMR measurement results of compound 10a were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.40-6.94 (m, 11 H), 2.42-2.34 (m, 3 H), 2.23-2.15 (M, 3H), 1.78-1.48 (m, 6H), 1.42-1.16 (m, 6H), 1.13-1.06 (m, 3H), 0.92-0 .77 (m, 3H).

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (1.1 g), compound 10a (4.0 g) and pentadecane (50 mL) were added, and the mixture was stirred for 52 hours under heating to reflux. Thereafter, toluene (32 mL) is added thereto, and the mixture is filtered with a filter covered with silica gel (16.0 g), and from the obtained silica gel, metal complex 10 is contained using a mixed solvent of toluene and ethyl acetate. The yellow solution was extracted. The obtained solution is concentrated under reduced pressure to obtain a solid, and the obtained solid is separated and purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate), and the obtained solid is further washed with ethanol did. Then, the obtained solid was separated and purified by reverse phase silica gel column chromatography (mixed solvent of methylene chloride and acetonitrile), and the obtained solid was further washed with acetonitrile. after that. The obtained solid was crystallized using a mixed solvent of toluene and ethanol, and further dried under reduced pressure at 50 ° C. to obtain metal complex B10 (1.5 g, yellow solid). The HPLC area percentage value of metal complex B10 was 99.4%.

The results of ¹ H-NMR measurement of the metal complex B10 were as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 7.33 to 7.08 (m, 18 H), 7.02 to 6.93 (m, 6 H), 6.73 to 6.48 (M, 3H), 5.81-5. 71 (m, 3H), 2.43-2.32 (m, 9H), 2.16-1.97 (m, 15H), 1.91-1 79 (m, 3 H), 1.58-1.03 (m, 36 H), 0.84-0.67 (m, 9 H).

  Synthesis Example B11 Synthesis of Metal Complex B11

  The reaction vessel was changed to an argon gas atmosphere, Compound 2b (28.0 g), chlorobenzene (360 mL), 2-fluoropyridine (11 mL) and trifluoromethanesulfonic anhydride (21 mL) were added, and the mixture was stirred at 90 ° C. Then, 3,4- dichlorobenzene carbohydrazide (25.5 g) was added to it, and it stirred at 90 degreeC for 9 hours. Then, after cooling the obtained reaction liquid to room temperature, sodium hydrogencarbonate aqueous solution was added there, and the organic layer was extracted. The obtained organic layer was washed with ion exchanged water (100 mL). The obtained organic layer was dried over magnesium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was washed with hexane and then crystallized using acetonitrile. Thereafter, the obtained solid was dried at 50 ° C. under reduced pressure to give compound 11a (37.8 g) as a white solid. The HPLC area percentage value of compound 11a was 99.5% or more.

The ¹ H-NMR measurement results of compound 11a were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 0.86 (t, 3 H),
1.04-1.50 (m, 11H), 1.58-1.90 (m, 4H), 2.40 (s, 3H), 6.98-7.36 (m, 5H), 7. 50 (s, 1 H).

The reaction vessel was changed to an argon gas atmosphere, and then compound 11a (35.0 g), 2,4-dimethylphenylboronic acid (26.0 g), toluene (700 mL), tris (dibenzylideneacetone) dipalladium (2.3 g) And 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (2.8 g) were added, and the mixture was heated and stirred at 90 ° C. Then, after adding 40 mass% tetrabutyl ammonium hydroxide aqueous solution (409 mL) to there, it stirred at 90 degreeC for 9 hours. After cooling the reaction vessel to room temperature, the resulting reaction mixture was separated. The obtained organic layer was washed twice with ion exchanged water (150 mL). Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. Activated carbon (4.0 g) was added to the obtained filtrate, and the mixture was stirred at room temperature for 1 hour, and then filtered with a filter covered with celite. The obtained filtrate was concentrated under reduced pressure, and then fractionated and purified by silica gel column chromatography (mixture of hexane and ethyl acetate) to obtain an oil.
The inside of the reaction vessel separately prepared is changed to an argon gas atmosphere, and then the oil obtained above (30.0 g), 2,4-dimethylphenylboronic acid (2.2 g), toluene (450 mL), tris (dibenzylidene) Acetone) dipalladium (1.0 g) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (1.2 g) were added, and the mixture was heated and stirred at 90 ° C. Then, after adding 40 mass% tetrabutyl ammonium hydroxide aqueous solution (234 mL) to there, it stirred at 90 degreeC for 5 hours. After cooling the reaction vessel to room temperature, the resulting reaction mixture was separated. The obtained organic layer was washed twice with ion exchanged water (150 mL). Thereafter, the obtained organic layer was dried over magnesium sulfate and filtered. Activated carbon (4.0 g) was added to the obtained filtrate, and the mixture was stirred at room temperature for 1 hour, and then filtered with a filter covered with celite. The resulting filtrate was concentrated to give a reddish brown oil. The obtained reddish brown oil was fractionated and purified by reverse phase silica gel column chromatography (acetonitrile), and then the obtained oil was fractionated and purified by silica gel column chromatography (a mixed solvent of chloroform and ethanol). Thereafter, the obtained oil was separated and purified by recycle preparative GPC. Thereafter, the obtained oil was dried at 50 ° C. under reduced pressure to obtain compound 11b (2.2 g, a colorless and transparent oil). The HPLC area percentage value of compound 11b was 99.5% or more.

The LC / MS and ¹ H-NMR measurement results of compound 11 b were as follows.
LC / MS (APCI, positive): m / z = 556 [M + H] ^+
1 H-NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 0.86 (t, 3 H), 1.12-1.44 (m, 11 H), 1.58-2.04 (m, 10 H) ), 2.20 (s, 6 H), 2.37 (s, 3 H), 6.46-7. 25 (m, 12 H).

  The reaction vessel was changed to an argon gas atmosphere, then trisacetylacetonatoiridium (0.4 g), compound 11b (2.0 g) and pentadecane (6 mL) were added, and the mixture was stirred for 54 hours under heating to reflux. Thereafter, toluene (30 mL) is added thereto, and the mixture is filtered by a filter covered with silica gel (20.0 g), and from the obtained silica gel, a mixed solvent of toluene and ethyl acetate is used to contain metal complex B11 The yellow solution was extracted. The resulting solution was concentrated under reduced pressure to give an oil. The obtained oil was separated and purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate) to obtain a solid. The obtained solid was separated and purified by reverse phase silica gel column chromatography (mixed solvent of acetonitrile and ethyl acetate), and further, the obtained solid was crystallized out with a mixed solvent of toluene and ethanol. Thereafter, the obtained solid was dried under reduced pressure at 50 ° C. to obtain metal complex B11 (0.6 g, yellow solid). The HPLC area percentage value of the metal complex B11 was 99.5% or more.

The LC / MS and ¹ H-NMR measurement results of the metal complex B11 were as follows.
LC / MS (APCI, positive): m / z = 1858 [M + H] ^+
1 H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 0.82-2.30 (m, 99 H), 5.69-7.27 (m, 33 H).

Example D1 Production and Evaluation of Light-Emitting Element D1 (Formation of Anode and Hole Injection Layer)
An anode was formed by depositing an ITO film with a thickness of 45 nm on a glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a hole injection agent of polythiophene sulfonic acid type, is formed into a film with a thickness of 35 nm by spin coating on the anode, and 170 ° C. on a hot plate under air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of second organic layer)
The polymer compound HTL-1 was dissolved in xylene at a concentration of 0.7% by mass. Using the obtained xylene solution, a film is formed to a thickness of 20 nm by spin coating on the hole injection layer, and the film is heated at 180 ° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere. Organic layer (hole transport layer) was formed. By this heating, the polymer compound HTL-1 became a crosslinked body.

(Formation of the first organic layer)
Compound HM-1 and metal complex B1 (compound HM-1 / metal complex B1 = 75% by mass / 25% by mass) were dissolved in toluene at a concentration of 2% by mass. Using the obtained toluene solution, a film is formed to a thickness of 75 nm by spin coating on the second organic layer, and the first organic layer is heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. The (first light emitting layer) was formed.

(Formation of third organic layer)
Polymer compound ET1 was dissolved in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol at a concentration of 0.25% by mass. Using the obtained 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution, a film is formed on the first organic layer by spin coating to a thickness of 10 nm. Then, the third organic layer (electron transport layer) was formed by heating at 130 ° C. for 10 minutes in a nitrogen gas atmosphere.

(Formation of cathode)
After reducing the pressure of the substrate on which the third organic layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride of about 4 nm is then formed on the electron transport layer as a cathode, and then sodium fluoride About 80 nm of aluminum was deposited on the layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D1.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting device D1. The driving voltage and the CIE chromaticity coordinates (x, y) at a current density of 10 mA / cm ² were measured. The results are shown in Table 4.

<Examples D2 to D6 and Comparative Examples CD1 to CD2> Preparation and Evaluation of Light-Emitting Elements D2 to D6, CD1 and CD2 “Compound HM-1 and Metal Complex B1 (Formation of First Organic Layer) in Example D1 “Polymer compound HTL in (Formation of a second organic layer) of Example D1 using a material described in Table 4 in place of“ compound HM-1 / metal complex B1 = 75 mass% / 25 mass%) ” In place of “polymer compound ET1” in Example D1 (formation of third organic layer) in place of “1”, and the material described in Table 4 is used. Light-emitting elements D2 to D6, CD1 and CD2 were produced in the same manner as in Example D1 except for the above.
EL light emission was observed by applying a voltage to the light emitting elements D2 to D6, CD1 and CD2. The driving voltage and the CIE chromaticity coordinates (x, y) at a current density of 10 mA / cm ² were measured. The results are shown in Table 4.

Example D7 and Comparative Example CD3 Preparation and Evaluation of Light-Emitting Element D7 and CD3 “Compound HTM-1” in place of “Polymer Compound HTL-1” in (Formation of the Second Organic Layer) of Example D1 In the same manner as in Example D1, except that the material described in Table 5 was used instead of “polymer compound ET1” in (Formation of the third organic layer) of Example D1 using Elements D7 and CD3 were produced.
By applying voltage to the light emitting elements D7 and CD3, EL light emission was observed. The driving voltage at a current density of 50 mA / cm ² and CIE chromaticity coordinates (x, y) were measured. The results are shown in Table 5.

Example D8 Preparation and Evaluation of Light-Emitting Element D8 (Formation of Anode and Hole Injection Layer)
An anode was formed by depositing an ITO film with a thickness of 45 nm on a glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a hole injection agent of polythiophene sulfonic acid type, is formed into a film with a thickness of 35 nm by spin coating on the anode, and 170 ° C. on a hot plate under air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of second organic layer)
The polymer compound HTL-3 was dissolved in xylene at a concentration of 0.7% by mass. Using the obtained xylene solution, a film is formed to a thickness of 20 nm by spin coating on the hole injection layer, and the film is heated at 180 ° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere. The organic layer (second light emitting layer) was formed. By this heating, the polymer compound HTL-3 became a crosslinked body.

(Formation of the first organic layer)
Compound HM-1, metal complex B2 and metal complex G2 (compound HM-1 / metal complex B2 / metal complex G2 = 74% by mass / 25% by mass / 1% by mass) are dissolved in toluene at a concentration of 2% by mass The Using the obtained toluene solution, a film is formed to a thickness of 75 nm by spin coating on the second organic layer, and the first organic layer is heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. The (first light emitting layer) was formed.

(Formation of third organic layer)
Polymer compound ET1 was dissolved in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol at a concentration of 0.25% by mass. Using the obtained 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution, a film is formed on the first organic layer by spin coating to a thickness of 10 nm. Then, the third organic layer (electron transport layer) was formed by heating at 130 ° C. for 10 minutes in a nitrogen gas atmosphere.

(Formation of cathode)
After reducing the pressure of the substrate on which the third organic layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride of about 4 nm is then formed on the electron transport layer as a cathode, and then sodium fluoride About 80 nm of aluminum was deposited on the layer. After vapor deposition, sealing was performed using a glass substrate to fabricate a light emitting device D8.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting element D8. The drive voltage at a current density of 1 mA / cm ² and CIE chromaticity coordinates (x, y) were measured. The results are shown in Table 6.

<Examples D9 to D14 and Comparative Examples CD4 to CD5> Preparation and evaluation of light emitting elements D9 to D14, CD4 and CD5 "Compound HM-1, metal complex B2 and (formation of first organic layer) in Example D8 (formation of first organic layer) Example D8 was used except that the material described in Table 6 was used instead of metal complex G2 (compound HM-1 / metal complex B2 / metal complex G2 = 74% by mass / 25% by mass / 1% by mass) Similarly, light emitting elements D9 to D14, CD4 and CD5 were produced.
EL light emission was observed by applying a voltage to the light emitting elements D9 to D14, CD4 and CD5. The drive voltage at a current density of 1 mA / cm ² and CIE chromaticity coordinates (x, y) were measured. The results are shown in Table 6.

Example D15 Production and Evaluation of Light-Emitting Element D15 (Formation of Anode and Hole Injection Layer)
An anode was formed by depositing an ITO film with a thickness of 45 nm on a glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a hole injection agent of polythiophene sulfonic acid type, is formed into a film with a thickness of 35 nm by spin coating on the anode, and 170 ° C. on a hot plate under air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of second organic layer)
The polymer compound HTL-2 was dissolved in xylene at a concentration of 0.7% by mass. Using the obtained xylene solution, a film is formed to a thickness of 20 nm by spin coating on the hole injection layer, and the film is heated at 180 ° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere. Organic layer (hole transport layer) was formed. By this heating, the polymer compound HTL-2 became a crosslinked body.

(Formation of the first organic layer)
Compound HM-1, metal complex B1, metal complex G2 and metal complex R2 (compound HM-1 / metal complex B1 / metal complex G2 / metal complex R2 = 73.9% by mass / 25% by mass / 1% by mass) in toluene /0.1% by weight) was dissolved at a concentration of 2% by weight. Using the obtained toluene solution, a film is formed to a thickness of 75 nm by spin coating on the second organic layer, and the first organic layer is heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. The (first light emitting layer) was formed.

(Formation of third organic layer)
Polymer compound ET1 was dissolved in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol at a concentration of 0.25% by mass. Using the obtained 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution, a film is formed on the first organic layer by spin coating to a thickness of 10 nm. Then, the third organic layer (electron transport layer) was formed by heating at 130 ° C. for 10 minutes in a nitrogen gas atmosphere.

(Formation of cathode)
After reducing the pressure of the substrate on which the third organic layer is formed to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, sodium fluoride of about 4 nm is then formed on the electron transport layer as a cathode, and then sodium fluoride About 80 nm of aluminum was deposited on the layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D15.

(Evaluation of light emitting element)
By applying a voltage to the light emitting device D15, EL light emission was observed. The drive voltage at a current density of 150 mA / cm ² and CIE chromaticity coordinates (x, y) were measured. The results are shown in Table 7.

Examples D16 to D27 and Comparative Examples CD6 to CD7 Preparation and Evaluation of Light-Emitting Elements D16 to D27, CD6, and CD7 “Compound HM-1, metal complex B1 in (Formation of first organic layer) of Example D15 In place of the metal complex G2 and the metal complex R2 (compound HM-1 / metal complex B1 / metal complex G2 / metal complex R2 = 73.9% by mass / 25% by mass / 1% by mass / 0.1% by mass) ”, Light-emitting elements D16 to D27, CD6 and CD7 were produced in the same manner as in Example D15 except that the materials listed in Table 7 were used.
EL light emission was observed by applying a voltage to the light emitting elements D16 to D27, CD6 and CD7. The drive voltage at a current density of 150 mA / cm ² and CIE chromaticity coordinates (x, y) were measured. The results are shown in Table 7.

Claims (11)

An anode, a cathode, a first organic layer provided between the anode and the cathode, a second organic layer provided between the anode and the first organic layer, the cathode, and the cathode And at least one layer selected from the group consisting of a third organic layer provided between one organic layer;
The first organic layer contains a metal complex represented by Formula (1),
The second organic layer contains a crosslinked product of a polymer compound containing a structural unit having a crosslinking group,
A polymer compound including the at least one structural unit selected from the group consisting of the structural unit represented by the formula (ET-1) and the structural unit represented by the formula (ET-2) A light emitting element containing

[In the formula,
M ¹ represents a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n ¹ represents an integer of 1 or more, and n ² represents an integer of 0 or more. However, if M ¹ is rhodium atom or an iridium atom, n ¹ + n ² is 3, when M ¹ is a palladium atom or a platinum atom, n ¹ + n ² is 2.
The ring R ^1A represents a diazole ring, a triazole ring or a tetrazole ring.
The ring R ² represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded. When a plurality of rings R ² exist, they may be the same or different.
E ¹ , E ² , E ^11A , E ^12A and E ^13A each independently represent a nitrogen atom or a carbon atom. When E ¹ , E ² , E ^11A , E ^12A and E ^13A are present in plurality, they may be the same or different. However, at least one of E ¹ and E ² is a carbon atom.
R ^11A , R ^12A and R ^13A are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen Represents an atom, and these groups may have a substituent. When there are a plurality of R ^11A , R ^12A and R ^13A , they may be the same or different.
However, at least one of E ^11A , E ^12A and E ^13A is a nitrogen atom, and at least one of R ^11A , R ^12A and R ^13A bonded to the nitrogen atom is represented by the formula (Ar-1A) Group.
R ^11A and R ^12A may be bonded to each other to form a ring with the atoms to which each is bonded. R ^12A and R ^13A may be bonded to each other to form a ring together with the atoms to which they are bonded. The substituent which the ring R ² may have and R ^11A may be bonded to each other to form a ring together with the atoms to which they are bonded.
When E ^11A is a nitrogen atom, R ^11A may be present or absent. When E ^12A is a nitrogen atom, R ^12A may be present or absent. When E ^13A is a nitrogen atom, R ^13A may be present or absent.
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. Each of A ¹ and A ² independently represents a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. G ¹ represents a single bond or an atomic group constituting a bidentate ligand with A ¹ and A ² . When ^two or more A ¹ -G ¹ -A ² are present, they may be the same or different. ]

[In the formula,
Ring A represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded.
R ² represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, and these groups have a substituent It may be ]

[In the formula,
nE1 represents an integer of 1 or more.
Ar ^E1 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
R ^E1 represents a group represented by the formula (ES-1). When a plurality of R ^E1 are present, they may be the same or different. ]

-R ^E3 -{(Q ^E1 ) _n ^E3- Y ^E1 (M ^E1 ) _aE1 (Z ^E1 ) _b ^E1 } _mE1 (ES-1)
[In the formula,
nE3 and bE1 each independently represent an integer of 0 or more, and aE1 and mE1 each independently represent an integer of 1 or more. When two or more nE3, aE1 and bE1 exist, they may be the same or different. However, mE1 is 1 when R ^E3 is a single bond. aE1 and bE1 are selected such that the charge of the group represented by the formula (ES-1) is zero.
R ^E3 represents a single bond, a hydrocarbon group, a heterocyclic group or O—R ^E3 ′ (R ^E3 ′ represents a hydrocarbon group or a heterocyclic group), and these groups have a substituent May be
Q ^E1 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups may have a substituent. When a plurality of Q ^E1 are present, they may be the same or different.
Y ^{E1 _{is, -CO 2 -, -SO 3 -}} , -SO 2 - represents a ^2- or -PO _3. When a plurality of Y ^E1 are present, they may be the same or different.
M ^E1 represents an alkali metal cation, an alkaline earth metal cation or an ammonium cation, and the ammonium cation may have a substituent. When a plurality of M ^E1 are present, they may be the same or different.
Z ^{E1 is, F -, Cl -, Br} -, I -, OH -, B (R E4) 4 -, R E4 SO 3 -, R E4 COO -, NO 3 -, SO 4 2-, HSO 4 - _{^{, PO 4 3-, HPO 4 2-}} , H 2 PO 4 -, BF 4 - or PF ₆ ^- represents a. R ^E4 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. When a plurality of Z ^E1 are present, they may be the same or different. ]

[In the formula,
nE2 represents an integer of 1 or more.
Ar ^E2 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
R ^E2 represents a group represented by the formula (ES-2). When two or more R ^E2 are present, they may be the same or different. ]

-R ^E5 -{(Q ^E2 ) _{n E4-} Y ^E2 (M ^E2 ) _aE2 (Z ^E2 ) _b ^E2 } _mE2 (ES-2)
[In the formula,
nE4 and bE2 each independently represent an integer of 0 or more, and aE2 and mE2 each independently represent an integer of 1 or more. When a plurality of nE4, aE2 and bE2 are present, they may be the same or different. However, mE2 is 1 when R ^E5 is a single bond. aE2 and bE2 are selected such that the charge of the group represented by the formula (ES-2) is zero.
R ^E5 represents a single bond, a hydrocarbon group, a heterocyclic group or O-R ^E5 '(R ^E5 ' represents a hydrocarbon group or a heterocyclic group), and these groups have a substituent May be
Q ^E2 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups may have a substituent. When two or more Q ^E2 are present, they may be the same or different.
Y ^E2 represents _{^{-C + R E6 2, -N +}} R E6 3, -P + R E6 3, -S + R E6 2 or -I ⁺ R ^E6 _2. R ^E6 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent. Plural R ^E6 may be the same or different. When a plurality of Y ^E2 are present, they may be the same or different.
M ^E2 is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , B (R ^E7 ) ₄ ⁻ , R ^E7 SO ₃ ⁻ , R ^E7 COO ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ or SbF ₆ ⁻ Represent. R ^E7 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.
When two or more M ^E2 are present, they may be the same or different.
Z ^E2 represents an alkali metal cation or an alkaline earth metal cation. When a plurality of Z ^E2 are present, they may be the same or different. ] The light emitting device according to claim 1, comprising the second organic layer, wherein the crosslinking group is a crosslinking group selected from a crosslinking group A group.
(Crosslinking group A group)

[Wherein, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5]. When two or more R ^XL exist, they may be the same or different. When there are a plurality of n ^XL , they may be the same or different. * 1 represents a bonding position. These crosslinking groups may have a substituent, and when there are a plurality of such substituents, they may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ] The light emitting element according to claim 2, wherein the structural unit having a crosslinking group is a structural unit represented by Formula (3) or Formula (4).

[In the formula,
nA represents an integer of 0 to 5, and n represents 1 or 2. When a plurality of nA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
L ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent It is also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. If L ^A is plurally present, they may be the same or different.
X represents a crosslinking group selected from the aforementioned crosslinking group A group. When two or more X exist, they may be same or different. ]

[In the formula,
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When there are a plurality of mAs, they may be the same or different.
Ar ⁵ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent It may be
Ar ⁴ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ⁴ , Ar ⁵ and Ar ⁶ are each directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, or bonded through an oxygen atom or a sulfur atom And may form a ring.
K ^A represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups each have a substituent It is also good. R 'represents the same meaning as described above. If K ^A there are a plurality, they may be the same or different.
X 'represents a bridging group selected from the above bridging group A, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent . When a plurality of X 'are present, they may be the same or different. However, at least one X ′ is a crosslinking group selected from the aforementioned crosslinking group A group. ] The light emitting device according to any one of claims 1 to 3, wherein the metal complex represented by the formula (1) is a metal complex represented by the formula (1-A1) or the formula (1-A2) .

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A , E ^11A , E ^12A , E ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
Ring R ^2A represents a benzene ring, a fluorene ring, a spirobifluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, and these rings may have a substituent Good. When a plurality of the aforementioned substituents are present, they may be bonded to each other to form a ring together with the atoms to which they are bonded. When a plurality of rings R ^2A are present, they may be the same or different.
The substituent which ring R ^2A may have and R ^11A may be bonded to each other to form a ring together with the atoms to which they are bonded.
However, in Formula (1-A1), at least one of R ^11A is a group represented by Formula (Ar-1A), and in Formula (1-A2), at least one of R ^12A is It is a group represented by Ar-1A). ] The metal complex represented by Formula (1) is a metal complex represented by Formula (1-A1), and the metal complex represented by Formula (1-A1) is a compound represented by Formula (1-A1) The light emitting element according to claim 4, which is a metal complex represented by the formula -1), the formula (1-A1-2) or the formula (1-A1-3).

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
R ^21A , R ^22A , R ^23A and R ^24A are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, substituted amino A group or a halogen atom is represented, and these groups may have a substituent. When there are a plurality of R ^21A , R ^22A , R ^23A and R ^24A , they may be the same or different. R ^21A and R ^22A , R ^22A and R ^23A , R ^23A and R ^24A , and R ^11A and R ^21A may combine with each other to form a ring together with the atoms to which they are attached. ] The light emitting element according to claim 4, wherein the metal complex represented by the formula (1-A2) is a metal complex represented by the formula (1-A2-1) or the formula (1-A2-2).

[Wherein, M ¹ , n ¹ , n ² , R ^11A , R ^12A , R ^13A and A ¹ -G ¹ -A ² represent the same meaning as described above.
R ^21A , R ^22A , R ^23A and R ^24A are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, substituted amino A group or a halogen atom is represented, and these groups may have a substituent. When there are a plurality of R ^21A , R ^22A , R ^23A and R ^24A , they may be the same or different. R ^21A and R ^22A , R ^22A and R ^23A , R ^23A and R ^24A , and R ^11A and R ^21A may combine with each other to form a ring together with the atoms to which they are attached. ] The light emitting element according to any one of claims 1 to 6, wherein the group represented by the formula (Ar-1A) is a group represented by the formula (Ar-2A).

[Wherein, R ² represents the same meaning as described above.
Ring A ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring.
E ^1A , E ^2A and E ^3A each independently represent a nitrogen atom or a carbon atom. When E ^1A is a nitrogen atom, R ^1A is absent. When E ^2A is a nitrogen atom, R ^2A is absent. When E ^3A is a nitrogen atom, R ^3A is absent.
R ^1A , R ^2A and R ^3A are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen Represents an atom, and these groups may have a substituent.
R ^1A and R ^2A , and R ^2A and R ^3A may be combined to form a ring together with the atoms to which they are attached. ] The light emitting element according to claim 7, wherein the group represented by the formula (Ar-2A) is a group represented by the formula (Ar-3A).

[Wherein, R ² , R ^1A , R ^2A and R ^3A represent the same meaning as described above. ] The method according to claim 1, wherein the first organic layer further contains a compound represented by the formula (H-1), a polymer compound containing a constitutional unit represented by the formula (Y), or a combination thereof. The light emitting element as described in any one of 1-8.

[In the formula,
Ar ^H1 and Ar ^H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
n ^H1 and n ^H2 each independently represent 0 or 1. When there are a plurality of n ^H1 , they may be the same or different. Plural n ^H2 may be the same or different.
n ^H3 represents an integer of 0 or more and 10 or less.
L ^H1 represents an arylene group, a divalent heterocyclic group, or a group represented ^by- [C (R ^H11 ) ₂ ] n ^H11- , and these groups may have a substituent. When two or more L ^H1 are present, they may be the same or different. n ^H11 represents an integer of 1 or more and 10 or less. R ^H11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^H11 may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
L ^H2 represents a group represented by -N (-L ^H21 -R ^H21 )-. When two or more L ^H2 are present, they may be the same or different. L ^H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups may have a substituent. R ^H21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. ]

[ ^Wherein , Ar ^{Y 1} represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one type of divalent heterocyclic group are directly bonded, Groups may have a substituent. ]   The light emitting layer includes the second organic layer and the third organic layer, and the first organic layer is a first light emitting layer, and the second organic layer is a hole transporting layer or a second light emitting layer. The light emitting device according to any one of claims 1 to 9, which is a layer, and the third organic layer is an electron transport layer.   The method according to claim 1, further comprising the second organic layer and the third organic layer, wherein the first organic layer, the second organic layer, and the third organic layer are adjacent to each other. 10. The light emitting device according to any one of 10.