JP7017908B2 - Light emitting element - Google Patents

Description

The present invention relates to a light emitting device.

Light emitting devices such as organic electroluminescence devices can be suitably used for displays and lighting applications, and research and development are being carried out. For example, Patent Document 1 describes a structural unit derived from the compound M1 represented by the following formula, a structural unit derived from the compound M2 represented by the following formula, and a structural unit derived from the compound M3 represented by the following formula. The structural unit having a crosslinked group is represented by the following formula and a hole transport layer containing a crosslinked product of a copolymer composed of a molar ratio of 50: 42.5: 7.5. A light emitting element having a light emitting layer containing a metal complex B11 is described.

International Publication No. 2015/156235

However, the drive voltage of the above-mentioned light emitting element is not always sufficiently low.

Therefore, an object of the present invention is to provide a light emitting element having a low drive voltage.

［式中、
Ｍ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。
ｎ^１は１以上の整数を表し、ｎ^２は０以上の整数を表し、ｎ^１＋ｎ^２は２又は３である。
Ｍがロジウム原子又はイリジウム原子の場合、ｎ^１＋ｎ^２は３であり、Ｍがパラジウム原子又は白金原子の場合、ｎ^１＋ｎ^２は２である。
Ｅ^１は、炭素原子又は窒素原子を表す。Ｅ^１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Ｂ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。該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。環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。
Ｚ^１Ａは、＝Ｎ－で表される基又は＝Ｃ（Ｒ^Ｚ１Ａ）－で表される基を表す。Ｚ^１Ａが複数存在する場合、それらは同一であっても異なっていてもよい。Ｒ^Ｚ１Ａは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、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^１は、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、ハロゲン原子又は炭素原子数２以上３０以下のアルキル基を表し、これらの基は置換基を有していてもよい。Ｒ^１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。
Ａｒ^１Ａは、式（Ａｒ－１Ａ）で表される基を表す。Ａｒ^１Ａ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。
Ａ^１－Ｇ^１－Ａ^２は、アニオン性の２座配位子を表す。Ａ^１及びＡ^２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。Ｇ^１は、単結合、又は、Ａ^１及びＡ^２とともに２座配位子を構成する原子団を表す。Ａ^１－Ｇ^１－Ａ^２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。］

［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。該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。
Ｒ^２及びＲ^３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、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。］
［２］前記架橋基を有する構成単位を含む高分子化合物が、式（Ｘ）で表される構成単位を含む、［１］に記載の発光素子。

［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、アリーレン基と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。］
［３］前記架橋基が、架橋基Ａ群から選ばれる少なくとも１種である、［１］又は［２］に記載の発光素子。
（架橋基Ａ群）

［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。複数存在するｎ^ＸＬ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い。］
［４］前記架橋基を有する構成単位が、式（Ｚ）で表される構成単位又は式（Ｚ’）で表される構成単位である、［３］に記載の発光素子。

［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。
Ａｒ^３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、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。］

［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の整数を表す。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。
Ａｒ^５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。
Ａｒ^４及びＡｒ^６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^４、Ａｒ^５及びＡｒ^６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、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。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、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、架橋基Ａ群から選ばれる架橋基である。］
［５］前記式（１）で表される金属錯体が、式（１－１）で表される金属錯体である、［１］～［４］のいずれかに記載の発光素子。

［式中、
Ｍ、Ｚ^１Ａ、ｎ^１、ｎ^２、Ｒ^１、Ａｒ^１Ａ及びＡ^１－Ｇ^１－Ａ^２は、前記と同じ意味を表す。
環Ｂ^１は、ベンゼン環、ピリジン環又はジアザベンゼン環を表し、Ｅ^１Ｂ、Ｅ^２Ｂ、Ｅ^３Ｂ及びＥ^４Ｂは、それぞれ独立に、窒素原子又は炭素原子を表す。Ｅ^１Ｂ、Ｅ^２Ｂ、Ｅ^３Ｂ及びＥ^４Ｂ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。Ｅ^１Ｂが窒素原子の場合、Ｒ^１Ｂは存在しない。Ｅ^２Ｂが窒素原子の場合、Ｒ^２Ｂは存在しない。Ｅ^３Ｂが窒素原子の場合、Ｒ^３Ｂは存在しない。Ｅ^４Ｂが窒素原子の場合、Ｒ^４Ｂは存在しない。
Ｒ^１Ｂ、Ｒ^２Ｂ、Ｒ^３Ｂ及びＲ^４Ｂ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^１Ｂ、Ｒ^２Ｂ、Ｒ^３Ｂ及びＲ^４Ｂ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^１ＢとＲ^２Ｂ、Ｒ^２ＢとＲ^３Ｂ、及び、Ｒ^３ＢとＲ^４Ｂ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。］
［６］前記式（１－１）で表される金属錯体が、式（１－２）で表される金属錯体である、［５］に記載の発光素子。

［式中、Ｍ、Ｚ^１Ａ、ｎ^１、ｎ^２、Ｒ^１、Ａｒ^１Ａ、Ａ^１－Ｇ^１－Ａ^２、Ｒ^１Ｂ、Ｒ^２Ｂ、Ｒ^３Ｂ及びＲ^４Ｂは、前記と同じ意味を表す。］
［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。

［式中、Ｒ^２及びＲ^３は、前記と同じ意味を表す。
環Ａ^１は、ベンゼン環、ピリジン環又はジアザベンゼン環を表し、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。

［式中、Ｒ^２、Ｒ^３、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）で表される化合物及び式（Ｙ）で表される構成単位を含む高分子化合物からなる群より選ばれる少なくとも１種を更に含有する、［１］～［８］のいずれかに記載の発光素子。

［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。］

［式中、Ａｒ^Ｙ１は、アリーレン基、２価の複素環基、又は、アリーレン基と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１の有機層が、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料及び酸化防止剤からなる群より選ばれる少なくとも１種を更に含有する、［１］～［９］のいずれか一項に記載の発光素子。
［１１］前記第１の有機層と前記第２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。
［１２］前記第２の有機層が、前記陽極及び前記第１の有機層の間に設けられた層である、［１］～［１１］のいずれかに記載の発光素子。 The present invention provides the following [1] to [12].
[1] It has an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode.
The first organic layer contains a metal complex represented by the formula (1) and contains.
A light emitting device in which the second organic layer contains a crosslinked body of a polymer compound containing a structural unit having a crosslinking group.

[During the ceremony,
M represents a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n ¹ represents an integer of 1 or more, n ² represents an integer of 0 or more, and n ¹ + n ² is 2 or 3.
When M is a rhodium atom or an iridium atom, n ¹ + n ² is 3, and when M is a palladium atom or a platinum atom, n ¹ + n ² is 2.
E ¹ represents a carbon atom or a nitrogen atom. When a plurality of E ^1s exist, they may be the same or different.
Ring B represents an aromatic hydrocarbon ring or an aromatic heterocycle, and these rings may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring with the atom to which each is bonded. When there are a plurality of rings B, they may be the same or different.
Z ^1A represents a group represented by = N- or a group represented by = C (R ^Z1A )-. When there are a plurality of Z ^1A , they may be the same or different. R ^Z1A represents 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 atom, and these groups are substituents. May have.
R ¹ represents a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group, a halogen atom or an alkyl group having 2 or more and 30 or less carbon atoms. The group of may have a substituent. When there are a plurality of ^R1 , they may be the same or different.
Ar ^1A represents a group represented by the formula (Ar-1A). When there are a plurality of Ar ^1A , they may be the same or different.
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. A ¹ and A ² independently represent 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 together with A ¹ and A ² . When there are a plurality of A ¹ -G ¹ -A ² , they may be the same or different. ]

[During the ceremony,
Ring A represents an aromatic hydrocarbon ring or an aromatic heterocycle, and these rings may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring with the atom to which each is bonded.
R ² and R ³ independently represent 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, respectively. The group may have a substituent. ]
[2] The light emitting device according to [1], wherein the polymer compound containing the structural unit having a crosslinking group contains the structural unit represented by the formula (X).

[During the ceremony,
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups are substituents. May have. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different.
^RX1 , ^RX2 and ^RX3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
When there are a plurality of ^RX2 and ^RX3 , they may be the same or different. ]
[3] The light emitting device according to [1] or [2], wherein the cross-linking group is at least one selected from the cross-linking group A group.
(Crosslinking group A group)

[In the formula, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5. If there are multiple ^RXLs , they may be the same or different. A plurality of n ^XLs may be the same or different. * 1 represents the bonding position. These cross-linking groups may have substituents. ]
[4] The light emitting device according to [3], wherein the structural unit having a cross-linking group is a structural unit represented by the formula (Z) or a structural unit represented by the formula (Z').

[During the ceremony,
nA represents an integer of 0 to 5, and n represents 1 or 2. When there are a plurality of nA, 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.
^LA 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 have a substituent. May be 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 there are multiple ^LAs , they may be the same or different.
X represents a cross-linking group selected from the group A of cross-linking groups. If there are multiple X's, they may be the same or different. ]

[During the ceremony,
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents an integer of 0 or 1. If there are multiple 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 heterocycle are directly bonded, and these groups have a substituent. 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 each form a ring by directly bonding or bonding with a group other than the group bonded to the nitrogen atom to which the group is bonded via an oxygen atom or a sulfur atom. You may be doing it.
^KA 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 have a substituent. May be 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 there are multiple ^KAs , they may be the same or different.
X'represents a cross-linking group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group selected from the cross-linking group A group, and these groups may have a substituent. If there are multiple X's, they may be the same or different. However, at least one X'is a cross-linking group selected from the group A of cross-linking groups. ]
[5] The light emitting device according to any one of [1] to [4], wherein the metal complex represented by the formula (1) is a metal complex represented by the formula (1-1).

[During the ceremony,
M, Z ^1A , n ¹ , n ² , R ¹ , Ar ^1A and A ¹ -G ¹ -A ² have the same meanings as described above.
Ring B ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring, and E ^1B , E ^2B , E ^3B and E ^4B independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ^1B , E ^2B , E ^3B and E ^4B , they may be the same or different from each other. If E ^1B is a nitrogen atom, then R ^1B does not exist. If E ^2B is a nitrogen atom, then R ^2B does not exist. If E ^3B is a nitrogen atom, then R ^3B does not exist. If E ^4B is a nitrogen atom, then R ^4B does not exist.
R ^1B , R ^2B , R ^3B and R ^4B are independently hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group and substituted amino. Representing a group or a halogen atom, these groups may have a substituent. When there are a plurality of R ^1B , R ^2B , R ^3B and R ^4B , they may be the same or different from each other. R ^1B and R ^2B , R ^2B and R ^3B , and R ^3B and R ^4B may be bonded to each other to form a ring together with the atoms to which they are bonded. ]
[6] The light emitting device according to [5], wherein the metal complex represented by the formula (1-1) is a metal complex represented by the formula (1-2).

[In the formula, M, Z ^1A , n ¹ , n ² , R ¹ , Ar ^1A , A ¹ -G ¹ -A ² , R ^1B , R ^2B , R ^3B and R ^4B have the same meanings as described above. ]
[7] The light emitting device according to any one of [1] to [6], wherein the group represented by the formula (Ar-1A) is a group represented by the formula (Ar-2A).

[In the formula, R ² and R ³ have the same meanings as described above.
Ring A ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring, and E ^1A , E ^2A and E ^3A independently represent a nitrogen atom or a carbon atom. If E ^1A is a nitrogen atom, then R ^1A does not exist. If E ^2A is a nitrogen atom, then R ^2A does not exist. If E ^3A is a nitrogen atom, then R ^3A does not exist.
R ^1A , R ^2A and R ^3A independently have 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. Representing an atom, these groups may have substituents. R ^1A and R ^2A , and R ^2A and R ^3A may be bonded to each other to form a ring together with the atoms to which they are bonded. ]
[8] The light emitting device according to [7], wherein the group represented by the formula (Ar-2A) is a group represented by the formula (Ar-3A).

[In the formula, R ² , R ³ , R ^1A , R ^2A and R ^3A have the same meanings as described above. ]
[9] The first organic layer further contains at least one selected from the group consisting of a compound represented by the formula (H-1) and a polymer compound containing a structural unit represented by the formula (Y). The light emitting element according to any one of [1] to [8].

[During the ceremony,
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 independently represent 0 or 1, respectively. When there are a plurality of n ^H1 , they may be the same or different. A plurality of n ^H2s 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 ( ^RH11 ) ₂ ] n ^H11 −, and these groups may have a substituent. When there are a plurality of L ^H1 , they may be the same or different. n ^H11 represents an integer of 1 or more and 10 or less. ^RH11 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 ^RH11s existing may be the same or different, or may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
L ^H2 represents a group represented by -N (-L ^H21 - ^RH21 )-. When there are a plurality of L ^H2s , 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. ^RH21 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. ]

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. May be. ]
[10] The first organic layer further contains at least one selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material and an antioxidant. 1] The light emitting element according to any one of [9].
[11] The light emitting device according to any one of [1] to [10], wherein the first organic layer and the second organic layer are adjacent to each other.
[12] The light emitting device according to any one of [1] to [11], wherein the second organic layer is a layer provided between the anode and the first organic layer.

According to the present invention, it is possible to provide a light emitting element having a low drive voltage.

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

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

Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

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

In the formula representing the metal complex, the solid line representing the bond with the central metal means a covalent bond or a coordinate bond.

The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more (for example, 1 × 10 ³ to 1 × 10 ⁸ ).

The polymer compound may be a block copolymer, a random copolymer, an alternate copolymer, a graft copolymer, or any other embodiment.

The terminal group of the polymer compound is preferably a stable group because if the polymerization active group remains as it is, the light emission characteristics or the luminance life may be deteriorated when the polymer compound is used for manufacturing a light emitting element. Is. The terminal group of the polymer compound is preferably a group conjugated to the main chain, for example, an aryl group or a monovalent heterocyclic group bonded to the main chain of the polymer compound via a carbon-carbon bond. The group bonded to is mentioned.

The “small molecule compound” means a compound having no molecular weight distribution and having a molecular weight of 1 × ¹⁰⁴ or less.

The “constituent unit” means a unit existing in one or more in a polymer compound.

The "alkyl group" may be linear or branched. The number of carbon atoms of the linear alkyl group is usually 1 to 50, preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 without including the number of carbon atoms of the substituent. ~ 10. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 3 to 15, and even more preferably 3 to 15, not including the number of carbon atoms of the substituent. It is 10.
The alkyl group may have a substituent. Examples of the alkyl group 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, an isoamyl group, a 2-ethylbutyl group, a hexyl group and a heptyl. Examples thereof include a group, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, a decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-hexyldecyl group and a dodecyl group. Further, the alkyl group may be a group in which a part or all of hydrogen atoms in these groups are substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like. Examples of such an alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group and a 3- (4-methylphenyl) propyl group. Examples include a group, a 3- (3,5-di-hexylphenyl) propyl group and a 6-ethyloxyhexyl group.
The number of carbon atoms of the "cycloalkyl group" is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20 without including the number of carbon atoms of the substituent.
The cycloalkyl group may have a substituent. Examples of the cycloalkyl group include a cyclohexyl group, a cyclohexylmethyl group and a cyclohexylethyl group.

"Aryl group" means the remaining atomic group excluding one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 10, not including the number of carbon atoms of the substituent.
The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group, a 2-anthrasenyl group, a 9-anthrasenyl group, a 1-pyrenyl group, a 2-pyrenyl group and a 4-pyrenyl group. Examples thereof include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group and the like. Further, the aryl group may be a group in which a part or all of hydrogen atoms in these groups are 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 either linear or branched. The number of carbon atoms of the linear alkoxy group is usually 1 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The alkoxy group may have a substituent. Examples of the alkoxy group 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, a heptyloxy group, an octyloxy group, and 2 -Ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the like can be mentioned. Further, the alkoxy group may be a group in which a part or all of hydrogen atoms in these groups are substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The number of carbon atoms of the "cycloalkoxy group" is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The cycloalkoxy group may have a substituent. Examples of the cycloalkoxy group include a cyclohexyloxy group.

The number of carbon atoms of the "aryloxy group" is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms of the substituent.
The aryloxy group may have a substituent. Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group, a 1-pyrenyloxy group and the like. Further, the aryloxy group may be a group in which a part or all of hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like.

A "p-valent heterocyclic group" (p represents an integer of 1 or more) is p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. It means the remaining atomic group excluding the hydrogen atom of. Among the p-valent heterocyclic groups, it is the remaining atomic group obtained by removing p hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the aromatic heterocyclic compound. A "p-valent aromatic heterocyclic group" is preferred.
The "aromatic heterocyclic compound" is a complex such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphor, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinolin, carbazole, dibenzophosphol and the like. Even if the compound whose ring itself exhibits aromaticity and the heterocycle itself such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran do not exhibit aromaticity, the aromatic ring is fused to the heterocycle. Means a compound.

The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent and is usually 2 to 60, preferably 4 to 20.
The monovalent heterocyclic group may have a substituent. Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a frill group, a pyridinyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group, a triazinyl group and the like. Further, the monovalent heterocyclic group may be a group in which a part or all of hydrogen atoms in these groups are substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like.

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

The "amino group" may have a substituent, and a substituted amino group is preferable. As the substituent contained in the amino group, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
As the substituted amino group, a disubstituted amino group is preferable. Examples of the disubstituted amino group include a dialkylamino group, a dicycloalkylamino group and a diarylamino group.
Examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, a bis (4-methylphenyl) amino group, a bis (4-tert-butylphenyl) amino group, and a bis (3,5-di-). tert-Butylphenyl) Amino group can be mentioned.

The "alkenyl group" may be either linear or branched. The number of carbon atoms of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, not including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkenyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 4 to 20.
The number of carbon atoms of the "cycloalkenyl group" is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkenyl group and the cycloalkenyl group may have a substituent. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group and a 5-hexenyl group. Examples thereof include a 7-octenyl group and a group in which a part or all of hydrogen atoms in these groups are substituted with a substituent. Examples of the cycloalkenyl group include a cyclohexenyl group, a cyclohexadienyl group, a cyclooctatrienyl group, a norbornylenyl group, and a group in which a part or all of hydrogen atoms in these groups are substituted with a substituent. ..

The "alkynyl group" may be either linear or branched. The number of carbon atoms of the alkynyl group is usually 2 to 20, preferably 3 to 20, without including the carbon atom of the substituent. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, without including the carbon atom of the substituent.
The number of carbon atoms of the "cycloalkynyl group" is usually 4 to 30, preferably 4 to 20, without including the carbon atom of the substituent.
The alkynyl group and the cycloalkynyl group may have a substituent. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group and a 5-hexynyl group. In addition, a group in which a part or all of the hydrogen atom in these groups is substituted with a substituent can be mentioned. Examples of the cycloalkynyl group include a cyclooctynyl group and the like.

The "arylene group" means the remaining atomic group excluding the two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the number of carbon atoms of the substituent.
The arylene group may have a substituent. Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracendyl group, a phenantrenidyl group, a dihydrophenantrangeyl group, a naphthalsendiyl group, a fluorinatedyl group, a pyrenidyl group, a perylenediyl group, a chrysendiyl group, and these groups. Examples thereof include a group in which a part or all of a hydrogen atom is substituted with a substituent. The arylene group is preferably a group represented by the formulas (A-1) to (A-20). The arylene group includes a group in which a plurality of these groups are bonded.

In the formula, R and Ra independently represent ^a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and preferably a hydrogen atom and an alkyl group. , Cycloalkyl group, aryl group or monovalent heterocyclic group. ^A plurality of R and Ra may be the same or different from each other, and Ra may be bonded to each other to form ^a ring together with the atoms to which each is bonded.

The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, and more preferably 4 to 15, not including the number of carbon atoms of the substituent.
The divalent heterocyclic group may have a substituent. Examples of the divalent heterocyclic group include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, aclysine, dihydroaclysine, furan, thiophene and azole. Examples thereof include diazoles or triazoles, which are divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring. Further, the divalent heterocyclic group may be a group in which a part or all of hydrogen atoms in these groups are substituted with a substituent. The divalent heterocyclic group is preferably a group represented by the formulas (AA-1) to (AA-34). A divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

In the formula, R and ^Ra have the same meanings as described above.

The "crosslinking group" is a group capable of forming a new bond by subjecting it to heat treatment, ultraviolet irradiation treatment, near-ultraviolet irradiation treatment, visible light irradiation treatment, infrared irradiation treatment, radical reaction, or the like. Preferably, it is a cross-linking group represented by the formulas (XL-1) to (XL-17) of the group A of the cross-linking group.

The "substituted group" is a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group and an alkenyl group. , Cycloalkenyl group, alkynyl group or cycloalkynyl group. The substituent may be a cross-linking group.

<Light emitting element>
The light emitting element of the present embodiment has an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode, and the first organic layer is the formula (1). A light emitting element containing a crosslinked body of a polymer compound containing a metal complex represented by the above and containing a structural unit (hereinafter, also referred to as “crosslinked structural unit”) in which a second organic layer has a crosslinking group. ..

Examples of the method for forming the first organic layer and the second organic layer include a dry method such as a vacuum vapor deposition method and a wet method such as a spin coating method and an inkjet printing method, and the wet method is preferable.

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

When the second organic layer is formed by the wet method, it is preferable to use the second ink described later. After forming the layer with the second ink, the polymer compound containing the cross-linking structural unit in the layer can be cross-linked by heating or irradiating with light. The cross-linking of the polymer compound containing the cross-linking structural unit is preferably carried out by heating. When the polymer compound containing the crosslinked building block is crosslinked (a crosslinked body of the polymer compound containing the crosslinked building block) and is contained in the second organic layer, the second organic layer is substantially relative to the solvent. Is 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., and even more preferably 180 ° C. to 210 ° C. ..
The heating time is usually 0.1 to 1000 minutes, preferably 0.5 to 500 minutes, more preferably 1 to 120 minutes, and even more preferably 10 to 60 minutes. ..

The types of light used for light irradiation are, for example, ultraviolet light, near-ultraviolet light, and visible light.

Examples of the method for analyzing the components contained in the first organic layer or the second organic layer include a chemical separation analysis method such as extraction, infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), and the like. Instrumental analysis methods such as mass spectrometry (MS), and analysis methods that combine chemical separation analysis methods and instrumental analysis methods can be mentioned.

By performing solid-liquid extraction of the first organic layer or the second organic layer using an organic solvent such as toluene, xylene, chloroform, or tetrahydrofuran, a component (insoluble) that is substantially insoluble in the organic solvent (insoluble). It is possible to separate a component) and a component (dissolving component) that dissolves in an organic solvent. 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 analysis.

<First organic layer>
[Metal complex represented by the formula (1)]
The metal complex represented by the formula (1) is usually a metal complex that exhibits phosphorescence emission at room temperature (25 ° C.), and is preferably a metal complex that exhibits emission from a triplet excited state at room temperature.

The metal complex represented by the formula (1) has M, which is a central metal, a ligand whose number is defined by the subscript n ¹ , and a coordination whose number is defined by the subscript n ² . It is composed of children.

Since the driving voltage of the light emitting element of the present embodiment is lower, M is preferably an iridium atom or a platinum atom, and more preferably an iridium atom.

When M is a rhodium atom or an iridium atom, n ¹ is preferably 2 or 3, and more preferably 3.

When M is a palladium atom or a platinum atom, n ¹ is preferably 2.

E ¹ is preferably a carbon atom.

The number of carbon atoms of the aromatic hydrocarbon ring in ring B 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.
Examples of the aromatic hydrocarbon ring in ring B include a benzene ring, a naphthalene ring, an indene ring, a fluorene ring, a phenanthrene ring, a dihydrophenanthrene ring, and a ring obtained by condensing these rings. The aromatic hydrocarbon ring in ring B is preferably a benzene ring, a naphthalene ring, an inden ring, a fluorene ring, a phenanthrene ring or a dihydrophenanthrene ring, and more preferably a benzene ring, a fluorene ring or a dihydrophenanthrene ring. More preferably, it is a benzene ring, and these rings may have a substituent.

The number of carbon atoms of the aromatic heterocycle in the ring B is usually 4 to 60, preferably 4 to 20, not including the number of carbon atoms of the substituent.
Examples of the aromatic heterocycle in ring B include a pyrrole ring, a diazole ring, a furan ring, a thiophene ring, a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, an indol ring, a benzodiazole ring, a benzofuran ring, and a benzothiophene. Examples thereof include a ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a ring in which an aromatic ring is condensed with these rings. The aromatic heterocycle in ring B is preferably a pyrrole ring, a diazole ring, a furan ring, a thiophene ring, a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, an indole ring, a benzodiazole ring, a benzofuran ring, and the like. It is a benzothiophene ring, a carbazole 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, and even more preferably a pyridine ring or a diazabenzene ring. These rings may have substituents.

Ring B is preferably a 5- or 6-membered aromatic hydrocarbon ring or a 5- or 6-membered aromatic heterocycle because the driving voltage of the light emitting element of the present embodiment is lower. It is preferably a benzene ring, a fluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a benzene ring, a pyridine ring or a diazabenzene ring, and particularly preferably benzene. It is a ring, and these rings may have a substituent. When ring B is a 6-membered aromatic heterocycle, E ¹ is preferably a carbon atom.

As the substituent that the ring B may have, 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 is preferable. , Alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, monovalent heterocyclic group, substituted amino group or fluorine atom is more preferable, alkyl group, cycloalkyl group, aryl group, monovalent heterocycle. A group or a substituted amino group is more preferable, an alkyl group, a cycloalkyl group or an aryl group is particularly preferable, and these groups may further have a substituent.

As the aryl group in the substituent which the ring B may have, a phenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a dihydrophenanthrenyl group, a fluorenyl group or a pyrenyl group is preferable, and a phenyl group, a naphthyl group or a phenyl group or a naphthyl group or A fluorenyl group is more preferable, a phenyl group is further preferable, and these groups may have a substituent.

The monovalent heterocyclic group in the substituent that the ring B may have includes a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and an azacarbazolyl group. , Diazacarbazolyl group, phenoxadinyl group or phenothiazinyl group is preferable, pyridyl group, pyrimidinyl group, triazinyl group, dibenzofuranyl group, dibenzothienyl group or carbazolyl group is more preferable, and pyridyl group, pyrimidinyl group or triazinyl group is preferable. More preferably, these groups may have substituents.

Among the substituted amino groups in the substituents that the ring B may have, the substituent of the amino group is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups are further substituted. It may have a group. The examples and preferred ranges of aryl groups in the substituents of the amino group are the same as the examples and preferred ranges of aryl groups in the substituents that ring B may have. The example and preferred range of the monovalent heterocyclic group in the substituent of the amino group is the same as the example and preferred range of the monovalent heterocyclic group in the substituent that the ring B may have.

Among the substituents that the ring B may have, the aryl group, the monovalent heterocyclic group and the substituted amino group have a lower driving voltage of the light emitting element of the present embodiment, and thus the formula (DA). ), (DB) or (DC) is preferable, and the group represented by the formula (DA) or (DC) is more preferable.

During the ceremony
m ^DA1 , m ^DA2 , and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 , and Ar ^DA3 , they may be the same or different from each other.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of ^TDAs may be the same or different.

During the ceremony
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 , and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. Multiple G ^DAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, even if these groups have a substituent. good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 , and Ar ^DA7 , they may be the same or different from each other.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of ^TDAs may be the same or different.

During the ceremony
m ^DA1 represents an integer greater than or equal to 0.
Ar ^DA1 represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are a plurality of Ar ^DA1 , they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are usually integers of 10 or less, preferably 5 or less, more preferably 2 or less, and further. It is preferably 0 or 1. m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are preferably the same integer, and m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are It is more preferable that they are the same integer.

^GDA is preferably a group represented by the formulas (GDA-11) to (GDA-15), and more preferably a group represented by the formulas (GDA-11) to the formula (GDA-14). , More preferably a group represented by the formula (GDA-11) or the formula (GDA-14), and particularly preferably a group represented by the formula (GDA-11).

During the ceremony
* Represents a bond with Ar ^DA1 in the formula (DA), Ar ^DA1 in the formula (DB), Ar ^DA2 in the formula (DB), or Ar ^DA3 in the formula (DB).
** represents a combination with Ar ^DA2 in the formula (DA), Ar ^DA2 in the formula (DB), Ar ^DA4 in the formula (DB), or Ar ^DA6 in the formula (DB). ..
*** is a combination with Ar ^DA3 in the formula (DA), Ar ^DA3 in the formula (DB), Ar DA5 in the formula (DB), or Ar ^DA7 in the formula ( ^DB ). show.
^RDA 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. If there are multiple R ^DAs , they may be the same or different.

The 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. You may.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably a phenylene group, a fluorinatedyl group or a carbazolediyl group, and more preferably a formula (A-1) to a formula. (A-3), formula (A-8), formula (A-9), formula (AA-10), formula (AA-11), formula (AA-33) or formula (AA-34). A group represented by the formulas (ArDA-1) to (ArDA-5), and particularly preferably a group represented by the formulas (ArDA-1) to (ArDA-3). It is particularly preferable that it is a group represented by the formula (ArDA-1).

During the ceremony
R ^DA has the same meaning as described above.
^RDB 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 RDBs exist, they may be the same or different.

The ^RDB 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, and these. The group may have a substituent.

^TDA is preferably a group represented by the formulas (TDA-1) to (TDA-3), and more preferably a group represented by the formula (TDA-1).

In the formula, R ^DA and R ^DB have the same meanings as described above.

The groups represented by the formula (DA) are preferably groups represented by the formulas (DA1) to (DA4), and more preferably the formulas (DA1) and the formula (D-A4). It is a group represented by A3) or the formula (D-A4), more preferably a group represented by the formula (D-A1) or the formula (D-A4), and particularly preferably a group represented by the formula (D-A1). It is a group represented by.

During the ceremony
R ^p1 , R ^p2 , R ^p3 and R ^p4 independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom, respectively. When there are a plurality of R ^p1 , R ^p2 and R ^p4 , they may be the same or different from each other.
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. A plurality of np1s may be the same or different.

The group represented by the formula (DB) is preferably a group represented by the formulas (DB1) to (DB3), and more preferably the formula (DB1) or the formula (D—). It is a group represented by B3), and more preferably a group represented by the formula (DB1).

During the ceremony
R ^p1 , R ^p2 and R ^p3 independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom, respectively. When there are a plurality of R ^p1 and R ^p2 , they may be the same or different from each other.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. When a plurality of np1 and np2 exist, they may be the same or different from each other.

The group represented by the formula (DC) is preferably a group represented by the formulas (DC1) to the formula (DC4), and more preferably the groups represented by the formulas (DC1) to the formula (D-C4). It is a group represented by the formula (C3), more preferably a group represented by the formula (DC1) or the formula (DC2), and particularly preferably a group represented by the formula (DC1). ..

During the ceremony
R ^p4 , R ^p5 and R ^p6 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 , R ^p5 and R ^p6 , they may be the same or different from each other.
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, more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0. np4 is preferably an integer of 0 to 2. np5 is preferably an integer of 1 to 3. np6 is preferably an integer of 0 to 2.

R ^p1 , R ^p2 , R ^p3 , R ^p4 , R ^p5 and R ^p6 are preferably alkyl or cycloalkyl groups, more preferably methyl, ethyl, isopropyl, tert-butyl, hexyl, etc. It is a 2-ethylhexyl group, a cyclohexyl group or a tert-octyl group, 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.

Examples of the group represented by the formula (DA) include groups represented by the formulas (DA-1) to (DA-12).

In the formula, ^RD is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a tert-octyl group, a cyclohexyl group, a methoxy group, a 2-ethylhexyloxy group or a cyclohexyloxy group. Represents. If there are multiple ^RDs , they may be the same or different.

Examples of the group represented by the formula (DB) include groups represented by the formulas (DB-1) to (DB-4).

In the formula, R ^D has the same meaning as described above.

Examples of the group represented by the formula (DC) include groups represented by the formulas (DC-1) to the formula (DC-13).

In the formula, R ^D has the same meaning as described above.

The ^RD is 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.

When there are a plurality of substituents that the ring B may have, they may be bonded to each other to form a ring together with the atoms to which the rings B are bonded, but the metal complex represented by the formula (1). Since the maximum peak wavelength of the emission spectrum of the above is a short wavelength, it is preferable not to form a ring.

The substituent which the ring B may have may further include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, and a monovalent heterocycle. A group, a substituted amino group or a halogen atom is preferable, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom is more preferable, and an alkyl group or a cycloalkyl group is preferable. Groups or aryl groups are more preferred, alkyl groups are particularly preferred, and these groups may further have substituents.

Examples and preferred ranges of the aryl group, the monovalent heterocyclic group or the substituted amino group in the substituent which the substituent which may be possessed by the ring B may further possess may be contained in the ring B. Same as for examples and preferred ranges of aryl groups, monovalent heterocyclic groups or substituted amino groups in good substituents.

Z ^1A is preferably a group represented by = N−.

R ^Z1A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom, and more preferably a hydrogen atom. It is 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, particularly preferably a hydrogen atom, and these groups are further substituted. It may have a group.

Examples of aryl groups, monovalent heterocyclic groups or substituted amino groups in R ^Z1A and preferred ranges are examples of aryl groups, monovalent heterocyclic groups or substituted amino groups in the substituents that ring B may have. And the same as the preferred range.

The examples and preferred ranges of substituents that R ^Z1A may have are the same as the examples and preferred ranges of substituents that ring B may further have.

R ¹ is preferably a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group, a fluorine atom or an alkyl group having 2 or more and 30 or less carbon atoms, and more preferably. Is a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a substituted amino group or an alkyl group having 2 or more and 30 or less carbon atoms, and more preferably a cycloalkyl group, an aryl group or an alkyl group having 2 or more and 30 carbon atoms. The following alkyl groups, particularly preferably an aryl group or an alkyl group having 2 or more and 30 or less carbon atoms, particularly preferably an aryl group, and these groups may further have a substituent. ..

Examples of aryl groups, monovalent heterocyclic groups or substituted amino groups in ^R1 and preferred ranges are examples of aryl groups, monovalent heterocyclic groups or substituted amino groups in the substituents that ring B may have. And the same as the preferred range.

The number of carbon atoms of the alkyl group in R ¹ does not include the number of carbon atoms of the substituent, and is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more. The number of carbon atoms of the alkyl group in R ¹ does not include the number of carbon atoms of the substituent, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably. It is an alkyl group of 10 or less, particularly preferably 8 or less.

When R ¹ is an alkyl group having 2 or more carbon atoms and 30 or less carbon atoms, the substituent that R ¹ may have is preferably a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an aryloxy group. It is a monovalent heterocyclic group, a substituted amino group or a halogen atom, more preferably a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom. , More preferably, it is a cycloalkyl group or an aryl group, and these groups may further have a substituent.

In the case where R ¹ is an alkyl group having 2 or more carbon atoms and 30 or less carbon atoms, examples and preferable ranges of aryl groups, monovalent heterocyclic groups or substituted amino groups in the substituents that R ¹ may have are rings. It is the same as the example and preferable range of the aryl group, the monovalent heterocyclic group or the substituted amino group in the substituent that B may have.

Since R ¹ facilitates the synthesis of the metal complex represented by the formula (1), it is preferably an alkyl group having no substituent and having 2 or more and 30 or less carbon atoms.

The alkyl group having 2 or more and 30 or less carbon atoms in R ¹ is preferably a branched alkyl group having 3 or more and 30 or less carbon atoms because the driving voltage of the light emitting element of the present embodiment is lower, and more preferably. It is a branched alkyl group having 3 or more and 15 or less carbon atoms, more preferably a branched alkyl group having 3 or more and 10 or less carbon atoms, and particularly preferably a branched alkyl group having 4 or more and 10 or less carbon atoms. Particularly preferably, it is a branched alkyl group having 5 or more and 8 or less carbon atoms. These groups preferably have no substituents.

Among the alkyl groups in ^R1 , the branched alkyl groups include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1,1-dimethylbutyl group and 1 -Ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylpentyl group, 1,1-diethylpropyl group, 1,2-dimethylpentyl group, 1,1-dimethylhexyl group, 1-ethyl-1-methylpentyl group , 1,1,3,3-tetramethylbutyl group, 1,2-dimethylhexyl group, 1-propylpentyl group, 2-ethylhexyl group, 1,1-dimethylheptyl group, 1,1-dipropylbutyl group, A 1-butylhexyl group, a 1-propylheptyl group, a 1,1,3,7-tetramethyloctyl group and a 1,1,2-triethyloctyl group are preferable.

When R ¹ is other than an alkyl group having 2 or more carbon atoms and 30 or less carbon atoms, examples of substituents that R ¹ may have and a preferable range are further included in the substituents that ring B may have. It is the same as the example and preferable range of substituents which may be present.

[A group represented by (Equation Ar-1A)]
The example and preferred range of the aromatic hydrocarbon ring in ring A is the same as the example and preferred range of the aromatic hydrocarbon ring in ring B. The example and preferred range of the aromatic heterocycle in ring A is the same as the example and preferred range of the aromatic hydrocarbon ring in ring B.

Ring A is preferably a 5- or 6-membered aromatic hydrocarbon ring or a 5- or 6-membered aromatic heterocycle because the driving voltage of the light emitting element of the present embodiment is lower. It is preferably a benzene ring, a fluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a benzene ring, a pyridine ring or a diazabenzene ring, and particularly preferably benzene. It is a ring, and these rings may have a substituent.

As the substituent that the ring A may have, 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 is preferable. , Alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, monovalent heterocyclic group, substituted amino group or fluorine atom is more preferable, alkyl group, cycloalkyl group, aryl group, monovalent heterocycle. A group or a substituted amino group is more preferable, an alkyl group, a cycloalkyl group or an aryl group is particularly preferable, an alkyl group is particularly preferable, and these groups may further have a substituent.

Examples and preferred ranges of the aryl group in the substituent that ring A may have and the monovalent heterocyclic group or the substituted amino group are the aryl group and monovalent in the substituent that ring B may have. It is the same as the example and preferable range of a heterocyclic group or a substituted amino group.

When there are a plurality of substituents that the ring A may have, they may be bonded to each other to form a ring together with the atoms to which the rings A are bonded, but the metal complex represented by the formula (1). Since the maximum peak wavelength of the emission spectrum of the above is a short wavelength, it is preferable not to form a ring.

Examples and preferred ranges of substituents that may be further possessed by the substituents that ring A may have are those of the substituents that may be further possessed by ring B. Same as example and preferred range.

R ² and R ³ are preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom, and more preferably an alkyl group. It is a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group or an aryl group, particularly preferably an alkyl group, and these groups are further preferred. It may have a substituent.

Examples and preferred ranges of aryl groups, monovalent heterocyclic groups or substituted amino groups in R ² and R ³ are aryl groups in substituents that ring B may have, monovalent heterocyclic groups or substituted aminos. Same as the group example and preferred range.

The alkyl group in R ² and R ³ is preferably an alkyl group having 1 to 7 carbon atoms, and more preferably an alkyl group having 1 to 7 carbon atoms, because the synthesis of the metal complex represented by the formula (1) is facilitated. It is an alkyl group of 1 to 5, more preferably an alkyl group having 1 to 3 carbon atoms, and it is particularly preferable that these groups have no substituent.

The examples and preferred ranges of substituents that R ² and R ³ may have are the same as the examples and preferred ranges of substituents that R ¹ may have.

It is preferable that R ² and R ³ are the same.

The group represented by the formula (Ar-1A) is preferably the group represented by the formula (Ar-2A) because the driving voltage of the light emitting element of the present embodiment is lower.

E ^1A , E ^2A and E ^3A are preferably carbon atoms.

R ^1A , R ^2A and R ^3A are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom, and more. A hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group is preferable, and a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group are more preferable. The group may have a substituent.

R ^1A and R ^3A are particularly preferably a hydrogen atom, an alkyl group or an aryl group, and particularly preferably a hydrogen atom, and these groups may have a substituent.
R ^2A is particularly preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably an alkyl group or an aryl group, particularly preferably an alkyl group, and these groups have a substituent. May be.

Examples and preferred ranges of aryl groups, monovalent heterocyclic groups or substituted amino groups in R ^1A , R ^2A and R ^3A are aryl groups and monovalent heterocyclic groups in the substituents that ring B may have. Alternatively, it is the same as the example of the substituted amino group and the preferable range.

Examples and preferred ranges of substituents that R ^1A , R ^2A and R ^3A may have are examples and preferred ranges of substituents that ring B may further have. Is the same as.

R ^1A and R ^2A , and R ^2A and R ^3A may be bonded to each other to form a ring together with the atom to which each bond is formed, but it is preferable not to form a ring.

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

[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 A1 ^- G1 ^{- A2} is different from the ligand whose ^number is defined by the subscript n1.

During the ceremony
* Represents a site that binds to M.
^RL1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, and these groups may have a substituent. A plurality of ^RL1s may be the same or different.
^RL2 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.

^RL1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a fluorine atom, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, and these groups are substituted. It may have a group.

^RL2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group or a cycloalkyl group, even if these groups have a substituent. good.

<Metal complex represented by the formula (1-1)>
The metal complex represented by the formula (1) is preferably a metal complex represented by the formula (1-1) because the driving voltage of the light emitting device of the present embodiment is lower.

E ^1B , E ^2B , E ^3B and E ^4B are preferably carbon atoms.

R ^1B , R ^2B , R ^3B and R ^4B preferably have a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a fluorine atom. A hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group is more preferable, and a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group is more preferable. Yes, these groups may further have substituents.

R ^1B , R ^3B and R ^4B are particularly preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom, and these groups may further have a substituent.
R ^2B is particularly preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom, and these groups may further have a substituent.

Examples and preferred ranges of aryl groups, monovalent heterocyclic groups or substituted amino groups in R ^1B , R ^2B , R ^3B and R ^4B are aryl groups and monovalent groups in the substituents that ring B may have. Same as for examples and preferred ranges of heterocyclic or substituted amino groups.

Examples and preferred ranges of substituents that R ^1B , R ^2B , R ^3B and R ^4B may have are examples of substituents that ring B may further have. And the same as the preferred range.

When ring B ¹ is a pyridine ring, ring B ¹ may be a pyridine ring in which E ^1B is a nitrogen atom, a pyridine ring in which E ^2B is a nitrogen atom, or a pyridine ring in which E ^3B is a nitrogen atom. It is more preferable that E ^2B is a pyridine ring which is a nitrogen atom.
When ring B ¹ is a diazabenzene ring, ring B ¹ is preferably a pyrimidine ring in which E ^2B and E ^4B are nitrogen atoms, or a pyrimidine ring in which E ^1B and E ^3B are nitrogen atoms, and E ^2B . ^{And E4B} is more preferably a pyrimidine ring which is a nitrogen atom.
Ring B ¹ is preferably a benzene ring.

The metal complex represented by the formula (1-1) is preferably the metal complex represented by the formula (1-2) because the driving voltage of the light emitting device of the present embodiment is lower.

Examples of the metal complex represented by the formula (1) include a metal complex represented by the following formula.

During the ceremony
Z ^A represents a group represented by -CH = or a group represented by -N =. If there are multiple ^ZAs , they may be the same or different. ^ZA is preferably a group represented by −N =.
Z ^B represents a group represented by —O— or a group represented by —S—.

<Method for producing a metal complex represented by the 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, a functional group conversion reaction of the ligand of the metal complex may be carried out.

The metal complex represented by the formula (1) is, for example, a step A in which a compound represented by the formula (M-1) is reacted with a metal compound or a hydrate thereof, and a compound obtained in the step A. (Hereinafter, also referred to as "metal complex intermediate (1)") and a compound represented by the formula (M-1) or a precursor of a ligand represented by A1 ^- G1 ^{- A2} . It can be produced by a method including the reaction step B.

In the formula, M, n ¹ , n ² , E ¹ , ring B, Z ^1A , R ¹ , Ar ^1A and A ¹ -G ¹ -A ² have the same meanings as described above.

In step A, examples of the metal compound include iridium chloride, iridium (acetylacetonato) iridium (III), chloro (cyclooctadiene) iridium (I) dimer, iridium (III) acetate and the like; Examples thereof include platinum compounds such as potassium; palladium compounds such as palladium chloride and palladium acetate; and rhodium compounds such as rhodium chloride. Examples of the hydrate of the metal compound include iridium chloride / trihydrate and rhodium chloride / trihydrate.

Examples of the metal complex intermediate (1) include a metal complex represented by the formula (M-2).

In the formula, M, E ¹ , ring B, Z ^1A , R ¹ , Ar ^1A and A ¹ -G ¹ -A ² have the same meanings as described above.
n ^1'represents 1 or 2. When M is a rhodium atom or an iridium atom, n ^1'is 2, and when M is a palladium atom or a platinum atom, n 1'is ¹ .

In step A, the amount of the compound represented by the formula (M-1) is usually 2 to 20 mol with respect to 1 mol of the metal compound or its hydrate.

In step B, the amount of the compound represented by the formula (M-1) or the precursor of the ligand represented by A ¹ − G ¹ − A ² is the amount with respect to 1 mol of the metal complex intermediate (1). Usually 1 to 100 mol.

In step B, the reaction is preferably carried out in the presence of a silver compound such as silver trifluoromethanesulfonate. When a silver compound is used, the amount thereof is usually 2 to 20 mol per 1 mol of the metal complex intermediate (1).

Step A and step B are usually carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol and 2-ethoxyethanol; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentylmethyl ether and jigglime. Halogen solvents such as methylene chloride and chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene and mesitylen; N, N-dimethylformamide, N, N-dimethylacetamide Amido-based solvents such as, acetone, dimethylsulfoxide, water and the like.

In step A and step B, the reaction time is usually from 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 compounds, catalysts and solvents used in the reaction described in <Method for producing a metal complex represented by the 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 embodiment is low, the first organic layer has the metal complex represented by the formula (1) and the hole injecting property, the hole transporting property, the electron injecting property and the electron transporting property. It is preferable that the layer contains a host material having at least one of the functions. When the first organic layer is a layer containing the metal complex represented by the formula (1) and the host material, the first organic layer may contain one kind of the host material alone. It may contain two or more kinds.

When the first organic layer is a layer containing a metal complex represented by the formula (1) and a host material, the content of the metal complex represented by the formula (1) is represented by the formula (1). When the total of the metal complex and the host material is 100 parts by mass, it is usually 0.1 to 50 parts by mass, preferably 1 to 45 parts by mass, and more preferably 5 to 40 parts by mass. More preferably, it is 10 to 30 parts by mass.

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

As the host material, since the light emitting element of the present embodiment can be produced by the solution coating process, it may be soluble in a solvent capable of dissolving the metal complex represented by the formula (1). preferable.

The host material is classified into a small molecule compound (small molecule host) and a polymer compound (polymer host), and the first organic layer may contain any host material. As the host material that may be contained in the first organic layer, a small molecule compound is preferable.

[Small molecule host]
A small molecule compound (hereinafter referred to as "small molecule host") preferable as a host material will be described.

The small molecule host is preferably a compound represented by the formula (H-1).

Ar ^H1 and Ar ^H2 are phenyl group, fluorenyl group, spirobifluorenyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, thienyl group, benzothienyl group, dibenzothienyl group, frill group, benzofuryl. Group, dibenzofuryl group, pyrrolyl group, indolyl group, azaindrill group, carbazolyl group, azacarbazolyl group, diazacarbazolyl group, phenoxadinyl group or phenothiazinyl group is preferable, and phenyl group, fluorenyl group, spirobifluole Nyl group, pyridyl group, pyrimidinyl group, triazinyl group, dibenzothienyl group, dibenzofuryl group, carbazolyl group or azacarbazolyl group is more preferable, and fluorenyl group, spirobifluorenyl group, dibenzothienyl group, dibenzofuryl group or It is more preferably a carbazolyl group, particularly preferably a group represented by the formula (TDA-3), and these groups may have a substituent.

As the substituent that Ar ^H1 and Ar ^H2 may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group is preferable, 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 further 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 further preferably 1.

^RH11 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, and a hydrogen atom or an alkyl group. More preferably, these groups may have a substituent.

L ^H1 is preferably an arylene group or a divalent heterocyclic group.

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

As the substituent that L ^H1 may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group and an aryl group are preferable. A group or a monovalent heterocyclic group is more preferable, an alkyl group, an aryl group or a monovalent heterocyclic group is more preferable, a monovalent heterocyclic group is particularly preferable, and these groups further have a substituent. May be 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 example of the arylene group or divalent heterocyclic group represented by L ^H21 are the same as the definition and example of the arylene group or divalent heterocyclic group represented by L ^H1 .

^RH21 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 represented by ^RH21 and the monovalent heterocyclic group are the same as the definitions and examples of the aryl group represented by Ar ^H1 and Ar ^H2 and the monovalent heterocyclic group.

The definitions and examples of substituents that ^RH21 may have are similar to the definitions and examples of substituents that Ar ^H1 and Ar ^H2 may have.

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

In the formula, Ar ^H1 , Ar ^H2 , n ^H3 and L ^H1 have the same meanings as described above.

Examples of the compound represented by the formula (H-1) include compounds represented by the formulas (H-101) to (H-118).

Examples of the polymer compound used as 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]
A preferred polymer compound as a host compound (hereinafter referred to as “polymer host”) is preferably a polymer compound containing a structural unit represented by the formula (Y).

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

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

In the divalent group in which the arylene group represented by Ar ^Y1 and the divalent heterocyclic group are directly bonded, the more preferable range and the more preferable range of the arylene group and the divalent heterocyclic group are the above-mentioned Ar, respectively. It is the same as the more preferable range of the arylene group represented by ^Y1 and the divalent heterocyclic group, and further the preferable range.

Examples of the "divalent group in which the arylene group and the divalent heterocyclic group are directly bonded" include a group represented by the following formula, which may have a substituent.

In the formula, ^RXX 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.

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

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

Examples of the structural unit represented by the formula (Y) include the structural units represented by the formulas (Y-1) to (Y-10), from the viewpoint of the drive voltage of the light emitting element of the present embodiment. Is preferably a structural unit represented by the formulas (Y-1) to (Y-3), and is preferably expressed by the formulas (Y-4) to (Y-4) from the viewpoint of electron transportability of the light emitting device of the present embodiment. It is a structural unit represented by the formula (Y-7), and is preferably represented by the formulas (Y-8) to (Y-10) from the viewpoint of the hole transport property of the light emitting device of the present embodiment. It is a structural unit.

In the formula, ^RY1 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 ^RY1s existing may be the same or different, and adjacent ^RY1s may be bonded to each other to form a ring together with the carbon atom to which each is bonded.

^RY1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may have a substituent.

The structural unit represented by the formula (Y-1) is preferably the structural unit represented by the formula (Y-1').

In the formula, ^RY11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of ^RY11s may be the same or different.

^RY11 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.

In the formula, ^RY1 has the same meaning as described above. ^XY1 represents a group represented by -C ( ^RY2 ) _2- , -C ( ^RY2 ) = C ( ^RY2 )-or -C ( ^RY2 ) ₂ -C ( ^RY2 ) _2- . ^RY2 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 ^RY2s existing may be the same or different, and the ^RY2s may be bonded to each other to form a ring together with the carbon atoms to which the RY2s are bonded.

^RY2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. You may be doing it.

^{In XY1} , the combination of two ^RY2s in the group represented by -C ( ^RY2 ) _2- is preferably a complex in which both are alkyl or cycloalkyl groups, both are aryl groups and both are monovalent. A ring group, or one of which is an alkyl or cycloalkyl group and the other of which is an aryl or monovalent heterocyclic group, more preferably one of which is an alkyl or cycloalkyl group and the other of which is an aryl group. May have a substituent. The two existing ^RY2s may be bonded to each other to form a ring with the atoms to which they are bonded, and when ^RY2 forms a ring, it is represented by -C ( ^RY2 ) _2- . Is preferably a group represented by the formulas (Y-A1) to (Y-A5), more preferably a group represented by the formula (Y-A4), and these groups have a substituent. You may be doing it.

^{In XY1} , the combination of two ^RY2s in the group represented by −C ( ^RY2 ) = C ( ^RY2 ) − is preferably both an alkyl group or a cycloalkyl group, or one of which is an alkyl group. Alternatively, it may be a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

^{In XY1} , the four ^RY2s among the groups represented by —C ( ^RY2 ) ₂ -C ( ^RY2 ) ₂ -are preferably alkyl or cycloalkyl groups which may have substituents. Is. A plurality of ^RY2s may be bonded to each other to form a ring together with the atoms to which each bond is formed. When ^RY2 forms a ring, -C (RY2) _{2 -} C ( ^RY2 ) ^2-- The group represented by is preferably a group represented by the formulas (Y-B1) to (Y-B5), and more preferably a group represented by the formula (Y-B3). It may have a substituent.

In the formula, ^RY2 has the same meaning as described above.

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

In the formula, ^{RY1 and XY1 have} the same meanings as described above.

In the formula, ^{RY1 and XY1 have} the same meanings as described above.

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

In the formula, ^RY11 and ^XY1 have the same meanings as described above.

In the formula, ^RY1 has the same meaning as described above. ^RY3 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.

^RY3 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 structural unit represented by the formula (Y-4) is preferably the structural unit represented by the formula (Y-4'), and the structural unit represented by the formula (Y-6) is the structural unit represented by the formula (Y-6). It is preferably a structural unit represented by -6').

In the formula, ^RY1 and ^RY3 have the same meanings as described above.

In the formula, ^RY1 has the same meaning as described above. ^RY4 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.

^RY4 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.

Examples of the structural unit represented by the formula (Y) include a structural unit composed of an arylene group represented by the formula (Y-101) to the formula (Y-121), and formulas (Y-201) to (Y-121). A building block consisting of a divalent heterocyclic group represented by 206), a divalent group in which an arylene group represented by the formulas (Y-300) to (Y-304) and a divalent heterocyclic group are directly bonded. The structural unit consisting of the base of is mentioned.

In the structural unit represented by the formula (Y) in which Ar ^Y1 is an arylene group, the drive voltage of the light emitting device of the present embodiment is low, so that the total amount of the structural units included in the polymer host is low. On the other hand, it is preferably 0.5 to 90 mol%, and more preferably 30 to 80 mol%.

The structural unit represented by the formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, is a structural unit. Since the light emitting element of the present embodiment has excellent charge transportability, it is preferably 0.5 to 40 mol%, more preferably 3 to 30 mol%, based on the total amount of the structural units contained in the polymer host. be.

The structural unit represented by the formula (Y) may be contained in only one kind or two or more kinds in the polymer host.

Since the polymer host has excellent hole transportability, it is preferable that the polymer host further contains a structural unit represented by the following formula (X).

During the ceremony
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups are substituents. May have. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different.
^RX1 , ^RX2 and ^RX3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RX2 and ^RX3 , they may be the same or different.

The a ^X1 is preferably 2 or less, and more preferably 1 because the drive voltage of the light emitting element of the present embodiment is lower.
The a ^X2 is preferably 2 or less, and more preferably 0, because the drive voltage of the light emitting element of the present embodiment is lower.

^RX1 , ^RX2 and ^RX3 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. May be good.

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

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

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 the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to the formula (A-11). ) Or a group represented by the formula (A-19), and these groups may have a substituent.

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

In the divalent group in which the arylene group represented by Ar ^X2 and Ar ^X4 and the divalent heterocyclic group are directly bonded, the more preferable range and the more preferable range of the arylene group and the divalent heterocyclic group are, respectively. It is the same as the more preferable range of the arylene group and the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 , and further preferable range.

The divalent group in which the arylene group represented by Ar ^X2 and Ar ^X4 and the divalent heterocyclic group are directly bonded is the arylene group represented by Ar ^Y1 of the formula (Y) and the divalent heterocyclic group. The same as the divalent group directly bonded to and is mentioned.

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

The substituents that the groups represented by Ar ^X1 to Ar ^X4 and ^RX1 to ^RX3 may have are preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups further have a substituent. You may be doing it.

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

In the formula, ^RX4 and ^RX5 are independently hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, halogen atom, monovalent heterocyclic group or cyano group. These groups may have a substituent. A plurality of ^RX4s may be the same or different. A plurality of ^RX5s existing may be the same or different, and adjacent ^RX5s may be bonded to each other to form a ring together with the carbon atom to which each is bonded.

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

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

In the polymer host, the structural unit represented by the formula (X) may contain only one kind or two or more kinds.

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

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

The polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and other embodiments, but a plurality of kinds of raw material monomers are used together. It is preferably 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 . It is ~ ^1.5 × 105.

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

In the above-mentioned polymerization method, as a method of charging the monomers, a method of charging the entire amount of the monomers in a batch, a method of charging a part of the monomers and reacting them, and then collectively charging the remaining monomers. Examples thereof include a method of continuously or separately charging, a method of continuously or separately charging a monomer, and the like.

Examples of the transition metal catalyst include a palladium catalyst, a nickel catalyst and the like.

The post-treatment of the polymerization reaction is carried out by a known method, for example, a method of removing water-soluble impurities by separating liquids, a reaction liquid after the polymerization reaction is added to a lower alcohol such as methanol, the precipitated precipitate is filtered, and then dried. The method of making the mixture is used 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 the metal complex represented by the formula (1), the above-mentioned host material, hole transport material, hole injection material, electron transport material, electron injection material, and light emitting material (however, the formula (1). ) And a composition containing at least one selected from the group consisting of antioxidants (hereinafter, also referred to as "first composition"). You may.

[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. The hole transport material may have a cross-linking group.

Examples of the low molecular weight compound include triphenylamine and its derivatives, N, N'-di-1-naphthyl-N, N'-diphenylbenzidine (α-NPD), and N, N'-diphenyl-N, Examples thereof include aromatic amine compounds such as N'-di (m-tolyl) benzidine (TPD).

Examples of the polymer compound include polyvinylcarbazole and its derivatives; polyarylene having an aromatic amine structure in its side chain or main chain and its derivatives. The polymer compound may be a compound to which an electron accepting site is bound. Examples of the electron-accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone and the like, and fullerene is preferable.

In the first composition, the content of the hole transporting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass. It is a department.

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

[Electronic transport material]
Electron transport materials are classified into low molecular weight compounds and high molecular weight compounds. The electron transport material may have a cross-linking group.

Examples of the low molecular weight compound include metal complexes having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinonedimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinonedimethane, fluorenone, diphenyldicyanoethylene and diphenoquinone. , And these derivatives.

Examples of the polymer compound include polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.

In the first composition, the content of the electron transporting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass. Is.

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

[Hole injection material and electron injection material]
Hole injection materials and electron injection materials are classified into low molecular weight compounds and high molecular weight compounds, respectively. The hole injection material and the electron injection material may have a cross-linking group.

Examples of the low molecular weight compound include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride and potassium fluoride.

Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; conductivity of polymers having an aromatic amine structure in the main chain or side chain. Examples include sex polymers.

In the first composition, the contents of the hole injection material and the electron injection material are usually 1 to 400 parts by mass, respectively, when the metal complex represented by the formula (1) is 100 parts by mass. It is preferably 5 to 150 parts by mass.

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

(Ion dope)
When the hole injection material or the electron injection material contains a conductive polymer, the electric conductivity of the conductive polymer is preferably 1 × ^10-5 S / cm to 1 × 10 ³ S / cm. In order to keep the electric conductivity of the conductive polymer within such a range, an appropriate amount of ions can be doped into the conductive polymer.

The type of ion to be doped is an anion in the case of a hole injection material and a cation in the case of an electron injection material. Examples of the anion include polystyrene sulfonic acid ion, alkylbenzene sulfonic acid ion, and cerebral sulfonic acid ion. Examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutylammonium ion.

The type of ion to be doped may be used alone or in combination of two or more.

[Luminescent material]
Luminescent materials (however, different from the metal complex represented by the formula (1)) are classified into low molecular weight compounds and high molecular weight compounds. The light emitting material may have a cross-linking group.

Examples of the low molecular weight compound include naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, and triple-term luminescent complexes having iridium, platinum or europium as a central metal.

Examples of the triplet luminescent complex include the following metal complexes.

Examples of the polymer compound include an arylene group such as a phenylene group, a naphthalenediyl group, a fluorinatedyl group, a phenantrangeyl group, a dihydrophenantrangeyl group, an anthracendil group and a pyrenedyl group; a structural unit represented by the formula (X). In addition, a polymer compound containing a group selected from a divalent heterocyclic group such as a carbazolediyl group, a phenoxazidinediyl group and a phenothiazinediyl group can be mentioned.

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

In the first composition, the content of the light emitting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass. be.

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

[Antioxidant]
The antioxidant is preferably a compound that is soluble in at least one solvent capable of dissolving the metal complex represented by the formula (1) and does not inhibit light emission and charge transport. Examples of the antioxidant include a phenol-based antioxidant and a phosphorus-based antioxidant.

In the first composition, the content of the antioxidant is usually 0.001 to 10 parts by mass when the metal complex represented by the formula (1) is 100 parts by mass.

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

<Ink>
The composition containing the metal complex represented by the formula (1) and the solvent (hereinafter, also referred to as “first ink”) includes a spin coating method, a casting method, a microgravia coating method, and a gravure coating method. 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, flexo printing method, offset printing method, inkjet printing method, capillary coating method, nozzle coating method, etc. 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 inkjet printing method is applied to the printing method via the ejection device, clogging and flight bending occur at the time of ejection. Since 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 capable of dissolving or uniformly dispersing the solid content in the ink. Examples of the solvent include chlorine-based solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, anisole, and 4-methylanisol; toluene, and the like. Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetophenone; esters such as ethyl acetate, butyl acetate, ethyl cellsolve acetate, methyl benzoate and phenyl acetate. System solvent; Polyhydric alcohol solvent such as ethylene glycol, glycerin, 1,2-hexanediol; Alcohol solvent such as isopropyl alcohol and cyclohexanol; Sulfoxide solvent such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N , N-Dimethylformamide and other amide-based solvents can be mentioned. The solvent may be used alone or in combination of two or more.

In the first ink, the content of the solvent is usually 1000 to 100,000 parts by mass, preferably 2000 to 20000 parts by mass, when the metal complex represented by the formula (1) is 100 parts by mass.

<Second organic layer>
The second organic layer is a layer containing a crosslinked product of a polymer compound containing a crosslinked structural unit (hereinafter, also referred to as “polymer compound of the second organic layer”).

The crosslinked product of the polymer compound of the second organic layer is obtained by cross-linking the polymer compound of the second organic layer by the above-mentioned method, conditions and the like.

The polymer compound of the second organic layer is a polymer compound containing a cross-linking structural unit having at least one cross-linking group selected from the cross-linking group A group because the driving voltage of the light emitting element of the present embodiment is lower. It is preferable to have.

As the cross-linking group selected from the group A, the driving voltage of the light emitting element of the present embodiment is lower, so that the formulas (XL-1) to (XL-4) and (XL-7) are preferable. It is a cross-linking group represented by the formula (XL-10) or the formula (XL-14) to the formula (XL-17), and more preferably, the formula (XL-1), the formula (XL-3), the formula ( XL-9), formula (XL-10), formula (XL-16) or crosslinking group represented by formula (XL-17), more preferably formula (XL-1), formula (XL-16). ) Or a cross-linking group represented by the formula (XL-17), particularly preferably a cross-linking group represented by the formula (XL-1) or the formula (XL-17), and particularly preferably the formula (XL). It is a cross-linking group represented by -17).

As the cross-linking group selected from the cross-linking group A group, the driving voltage of the light emitting element of the present embodiment is lower and the cross-linking property of the polymer compound of the second organic layer is more excellent. It is represented by the formula (XL-2) to the formula (XL-4), the formula (XL-7) to the formula (XL-10), the formula (XL-14), the formula (XL-15) or the formula (XL-17). It is a cross-linking group, more preferably a cross-linking group represented by the formula (XL-9), the formula (XL-10) or the formula (XL-17), and particularly preferably a cross-linking group represented by the formula (XL-17). It is a cross-linking group to be cross-linked.

[Polymer compound of the second organic layer]
The structural unit having at least one cross-linking group selected from the group A of the cross-linking group contained in the polymer compound of the second organic layer is represented by the structural unit represented by the formula (Z) or the structural unit represented by the formula (Z'). It is preferable that the structural unit is a structural unit, but it may be a structural unit represented by the following formula.

When the polymer compound of the second organic layer contains two or more structural units having at least one cross-linking group selected from the cross-linking group A group, it has at least one cross-linking group selected from the cross-linking group A group. It is preferable that at least two constituent units have different cross-linking groups from each other. As a combination of different cross-linking groups, the formula (XL-1), the formula (XL-2), the formula (XL-5) to the formula (XL-8) or the formula (XL-14) to the formula (XL-16) are used. A combination of the cross-linking group represented by the formula (XL-3), the formula (XL-4), the cross-linking group represented by the formula (XL-13) or the formula (XL-17) is preferable, and the cross-linking group represented by the formula (XL-17) is preferable. A combination of the cross-linking group represented by -1) or the formula (XL-16) and the cross-linking group represented by the formula (XL-17) is more preferable, and the cross-linking group represented by the formula (XL-1). , A combination with a cross-linking group represented by the formula (XL-17) is more preferable.

The structural unit nA represented by the formula (Z) is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, because the drive voltage of the light emitting element of the present embodiment is lower. More preferably, it is 1.

n is preferably 2 because the drive voltage of the light emitting element of the present embodiment is lower.

Ar ³ is an aromatic hydrocarbon group which may have a substituent because the driving voltage of the light emitting element of the present embodiment is lower.

The number of carbon atoms 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 number of carbon atoms of the substituent. be.
The arylene group moiety excluding the n substituents of the aromatic hydrocarbon group represented by Ar ³ is preferably a group represented by the formulas (A-1) to (A-20). More preferably, a group represented by the formula (A-1), the formula (A-2), the formula (A-6) to the formula (A-10), the formula (A-19) or the formula (A-20). The group is more preferably represented by the formula (A-1), the formula (A-2), the formula (A-7), the formula (A-9) or the formula (A-19), and these are the groups. The group of may have a substituent.

The number of carbon atoms 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 number of carbon atoms of the substituent.
The divalent heterocyclic group moiety excluding the n substituents of the heterocyclic group represented by Ar ³ is preferably a group represented by the formulas (AA-1) to (AA-34). be.

The aromatic hydrocarbon group and the heterocyclic group represented by Ar ³ may have a substituent, and the substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group and an aryloxy group. Groups, halogen atoms, monovalent heterocyclic groups and cyano groups are preferred.

The number of carbon atoms of the alkylene group represented by ^LA is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10, not including the number of carbon atoms of the substituent.
The number of carbon atoms of the cycloalkylene group represented by ^LA is usually 3 to 20 without including the number of carbon atoms of the substituent.
Examples of the alkylene group and the cycloalkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group and an octylene group, and these groups may have a substituent.

The alkylene group and the cycloalkylene group represented by ^LA may have a substituent. As the substituent which the alkylene group and the cycloalkylene group may have, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom or a cyano group are preferable, and these groups further have a substituent. May be.

The arylene group represented by ^LA may have a substituent. As the arylene group, a phenylene group or a fluoreneyl group is preferable, and an m-phenylene group, a p-phenylene group, a fluorene-2,7-diyl group, and a fluorene-9,9-diyl group are more preferable. The substituent that the arylene group may have includes an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom, a cyano group or a bridging group A. Bridging groups selected from the group are preferred, and these groups may further have substituents.

The divalent heterocyclic group represented by LA is preferably a group represented by the formulas ( ^AA -1) to (AA-34).

^LA is preferably an arylene group or an alkylene group, and more preferably a phenylene group, a fluorinatedyl group or an alkylene group because it facilitates the production of the polymer compound of the second organic layer. The group of may have a substituent.

As the cross-linking group represented by X, the driving voltage of the light emitting element of the present embodiment is lower, so that the equations (XL-1) to (XL-4) and the equations (XL-7) to (XL-7) are preferable. (XL-10) or a cross-linking group represented by the formulas (XL-14) to (XL-17), more preferably the formula (XL-1), the formula (XL-3), the formula (XL-). 9), a cross-linking group represented by the formula (XL-10), the formula (XL-16) or the formula (XL-17), more preferably the formula (XL-1), the formula (XL-16) or the like. It is a cross-linking group represented by the formula (XL-17), particularly preferably a cross-linking group represented by the formula (XL-1) or the formula (XL-17), and particularly preferably a cross-linking group represented by the formula (XL-17). ) Is a cross-linking group.

As the cross-linking group represented by X, the driving voltage of the light emitting element of the present embodiment is lower and the cross-linking property of the polymer compound of the second organic layer is more excellent, so that the formula (XL-) is preferable. 2) -Crosslink group represented by the formula (XL-4), the formula (XL-7) to the formula (XL-10), the formula (XL-14), the formula (XL-15) or the formula (XL-17). It is more preferably a cross-linking group represented by the formula (XL-9), the formula (XL-10) or the formula (XL-17), and particularly preferably the cross-linked group represented by the formula (XL-17). It is a cross-linking group.

Since the structural unit represented by the formula (Z) is excellent in stability and crosslinkability of the polymer compound of the second organic layer, it is relative to the total amount of the structural units contained in the polymer compound of the second organic layer. It is preferably 0.5 to 80 mol%, more preferably 3 to 65 mol%, and further preferably 5 to 50 mol%.
The structural unit represented by the formula (Z) may be contained in only one kind or two or more kinds 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 (Z), at least two structural units represented by the formula (Z) are crosslinked by X. It is preferable that the groups are different from each other. The preferred range of combinations of cross-linking groups represented by different Xs is the same as the preferred range of combinations of cross-linking groups different from each other described above.

The structural unit mA represented by the equation (Z') is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, because the drive voltage of the light emitting element of the present embodiment is lower. , More preferably 0 or 1, and particularly preferably 0.

m is preferably 1 or 2, and more preferably 2 because the drive voltage of the light emitting element of the present embodiment is lower.

c is preferably 0 because the production of the polymer compound of the second organic layer becomes easy and the driving voltage of the light emitting device of the present embodiment becomes lower.

Ar ⁵ is an aromatic hydrocarbon group which may have a substituent because the driving voltage of the light emitting element of the present embodiment is lower.

The definition and example of the arylene group portion excluding the m substituents of the aromatic hydrocarbon group represented by Ar ⁵ are the same as the definition and example of the arylene group represented by Ar ^X2 in the formula (X). ..

The definition and example of the divalent heterocyclic group portion excluding the m substituents of the heterocyclic group represented by Ar ⁵ are the divalent heterocyclic group portion represented by Ar ^X2 in the formula (X). Same as definition and example.

The definition and example of a divalent group excluding m substituents of a group in which at least one aromatic hydrocarbon ring represented by Ar ⁵ and at least one heterocyclic ring are directly bonded are given in the formula (X). It is the same as the definition and the example of the divalent group in which the arylene group represented by Ar ^X2 and the divalent heterocyclic group are directly bonded in.

Ar ⁴ and Ar ⁶ are arylene groups which may have a substituent because the driving voltage of the light emitting device of the present embodiment is lower.

The definitions and examples of the arylene groups represented by Ar ⁴ and Ar ⁶ are the same as the definitions and examples of the arylene groups represented by Ar ^X1 and Ar ^X3 in the formula (X).

The definitions and examples of the divalent heterocyclic groups represented by Ar ⁴ and Ar ⁶ are the same as the definitions and examples of the divalent heterocyclic groups represented by Ar ^X1 and Ar ^X3 in the formula (X).

The groups represented by Ar ⁴ , Ar ⁵ and Ar ⁶ may have a substituent, and the substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group and an aryloxy group. Halogen atoms, monovalent heterocyclic groups and cyano groups are preferred.

The definitions and examples of the alkylene group, cycloalkylene group, arylene group and divalent heterocyclic group represented by ^KA are the alkylene group, cycloalkylene group, arylene group and divalent complex represented by ^LA , respectively. It is the same as the definition and example of the ring group.

^KA is preferably a phenylene group or a methylene group because it facilitates the production of the polymer compound of the second organic layer.

The definition and example of the cross-linking group represented by X'are the same as the definition and example of the cross-linking group represented by X.

The structural unit represented by the formula (Z') has excellent stability of the polymer compound of the second organic layer and excellent cross-linking property of the polymer compound of the second organic layer, so that the second organic It is preferably 0.5 to 50 mol%, more preferably 3 to 30 mol%, still more preferably 5 to 20 mol%, based on the total amount of the constituent units contained in the polymer compound of the layer. .. The structural unit represented by the formula (Z') may be contained in only one kind or two or more kinds 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 (Z'), at least two structural units represented by the formula (Z') are represented by X'. It is preferable that the cross-linking groups to be formed are different from each other. The preferred range of combinations of cross-linking groups represented by different X's is the same as the preferred range of combinations of cross-linking groups different from each other described above.

-Preferable mode of the structural unit represented by the formula (Z) or (Z') The structural unit represented by the formula (Z) is represented by, for example, formulas (Z-1) to (Z-30). Examples of the structural unit represented by the equation (Z') include the structural units represented by the equations (Z'-1) to (Z'-9). Among these, since the polymer compound of the second organic layer has excellent crosslinkability, it is preferably a structural unit represented by the formulas (Z-1) to (Z-30), and more preferably the formula (Z). -1) to formula (Z-15), formula (Z-19), formula (Z-20), formula (Z-23), formula (Z-25) or formula (Z-30). It is a unit, and more preferably a structural unit represented by the formula (Z-1) to the formula (Z-9) or the formula (Z-30).

-Other Structural Units Since the polymer compound of the second organic layer has excellent hole transportability, it is preferable to further contain a structural unit represented by the formula (X). Further, the polymer compound of the second organic layer preferably further contains a structural unit represented by the formula (Y) because the driving voltage of the light emitting device of the present embodiment is lower.

Since the polymer compound of the second organic layer has excellent hole transportability and the driving voltage of the light emitting device of the present embodiment is lower, the structural unit and the formula (X) are further represented. It is preferable to include a structural unit represented by Y).

Definitions and examples of structural 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 described above. It is the same as the definition and example of the structural unit. Definitions and examples of structural 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 described above. It is the same as the definition and example of the structural unit.

The structural unit represented by the formula (X) may be contained in only one kind or two or more kinds in the polymer compound of the second organic layer. The structural unit represented by the formula (Y) may be contained in only one kind or two or more kinds in the polymer compound of the second organic layer.

When the polymer compound of the second organic layer contains a structural unit represented by the formula (X), the structural unit represented by the formula (X) has excellent hole transportability, and therefore, the structural unit of the second organic layer has excellent hole transportability. It is preferably 0.1 to 90 mol%, more preferably 1 to 70 mol%, still more preferably 10 to 50 mol%, based on the total amount of the structural units contained in the polymer compound.

When the polymer compound of the second organic layer contains a structural unit represented by the formula (Y) and Ar ^Y1 is a structural unit of an arylene group, it is contained in the polymer compound of the second organic layer. Since the driving voltage of the light emitting element of the present embodiment is lower in the structural unit represented by the formula (Y), it is preferable with respect to the total amount of the structural units contained in the polymer compound of the second organic layer. It is 0.5 to 90 mol%, more preferably 30 to 60 mol%.

The polymer compound of the second organic layer contains a structural unit represented by the formula (Y), and Ar ^Y1 is a divalent heterocyclic group, or an arylene group and a divalent heterocyclic group are directly bonded. In the case of the structural unit which is the divalent group, the structural unit represented by the formula (Y) contained in the polymer compound of the second organic layer has the charge transport property of the polymer compound of the second organic layer. Is more preferable, and is preferably 0.1 to 90 mol%, more preferably 1 to 70 mol%, still more preferably, with respect to the total amount of the structural units contained in the polymer compound of the second organic layer. Is 10 to 50 mol%.

Examples of the polymer compound of the second organic layer include polymer compounds P-7 to P-14. Here, the "other structural unit" means a structural unit other than the structural unit represented by the formula (Z), the formula (Z'), the formula (X), and the formula (Y).

In the table, p', q', r', s'and t'represent the molar ratio of each structural unit. p'+ q'+ r'+ s'+ t'= 100, and 70 ≦ p'+ q'+ r'+ s'≦ 100.

The polymer compound of the second organic layer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or may be another embodiment, but may be plural. It is preferably a copolymer in which the seed raw material monomer is copolymerized.

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 × 105, and even more preferably. It is 1.5 × 10 ⁴ to 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 above-mentioned method for producing a polymer host.

[Second composition]
The second organic layer is selected from the group consisting of a crosslinked body of the polymer compound of the second organic layer, a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material and an antioxidant. It may be a layer containing a composition containing at least one of these (hereinafter, also referred to as “second 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 second composition are the hole transporting material contained in the first composition. Same as examples and preferred ranges of electron transport materials, hole injection materials, electron injection materials and luminescent materials. In the second composition, the blending amounts of the hole transport material, the electron transport material, the hole injection material, the electron injection material and the light emitting material are 100 parts by mass, respectively, of the crosslinked product of the polymer compound of the second organic layer. In the case of, it is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass.

The examples and preferred ranges of the antioxidant contained in the second composition are the same as the examples and preferred ranges of the antioxidant contained in the first composition. In the second composition, the blending amount of the antioxidant is usually 0.001 to 10 parts by mass when the crosslinked body of the polymer compound of the second organic layer is 100 parts by mass.

[Second ink]
The composition containing the polymer compound of the second organic layer and the solvent (hereinafter, also referred to as “second ink”) is suitably used for the wet method described in the section of the first ink. Can be done. The preferred range of the viscosity of the second ink is the same as the preferred range of the viscosity of the first ink. The examples and preferred ranges of the solvent contained in the second ink are the same as the examples and preferred ranges of the solvent contained in the first ink.

In the second ink, the blending amount of the solvent is usually 1000 to 100,000 parts by mass, preferably 2000 to 20000 parts by mass, when the polymer compound of the second organic layer is 100 parts by mass.

<Layer structure of light emitting element>
The light emitting device of the present embodiment may have a layer other than the anode, the cathode, the first organic layer, and the second organic layer.

In the light emitting device of the present embodiment, the first organic layer is usually a light emitting layer (hereinafter referred to as "first light emitting layer").
In the light emitting device of the present embodiment, the second organic layer is usually a hole transport layer, a second light emitting layer or an electron transport layer, and is preferably a hole transport layer or a second light emitting layer.

In the light emitting element of the present embodiment, the first organic layer and the second organic layer are preferably adjacent to each other because the driving voltage of the light emitting element of the present embodiment is lower.
In the light emitting device of the present embodiment, the second organic layer is preferably a layer provided between the anode and the first organic layer because the driving voltage of the light emitting device of the present embodiment is lower. It is more preferable that the hole transport layer or the second light emitting layer is provided between the anode and the first organic layer.

In the first organic layer of the light emitting device of the present embodiment, the metal complex represented by the formula (1) may be contained alone or in combination of two or more. In the second organic layer of the light emitting device of the present embodiment, the crosslinked body of the polymer compound of the second organic layer may be contained alone or in combination of two or more.

In the light emitting device of the present embodiment, when the second organic layer is a hole transport layer provided between the anode and the first organic layer, the drive voltage of the light emitting device of the present embodiment becomes lower. It is preferable to further have a hole injection layer between the anode and the second organic layer. When the second organic layer is a hole transport layer provided between the anode and the first organic layer, the driving voltage of the light emitting device of the present embodiment is lower, so that the cathode and the first organic layer are used. It is preferable to further have at least one layer of an electron injecting layer and an electron transporting layer between the two.

In the light emitting device of the present embodiment, when the second organic layer is the second light emitting layer provided between the anode and the first organic layer, the drive voltage of the light emitting element of the present embodiment becomes lower. It is preferable to further have at least one layer of a hole injection layer and a hole transport layer between the anode and the second organic layer. When the second organic layer is a second light emitting layer provided between the anode and the first organic layer, the driving voltage of the light emitting element of the present embodiment is lower, so that the cathode and the first organic layer are formed. It is preferable to further have at least one layer of an electron injecting layer and an electron transporting layer between the two.

In the light emitting element of the present embodiment, when the second organic layer is the second light emitting layer provided between the cathode and the first organic layer, the drive voltage of the light emitting element of the present embodiment becomes lower. It is preferable to further have at least one layer of a hole injection layer and a hole transport layer between the anode and the first organic layer. When the second organic layer is a second light emitting layer provided between the cathode and the first organic layer, the driving voltage of the light emitting element of the present embodiment is lower, so that the cathode and the second organic layer are formed. It is preferable to further have at least one layer of an electron injection layer and an electron transport layer between the two.

In the light emitting device of the present embodiment, when the second 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 embodiment is lower, so that the anode It is preferable to further have at least one layer of a hole injection layer and a hole transport layer between the first organic layer and the first organic layer. When the second 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 embodiment is lower, so that the cathode and the second organic layer are separated from each other. It is preferable to have an electron injection layer in between.

Specific layer configurations of the light emitting element of the present embodiment include, for example, layer configurations represented by (D1) to (D15). The light emitting device of the present embodiment usually 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 / second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / cathode (D2) anode / hole transport layer (second organic layer) / second 1 light emitting layer (first organic layer) / cathode (D3) anode / hole injection layer / second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / cathode (D4) anode / hole injection layer / second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / electron transport layer / cathode (D5) anode / hole injection layer / Second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / electron injection layer / cathode (D6) 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 (D7) anode / hole injection layer / hole transport layer (second organic layer) / second 1 light emitting layer (first organic layer) / cathode (D8) anode / hole injection layer / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / electron transport Layer / cathode (D9) anode / hole injection layer / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / electron injection layer / cathode (D10) anode / hole Injection layer / hole transport layer (second organic layer) / first light emitting layer (first organic layer) / electron transport layer / electron injection layer / cathode (D11) anode / hole injection layer / hole transport Layer / second light emitting layer (second organic layer) / first light emitting layer (first organic layer) / electron transport 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 / electron injection layer / cathode (D13) anode / hole injection layer / hole transport Layer / first light emitting layer (first organic layer) / second light emitting layer (second organic layer) / electron transport layer / electron injection layer / cathode (D14) anode / hole injection layer / hole transport Layer / first light emitting layer (first organic layer) / electron transport layer (second organic layer) / electron injection layer / cathode (D15) anode / hole injection layer / hole transport layer (second organic) Layer) / second light emitting layer / first light emitting layer (first organic layer) / electron transport layer / electron injection layer / cathode

In the above (D1) to (D15), "/" means that the layers before and after the layer are adjacent to each other. Specifically, the "second light emitting layer (second organic layer) / first light emitting layer (first organic layer)" means the second light emitting layer (second organic layer) and the first. It means that the light emitting layer (first organic layer) of the above is adjacently laminated.

Since the drive voltage of the light emitting element of the present embodiment is lower, the layer configuration represented by (D3) to (D12) is preferable.

In the light emitting device of the present embodiment, 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 with two or more layers, if necessary. You may.
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, the materials constituting them may be the same or different.

The thickness 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 is usually 1 nm to 1 μm, preferably 2 nm to 2 nm. It is 500 nm, more preferably 5 nm to 150 nm.

In the light emitting element of the present embodiment, the order, number, and thickness of the layers to be laminated may be adjusted in consideration of the luminous 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 that may be contained in the above-mentioned first composition. Be done. The light emitting material contained in the second light emitting layer may be contained alone or in combination of two or more.
When the light emitting device of the present embodiment has a second light emitting layer, and the hole transport layer and the electron transport layer described later are not the second organic layer, the second light emitting layer is the second organic layer. It is preferably a 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 transporting layer is a layer containing a hole transporting material, examples of the hole transporting material include a hole transporting material that may be contained in the above-mentioned first composition. The hole transport material contained in the hole transport layer may be contained alone or in combination of two or more.
When the light emitting device of the present embodiment has a hole transport layer and the second light emitting layer described above and the electron transport layer described later are not the second organic layer, the hole transport layer is the second organic layer. Is preferable.

[Electron transport layer]
The electron transport layer is usually a layer containing a second organic layer or an electron transport material, and is preferably a layer containing an electron transport material. 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 that may contain the above-mentioned first composition. .. The electron transport material contained in the electron transport layer may be contained alone or in combination of two or more.
When the light emitting device of the present embodiment has an electron transport layer and the above-mentioned second light emitting layer and the above-mentioned hole transport layer are not the second organic layer, the electron transport layer is the second organic layer. It is preferable to have.

[Hole injection layer and electron injection layer]
The hole injection layer is a layer containing a hole injection material. Examples of the hole injection material contained in the hole injection layer include the hole injection material that may be contained in the above-mentioned first composition. The hole injection material contained in the hole injection layer may be contained alone or in combination of two or more.
The electron injection layer is a layer containing an electron injection material. Examples of the electron-injecting material contained in the electron-injecting layer include an electron-injecting material that may be contained in the above-mentioned first composition. The electron injection material contained in the electron injection layer may be contained alone or in combination of two or more.

[Substrate / Electrode]
The substrate in the light emitting device is preferably a substrate that does not chemically change during the formation of the electrode and the formation of the organic layer. The substrate may be, for example, a substrate made of a material such as glass, plastic, or silicon. When using an opaque substrate, it is preferable that the electrode farthest from the substrate is transparent or translucent.

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

Materials for the cathode include, for example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, indium; two or more alloys thereof; one of them. Alloys of more than one species with one or more of silver, copper, manganese, titanium, cobalt, nickel, tungsten, tin; as well as 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 element of the present embodiment, at least one of the anode and the cathode is usually transparent or translucent, but it is preferable that the anode is transparent or translucent.
Examples of the method for forming the anode and the cathode include a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method and a laminating method.

[Manufacturing method of light emitting element]
In the light emitting element of the present embodiment, as a method for forming each layer such as the first light emitting layer, the second light emitting layer, the hole transport layer, the electron transport layer, the hole injection layer, and the electron injection layer, a low molecular weight compound is used. When used, for example, a vacuum vapor deposition method from a powder, a method by forming a film from a solution or a molten state can be mentioned, and when using a polymer compound, for example, a method by forming a film from a solution or a molten state can be mentioned.
The first light emitting layer, the second light emitting layer, the hole transport layer, the electron transport layer, the hole injection layer and the electron injection layer are the first ink, the second ink, and the above-mentioned light emitting material and holes. It can be formed by a wet method such as a spin coat method or an inkjet printing method using an ink containing a transport material, an electron transport material, a hole injection material, and an electron injection material, respectively.

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

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.

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 the examples, the polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are determined by size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Asked by. The measurement conditions of SEC are as follows.
[Measurement condition]
The polymer compound to be measured was dissolved in tetrahydrofuran (THF) at a concentration of about 0.05% by mass, and 10 μL was injected into SEC. THF was used as the mobile phase of the SEC and the flow was performed at a flow rate of 2.0 mL / min. PLgel MIXED-B (manufactured by Polymer Laboratories) was used as a column. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

LC-MS was measured by the following method.
The measurement sample was dissolved in chloroform or tetrahydrofuran so as to have a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent, trade name: 1100LCMSD). For the mobile phase of LC-MS, the ratio of acetonitrile and tetrahydrofuran was changed, and the flow rate was 0.2 mL / min. As a column, L-volume 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size 3 μm) was used.

NMR was measured by the following method.
About 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated tetrahydrofuran, deuterated dimethylsulfoxide, deuterated acetone, deuterated N, N-dimethylformamide, deuterated toluene, deuterated methanol, deuterated ethanol, deuterated 2-propanol, 5 to 10 mg of measurement sample Alternatively, it was dissolved in deuterated methylene chloride and measured using an NMR apparatus (manufactured by Varian, Inc., trade name: INOVA300 or MERCURY 400VX, or manufactured by Bruker, trade name: AVANCE600).

The value of high performance liquid chromatography (HPLC) area percentage was used as an index of the purity of the compound. Unless otherwise specified, this value is a value at UV = 254 nm by 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 depending on the concentration. For the mobile phase of HPLC, the ratio of acetonitrile / tetrahydrofuran was changed from 100/0 to 0/100 (volume ratio), and the flow rate was 1.0 mL / min. As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having equivalent performance was used. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

<Synthesis Examples M1 to M8, RM1> Synthesis of Compounds M1 to M8 and Metal Complex RM1 Compounds M1 and M2 were synthesized according to the method described in International Publication No. 2002/045184.
Compound M3 was synthesized according to the method described in International Publication No. 2011/049241.
Compounds M4, M5 and M6 were synthesized according to the method described in WO 2013/146806.
Compound M7 was synthesized according to the method described in WO 2015/145871.
Compound M8 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 HTL1> Synthesis of Polymer Compound HTL-1 Polymer compound HTL-1 was synthesized by using Compound M1, Compound M2 and Compound M3 according to the method described in International Publication No. 2011/049241. 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 × 105, respectively.
In the theoretical value obtained from the amount of the charged raw material, 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. It is a copolymer composed of a molar ratio of 50: 42.5: 7.5.

<Synthesis Example HTL2> Synthesis of Polymer Compound HTL-2 Polymer compound HTL-2 was synthesized by the method described in International Publication No. 2015/145871 using Compound M7, Compound M5 and Compound M8. The polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound HTL-2 were Mn = 2.3 × ^{10 4} and Mw = 1.2 × 105, respectively.
In the theoretical value obtained from the amount of the charged raw material, the polymer compound HTL-2 has a structural unit derived from the compound M7, a structural unit derived from the compound M5, and a structural unit derived from the compound M8. It is a copolymer composed of a molar ratio of 45: 5: 50.

<Synthesis Example EML1> Synthesis of Polymer Compound EML-1 (Step 1) After setting the inside of the reaction vessel to an inert gas atmosphere, compound M4 (2.52 g), compound M5 (0.470 g), and compound M6 (4. 90 g), metal complex RM1 (0.530 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (4.2 mg) and toluene (158 mL) were added and heated to 100 ° C.
(Step 2) A 20 mass% tetraethylammonium hydroxide aqueous solution (16 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 8 hours.
(Step 3) After the reaction, phenylboronic acid (116 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (4.2 mg) were added thereto, and the mixture was refluxed for 15 hours.
(Step 4) Then, an aqueous sodium diethyldithiacarbamate solution 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 to cause precipitation. The precipitate was dissolved in toluene and purified by passing it through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol, stirred, and then the obtained precipitate was collected by filtration and dried to obtain 6.02 g of the polymer compound EML-1. The Mn of the polymer compound EML-1 was 3.8 × 10 ⁴ , and the Mw was ^4.5 × 105.

In the theoretical value obtained from the amount of the charged raw material, the polymer compound EML-1 has a structural unit derived from the compound M4, a structural unit derived from the compound M5, a structural unit derived from the compound M6, and a metal. The structural unit derived from the complex RM1 is a copolymer composed of a molar ratio of 40:10:47: 3.

<Synthesis Example ET1> Synthesis of Polymer Compound ET1 (Synthesis of Polymer Compound ET1a)
The polymer compound ET1a is particularly prepared by using the compound ET1-1 synthesized according to the method described in JP2012-33845 and the compound ET1-2 synthesized according to the method described in JP2012-33845. It was synthesized according to the method described in Kai 2012-33845.

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

In the theoretical value obtained from the amount of the charged raw material, the polymer compound ET1a is composed of a structural unit derived from the compound ET1-1 and a structural unit derived from the compound ET1-2 in a molar ratio of 50:50. It is a copolymerized product.

(Synthesis of polymer compound ET1)
After the inside of the reaction vessel was made to have an inert gas atmosphere, the polymer compound ET1a (200 mg), tetrahydrofuran (20 mL) and ethanol (20 mL) were added, and the mixture was heated to 55 ° C. Then, 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, it was concentrated under reduced pressure to obtain a solid. The obtained solid was washed with water and then dried under reduced pressure to obtain the 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 at the ethyl ester moiety of the polymer compound ET1a was completely eliminated.

<Synthesis Example B1> Synthesis of Metal Complex B1 The metal complex B1 was synthesized by the following method.

(Synthesis of compound L1-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (100 g) and tetrahydrofuran (1 L) were added, and the mixture was cooled to 0 ° C. Triethylamine (54 mL) was slowly added thereto, and the mixture was stirred at 0 ° C. for 10 minutes. After the compound L1-2 was added dropwise thereto, the mixture was stirred at room temperature for 16 hours. The obtained reaction solution was concentrated under reduced pressure, ion-exchanged water was added, and the mixture was stirred for 1 hour to form a solid. The obtained solid was collected by filtration, washed with ethyl acetate, and dried under reduced pressure to give compound L1-3 (110 g). The HPLC area percentage value of compound L1-3 was 99.5% or more.

The analysis results of compound L1-3 were as follows.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 1.03 (s, 9H), 2.07 (s, 2H), 7.48-7.60 (m, 3H), 7 .87-7.89 (m, 2H), 9.74 (s, 1H), 10.26 (s, 1H).

(Synthesis of compound L1-5)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-3 (40 g) and xylene (400 mL) were added to bring the temperature to 0 ° C. Compound L1-4 (36.3 g) was added thereto, and the mixture was stirred at 0 ° C. for 10 minutes. Phosphorus pentachloride (53.3 g) was added dropwise thereto, and the mixture was stirred at 130 ° C. for 5 days. Then, the obtained reaction solution was cooled to room temperature and concentrated under reduced pressure. The obtained reaction mixture was extracted with ethyl acetate and saturated aqueous sodium hydrogen carbonate solution. The obtained organic layer was washed successively with water and saturated brine. Then, the obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was sequentially purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and reverse phase column chromatography (mixed solvent of water and acetonitrile), and further dried under reduced pressure to obtain compound L1-. 5 (8 g) was obtained. The HPLC area percentage value of compound L1-5 was 99.5%.

The analysis results of compound L1-5 were as follows.
LC-MS (APCI, positive): m / z = 376 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.09 (s, 9H), 1.36 (s, 9H), 1.90 (s, 6H), 2.35 (s, 2H) ), 7.17 (s, 2H), 7.22-7.31 (m, 3H), 7.37-7.39 (m, 2H).

(Synthesis of metal complex B1)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (1.5 g), compound L1-5 (5.8 g) and pentadecane (2 mL) were added, and the mixture was stirred at 300 ° C. for 22 hours. .. Then, the obtained reaction solution was cooled to room temperature, toluene was added thereto, and the mixture was dissolved and then concentrated under reduced pressure to obtain a crude product. The obtained crude product is purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate), further crystallized using a mixed solvent of toluene and heptane, and then dried under reduced pressure to obtain a metal complex. B1 (1.8 g) was obtained. The HPLC area percentage value of the metal complex B1 was 99.5% or more.

The analysis results of the metal complex B1 were as follows.
¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.33 (s, 6H), 6.91-6.94 (m, 3H), 6.50 (td, 3H), 6 .30-6.34 (m, 3H), 6.09-6.12 (m, 3H), 2.21-2.25 (m, 3H), 2.13-2.16 (m, 3H) , 2.09 (s, 9H), 1.86 (s, 9H), 1.36-1.42 (m, 27H), 1.00-1.04 (m, 27H).

<Synthesis Example B2> Synthesis of Metal Complex B2 The metal complex B2 was synthesized by the following method.

(Synthesis of compound L2-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (500 g), tetrahydrofuran (5 L) and triethylamine (585 mL) were added, and the mixture was stirred at 0 ° C. After the compound L2-1 was added dropwise thereto, the mixture was stirred at room temperature for 16 hours. After filtering the obtained reaction solution, the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was washed with ethyl acetate and then dried under reduced pressure to obtain compound L2-2 (500 g). The HPLC area percentage value of compound L2-2 was 99.4%.

The analysis results of compound L2-2 were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.22 (d, 6H), 2.54-2.63 (m, 1H), 7.40-7.56 (m, 3H) , 7.80-7.83 (m, 2H), 9.06 (s, 1H), 9.42 (s, 1H).

(Synthesis of compound L2-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L2-2 (40 g), dichlorobenzene (400 mL) and compound L1-4 (85 g) were added, and the mixture was stirred at −10 ° C. Phosphorus pentachloride (22 mL) was added dropwise thereto. Then, the mixture was stirred at −10 ° C. for 30 minutes, further at room temperature for 1 hour, and then at 185 ° C. for 18 hours. Then, the obtained reaction solution was cooled to room temperature and concentrated under reduced pressure. The obtained reaction mixture was extracted with methylene chloride and ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate), further crystallized with acetonitrile, and then dried under reduced pressure to obtain compound L2-3 (10 g). Got The HPLC area percentage value of compound L2-3 was 99.4%.

The analysis results of compound L2-3 were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.32 (d, 6H), 1.35 (s, 9H), 1.94 (s, 6H), 2.55-2.62 (M, 1H), 7.17 (s, 2H), 7.22-7.33 (m, 3H), 7.39-7.41 (m, 2H).

(Synthesis of metal complex B2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (3.5 g), compound L2-3 (10 g) and pentadecane (2 mL) were added, and the mixture was stirred at 285 ° C. for 18 hours. Then, the obtained reaction solution is cooled to room temperature, purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate) and silica gel column chromatography (mixed solvent of methylene chloride and ethyl acetate), and further purified by heptane and toluene. Crystallization was performed using the mixed solvent of. Then, the obtained solid was dried under reduced pressure to obtain a metal complex B2 (1.2 g). The HPLC area percentage value of the metal complex B2 was 99.5% or more. By repeating the above operation, a required amount of metal complex B2 was obtained.

The analysis results of the metal complex B2 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.35 (brs, 3H), 7.34 (brs, 3H), 6.86 (dd, 3H), 6.49 (td) , 3H), 6.33 (td, 3H), 6.13 (d, 3H), 2.53 (spt, 3H), 2.15 (s, 9H), 1.90 (s, 9H), 1 .39 (s, 27H), 1.23 (d, 9H), 1.11 (d, 9H).

<Synthesis Example B3> Synthesis of Metal Complex B3 The metal complex B3 was synthesized by the following method.

(Synthesis of compound L3-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (50 g) and N-methyl-2-pyrrolidone (200 mL) were added, and the mixture was stirred at 0 ° C. The compound L3-1 (40 g) dissolved in N-methyl-2-pyrrolidone (40 mL) was added dropwise thereto, and the mixture was stirred at room temperature for 18 hours. Then, the obtained reaction solution was poured into ion-exchanged water (1.2 L) to obtain a precipitate. The obtained precipitate was collected by filtration and further washed with 1M aqueous hydrochloric acid solution, ion-exchanged water and heptane in sequence. Then, the obtained solid was dried under reduced pressure to obtain compound L3-2 (43 g, white solid).

The analysis results of compound L3-2 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ ) δ (ppm) = 9.64 (br, 1H), 8.90 (br, 1H), 7.86 (d, 2H), 7.56 (t, 1H) , 7.45 (t, 2H), 7.02-7.08 (m, 3H), 2.41 (s, 6H).

(Synthesis of compound L3-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L3-2 (43 g) and toluene (740 mL) were added, and the mixture was stirred at room temperature. Phosphorus pentachloride (67 g) was added thereto little by little, and then the mixture was stirred at 110 ° C. for 21 hours. The obtained reaction solution was cooled to room temperature, poured into ice water (500 mL), stirred for 2 hours, and the aqueous layer was removed. The obtained organic layer was washed with ion-exchanged water and a 10 mass% sodium hydrogen carbonate aqueous solution, and the obtained organic layer was further dried over magnesium sulfate and then filtered. The obtained filtrate was concentrated under reduced pressure to give compound L3-3 (40 g).

(Synthesis of compound L3-5)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L3-3 (40 g), compound L3-4 (32 g) and xylene (800 mL) were added, and the mixture was stirred at room temperature. P-Toluenesulfonic acid (3 g) was added thereto, and the mixture was stirred at 120 ° C. for 116 hours. Then, the obtained reaction solution was cooled to room temperature, ion-exchanged water (800 mL) was added thereto, and the mixture was stirred at room temperature for 1 hour. Then, after removing the aqueous layer, the obtained organic layer was washed with a 5% by mass sodium hydrogen carbonate aqueous solution. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was sequentially purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate) and silica gel column chromatography (acetoyl and tetrahydrofuran) to obtain compound L3-5 (1.3 g, white solid). Obtained. The HPLC area percentage value of compound L3-5 was 99.5% or more. By repeating the above operation, a required amount of compound L3-5 was obtained.

The analysis results of compound L3-5 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ) δ (ppm) = 7.42 (d, 2H), 7.30 (t, 1H), 7.24 (t, 2H), 7.15 (t, 1H), 6.98 (d, 2H), 6.85 (s, 2H), 2.51 (t, 2H), 2.07 (s, 6H), 1.81 (s, 6H), 1. 56 (m, 2H), 1.26-1.32 (m, 6H), 0.88 (t, 3H).

(Synthesis of metal complex B3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (0.6 g), compound L3-5 (2.0 g) and tridecane (2 mL) were added, and the mixture was stirred at 250 ° C. for 120 hours. .. Then, the obtained reaction solution was cooled to room temperature, purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate), and further crystallized using a mixed solvent of methylene chloride and acetonitrile. The obtained solid was dried under reduced pressure to obtain a metal complex B3 (0.6 g, yellow solid). The HPLC area percentage value of the metal complex B3 was 99.2%.

The analysis results of the metal complex B3 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ) δ (ppm) = 7.04-7.08 (m, 6H), 6.93 (s, 3H), 6.92 (s, 3H), 6. 88 (d, 3H), 6.84 (d, 3H), 6.61 (t, 3H), 6.43 (t, 3H), 6.29 (d, 3H), 2.57 (t, 6H) ), 2.12 (s, 9H), 1.95 (s, 9H), 1.82 (s, 9H), 1.70 (s, 9H), 1.62 (m, 6H), 1.28 -1.36 (m, 18H), 0.89 (t, 9H).

<Synthesis Example B4> Synthesis of Metal Complex B4 The metal complex B4 was synthesized by the following method.

(Synthesis of compound L4-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (100 g), triethylamine (114 mL) and tetrahydrofuran (1.5 L) were added, and the mixture was stirred at 0 ° C. Compound L4-1 (52 mL) was added dropwise thereto, and the mixture was stirred at room temperature for 16 hours. Then, the obtained reaction solution was filtered, and then the obtained filtrate was concentrated to obtain a crude product. The obtained crude product was crystallized from ethyl acetate and then dried under reduced pressure to give compound L4-2 (70 g). The HPLC area percentage value of compound L4-2 was 98.7%.

The analysis results of compound L4-2 were as follows.
LC-MS (APCI, positive): m / z = 179 [M + H] ^{+
1 1} H-NMR (300 MHz, DMSO-d ₆ ) δ (ppm) = 10.26 (br, 1H), 9.86 (br, 1H), 7.83-7.86 (m, 2H), 7. 45-7.56 (m, 3H), 1.90 (s, 3H).

(Synthesis of compound L4-4)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L4-2 (70 g) and xylene (700 mL) were added, and the mixture was stirred at room temperature. Phosphorus pentachloride (123 g) was added little by little, and the mixture was stirred at 130 ° C. for 2 hours and then cooled to room temperature. Compound L4-3 (70 g) was added thereto little by little, and then the mixture was stirred at 130 ° C. for 8 hours. Then, the obtained reaction solution was cooled to room temperature and then concentrated under reduced pressure. Ethyl acetate was added thereto, and the obtained organic layer was washed successively with ion-exchanged water, 10% by mass sodium hydrogen carbonate aqueous solution, and saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate), and further crystallized using a mixed solvent of N, N-dimethylformamide and water. The obtained solid was dried under reduced pressure to obtain compound L4-4 (70 g, white solid). The HPLC area percentage value of compound L4-4 was 99.2%.

The analysis results of compound L4-4 were as follows.
LC-MS (APCI, positive): m / z = 320 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 7.53-7.58 (m, 1H), 7.48 (d, 2H), 7.33 (d, 2H), 7.28- 7.30 (m, 1H), 7.21-7.25 (m, 2H), 2.39 (q, 2H), 2.26 (s, 3H), 1.14 (d, 6H), 0 .87 (d, 6H).

(Synthesis of metal complex B4)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (1.2 g), compound L4-4 (4.0 g) and tridecane (1 mL) were added, and the mixture was stirred at 280 ° C. for 18 hours. .. Then, the obtained reaction solution was cooled to room temperature, purified by silica gel column chromatography (mixed solvent of ethyl acetate and methanol), and further crystallized using a mixed solvent of toluene and acetonitrile. The obtained solid was dried under reduced pressure to obtain a metal complex B4 (1.7 g, yellow solid). The HPLC area percentage value of the metal complex B4 was 99.5% or more.

The analysis results of the metal complex B4 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ) δ (ppm) = 7.56 (t, 3H), 7.42 (dd, 3H), 7.40 (dd, 3H), 6.87 (dd, dd, 3H), 6.52 (td, 3H), 6.35 (td, 3H), 6.17 (dd, 3H), 2.83 (hept, 3H), 2.34 (hept, 3H), 2. 10 (s, 9H), 1.23 (d, 9H), 0.98 (d, 9H), 0.96 (d, 9H), 0.92 (d, 9H).

<Synthesis Example B5> Synthesis of Metal Complex B5 The metal complex B5 was synthesized by the following method.

(Synthesis of compound L5-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (200 g), triethylamine (225 mL) and tetrahydrofuran (3 L) were added, and the mixture was cooled to 0 ° C. Compound L5-1 (198 g) was added dropwise thereto, and the mixture was stirred at room temperature for 16 hours. After filtering the obtained reaction solution, the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with ethyl acetate and then dried under reduced pressure to obtain compound L5-2 (172 g). The HPLC area percentage value of compound L5-2 was 99.2%.

The analysis results of compound L5-2 were as follows.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 0.88 (t, 3H), 1.18 (s, 6H), 1.57 (q, 2H), 7.47-7 .58 (m, 3H), 7.89-7.91 (m, 2H), 9.51 (s, 1H), 10.20 (s, 1H).

(Synthesis of compound L5-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L5-2 (100 g) and toluene (700 mL) were added, and the mixture was stirred at room temperature. Phosphorus pentachloride (178 g) was added little by little, and the mixture was stirred at 110 ° C. for 18 hours and then cooled to room temperature. The obtained reaction solution was concentrated to obtain a crude product L5-2'(65 g). Then, after the inside of the reaction vessel was made into a nitrogen atmosphere again, toluene (1 L), compound L1-4 (43 g) and p-toluenesulfonic acid (6.5 g) were added, and the mixture was stirred at 110 for 3 days. Then, the obtained reaction solution was cooled to room temperature and then concentrated under reduced pressure. Ethyl acetate was added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over sodium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate), and further crystallized using a mixed solvent of acetonitrile and ethyl acetate. The obtained solid was purified by reverse phase column chromatography and then dried under reduced pressure to obtain compound L5-3 (16 g). The HPLC area percentage value of compound L5-3 was 99.4%.

The analysis results of compound L5-3 were as follows.
LC-MS (APCI, positive): m / z = 376 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.89 (t, 3H), 1.19 (s, 6H), 1.33 (s, 9H), 1.71 (q, 2H) ), 1.97 (s, 6H), 7.12 (s, 2H), 7.19-7.23 (m, 2H), 7.27-7.28 (m, 1H), 7.33- 7.36 (m, 2H).

(Synthesis of metal complex B5)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (1.5 g), compound L5-3 (4.0 g) and tridecane (2 mL) were added, and the mixture was stirred at 280 ° C. for 28 hours. .. Then, the obtained reaction solution was cooled to room temperature, purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate), and further crystallized using a mixed solvent of toluene and methanol. The obtained solid was dried under reduced pressure to obtain a metal complex B5 (1.0 g, yellow solid). The HPLC area percentage value of the metal complex B5 was 99.5% or more.

The analysis results of the metal complex B5 were as follows.
¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.31 (s, 6H), 6.91 (d, 3H), 6.48 (td, 3H), 6.24-6 .30 (m, 3H), 5.87 (d, 3H), 2.12-2.15 (m, 9H), 1.94 (s, 9H), 1.58-1.66 (m, 3H) ), 1.50-1.57 (m, 3H), 1.38 (s, 27H), 1.12-1.16 (m, 9H), 1.04-1.08 (m, 9H), 0.84 (t, 9H).

<Synthesis Example B6> Synthesis of Metal Complex B6 The metal complex B6 was synthesized by the following method.

(Synthesis of reaction mixture L6-1')
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L6-1 (50 g) and thionyl chloride (100 mL) were added, and the mixture was stirred under reflux for 3 hours. Then, after cooling the reaction mixture to room temperature, thionyl chloride was distilled off under reduced pressure to obtain a reaction mixture L6-1'.

(Synthesis of compound L6-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-1 (47 g) and tetrahydrofuran (1 L) were added, and the mixture was cooled to 0 ° C. Triethylamine (54 mL) was slowly added thereto, and the mixture was stirred at 0 ° C. for 45 minutes. The reaction mixture L6-1'(total amount) obtained in (Synthesis of reaction mixture L6-1') was slowly added thereto. Then, the mixture was stirred at room temperature for 16 hours. After filtering the obtained reaction solution, the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with a mixed solvent of ethyl acetate and hexane and then dried under reduced pressure to obtain compound L6-2 (50 g). The HPLC area percentage value of compound L6-2 was 95.2%. By repeating the above operation, a required amount of compound L6-2 was obtained.

The analysis results of compound L6-2 were as follows.
LC-MS (APCI, positive): m / z = 263 [M + H] ^{+
1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.84 (t, 9H), 1.64 (q, 6H), 7.39-7.54 (m, 3H), 7.81 -7.84 (m, 2H), 8.72-8.74 (m, 1H), 9.66-9.68 (m, 1H).

(Synthesis of compound L6-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L6-2 (58 g) and toluene (600 mL) were added, and the mixture was stirred at room temperature. Phosphorus pentachloride (92 g) was slowly added thereto, and then the mixture was stirred at 110 ° C. for 3 hours. Then, the obtained reaction solution was cooled to room temperature, and compound L1-4 (78.2 g) and p-toluenesulfonic acid (3 g) were added thereto. Then, after stirring at 130 ° C. for 4 days, the reaction solution was cooled to room temperature. The obtained reaction solution was concentrated under reduced pressure, ethyl acetate (2 L) was added thereto, and the mixture was washed with a 10 mass% aqueous sodium hydrogen carbonate solution. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. This crude product was purified by silica gel column chromatography (mixed solvent of methanol and chloroform), further crystallized with acetonitrile, and then dried under reduced pressure to obtain compound L6-3 (6 g). .. The HPLC area percentage value of compound L6-3 was 99.1%.

The analysis results of compound L6-3 were as follows.
LC-MS (APCI, positive): m / z = 404 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.83 (t, 9H), 1.34 (s, 9H), 1.64 (q, 6H), 1.96 (s, 6H) ), 7.12 (s, 2H), 7.20-7.23 (m, 2H), 7.28-7.34 (m, 3H).

(Synthesis of metal complex B6)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (1.4 g), compound L6-3 (4.6 g) and pentadecane (2 mL) were added, and the mixture was stirred at 300 ° C. for 18 hours. .. Then, the obtained reaction solution was cooled to room temperature, toluene was added thereto, and the mixture was dissolved and then concentrated under reduced pressure to obtain a crude product. The obtained crude product is purified by silica gel column chromatography (mixed solvent of heptane and ethyl acetate), further crystallized using a mixed solvent of acetonitrile and toluene, and then dried under reduced pressure to obtain a metal complex. B6 (2.8 g) was obtained. The HPLC area percentage value of the metal complex B6 was 99.5% or more.

The analysis results of the metal complex B6 were as follows.
¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.30 (s, 6H), 6.90 (d, 3H), 6.44-6.48 (m, 3H), 6 .22-6.26 (m, 3H), 5.77 (d, 3H), 2.10 (s, 9H), 1.89 (s, 9H), 1.56 (s, 18H), 1. 38 (s, 27H), 0.73 (t, 27H).

<Synthesis Example B7> Synthesis of Metal Complex B7 The metal complex B7 was synthesized by the following method.

(Synthesis of metal complex B7')
After setting the inside of the reaction vessel to a nitrogen atmosphere, the metal complex B2 (2.2 g) and methylene chloride (30 mL) were added, and the mixture was stirred at 0 ° C. N-Bromosuccinimide (0.95 g) was slowly added thereto over 15 minutes, then the reaction solution was slowly heated from 0 ° C. to room temperature, and further stirred at room temperature for 20 hours. Then, methanol (100 mL) was added thereto, and the mixture was stirred for 15 minutes to obtain a precipitate. The obtained precipitate was collected by filtration, washed with methanol, and dried under reduced pressure to obtain a metal complex B7'(2.1 g). The HPLC area percentage value of the metal complex B7'was 99.3%.

The analysis results of the metal complex B7'are as follows.
LC-MS (APCI, positive): m / z = 1468 [M + H] ⁺

(Synthesis of metal complex B7)
After setting the inside of the reaction vessel to a nitrogen atmosphere, the metal complex B7'(1.0 g), compound L7-1 (1.2 g), toluene (50 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (Pd 2) dba) ₃ ) (9.4 mg), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (SPhos) (8.4 mg) were added, and the temperature was raised to 80 ° C. Then, a 20 mass% tetraethylammonium hydroxide aqueous solution (1.8 mL) was added thereto, and the mixture was stirred under heating under reflux for 20 hours. Then, the obtained reaction solution was cooled to room temperature, the aqueous layer was removed, and then the obtained organic layer was filtered through a filter covered with silica gel. The obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid is purified by silica gel column chromatography (mixed solvent of methylene chloride and ethyl acetate), further crystallized using a mixed solvent of acetonitrile and toluene, and then dried under reduced pressure to obtain the metal complex B7. (0.72 g) was obtained. The HPLC area percentage value of the metal complex B7 was 99.5% or more.

The analysis results of the metal complex B7 were as follows.
¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.57-7.61 (m, 15H), 7.49 (d, 12H), 7.43 (d, 6H), 7 .27 (d, 3H), 7.23 (d, 3H), 7.21 (d, 3H), 7.09 (dd, 3H), 6.65 (d, 3H), 2.61 (spt, spt, 3H), 2.24 (s, 9H), 2.08 (s, 9H), 1.38 (s, 54H), 1.28 (d, 9H), 1.18 (d, 9H), 0. 93 (s, 27H).

<Synthesis Example B8> Synthesis of Metal Complex B8 The metal complex B8 was synthesized by the following method.

(Synthesis of compound L8-1)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L1-4 (200 g), triethylamine (472 mL) and tetrahydrofuran (2 L) were added, and the mixture was cooled to 0 ° C. Compound L5-1 (228 g) was slowly added dropwise thereto, and then the mixture was stirred at room temperature for 16 hours. After filtering the obtained reaction solution, the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with ethyl acetate and then dried under reduced pressure to obtain compound L8-1 (205 g). The HPLC area percentage value of compound L8-1 was 99.5% or more.

The analysis results of compound L8-1 were as follows.
LC-MS (APPI, positive): m / z = 276 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.01 (t, 3H), 1.31 (s, 6H), 1.33 (s, 9H), 1.70 (q, 2H) ), 2.23 (s, 6H), 6.84-7.09 (m, 3H).

(Synthesis of compound L8-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L8-1 (115 g), monochlorobenzene (1.2 L), 2-fluoropyridine (44.6 g) and trifluoromethanesulfonic anhydride (130 g) were added at room temperature. Stirred. Compound L8-2 (23 g) was added thereto, and the mixture was stirred at room temperature for 1 hour and then at 90 ° C. for 18 hours. Then, the obtained reaction solution was cooled to room temperature, and chloroform was added thereto. The obtained reaction solution was washed with a 10 mass% sodium hydrogen carbonate aqueous solution, and further washed twice with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate), further crystallized with acetonitrile, and then dried under reduced pressure to obtain compound L8-3 (100 g). Got The HPLC area percentage value of compound L8-3 was 99.5% or more.

The analysis results of compound L8-3 were as follows.
LC-MS (APCI, positive): m / z = 454 [M + H] ^{+
1 1} H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 0.79 (t, 3H), 1.12 (s, 6H), 1.31 (s, 9H), 1.62 (q) , 2H), 1.91 (s, 6H), 7.16 (s, 2H), 7.27-7.39 (m, 3H), 7.56 (d, 1H).

(Synthesis of compound L8-5)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L8-3 (50 g), compound L8-4 (22 g), toluene (500 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) (1 g), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (SPhos) (0.9 g) was added, and the temperature was raised to 60 ° C. A 25 mass% tetraethylammonium hydroxide aqueous solution (260 mL) was added thereto, and the mixture was stirred under heating under reflux for 18 hours. Then, the obtained reaction solution was filtered through a filter covered with cerite, and then the cerite was washed with ethyl acetate. After removing the aqueous layer from the obtained filtrate, the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate), further crystallized with acetonitrile, and then dried under reduced pressure to obtain compound L8-5 (36 g). Got The HPLC area percentage value of compound L8-5 was 99.5% or more.

The analysis results of compound L8-5 were as follows.
LC-MS (APCI, positive): m / z = 508 [M + H] ^{+
1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.92 (t, 3H), 1.23 (s, 6H), 1.35 (s, 9H), 1.37 (s, 9H) ), 1.73 (q, 2H), 2.01 (s, 6H), 7.19 (d, 2H), 7.20 (s, 2H), 7.26-7.28 (m, 1H) , 7.34-7.39 (m, 3H), 7.51-7.54 (m, 1H), 7.69-7.72 (m, 1H).

(Synthesis of metal complex B8)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (2.1 g), compound L8-5 (8.6 g) and pentadecane (3 mL) were added, and the mixture was stirred at 300 ° C. for 24 hours. .. Then, the reaction solution was cooled to room temperature to precipitate a solid. The precipitated solid is collected by filtration, the obtained solid is purified by silica gel column chromatography (mixed solvent of methylene chloride and ethyl acetate), and further crystallized using a mixed solvent of acetonitrile and methylene chloride. By drying under reduced pressure, a metal complex B8 (4.0 g) was obtained. The HPLC area percentage value of the metal complex B8 was 99.5% or more.

The analysis results of the metal complex B8 were as follows.
LC-MS (ESI, positive): m / z = 1713 [M + H] ^+
1 H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 0.92 (t, 9H), 1.11 (s, 9H), 1.22 (s, 9H), 1.27 (s) , 27H), 1.42 (s, 27H), 1.56-1.62 (m, 3H), 1.64-1.72 (m, 3H), 2.02 (s, 9H), 2. 18 (s, 9H), 6.24 (d, 3H), 6.92 (dd, 3H), 7.04 (d, 6H), 7.15 (d, 3H), 7.19 (d, 6H) ), 7.38 (d, 6H).

<Synthesis Example B9> Synthesis of Metal Complex B9 The metal complex B9 was synthesized by the following method.

(Synthesis of compound L9-1)
After setting the inside of the reaction vessel to a nitrogen atmosphere, 4-bromo-2,6-dimethylaniline (100 g), triethylamine (253 mL) and tetrahydrofuran (1.5 L) were added, and the mixture was cooled to 0 ° C. Compound L5-1 (124 mL) was slowly added dropwise thereto, and then the mixture was stirred at room temperature for 16 hours. After filtering the obtained reaction solution, the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was crystallized from acetonitrile and then dried under reduced pressure to give compound L9-1 (125 g). The HPLC area percentage value of compound L9-1 was 98.7%.

The analysis results of compound L9-1 were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.96 (t, 3H), 1.29 (s, 6H), 1.68 (q, 2H), 2.16 (s, 6H) ), 6.93 (brs, 1H), 7.08 (s, 2H).

(Synthesis of compound L9-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L9-1 (120 g), monochlorobenzene (1.2 L), 2-fluoropyridine (43 g) and trifluoromethanesulfonic anhydride (125 g) were added, and the mixture was stirred at room temperature. .. Compound L8-2 (95.2 g) was added thereto, and the mixture was stirred at room temperature for 1 hour, then at 90 ° C. for 18 hours, and further at 130 ° C. for 12 hours. Then, the obtained reaction solution was cooled to room temperature, and ethyl acetate was added thereto. The obtained reaction solution was washed with a 10 mass% sodium hydrogen carbonate aqueous solution, and further washed twice with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was crystallized from acetonitrile and then dried under reduced pressure to give compound L9-2 (70 g). The HPLC area percentage value of compound L9-2 was 99.5% or more.

The analysis results of compound L9-2 were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.89 (t, 3H), 1.22 (s, 6H), 1.71 (q, 2H), 1.99 (s, 6H) ), 7.11-7.14 (m, 2H), 7.37 (s, 2H), 7.46-7.49 (m, 1H), 7.64-7.65 (m, 1H).

(Synthesis of compound L9-3)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L9-2 (60 g), phenylboronic acid (38.3 g), toluene (600 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) ) (2.3 g), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (SPhos) (2.1 g) was added, and the temperature was raised to 60 ° C. A 25 mass% tetraethylammonium hydroxide aqueous solution (300 mL) was added thereto, and the mixture was stirred under heating under reflux for 18 hours. Then, the obtained reaction solution was filtered through a filter covered with cerite, and then the cerite was washed with ethyl acetate. After removing the aqueous layer from the obtained filtrate, the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was crystallized with acetonitrile, and further crystallized with a mixed solvent of acetonitrile and toluene. The obtained solid is sequentially purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and reverse phase column chromatography (mixed solvent of water and acetonitrile), and then dried under reduced pressure to obtain compound L9. -3 (34 g) was obtained. The HPLC area percentage value of compound L9-3 was 99.5% or more.

The analysis results of compound L9-3 were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.95 (t, 3H), 1.29 (s, 6H), 1.79 (q, 2H), 2.01 (s, 6H) ), 7.26-7.31 (m, 5H), 7.36-7.57 (m, 8H), 7.65-7.69 (m, 3H).

(Synthesis of metal complex B9)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (1.3 g), compound L9-3 (5.0 g) and pentadecane (2 mL) were added, and the mixture was stirred at 300 ° C. for 24 hours. .. Then, the reaction solution was cooled to 50 ° C., and toluene was added thereto. Then, the obtained reaction solution was cooled to room temperature and then washed with ion-exchanged water. The obtained organic layer was concentrated under reduced pressure to obtain a solid. The obtained solid is purified by silica gel column chromatography (mixed solvent of methylene chloride and ethyl acetate), further crystallized using a mixed solvent of acetonitrile and toluene, and then dried under reduced pressure to obtain the metal complex B9. (0.65 g) was obtained. The HPLC area percentage value of the metal complex B9 was 99.5% or more.

The analysis results of the metal complex B9 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.77 (dd, 6H), 7.65 (s, 6H), 7.50 (t, 6H), 7.41 (tt) , 3H), 7.25 (d, 3H), 7.11 (dd, 6H), 6.98-7.02 (m, 9H), 6.93-6.97 (m, 3H), 6. 33 (d, 3H), 2.27 (s, 9H), 2.13 (s, 9H), 1.75-1.79 (m, 4H), 1.64-1.70 (m, 4H) , 1.30 (s, 9H), 1.22 (s, 9H), 1.00 (t, 9H).

<Synthesis Example B10> The synthetic metal complex B10 of the metal complex B10 was synthesized by the following method.

(Synthesis of compound L10-2)
After setting the inside of the reaction vessel to a nitrogen atmosphere, compound L10-1 (21.4 g), triethylamine (13.0 mL) and tetrahydrofuran (300 mL) were added, and the mixture was cooled to 0 ° C. Compound L5-1 (12.8 mL) was added dropwise thereto, and the mixture was stirred at room temperature for 16 hours. Then, by adding ion-exchanged water (100 mL) to it, a precipitate was formed. The reaction solution in which the precipitate was formed was filtered to obtain a residue L10-2-1 and a filtrate L10-2-2. The residue L10-2-1 was washed with toluene and then dried under reduced pressure to obtain a solid L10-2'(24.5 g).
Further, the aqueous layer was removed from the filtrate L10-2-2, and the obtained organic layer was dried over magnesium sulfate and then filtered. The obtained filtrate was concentrated under reduced pressure and then crystallized with a mixed solvent of toluene and heptane. Then, the obtained solid was dried under reduced pressure to obtain a solid L10-2'' (3.9 g).
After combining the solid L10-2'and the solid L10-2' obtained above, crystallization was performed using a mixed solvent of toluene and heptane, and the mixture was further dried under reduced pressure to obtain the compound L10-2 ( 27.8 g (white solid) was obtained. The HPLC area percentage value of compound L10-2 was 98.9%.

The analysis results of compound L10-2 were as follows.
¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.57 (d, 2H), 7.43 (t, 2H), 7.35 (s, 2H), 7.34 (t) , 1H), 6.82 (brs, 1H), 3.08 (septet, 2H), 1.73 (q, 2H), 1.34 (s, 6H), 1.25 (d, 12H), 1 .00 (t, 3H).

(Synthesis of compound L10-4)
Compound L10-4 was prepared using Compound L10-2 (19.1 g), chlorobenzene (150 mL), 2-fluoropyridine (5.15 mL) and trifluoromethanesulfonic anhydride (10.0 mL), Organic Letters, 17. It was synthesized according to the method described in Vol., pp. 1184-1187, 2015.

The analysis results of compound L10-4 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 7.68 (d, 2H), 7.52 (t, 2H), 7.50 (s, 2H), 7.43 (t, 1H) ), 7.26 (s, 1H), 7.05-6.98 (m, 3H), 2.53 (septet, 2H), 2.15 (s, 3H), 1.88 (q, 2H) , 1.28 (d, 6H), 1.23 (s, 6H), 0.89 (t, 3H), 0.77 (d, 6H).

(Synthesis of metal complex B10)
After setting the inside of the reaction vessel to a nitrogen atmosphere, tris (acetylacetonato) iridium (III) (0.72 g), compound L10-4 (2.8 g) and pentadecane (2 mL) were added, and the mixture was stirred at 300 ° C. for 24 hours. .. Then, the obtained reaction solution is cooled to room temperature and then purified by silica gel column chromatography (mixed solvent of methylene chloride and ethyl acetate), and further, a mixed solvent of acetonitrile and toluene, a mixed solvent of toluene and methanol, and a mixed solvent of toluene and methanol are used. Crystallization was performed using a mixed solvent of methylene chloride and acetonitrile in sequence. The obtained solid was washed with methylene chloride and then dried under reduced pressure to obtain a metal complex B10 (0.82 g). The HPLC area percentage value of the metal complex B10 was 98.8%.

The analysis results of the metal complex B10 were as follows.
^{1 1} H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.74 (d, 6H), 7.64 (dd, 6H), 7.48 (t, 6H), 7.38 (t) , 3H), 6.68 (d, 3H), 6.30 (d, 3H), 5.62 (s, 3H), 2.94 (septet, 3H), 2.37 (septet, 3H), 1 .75 (s, 9H), 1.71-1.64 (m, 6H), 1.34 (d, 9H), 1.22-1.17 (m, 27H), 0.98 (d, 9H) ), 0.90 (d, 9H), 0.81 (d, 9H).

<Synthesis Example B11> Synthesis of Metal Complex B11 The metal complex B11 was synthesized according to the method described in JP2012-6914A.

<Synthesis of metal complex G1 and metal complex R1>
The metal complex G1 was synthesized according to the method described in International Publication No. 2009/131255.
The metal complex R1 was synthesized according to the method described in International Publication No. 2002/44189.

<Example D1> Fabrication and evaluation of light emitting device D1 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film to a glass substrate with a thickness of 45 nm by a sputtering method. AQ-1200 (manufactured by Plextronics), which is a polythiophene-sulfonic acid-based hole injection agent, is formed on the anode to a thickness of 35 nm by a spin coating method, and is formed at 170 ° C. on a hot plate in an air atmosphere. , The hole injection layer was formed by heating for 15 minutes.

(Formation of the 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 was formed on the hole injection layer to a thickness of 20 nm by a spin coating method, and heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere to obtain a second film. An organic layer (hole transport layer) was formed. By this heating, the polymer compound HTL-1 became a crosslinked product.

(Formation of the first organic layer)
Compound HM-1 and metal complex B3 (compound HM-1 / metal complex B3 = 75% by mass / 25% by mass) were dissolved in toluene at a concentration of 2% by mass. Using the obtained toluene solution, a film was formed on the second organic layer to a thickness of 75 nm by a spin coating method, and the first organic layer was heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. (First light emitting layer) was formed. As the compound HM-1, the compound purchased from Luminescence Technology was used.

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

(Cathode formation)
After reducing the pressure of the substrate on which the electron transport layer was formed to 1.0 × 10 ^-4 Pa or less in the vapor deposition machine, sodium fluoride was placed on the electron transport layer at about 4 nm as a cathode, and then the sodium fluoride layer was formed. About 80 nm of aluminum was deposited on top. After the vapor deposition, the light emitting element D1 was manufactured by sealing with a glass substrate.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting element D1. The drive voltage at a current density of 300 mA / cm ² was 10.1 V, and the chromaticity coordinates (x, y) were (0.21, 0.42).

<Example D2> Fabrication and evaluation of light emitting element D2 In Example D1 (formation of the first organic layer), "Compound HM-1 and metal complex B3 (compound HM-1 / metal complex B3 = 75% by mass /)". 25% by mass) ”in the same manner as in Example D1 except that“ Compound HM-1 and Metal Complex B6 (Compound HM-1 / Metal Complex B6 = 75% by Mass / 25% by mass) ”was used. A light emitting element D2 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D2. The drive voltage at a current density of 300 mA / cm ² was 10.3 V, and the chromaticity coordinates (x, y) were (0.23, 0.45).

<Example D3> Fabrication and evaluation of light emitting element D3 In Example D1 (formation of the first organic layer), "Compound HM-1 and metal complex B3 (compound HM-1 / metal complex B3 = 75% by mass /)". 25% by mass) ”in the same manner as in Example D1 except that“ Compound HM-1 and Metal Complex B1 (Compound HM-1 / Metal Complex B1 = 75% by mass / 25% by mass) ”was used. A light emitting element D3 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D3. The drive voltage at a current density of 300 mA / cm ² was 10.6 V, and the chromaticity coordinates (x, y) were (0.21, 0.42).

<Example D4> Fabrication and evaluation of light emitting element D4 In Example D1 (formation of the first organic layer), "Compound HM-1 and metal complex B3 (compound HM-1 / metal complex B3 = 75% by mass /)". 25% by mass) ”in the same manner as in Example D1 except that“ Compound HM-1 and Metal Complex B5 (Compound HM-1 / Metal Complex B5 = 75% by mass / 25% by mass) ”was used. A light emitting element D4 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D4. The drive voltage at a current density of 300 mA / cm ² was 10.4 V, and the chromaticity coordinates (x, y) were (0.22, 0.43).

<Example D5> Fabrication and evaluation of light emitting element D5 In Example D1 (formation of the first organic layer), "Compound HM-1 and metal complex B3 (compound HM-1 / metal complex B3 = 75% by mass /)". "Compound HM-1 and metal complex B6 (Compound HM-1 / Metal complex B6 = 75% by mass / 25% by mass)" is used instead of "25% by mass)", and further, (second) of Example D1 is used. A light emitting element D5 was produced in the same manner as in Example D1 except that "polymer compound HTL-2" was used instead of "polymer compound HTL-1" in the formation of the organic layer). EL light emission was observed by applying a voltage to the light emitting element D5. The drive voltage at a current density of 300 mA / cm ² was 10.4 V, and the chromaticity coordinates (x, y) were (0.20, 0.38).

<Example D6> Fabrication and evaluation of light emitting element D6 In Example D5 (formation of the first organic layer), "Compound HM-1 and metal complex B6 (compound HM-1 / metal complex B6 = 75% by mass /)". In the same manner as in Example D5, except that "Compound HM-1 and metal complex B10 (Compound HM-1 / Metal complex B10 = 75% by mass / 25% by mass)" was used instead of "25% by mass)". A light emitting element D6 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D6. The drive voltage at a current density of 300 mA / cm ² was 10.2 V, and the chromaticity coordinates (x, y) were (0.20, 0.44).

<Example D7> Fabrication and evaluation of light emitting element D7 In Example D5 (formation of the first organic layer), "Compound HM-1 and metal complex B6 (compound HM-1 / metal complex B6 = 75% by mass /)". In the same manner as in Example D5, except that "Compound HM-1 and metal complex B1 (Compound HM-1 / Metal complex B1 = 75% by mass / 25% by mass)" was used instead of "25% by mass)". A light emitting element D7 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D7. The drive voltage at a current density of 300 mA / cm ² was 10.1 V, and the chromaticity coordinates (x, y) were (0.18, 0.35).

<Example D8> Fabrication and evaluation of light emitting element D8 In Example D5 (formation of the first organic layer), "Compound HM-1 and metal complex B6 (compound HM-1 / metal complex B6 = 75% by mass /)". In the same manner as in Example D5, except that "Compound HM-1 and metal complex B7 (Compound HM-1 / Metal complex B7 = 75% by mass / 25% by mass)" was used instead of "25% by mass)". A light emitting element D8 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D8. The drive voltage at a current density of 300 mA / cm ² was 9.9 V, and the chromaticity coordinates (x, y) were (0.18, 0.41).

<Example D9> Fabrication and evaluation of light emitting element D9 In Example D5 (formation of the first organic layer), "Compound HM-1 and metal complex B6 (compound HM-1 / metal complex B6 = 75% by mass /)". In the same manner as in Example D5, except that "Compound HM-1 and metal complex B8 (Compound HM-1 / Metal complex B8 = 75% by mass / 25% by mass)" was used instead of "25% by mass)". A light emitting element D9 was manufactured. EL light emission was observed by applying a voltage to the light emitting element D9. The drive voltage at a current density of 300 mA / cm ² was 9.7 V, and the chromaticity coordinates (x, y) were (0.18, 0.42).

<Comparative Example CD1> Preparation and evaluation of light emitting element CD1 In Example D1 (formation of the first organic layer), "Compound HM-1 and Metal Complex B3 (Compound HM-1 / Metal Complex B3 = 75% by mass /)". 25% by mass) ”in the same manner as in Example D1 except that“ Compound HM-1 and Metal Complex B11 (Compound HM-1 / Metal Complex B11 = 75% by Mass / 25% by mass) ”was used. A light emitting element CD1 was manufactured. EL light emission was observed by applying a voltage to the light emitting element CD1. The drive voltage at a current density of 300 mA / cm ² was 11.6 V, and the chromaticity coordinates (x, y) were (0.27, 0.53).

<Comparative Example CD2> Fabrication and evaluation of light emitting element CD2 In Example D1 (formation of the first organic layer), "Compound HM-1 and Metal Complex B3 (Compound HM-1 / Metal Complex B3 = 75% by mass /)". 25% by mass) ”in the same manner as in Example D1 except that“ Compound HM-1 and Metal Complex B4 (Compound HM-1 / Metal Complex B4 = 75% by mass / 25% by mass) ”was used. A light emitting element CD2 was produced. EL light emission was observed by applying a voltage to the light emitting element CD2. The drive voltage at a current density of 300 mA / cm ² was 11.6 V, and the chromaticity coordinates (x, y) were (0.18, 0.36).

<Example D10> Fabrication and evaluation of light emitting device D10 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film to a glass substrate with a thickness of 45 nm by a sputtering method. AQ-1200 (manufactured by Plextronics), which is a polythiophene-sulfonic acid-based hole injection agent, is formed on the anode to a thickness of 35 nm by a spin coating method, and is formed at 170 ° C. on a hot plate in an air atmosphere. , The hole injection layer was formed by heating for 15 minutes.

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

(Formation of the first organic layer)
Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 / metal complex G1 = 74% by mass / 25% by mass / 1% by mass) are dissolved in toluene at a concentration of 2% by mass. rice field. Using the obtained toluene solution, a film was formed on the second organic layer to a thickness of 75 nm by a spin coating method, and the first organic layer was heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. (First light emitting layer) was formed.

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

(Cathode formation)
After reducing the pressure of the substrate on which the electron transport layer was formed to 1.0 × 10 ^-4 Pa or less in the vapor deposition machine, sodium fluoride was placed on the electron transport layer at about 4 nm as a cathode, and then the sodium fluoride layer was formed. About 80 nm of aluminum was deposited on top. After the vapor deposition, the light emitting device D10 was manufactured by sealing with a glass substrate.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting element D10. The drive voltage at a current density of 300 mA / cm ² was 10.9 V, and the chromaticity coordinates (x, y) were (0.42, 0.43).

<Example D11> Fabrication and evaluation of light emitting element D11 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B2 and metal complex G1 (compound HM-1 / metal complex B2 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D11 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D11. The drive voltage at a current density of 300 mA / cm ² was 11.0 V, and the chromaticity coordinates (x, y) were (0.39, 0.44).

<Example D12> Fabrication and evaluation of light emitting element D12 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B6 and metal complex G1 (compound HM-1 / metal complex B6 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D12 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D12. The drive voltage at a current density of 300 mA / cm ² was 10.7 V, and the chromaticity coordinates (x, y) were (0.43, 0.43).

<Example D13> Fabrication and evaluation of light emitting element D13 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B3 and metal complex G1 (compound HM-1 / metal complex B3 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D13 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D13. The drive voltage at a current density of 300 mA / cm ² was 8.6 V, and the chromaticity coordinates (x, y) were (0.50, 0.42).

<Example D14> Fabrication and evaluation of light emitting element D14 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B7 and metal complex G1 (compound HM-1 / metal complex B7 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D14 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D14. The drive voltage at a current density of 300 mA / cm ² was 10.2 V, and the chromaticity coordinates (x, y) were (0.40, 0.45).

<Example D15> Fabrication and evaluation of light emitting element D15 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B8 and metal complex G1 (compound HM-1 / metal complex B8 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D15 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D15. The drive voltage at a current density of 300 mA / cm ² was 10.4 V, and the chromaticity coordinates (x, y) were (0.41, 0.45).

<Example D16> Fabrication and evaluation of light emitting element D16 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B9 and metal complex G1 (compound HM-1 / metal complex B9 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element D16 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element D16. The drive voltage at a current density of 300 mA / cm ² was 9.8 V, and the chromaticity coordinates (x, y) were (0.37, 0.46).

<Example D17> Fabrication and evaluation of light emitting element D17 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Compound HM-1 and metal complex B6 (Compound HM-1 / Metal complex B6 = 75% by mass / 25% by mass)" instead of "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" The light emitting element D17 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D17. The drive voltage at a current density of 300 mA / cm ² was 10.6 V, and the chromaticity coordinates (x, y) were (0.42, 0.38).

<Example D18> Fabrication and evaluation of light emitting element D18 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" is replaced with "Compound HM-1 and metal complex B3 (Compound HM-1 / Metal complex B3 = 75% by mass / 25% by mass)". The light emitting element D18 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D18. The drive voltage at a current density of 300 mA / cm ² was 8.5 V, and the chromaticity coordinates (x, y) were (0.48, 0.38).

<Example D19> Fabrication and evaluation of light emitting element D19 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Compound HM-1 and metal complex B5 (Compound HM-1 / Metal complex B5 = 75% by mass / 25% by mass)" instead of "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" The light emitting element D19 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D19. The drive voltage at a current density of 300 mA / cm ² was 10.6 V, and the chromaticity coordinates (x, y) were (0.39, 0.36).

<Example D20> Fabrication and evaluation of light emitting element D20 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Compound HM-1 and metal complex B7 (Compound HM-1 / Metal complex B7 = 75% by mass / 25% by mass)" instead of "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" The light emitting element D20 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D20. The drive voltage at a current density of 300 mA / cm ² was 10.3 V, and the chromaticity coordinates (x, y) were (0.38, 0.41).

<Example D21> Fabrication and evaluation of light emitting element D21 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Compound HM-1 and metal complex B8 (Compound HM-1 / Metal complex B8 = 75% by mass / 25% by mass)" instead of "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" The light emitting element D21 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D21. The drive voltage at a current density of 300 mA / cm ² was 10.3 V, and the chromaticity coordinates (x, y) were (0.38, 0.40).

<Example D22> Fabrication and evaluation of light emitting element D22 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). "Compound HM-1 and metal complex B9 (Compound HM-1 / Metal complex B9 = 75% by mass / 25% by mass)" instead of "Metal complex G1 = 74% by mass / 25% by mass / 1% by mass)" The light emitting element D22 was produced in the same manner as in Example D10 except that it was used. EL light emission was observed by applying a voltage to the light emitting element D22. The drive voltage at a current density of 300 mA / cm ² was 9.9 V, and the chromaticity coordinates (x, y) were (0.35, 0.41).

<Comparative Example CD3> Fabrication and evaluation of light emitting element CD3 In Example D10 (formation of the first organic layer), "Compound HM-1, metal complex B5 and metal complex G1 (compound HM-1 / metal complex B5 /). Instead of "metal complex G1 = 74% by mass / 25% by mass / 1% by mass)", "compound HM-1, metal complex B4 and metal complex G1 (compound HM-1 / metal complex B4 / metal complex G1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element CD3 was produced in the same manner as in Example D10. EL light emission was observed by applying a voltage to the light emitting element CD3. The drive voltage at a current density of 300 mA / cm ² was 11.8 V, and the chromaticity coordinates (x, y) were (0.36, 0.44).

<Example D23> Fabrication and evaluation of light emitting device D23 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film to a glass substrate with a thickness of 45 nm by a sputtering method. AQ-1200 (manufactured by Plextronics), which is a polythiophene-sulfonic acid-based hole injection agent, is formed on the anode to a thickness of 35 nm by a spin coating method, and is formed at 170 ° C. on a hot plate in an air atmosphere. , The hole injection layer was formed by heating for 15 minutes.

(Formation of the 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 was formed on the hole injection layer to a thickness of 20 nm by a spin coating method, and heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere to obtain a second film. An organic layer (hole transport layer) was formed. By this heating, the polymer compound HTL-2 became a crosslinked product.

(Formation of the first organic layer)
Compound HM-1, metal complex B3 and metal complex R1 (compound HM-1 / metal complex B3 / metal complex R1 = 74% by mass / 25% by mass / 1% by mass) are dissolved in toluene at a concentration of 2% by mass. rice field. Using the obtained toluene solution, a film was formed on the second organic layer to a thickness of 75 nm by a spin coating method, and the first organic layer was heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. (First light emitting layer) was formed.

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

(Cathode formation)
After reducing the pressure of the substrate on which the electron transport layer was formed to 1.0 × 10 ^-4 Pa or less in the vapor deposition machine, sodium fluoride was placed on the electron transport layer at about 4 nm as a cathode, and then the sodium fluoride layer was formed. About 80 nm of aluminum was deposited on top. After the vapor deposition, the light emitting element D23 was manufactured by sealing with a glass substrate.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting element D23. The drive voltage at a current density of 250 mA / cm ² was 8.7 V, and the chromaticity coordinates (x, y) were (0.47, 0.32).

<Comparative Example CD4> Fabrication and evaluation of light emitting element CD4 In Example D23 (formation of the first organic layer), "Compound HM-1, metal complex B3 and metal complex R1 (compound HM-1 / metal complex B3 /). Instead of "Metal complex R1 = 74% by mass / 25% by mass / 1% by mass", "Compound HM-1, Metal complex B4 and Metal complex R1 (Compound HM-1 / Metal complex B4 / Metal complex R1 = 74% by mass)" % / 25% by mass / 1% by mass) ”was used, and the light emitting element CD4 was produced in the same manner as in Example D23. EL light emission was observed by applying a voltage to the light emitting element CD4. The drive voltage at a current density of 250 mA / cm ² was 11.4 V, and the chromaticity coordinates (x, y) were (0.48, 0.32).

Claims (12)

It has an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode.
The first organic layer contains a metal complex represented by the formula (1) and contains.
A light emitting device in which the second organic layer contains a crosslinked body of a polymer compound containing a structural unit having a crosslinking group.

[During the ceremony,
M represents a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n ¹ represents an integer of 1 or more, n ² represents an integer of 0 or more, and n ¹ + n ² is 2 or 3.
When M is a rhodium atom or an iridium atom, n ¹ + n ² is 3, and when M is a palladium atom or a platinum atom, n ¹ + n ² is 2.
E ¹ represents a carbon atom or a nitrogen atom. When a plurality of E ^1s exist, they may be the same or different.
Ring B represents an aromatic hydrocarbon ring or an aromatic heterocycle, and these rings may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring with the atom to which each is bonded. When there are a plurality of rings B, they may be the same or different.
Z ^1A represents a group represented by = N− .
R ¹ represents an alkyl group having 4 or more carbon atoms and 30 or less carbon atoms, and these groups may have a substituent. When there are a plurality of ^R1 , they may be the same or different.
Ar ^1A represents a group represented by the formula (Ar-1A). When there are a plurality of Ar ^1A , they may be the same or different.
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. A ¹ and A ² independently represent 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 together with A ¹ and A ² . When there are a plurality of A ¹ -G ¹ -A ² , they may be the same or different. ]

[During the ceremony,
Ring A represents an aromatic hydrocarbon ring or an aromatic heterocycle, and these rings may have a substituent. When a plurality of the substituents are present, they may be bonded to each other to form a ring with the atom to which each is bonded.
R ² and R ³ independently represent 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, respectively. The group may have a substituent. ] The light emitting device according to claim 1, wherein the polymer compound containing a structural unit having a cross-linking group contains a structural unit represented by the formula (X).

[During the ceremony,
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups are substituents. May have. When there are a plurality of Ar ^X2 and Ar ^X4 , they may be the same or different.
^RX1 , ^RX2 and ^RX3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
When there are a plurality of ^RX2 and ^RX3 , they may be the same or different. ] The light emitting device according to claim 1 or 2, wherein the cross-linking group is at least one selected from the cross-linking group A group.
(Crosslinking group A group)

[In the formula, R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5. If there are multiple ^RXLs , they may be the same or different. A plurality of n ^XLs may be the same or different. * 1 represents the bonding position. These cross-linking groups may have substituents. ] The light emitting device according to claim 3, wherein the structural unit having a cross-linking group is a structural unit represented by the formula (Z) or a structural unit represented by the formula (Z').

[During the ceremony,
nA represents an integer of 0 to 5, and n represents 1 or 2. When there are a plurality of nA, 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.
^LA 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 have a substituent. May be 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 there are multiple ^LAs , they may be the same or different.
X represents a cross-linking group selected from the group A of cross-linking groups. If there are multiple X's, they may be the same or different. ]

[During the ceremony,
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents an integer of 0 or 1. If there are multiple 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 heterocycle are directly bonded, and these groups have a substituent. 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 each form a ring by directly bonding or bonding with a group other than the group bonded to the nitrogen atom to which the group is bonded via an oxygen atom or a sulfur atom. You may be doing it.
^KA 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 have a substituent. May be 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 there are multiple ^KAs , they may be the same or different.
X'represents a cross-linking group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group selected from the cross-linking group A group, and these groups may have a substituent. If there are multiple X's, they may be the same or different. However, at least one X'is a cross-linking group selected from the group A of cross-linking groups. ] The light emitting device according to any one of claims 1 to 4, wherein the metal complex represented by the formula (1) is a metal complex represented by the formula (1-1).

[During the ceremony,
M, Z ^1A , n ¹ , n ² , R ¹ , Ar ^1A and A ¹ -G ¹ -A ² have the same meanings as described above.
Ring B ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring, and E ^1B , E ^2B , E ^3B and E ^4B independently represent a nitrogen atom or a carbon atom. When there are a plurality of E ^1B , E ^2B , E ^3B and E ^4B , they may be the same or different from each other. If E ^1B is a nitrogen atom, then R ^1B does not exist. If E ^2B is a nitrogen atom, then R ^2B does not exist. If E ^3B is a nitrogen atom, then R ^3B does not exist. If E ^4B is a nitrogen atom, then R ^4B does not exist.
R ^1B , R ^2B , R ^3B and R ^4B are independently hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group and substituted amino. Representing a group or a halogen atom, these groups may have a substituent. When there are a plurality of R ^1B , R ^2B , R ^3B and R ^4B , they may be the same or different from each other. R ^1B and R ^2B , R ^2B and R ^3B , and R ^3B and R ^4B may be bonded to each other to form a ring together with the atoms to which they are bonded. ] The light emitting device according to claim 5, wherein the metal complex represented by the formula (1-1) is a metal complex represented by the formula (1-2).

[In the formula, M, Z ^1A , n ¹ , n ² , R ¹ , Ar ^1A , A ¹ -G ¹ -A ² , R ^1B , R ^2B , R ^3B and R ^4B have the same meanings as described above. ] The light emitting device 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).

[In the formula, R ² and R ³ have the same meanings as described above.
Ring A ¹ represents a benzene ring, a pyridine ring or a diazabenzene ring, and E ^1A , E ^2A and E ^3A independently represent a nitrogen atom or a carbon atom. If E ^1A is a nitrogen atom, then R ^1A does not exist. If E ^2A is a nitrogen atom, then R ^2A does not exist. If E ^3A is a nitrogen atom, then R ^3A does not exist.
R ^1A , R ^2A and R ^3A independently have 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. Representing an atom, these groups may have substituents. R ^1A and R ^2A , and R ^2A and R ^3A may be bonded to each other to form a ring together with the atoms to which they are bonded. ] The light emitting device according to claim 7, wherein the group represented by the formula (Ar-2A) is a group represented by the formula (Ar-3A).

[In the formula, R ² , R ³ , R ^1A , R ^2A and R ^3A have the same meanings as described above. ] Claimed that the first organic layer further contains at least one selected from the group consisting of a compound represented by the formula (H-1) and a polymer compound containing a structural unit represented by the formula (Y). Item 6. The light emitting element according to any one of Items 1 to 8.

[During the ceremony,
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 independently represent 0 or 1, respectively. When there are a plurality of n ^H1 , they may be the same or different. A plurality of n ^H2s 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 ( ^RH11 ) ₂ ] _nH11 −, and these groups may have a substituent. When there are a plurality of L ^H1 , they may be the same or different. nH11 represents an integer of 1 or more and 10 or less. ^RH11 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 ^RH11s existing may be the same or different, or may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
L ^H2 represents a group represented by -N (-L ^H21 - ^RH21 )-. When there are a plurality of L ^H2s , 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. ^RH21 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. ]

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. May be. ] The first organic layer further contains at least one selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material and an antioxidant. The light emitting element according to any one of 9. The light emitting device according to any one of claims 1 to 10, wherein the first organic layer and the second organic layer are adjacent to each other. The light emitting device according to any one of claims 1 to 11, wherein the second organic layer is a layer provided between the anode and the first organic layer.