JP7242283B2 - organic electroluminescent device - Google Patents

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescence device having a light-emitting layer containing both an anthracene-based compound and a pyrene-based compound as host materials, and a display device and a lighting device using the same.

Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied in various ways because they can be reduced in power consumption and thickness. It has been actively studied because it is easy to make and enlarge. In particular, the development of organic materials that emit light in blue, one of the three primary colors of light, and the combination of multiple materials that achieve optimal light emission properties have been actively pursued, regardless of whether they are high-molecular compounds or low-molecular-weight compounds. has been studied.

An organic EL element has a structure comprising a pair of electrodes consisting of an anode and a cathode, and one or more layers interposed between the pair of electrodes and containing an organic compound. Layers containing organic compounds include light-emitting layers and charge transport/injection layers that transport or inject charges such as holes and electrons. Various organic materials suitable for these layers have been developed.

The light-emitting layer is a layer that emits light by recombination of holes injected from the anode and electrons injected from the cathode between electrodes to which an electric field is applied. As the light-emitting layer of a general blue device, a structure of a single light-emitting layer composed of one type of pyrene-based dopant and one type of anthracene-based host is widely adopted. Generally, anthracene-based compounds are known as host materials (International Publication No. 2014/141725, International Publication No. 2016/152544), and dibenzochrysene-based compounds are also known as host materials. Japanese Patent Laid-Open No. 2011-6397).

International Publication No. 2014/141725 International Publication No. 2016/152544 JP 2011-006397 A

However, in such a structure of a single light-emitting layer, it is often difficult to adjust the carrier balance between the dopant and the host and emit light from the center of the light-emitting layer. It is said that the recombination region is often biased. As a result, carriers flow into the hole-transporting layer and the electron-transporting layer, which is thought to lead to a decrease in device efficiency and device life.

As a result of intensive studies to solve the above problems, the present inventors have found that the recombination region is formed at the interface between the light-emitting layer and the adjacent layer by forming the light-emitting layer into, for example, a two-layer structure using two or more kinds of host materials. It is considered that the carrier balance can be improved by keeping the carrier away from the adjacent layer and suppressing the flow of carriers to the adjacent layer. In the examples of the present application, it was demonstrated that such a device configuration leads to improvement in device efficiency and device life. This is because the carrier balance is improved and the burden on the carrier transport layer can be suppressed. it is conceivable that.

（上記式（１）中、
ＸおよびＡｒ^４は、それぞれ独立して、水素、置換されていてもよいアリール、置換されていてもよいヘテロアリール、置換されていてもよいジアリールアミノ、置換されていてもよいジヘテロアリールアミノ、置換されていてもよいアリールヘテロアリールアミノ、置換されていてもよいアルキル、置換されていてもよいシクロアルキル、置換されていてもよいアルケニル、置換されていてもよいアルコキシ、置換されていてもよいアリールオキシ、置換されていてもよいアリールチオまたは置換されていてもよいシリルであり、全てのＸおよびＡｒ^４は同時に水素になることはなく、
式（１）で表される化合物における少なくとも１つの水素はハロゲン、シアノ、重水素または置換されていてもよいヘテロアリールで置換されていてもよい。）
（上記式（２）中、
ｓ個のピレン部分とｐ個のＡｒ部分とがピレン部分の＊のいずれかの位置とＡｒ部分のいずれかの位置とで結合し、
ピレン部分の少なくとも１つの水素は、それぞれ独立して、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキル、炭素数３～２４のシクロアルキル、炭素数２～３０のアルケニル、炭素数１～３０のアルコキシまたは炭素数６～３０のアリールオキシで置換されていてもよく、これらにおける少なくとも１つの水素は、それぞれ独立して、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキル、炭素数３～２４のシクロアルキル、炭素数２～３０のアルケニル、炭素数１～３０のアルコキシまたは炭素数６～３０のアリールオキシで置換されていてもよく、
Ａｒは、それぞれ独立して、炭素数１４～４０のアリールまたは炭素数１２～４０のヘテロアリールであり、これらにおける少なくとも１つの水素は、それぞれ独立して、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキル、炭素数３～２４のシクロアルキル、炭素数２～３０のアルケニル、炭素数１～３０のアルコキシまたは炭素数６～３０のアリールオキシで置換されていてもよく、
ｓおよびｐはそれぞれ独立して１または２の整数であり、ｓおよびｐは同時に２になることはなく、ｓが２である場合は２個のピレン部分は置換基を含めて構造的に同一であっても異なっていてもよく、ｐが２である場合は２個のＡｒ部分は置換基を含めて構造的に同一であっても異なっていてもよく、そして、
式（２）で表される化合物における少なくとも１つの水素は、それぞれ独立して、ハロゲン、シアノまたは重水素で置換されていてもよい。） Section 1.
An organic electroluminescence device having a pair of electrode layers consisting of an anode layer and a cathode layer, and a light-emitting layer disposed between the pair of electrode layers, wherein the light-emitting layer contains a host material represented by the following general formula (1) An organic electroluminescence device comprising an anthracene-based compound represented by and a pyrene-based compound represented by the following general formula (2), and further including a dopant material.

(In the above formula (1),
X and Ar ⁴ are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio or optionally substituted silyl, wherein not all X and Ar ⁴ are simultaneously hydrogen,
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, deuterium or optionally substituted heteroaryl. )
(in the above formula (2),
s pyrene moieties and p Ar moieties are bound at any position of * of the pyrene moiety and any position of the Ar moiety,
At least one hydrogen in the pyrene moiety is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms. may be substituted with alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these is independently aryl having 6 to 10 carbon atoms , heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryl having 6 to 30 carbon atoms. optionally substituted with oxy,
Each Ar is independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in these is each independently an aryl having 6 to 10 carbon atoms, substituted with heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms may have been
s and p are each independently an integer of 1 or 2, s and p are not 2 at the same time, and when s is 2, the two pyrene moieties are structurally identical including substituents may be different, and when p is 2, the two Ar moieties may be structurally the same or different, including substituents, and
At least one hydrogen in the compound represented by formula (2) may be independently substituted with halogen, cyano or deuterium. )

（上記式（１）中、
Ｘはそれぞれ独立して上記式（１－Ｘ１）、式（１－Ｘ２）または式（１－Ｘ３）で表される基であり、式（１－Ｘ１）および式（１－Ｘ２）におけるナフチレン部位は１つのベンゼン環で縮合されていてもよく、式（１－Ｘ１）、式（１－Ｘ２）または式（１－Ｘ３）で表される基は＊において式（１）のアントラセン環と結合し、Ａｒ^１、Ａｒ^２およびＡｒ^３は、それぞれ独立して、水素（Ａｒ^３を除く）、フェニル、ビフェニリル、テルフェニリル、クアテルフェニリル、ナフチル、フェナントリル、フルオレニル、ベンゾフルオレニル、クリセニル、トリフェニレニル、ピレニル、または、上記式（Ａ）で表される基であり、Ａｒ^３における少なくとも１つの水素は、さらにフェニル、ビフェニリル、テルフェニリル、ナフチル、フェナントリル、フルオレニル、クリセニル、トリフェニレニル、ピレニル、または、上記式（Ａ）で表される基で置換されていてもよく、
Ａｒ^４は、それぞれ独立して、水素、フェニル、ビフェニリル、ターフェニリル、ナフチル、または、炭素数１～４のアルキルもしくは炭素数５～１０のシクロアルキルで置換されているシリルであり、そして、
式（１）で表される化合物における少なくとも１つの水素はハロゲン、シアノ、重水素または上記式（Ａ）で表される基で置換されていてもよく、
上記式（Ａ）中、Ｙは－Ｏ－、－Ｓ－または＞Ｎ－Ｒ^２９であり、Ｒ^２１～Ｒ^２８はそれぞれ独立して水素、置換されていてもよいアルキル、置換されていてもよいシクロアルキル、置換されていてもよいアリール、置換されていてもよいヘテロアリール、置換されていてもよいアルコキシ、置換されていてもよいアリールオキシ、置換されていてもよいアリールチオ、トリアルキルシリル、トリシクロアルキルシリル、置換されていてもよいアミノ、ハロゲン、ヒドロキシまたはシアノであり、Ｒ^２１～Ｒ^２８のうち隣接する基は互いに結合して炭化水素環、アリール環またはヘテロアリール環を形成していてもよく、Ｒ^２９は水素または置換されていてもよいアリールであり、式（Ａ）で表される基は＊において式（１－Ｘ１）または式（１－Ｘ２）のナフタレン環、式（１－Ｘ３）の単結合、式（１－Ｘ３）のＡｒ^３と結合し、また式（１）で表される化合物における少なくとも１つの水素と置換し、式（Ａ）の構造においてはいずれかの位置でこれらと結合する。） Section 2.
Item 2. The organic electroluminescence device according to Item 1, wherein the light-emitting layer contains an anthracene-based compound represented by the following general formula (1) as a host material.

(In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), and naphthylene in formula (1-X1) and formula (1-X2) The site may be condensed with one benzene ring, and the group represented by formula (1-X1), formula (1-X2) or formula (1-X3) is the anthracene ring of formula (1) in *. and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the above formula (A), wherein at least one hydrogen in Ar ³ is further phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or the above optionally substituted with a group represented by formula (A),
Ar ⁴ is each independently hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or silyl substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, deuterium or a group represented by formula (A) above,
In formula (A) above, Y is —O—, —S— or >N—R ²⁹ , and R ²¹ to R ²⁸ are each independently hydrogen, optionally substituted alkyl, optionally substituted optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, tricycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, wherein adjacent groups among R ²¹ to R ²⁸ are bonded together to form a hydrocarbon ring, an aryl ring or a heteroaryl ring; R ²⁹ is hydrogen or optionally substituted aryl, and the group represented by formula (A) in * is a naphthalene ring of formula (1-X1) or formula (1-X2), formula ( 1-X3) single bond, bonded to Ar ³ of formula (1-X3) and also replaces at least one hydrogen in the compound represented by formula (1), and in the structure of formula (A) any are combined with these at the positions of )

（上記式（１）中、
Ｘはそれぞれ独立して上記式（１－Ｘ１）、式（１－Ｘ２）または式（１－Ｘ３）で表される基であり、式（１－Ｘ１）、式（１－Ｘ２）または式（１－Ｘ３）で表される基は＊において式（１）のアントラセン環と結合し、Ａｒ^１、Ａｒ^２およびＡｒ^３は、それぞれ独立して、水素（Ａｒ^３を除く）、フェニル、ビフェニリル、テルフェニリル、ナフチル、フェナントリル、フルオレニル、クリセニル、トリフェニレニル、ピレニル、または、上記式（Ａ－１）～式（Ａ－１１）のいずれかで表される基であり、Ａｒ^３における少なくとも１つの水素は、さらにフェニル、ビフェニリル、テルフェニリル、ナフチル、フェナントリル、フルオレニル、クリセニル、トリフェニレニル、ピレニル、または、上記式（Ａ－１）～式（Ａ－１１）のいずれかで表される基で置換されていてもよく、
Ａｒ^４は、それぞれ独立して、水素、フェニル、または、ナフチルであり、そして、
式（１）で表される化合物における少なくとも１つの水素はハロゲン、シアノ、重水素で置換されていてもよく、
上記式（Ａ－１）～式（Ａ－１１）中、Ｙは－Ｏ－、－Ｓ－または＞Ｎ－Ｒ^２９であり、Ｒ^２９は水素またはアリールであり、式（Ａ－１）～式（Ａ－１１）で表される基における少なくとも１つの水素はアルキル、シクロアルキル、アリール、ヘテロアリール、アルコキシ、アリールオキシ、アリールチオ、トリアルキルシリル、トリシクロアルキルシリル、ジアリール置換アミノ、ジヘテロアリール置換アミノ、アリールヘテロアリール置換アミノ、ハロゲン、ヒドロキシまたはシアノで置換されていてもよく、式（Ａ－１）～式（Ａ－１１）で表される基は＊において式（１－Ｘ１）または式（１－Ｘ２）のナフタレン環、式（１－Ｘ３）の単結合、式（１－Ｘ３）のＡｒ^３と結合し、式（Ａ－１）～式（Ａ－１１）の構造においてはいずれかの位置でこれらと結合する。） Item 3.
Item 2. The organic electroluminescence device according to Item 1, wherein the light-emitting layer contains an anthracene-based compound represented by the following general formula (1) as a host material.

(In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), formula (1-X1), formula (1-X2) or formula The group represented by (1-X3) is bonded to the anthracene ring of formula (1) at *, and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl , terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by any of the above formulas (A-1) to (A-11), wherein at least one hydrogen in Ar ³ is , further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by any of the above formulas (A-1) to (A-11) often,
each Ar ⁴ is independently hydrogen, phenyl, or naphthyl; and
at least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano or deuterium,
In formulas (A-1) to (A-11) above, Y is —O—, —S— or >N—R ²⁹ , R ²⁹ is hydrogen or aryl, and formulas (A-1) to At least one hydrogen in the group represented by formula (A-11) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, tricycloalkylsilyl, diaryl-substituted amino, diheteroaryl optionally substituted with substituted amino, arylheteroaryl substituted amino, halogen, hydroxy or cyano, the groups represented by formulas (A-1) to (A-11) are represented by formula (1-X1) or Naphthalene ring of formula (1-X2), single bond of formula (1-X3), bond to Ar ³ of formula (1-X3), and in the structures of formulas (A-1) to (A-11) Combine with these at any position. )

Section 4.
In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), formula (1-X1), formula (1-X2) or formula The group represented by (1-X3) is bonded to the anthracene ring of formula (1) at *, and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl , terphenylyl, naphthyl, phenanthryl, fluorenyl, or a group represented by any of the above formulas (A-1) to (A-4), wherein at least one hydrogen in Ar ³ is further phenyl, naphthyl, phenanthryl, fluorenyl, or optionally substituted with a group represented by any of the above formulas (A-1) to (A-4),
each Ar ⁴ is independently hydrogen, phenyl, or naphthyl; and
at least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, or deuterium;
Item 4. An organic electroluminescence device according to item 3.

Item 5.
Item 1. The organic electroluminescence device according to item 1, wherein the compound represented by the formula (1) is a compound represented by the following structural formula.

上記各式中、
Ｚは、＞ＣＲ_２、＞Ｎ－Ｒ、＞Ｏまたは＞Ｓであり、
＞ＣＲ_２におけるＲは、それぞれ独立して、炭素数１～６のアルキル、炭素数３～１４のシクロアルキル、炭素数６～１２のアリールまたは炭素数２～１２のヘテロアリールであり、前記アリールおよびヘテロアリールにおける少なくとも１つの水素は炭素数１～４のアルキルまたは炭素数５～１０のシクロアルキルで置換されていてもよく、Ｒは互いに結合して環を形成していてもよく、
＞Ｎ－ＲにおけるＲは、炭素数１～４のアルキル、炭素数５～１０のシクロアルキル、炭素数６～１２のアリールまたは炭素数２～１２のヘテロアリールであり、前記アリールおよびヘテロアリールにおける少なくとも１つの水素は炭素数１～４のアルキルまたは炭素数５～１０のシクロアルキルで置換されていてもよく、
Ｒ^１からＲ^８およびＲ^１０からＲ^１９は、それぞれ独立して、水素、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキル、炭素数３～２４のシクロアルキル、炭素数２～３０のアルケニル、炭素数１～３０のアルコキシまたは炭素数６～３０のアリールオキシであり、これらにおける少なくとも１つの水素は炭素数１～６のアルキルまたは炭素数３～１４のシクロアルキルで置換されていてもよく、Ｒ^１からＲ^８のうち隣接する基同士またはＲ^１０からＲ^１９のうち隣接する基同士が互いに結合して縮合環を形成していてもよく、形成された環は、それぞれ独立して、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキル、炭素数３～２４のシクロアルキル、炭素数２～３０のアルケニル、炭素数１～３０のアルコキシまたは炭素数６～３０のアリールオキシで置換されていてもよく、これらにおける少なくとも１つの水素は炭素数１～６のアルキルまたは炭素数３～１４のシクロアルキルで置換されていてもよく、そして、
上記式（Ａｒ－１）または式（Ａｒ－２）で表される基における少なくとも１つの水素は、それぞれ独立して、ハロゲン、シアノまたは重水素で置換されていてもよく、
上記式（Ａｒ－１）または式（Ａｒ－２）で表される基は＊においてピレン部分のいずれかの位置で結合し、ピレン部分は上記式（Ａｒ－１）または式（Ａｒ－２）で表される基中のいずれかの位置で結合する。 Item 6.
Any one of items 1 to 5, wherein each Ar in the general formula (2) is independently a group represented by the following general formula (Ar-1) or general formula (Ar-2) Organic electroluminescence device.

In each of the above formulas,
Z is >CR ₂ , >NR, >O or >S;
> Each R in CR ₂ is independently alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and the aryl and at least one hydrogen in heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may combine with each other to form a ring,
>R in NR is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and at least one hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms;
R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ are each independently hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, and 3 to 24 carbon atoms. cycloalkyl, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, wherein at least one hydrogen in these is alkyl having 1 to 6 carbon atoms or 3 to may be substituted with 14 cycloalkyls, adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, The formed rings are each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and 2 to 30 carbon atoms. alkenyl, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, at least one hydrogen in which is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms may be replaced with, and
at least one hydrogen in the group represented by the above formula (Ar-1) or formula (Ar-2) may be independently substituted with halogen, cyano or deuterium,
The group represented by the above formula (Ar-1) or formula (Ar-2) is bonded at any position of the pyrene moiety in *, and the pyrene moiety is the above formula (Ar-1) or formula (Ar-2) It binds at any position in the group represented by.

上記各式中、
Ｚは、＞ＣＲ_２、＞Ｎ－Ｒ、＞Ｏまたは＞Ｓであり、
＞ＣＲ_２におけるＲは、それぞれ独立して、炭素数１～６のアルキル、炭素数３～１４のシクロアルキルまたは炭素数６～１２のアリールであり、Ｒは互いに結合して環を形成していてもよく、
＞Ｎ－ＲにおけるＲは、炭素数１～４のアルキル、炭素数５～１０のシクロアルキルまたはまたは炭素数６～１２のアリールであり、
上記各式で表される基における少なくとも１つの水素は、それぞれ独立して、炭素数６～１０のアリール、炭素数２～１１のヘテロアリール、炭素数１～３０のアルキルまたは炭素数３～２４のシクロアルキルで置換されていてもよく、そして、
上記各式で表される基における少なくとも１つの水素は、それぞれ独立して、ハロゲン、シアノまたは重水素で置換されていてもよく、
上記式（Ａｒ－１－１）～式（Ａｒ－１－１２）及び式（Ａｒ－２－１）～式（Ａｒ－２－４）のいずれかで表される基は＊においてピレン部分のいずれかの位置で結合し、ピレン部分は上記式（Ａｒ－１－１）～式（Ａｒ－１－１２）及び式（Ａｒ－２－１）～式（Ａｒ－２－４）のいずれかで表される基中のいずれかの位置で結合する。 Item 7.
Ar in the general formula (2) is each independently represented by the following general formulas (Ar-1-1) to (Ar-1-12) and general formulas (Ar-2-1) to (Ar- The organic electroluminescence device according to any one of Items 1 to 5, which is a group represented by any one of 2-4).

In each of the above formulas,
Z is >CR ₂ , >NR, >O or >S;
>R in CR ₂ is each independently alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms or aryl having 6 to 12 carbon atoms, and the Rs are bonded to each other to form a ring. may be
>R in NR is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or aryl having 6 to 12 carbon atoms,
At least one hydrogen in the groups represented by the above formulas is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms or 3 to 24 carbon atoms. and optionally substituted with a cycloalkyl of
At least one hydrogen in the groups represented by the above formulas may be independently substituted with halogen, cyano or deuterium,
The group represented by any of the above formulas (Ar-1-1) to (Ar-1-12) and formulas (Ar-2-1) to (Ar-2-4) is the pyrene moiety in * bonded at any position, and the pyrene moiety is any of the above formulas (Ar-1-1) to (Ar-1-12) and formulas (Ar-2-1) to (Ar-2-4) It binds at any position in the group represented by.

Item 8.
Item 6. The organic electroluminescence device according to any one of items 1 to 5, wherein the pyrene-based compound represented by the general formula (2) is a compound represented by any one of the following structural formulas.

Item 9.
Item, wherein the light-emitting layer is configured by laminating at least a first light-emitting layer and a second light-emitting layer, the first light-emitting layer contains the anthracene-based compound, and the second light-emitting layer contains the pyrene-based compound 9. The organic electroluminescence device according to any one of 1 to 8.

Item 10.
A mixed region containing the anthracene-based compound and the pyrene-based compound is provided between the first light-emitting layer and the second light-emitting layer, and the concentration of the anthracene-based compound in the mixed region varies from the first light-emitting layer to the second light-emitting layer. Item 10. The organic electroluminescent device according to Item 9, wherein the concentration of the pyrene-based compound decreases in the layer direction, or decreases in the direction from the second light-emitting layer to the first light-emitting layer, or both.

Item 11.
In the light-emitting layer, the concentration of the anthracene-based compound decreases in the direction from one layer sandwiching the light-emitting layer to the other layer, or the concentration of the pyrene-based compound decreases in the direction from the one layer to the other layer. Item 9. The organic electroluminescent device according to any one of items 1 to 8, wherein the is increased or both.

Item 12.
Item 12. The organic electroluminescence device according to any one of Items 1 to 11, wherein the dopant material includes a boron-containing compound or a pyrene-based compound different from the pyrene-based compound represented by the general formula (2).

Item 13.
Further, an electron-transporting layer and/or an electron-injecting layer disposed between the cathode layer and the light-emitting layer, wherein at least one of the electron-transporting layer and the electron-injecting layer is a borane derivative, a pyridine derivative, or a fluoranthene Contains at least one selected from the group consisting of derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes Item 13. The organic electroluminescence device according to any one of Items 1 to 12.

Item 14.
The electron-transporting layer and/or electron-injecting layer may further comprise an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal Item 13 containing at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes 3. The organic electroluminescence device according to .

Item 15.
A display device or a lighting device comprising the organic electroluminescence device according to any one of Items 1 to 14.

According to a preferred embodiment of the present invention, in the organic electroluminescent device, by forming a light-emitting layer containing both an anthracene-based compound and a pyrene-based compound as host materials, either device efficiency or device life, particularly preferably Device efficiency and device life can be improved.

1 is a schematic cross-sectional view showing an organic EL element according to this embodiment; FIG.

1. Characteristic light-emitting layer in organic EL device The present invention is an organic EL device having a pair of electrode layers consisting of an anode layer and a cathode layer, and a light-emitting layer disposed between the pair of electrode layers, wherein the light-emitting layer is an organic EL device containing an anthracene-based compound represented by the above general formula (1) and a pyrene-based compound represented by the above general formula (2) as host materials, and further including a dopant material.

The light-emitting layer may contain both the anthracene-based compound and the pyrene-based compound as host materials.
(1) A form in which both compounds are mixed in the light-emitting layer,
(2) A mode in which the concentration of the anthracene-based compound in the light-emitting layer changes continuously from one layer sandwiching the light-emitting layer to the other layer;
(3) A form in which the concentration of the pyrene-based compound in the light-emitting layer changes continuously from one layer sandwiching the light-emitting layer toward the other layer,
(4) The concentration of the anthracene-based compound in the light-emitting layer decreases from one layer sandwiching the light-emitting layer toward the other layer, and the concentration of the pyrene-based compound in the light-emitting layer decreases across the light-emitting layer. morphology that increases in the direction from one sandwiching layer to the other;
(5) A form in which the light-emitting layer is configured by laminating at least a first light-emitting layer and a second light-emitting layer, the first light-emitting layer contains an anthracene-based compound, and the second light-emitting layer contains a pyrene-based compound;
(6) A form having the first light-emitting layer and the second light-emitting layer of (5) above, and having a mixed region containing an anthracene-based compound and a pyrene-based compound between these light-emitting layers,
(7) having the first light-emitting layer and the second light-emitting layer of (5) above, having a mixed region containing an anthracene-based compound and a pyrene-based compound between these light-emitting layers, and anthracene in the mixed region; A form in which the concentration of the compound changes continuously from the first light-emitting layer toward the second light-emitting layer,
(8) having the first light-emitting layer and the second light-emitting layer of (5) above, having a mixed region containing an anthracene-based compound and a pyrene-based compound between these light-emitting layers, and pyrene in the mixed region; A form in which the concentration of the compound changes continuously from the first light-emitting layer toward the second light-emitting layer,
(9) having the first light-emitting layer and the second light-emitting layer of (5) above, having a mixed region containing an anthracene-based compound and a pyrene-based compound between these light-emitting layers, and anthracene in the mixed region; A form in which the concentration of the pyrene-based compound decreases from the first light-emitting layer toward the second light-emitting layer, and the concentration of the pyrene-based compound increases from the first light-emitting layer toward the second light-emitting layer,
etc.
The concentration gradient of the continuous change in concentration is not particularly limited, and may be changed stepwise instead of continuously.

The anthracene-based compound has two layers sandwiching the light-emitting layer, for example, a layer on the positive electrode or hole layer (hole transport layer or hole injection layer) side, and a cathode or electron layer (electron transport layer or electron injection layer) side. In the light-emitting layer, it may be biased toward the positive electrode or hole layer side, or it may be biased toward the cathode or electron layer side in the light-emitting layer. Further, the pyrene-based compound may exist in the light-emitting layer in a biased manner toward the positive electrode or the hole layer side, or may exist in a biased manner in the light-emitting layer toward the cathode or the electron layer side. When the amount of electrons in the light-emitting layer is relatively abundant with respect to the amount of holes, the anthracene-based compound is concentrated on the cathode and electron layer side, and the pyrene-based compound is concentrated on the positive electrode and hole layer side. is preferably present. When the amount of holes in the light-emitting layer is relatively abundant with respect to the amount of electrons, the anthracene-based compound is concentrated on the positive electrode and hole layer side, and the pyrene-based compound is concentrated on the cathode and electron layer side. is preferably present.

1-1. Anthracene Compound Represented by Formula (1) The anthracene compound, which is an essential component of the host material in the present invention, has the following structure.

In formula (1),
X and Ar ⁴ are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio or optionally substituted silyl, wherein not all X and Ar ⁴ are simultaneously hydrogen,
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, deuterium or optionally substituted heteroaryl.

Details of the above aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl are described in the Preferred Embodiments section below. Substituents for these include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio and silyl. Details are also provided in the Preferred Embodiments section below.

Preferred embodiments of the anthracene-based compound are described below. The definitions of symbols in the structure below are the same as those defined above.

In formula (1), X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), formula (1-X1), formula ( 1-X2) or the group represented by formula (1-X3) is bonded to the anthracene ring of formula (1) at *. Preferably, two X's are not simultaneously represented by formula (1-X3), and more preferably, two X's are not simultaneously represented by formula (1-X2).

The naphthylene moiety in formulas (1-X1) and (1-X2) may be fused with one benzene ring. The structure fused in this way is as follows.

Ar ¹ and Ar ² each independently represent hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or the above formula (A) (including carbazolyl, benzocarbazolyl and phenyl-substituted carbazolyl groups). When Ar ¹ or Ar ² is a group represented by formula (A), the group represented by formula (A) is represented by * in formula (1-X1) or formula (1-X2). Bonds with the naphthalene ring.

Ar ³ is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the above formula (A) (carbazolyl group, benzocarba Also includes solyl and phenyl-substituted carbazolyl groups). When Ar ³ is a group represented by formula (A), the group represented by formula (A) is bonded to the single bond represented by the straight line in formula (1-X3) at *. . That is, the anthracene ring of formula (1) and the group represented by formula (A) are directly bonded.

Ar ³ may have a substituent, and at least one hydrogen in Ar ³ is further phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or It may be substituted with the represented groups (including carbazolyl groups and phenyl-substituted carbazolyl groups). When the substituent of Ar ³ is a group represented by formula (A), the group represented by formula (A) is bonded to Ar ³ in formula (1-X3) at *.

Each Ar ⁴ is independently hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or silyl substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms.

Examples of alkyl having 1 to 4 carbon atoms to be substituted on silyl include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc. Three hydrogen atoms in silyl are each independently , substituted with these alkyls.

Specific "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyl dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi-i-propylsilyl, ethyldi-i-propylsilyl, butyldi-i-propylsilyl, sec-butyldi-i-propylsilyl, t-butyldi-i-propylsilyl and the like.

Cycloalkyl having 5 to 10 carbon atoms substituted on silyl is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[ 1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthalenyl, decahydroazulenyl and the like, and each of the three hydrogens in the silyl is independently substituted with these cycloalkyls.

Specific examples of "silyl substituted with cycloalkyl having 5 to 10 carbon atoms" include tricyclopentylsilyl, tricyclohexylsilyl and the like.

Further, hydrogen in the chemical structure of the anthracene-based compound represented by general formula (1) may be substituted with a group represented by the above formula (A). When substituted with a group of formula (A), the group of formula (A) replaces at least one hydrogen in the compound of formula (1) at *.

The group represented by Formula (A) is one of the substituents that the anthracene-based compound represented by Formula (1) may have.

In formula (A) above, Y is —O—, —S— or >N—R ²⁹ , and R ²¹ to R ²⁸ are each independently hydrogen, optionally substituted alkyl, optionally substituted optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, tricycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, wherein adjacent groups among R ²¹ to R ²⁸ are bonded together to form a hydrocarbon ring, an aryl ring or a heteroaryl ring; and R ²⁹ is hydrogen or optionally substituted aryl.

“Alkyl” of “optionally substituted alkyl” for R ²¹ to R ²⁸ may be either straight chain or branched chain, for example, straight chain alkyl having 1 to 24 carbon atoms or alkyl having 3 to 24 carbon atoms. Branched chain alkyl can be mentioned. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms (Branched-chain alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched-chain alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

“Cycloalkyl” of “optionally substituted cycloalkyl” for R ²¹ to R ²⁸ includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms. , cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (especially methyl)-substituted products thereof having 1 to 4 carbon atoms, and bicyclo[1 .0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2 .1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The “aryl” of “optionally substituted aryl” for R ²¹ to R ²⁸ includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 16 carbon atoms, and aryl having 6 to 12 carbon atoms. is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.

Specific “aryl” includes monocyclic phenyl, bicyclic biphenylyl, condensed bicyclic naphthyl, and tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl). , condensed tricyclic acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclic triphenylenyl, pyrenyl, naphthacenyl, and condensed pentacyclic ring perylenyl, pentacenyl, and the like.

The “heteroaryl” of “optionally substituted heteroaryl” for R ²¹ to R ²⁸ includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms. Heteroaryl having 2 to 20 carbon atoms is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of "heteroaryl" include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H- indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiinyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolidinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuranyl, naphthobenzothienyl and the like.

The “alkoxy” of “optionally substituted alkoxy” for R ²¹ to R ²⁸ includes, for example, straight chain alkoxy having 1 to 24 carbon atoms or branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (branched alkoxy having 3 to 18 carbon atoms) is preferable, alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferable, and 1 to 6 carbon atoms. is more preferred (branched alkoxy having 3 to 6 carbon atoms), and particularly preferred is alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 4 carbon atoms).

Specific examples of "alkoxy" include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

The “aryloxy” of “optionally substituted aryloxy” for R ²¹ to R ²⁸ is a group in which the hydrogen of —OH group is substituted with aryl, and this aryl is the above-mentioned R ²¹ to R ²⁸ Reference may be made to groups described as "aryl".

The ^“ arylthio” of “optionally substituted arylthio” for R ²¹ to R ²⁸ is a group in which the hydrogen of —SH group is substituted with aryl, ^and this aryl is the same as the “aryl The group described as "" can be cited.

Examples of “trialkylsilyl” for R ²¹ to R ²⁸ include groups in which three hydrogen atoms in a silyl group are each independently substituted with alkyl, and this alkyl is the same as the “alkyl” for R ²¹ to R ²⁸ described above. The groups mentioned can be cited. Preferred alkyl for substitution is alkyl having 1 to 4 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like.

Specific "trialkylsilyl" includes trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi-i-propylsilyl, ethyldi-propylsilyl, butyldi-i-propylsilyl, sec-butyldi-i -propylsilyl, t-butyldi-i-propylsilyl and the like.

Examples of the "tricycloalkylsilyl" for R ²¹ to R ²⁸ include groups in which three hydrogen atoms ⁱⁿ the silyl group are each independently substituted with cycloalkyl, and this ^cycloalkyl is the above-mentioned " Reference may be made to groups described as "cycloalkyl". Preferred cycloalkyls for substitution are cycloalkyls having 5 to 10 carbon atoms, specifically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

Specific examples of "tricycloalkylsilyl" include tricyclopentylsilyl, tricyclohexylsilyl and the like.

The “substituted amino” of the “optionally substituted amino” for R ²¹ to R ²⁸ includes, for example, an amino group in which two hydrogen atoms are substituted with aryl or heteroaryl. Amino in which two hydrogens are replaced by aryl is diaryl-substituted amino, amino in which two hydrogens are replaced by heteroaryl is diheteroaryl-substituted amino, and amino in which two hydrogens are replaced by aryl and heteroaryl is an arylheteroaryl-substituted amino. For this aryl and heteroaryl, the groups explained as “aryl” and “heteroaryl” for R ²¹ to R ²⁸ above can be cited.

Specific "substituted amino" include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, and the like.

“Halogen” for R ²¹ to R ²⁸ includes fluorine, chlorine, bromine and iodine.

Some of the groups illustrated as R ²¹ -R ²⁸ may be substituted as described above, where substituents include alkyl, cycloalkyl, aryl or heteroaryl. This alkyl, cycloalkyl, aryl or heteroaryl can refer to the groups described as “alkyl”, “cycloalkyl”, “aryl” or “heteroaryl” for R ²¹ to R ²⁸ above.

R ²⁹ in “>N—R ²⁹ ” as Y is hydrogen or optionally substituted aryl, and as this aryl, the groups described as “aryl” for R ²¹ to R ²⁸ above can be cited. Also, as the substituent, the groups described as the substituents for R ²¹ to R ²⁸ can be cited.

Adjacent groups among R ²¹ to R ²⁸ may be bonded to each other to form a hydrocarbon ring, aryl ring or heteroaryl ring. A group represented by the following formula (A-1) does not form a ring, and a group represented by the following formulas (A-2) to (A-14) is an example of a ring formed group. be done. At least one hydrogen in the group represented by any one of formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, may be substituted with tricycloalkylsilyl, diaryl-substituted amino, diheteroaryl- ^substituted amino, arylheteroaryl-substituted amino, halogen, ^hydroxy or cyano; can do.

Examples of the ring formed by bonding adjacent groups to each other include a hydrocarbon ring such as a ^{cyclohexane ring} . , and these rings are formed so as to be fused with one or two benzene rings in the above formula (A-1).

Examples of the group represented by the formula (A) include groups represented by any one of the above formulas (A-1) to (A-14), and the above formulas (A-1) to (A -5) and a group represented by any one of formulas (A-12) to (A-14), and a group represented by any one of the above formulas (A-1) to (A-4) is more preferable, a group represented by any one of the formula (A-1), formula (A-3) and formula (A-4) is more preferable, and a group represented by the formula (A-1) is Especially preferred.

The group represented by formula (A) is, in * in formula (A), the naphthalene ring in formula (1-X1) or formula (1-X2), the single bond in formula (1-X3), the formula Bonding with Ar ³ in (1-X3) and substituting at least one hydrogen in the compound represented by formula (1) is as described above, but among these bonding forms, formula (1-X1) Alternatively, a form bonded to a naphthalene ring in formula (1-X2), a single bond in formula (1-X3) and/or Ar ³ in formula (1-X3) is preferred.

Further, in the structure of the group represented by formula (A), the naphthalene ring in formula (1-X1) or formula (1-X2), the single bond in formula (1-X3), the formula (1-X3 ) to which Ar ³ is bonded, and in the structure of the group represented by formula (A), the position substituted with at least one hydrogen in the compound represented by formula (1) is represented by formula (A) For example, any of the two benzene rings in the structure of formula (A) or adjacent groups among R ²¹ to R ²⁸ in the structure of formula (A) It can be bonded at any ring formed by bonding to each other or at any position in R ²⁹ in “>N—R ²⁹ ” as Y in the structure of formula (A).

Examples of the group represented by formula (A) include the following groups. Y and * in the formula have the same definitions as above.

All or part of the hydrogen in the chemical structure of the anthracene compound represented by formula (1) may be halogen, cyano, or deuterium.

Specific examples of anthracene compounds include compounds represented by the following formulas (1-101) to (1-127).

Further, other specific examples of the anthracene-based compound include compounds represented by the following formulas (1-131-Y) to (1-179-Y), and the following formula (1-180-Y). to the compound represented by the formula (1-182-Y) and the compound represented by the following formula (1-183-N). Y in each formula may be -O-, -S- or >NR ²⁹ (R ²⁹ is defined as above), and R ²⁹ is, for example, a phenyl group. For example, when Y is O, formula (1-131-Y) becomes formula (1-131-O), and when Y is -S- or >NR ²⁹ , formula (1- 131-S) or formula (1-131-N).

Further, specific examples of anthracene-based compounds include compounds represented by the following formulas (1-191) to (1-216).

1-2. Method for producing anthracene-based compound represented by formula (1) The anthracene-based compound represented by formula (1) consists of a compound having a reactive group at a desired position of the anthracene skeleton, X, Ar ⁴ and formula (A ) can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using a compound having a reactive group in a partial structure such as the structure of ) as a starting material. Examples of reactive groups of these reactive compounds include halogen and boronic acid. As a specific production method, for example, reference can be made to the synthesis method in paragraphs [0089] to [0175] of WO 2014/141725.

1-3. Pyrene Compound Represented by Formula (2) The pyrene compound, which is an essential component of the host material in the present invention, has the following structure.

In the above formula (2),
s pyrene moieties and p Ar moieties are bound at any position of * of the pyrene moiety and any position of the Ar moiety,
At least one hydrogen in the pyrene moiety is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms. may be substituted with alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these is independently aryl having 6 to 10 carbon atoms , heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryl having 6 to 30 carbon atoms. optionally substituted with oxy,
Each Ar is independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in these is each independently an aryl having 6 to 10 carbon atoms, substituted with heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms may have been
s and p are each independently an integer of 1 or 2, s and p are not 2 at the same time, and when s is 2, the two pyrene moieties are structurally identical including substituents may be different, and when p is 2, the two Ar moieties may be structurally the same or different, including substituents, and
At least one hydrogen in the compound represented by formula (2) may be independently substituted with halogen, cyano or deuterium.

Ar is an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and various substituents may be bonded thereto. Specific examples of Ar include general formula (Ar-1) below or general A group represented by formula (Ar-2) can be mentioned. R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ are substituents. * indicates a bond with the pyrene moiety.

Further, in the group represented by the formula (Ar-2), an example in which the adjacent R ¹⁸ and R ¹⁹ are bonded to each other to form a condensed ring is a group represented by the following general formula (Ar-3). be done. ^R20 to ^R35 are substituents. * indicates a bond with the pyrene moiety.

More specific examples of the group represented by formula (Ar-1) or formula (Ar-2) include groups represented by any of the following general formulas. Among these, formula (Ar-1-1), formula (Ar-1-2), formula (Ar-1-3), formula (Ar-1-4), formula (Ar-2-2) or formula A group represented by (Ar-2-4) is preferred, and formula (Ar-1-2), formula (Ar-1-3), formula (Ar-1-4) or formula (Ar-2-4) A group represented by is more preferable. Although substituents are not specified in each structural formula below, at least one hydrogen in each structure may be substituted. * indicates a bond with the pyrene moiety. The group represented by formula (Ar-2-4) below corresponds to the group represented by formula (Ar-3) above.

C14-40 aryl or C12-40 heteroaryl as Ar, the first substituent to the pyrene moiety (C6-10 aryl, C2-11 heteroaryl, C1 ~30 alkyl, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, preferably aryl having 6 to 10 carbon atoms) and Second substituent to the first substituent (aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, 2 carbon atoms to 30 alkenyl, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, preferably aryl having 6 to 10 carbon atoms), and a substituent to Ar (R 1 in formula (Ar- ¹ ) to R ⁸ , R ¹⁰ to R ¹⁹ of formula (Ar-2), R ²⁰ to R ³⁵ of formula (Ar-3), and formulas (Ar-1-1) to (Ar-2-4) unspecified substituents, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and alkenyl having 2 to 30 carbon atoms , alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, preferably alkyl having 1 to 30 carbon atoms) are collectively described below.

Aryl having 14 to 40 carbon atoms or heteroaryl having 12 to 40 carbon atoms as Ar is preferably aryl having 14 to 35 carbon atoms or heteroaryl having 12 to 35 carbon atoms, more preferably 14 to 30 carbon atoms. or heteroaryl having 12 to 30 carbon atoms, more preferably aryl having 14 to 25 carbon atoms or heteroaryl having 12 to 25 carbon atoms, particularly preferably aryl having 14 to 20 carbon atoms or 12 carbon atoms ∼20 heteroaryl, most preferably aryl of 14 to 18 carbon atoms or heteroaryl of 12 to 18 carbon atoms.

Specific aryls include monocyclic phenyl, bicyclic biphenylyl, condensed bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl), condensed tricyclic anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl; condensed tetracyclic triphenylenyl and naphthacenyl; condensed pentacyclic perylenyl and pentacenyl;

Examples of specific heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiinyl, phenoxazinyl, phenothiazinyl, phenazinyl, Indolizinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuranyl and naphthobenzothienyl, and the like.

Further, the first substituent to the pyrene moiety, the second substituent to the first substituent, and the substituent to Ar, specific examples of aryl having 6 to 10 carbon atoms are phenyl or naphthyl and specific examples of the heteroaryl having 2 to 11 carbon atoms can be cited from the heteroaryl groups described above.

Aryloxy having 6 to 30 carbon atoms is a group in which hydrogen of a hydroxyl group is substituted with aryl having 6 to 30 carbon atoms, and this aryl is preferably aryl having 6 to 25 carbon atoms, more preferably carbon aryl having 6 to 20 carbon atoms, more preferably aryl having 6 to 15 carbon atoms, particularly preferably aryl having 6 to 10 carbon atoms, and specific examples of the aryl are cited from the aryl groups described above. can do.

Alkyl having 1 to 30 carbon atoms may be either linear or branched, and for example, linear alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms is preferable, and alkyl having 1 to 18 carbon atoms is preferable. (Branched chain alkyl having 3 to 18 carbon atoms) is more preferable, alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms) is more preferable. branched chain alkyl) is particularly preferred, C 1-4 alkyl (C 3-4 branched chain alkyl) is particularly preferred, methyl, ethyl, isopropyl or t-butyl is more preferred among them, and methyl or t-butyl is most preferred.

Specific alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methyl Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.

Cycloalkyl having 3 to 24 carbon atoms is, for example, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, Examples include cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (especially methyl)-substituted products thereof having 1 to 4 carbon atoms, and bicyclo[1 .0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2 .1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

Alkenyl having 2 to 30 carbon atoms is, for example, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, still more preferably alkenyl having 2 to 6 carbon atoms, and particularly Alkenyl having 2 to 4 carbon atoms is preferred.

Specific alkenyls include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2 -hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl and the like.

The alkoxy having 1 to 30 carbon atoms is, for example, preferably alkoxy having 1 to 24 carbon atoms (branched alkoxy having 3 to 24 carbon atoms), more preferably alkoxy having 1 to 18 carbon atoms (3 to 3 carbon atoms). 18 branched alkoxy), more preferably 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms), particularly preferably 1 to 6 carbon atoms (3 to 12 carbon atoms). 6 branched chain alkoxy), most preferably C 1-4 alkoxy (C 3-4 branched alkoxy).

Specific alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy, and the like.

In formulas (Ar-1) and (Ar-2), adjacent groups among R ¹ to R ⁸ and adjacent groups among R ¹⁰ to R ¹⁹ are bonded to each other to form condensed rings. may Adjacent groups are combinations other than R ⁴ and R ⁵ or R ¹³ and R ¹⁴ , such as R ¹ and R ² . The structure in which the condensed ring is formed in this way has the above formulas (Ar-1-2) to (Ar-1-12) and the above formulas (Ar-2-2) to (Ar-2-4) ( Formula (Ar-3)). On the other hand, the above formulas (Ar-1-1) and (Ar-2-1) are structures that do not contain condensed rings. The formed condensed ring includes, for example, a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, a pyrrole ring, a furan ring and the like, and preferably an aryl ring such as a benzene ring, a naphthalene ring or a phenanthrene ring, A benzene ring is more preferred.

Condensed rings formed by bonding adjacent groups to each other include aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and carbon may be substituted with alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and these are alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms. and the detailed description of these groups can be referred to the description given above.

Z is > _{CR 2} , >NR, >O or >S, and among these, preferably >CR ₂ or >O, more preferably >CR ₂ , R (alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 12 carbon atoms optionally substituted by alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, or heteroaryl having 2 to 12 carbon atoms optionally substituted by alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms), and R in >NR (alkyl having 1 to 4 carbon atoms) , cycloalkyl having 5 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or aryl having 6 to 12 carbon atoms optionally substituted with cycloalkyl having 5 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms or heteroaryl having 2 to 12 carbon atoms which may be substituted with cycloalkyl having 5 to 10 carbon atoms), the details of these groups refer to the above descriptions of alkyl, cycloalkyl, aryl and heteroaryl. be able to.

For Z> _CR2 , the Rs may be joined together to form a ring, in which case a spiro structure is formed.

The above formula (2) means that s pyrene moieties and p Ar moieties are bonded at * positions (1 and / or 2 positions) of the pyrene moieties, and s and p are each It is independently an integer of 1 or 2, and s and p are not 2 at the same time. Since the pyrene moiety has a symmetrical structure, when s = 1, p = 1 or when s = 2, p = 1, the 1-position and 2-position of the pyrene moiety can be indicated by two *, but s = 1, Six * indicate that two Ar moieties can each bind to six positions of the pyrene moiety when p=2. When s is 2, the two pyrene moieties may be structurally identical or different including substituents, and when p is 2, the two Ar moieties including substituents are They may be structurally identical or different. That is, the pyrene moiety may have various substituents bonded to the pyrene structure as described above, and when the substituents are bonded, the pyrene moiety including the bonded substituents constitutes the pyrene moiety. Likewise, the Ar moiety, including the attached substituents, constitutes an Ar moiety. Then, when the pyrene-based compound represented by formula (2) contains a plurality of pyrene moieties and Ar moieties, the pyrene moieties including substituents and the Ar moieties including substituents are structurally the same. may be different, preferably the same.

Regarding the bond between the pyrene moiety and the Ar moiety, in the pyrene moiety, Ar is bonded at the * position (1-position and/or 2-position). good too. For example, in formula (Ar-1) or formula (Ar-2), which are examples of Ar, pyrene moieties may be bound at any position of R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ , and When adjacent groups are bonded to each other to form a condensed ring, they may be bonded to the condensed ring. In addition, when substituents such as aryl are selected as R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ , any position on the aryl, >CR ₂ as Z and aryl etc. as R in >NR may be attached at any position on the aryl when the substituent of is selected. Among these binding positions, any one of R ¹ to R ⁸ or R ¹⁰ to R ¹⁹ in formula (Ar-1) or formula (Ar-2) is preferred. These explanations are the same for formulas subordinate to formulas (Ar-1) and (Ar-2).

All or part of hydrogen in the pyrene-based compound represented by formula (2) may be substituted with halogen, cyano, or deuterium. For example, in formula (2), hydrogen in the pyrene moiety or Ar moiety can be replaced with halogen, cyano or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.

Specific examples of the pyrene-based compound of the present invention include compounds represented by the following structural formulas. In the following structural formulas, "Me" is a methyl group, "Et" is an ethyl group, "tBu" is a tertiary butyl group, "iPr" is an isopropyl group, and "D" is deuterium.

Among the above compounds, formula (2-1), formula (2-2) to formula (2-20), formula (2-41) to formula (2-43), formula (2-46), formula ( 2-47) ~ formula (2-173), formula (2-174), formula (2-175) ~ formula (2-215), formula (2-350), formula (2-351) ~ formula (2 -354), formula (2-356), formula (2-357), formula (2-358), formula (2-359), formula (2-360) ~ formula (2-430), formula (2- 1001), formulas (2-1002) to (2-1012), formulas (2-1080), formulas (2-1081) to (2-1091), and formulas (2-1223) are preferred.

Also, formula (2-1), formula (2-46), formula (2-174), formula (2-350), formula (2-356), formula (2-359), formula (2-1001) , Formula (2-1080) and Formula (2-1223) are more preferred.

1-4. Method for producing pyrene-based compound represented by formula (2) The pyrene-based compound represented by formula (2) has a structure in which various substituents are bonded to the pyrene skeleton or the skeleton of the compound represented by Ar. and can be produced using a known method. An intermediate is produced by a commonly used halogenation reaction, boron oxidation reaction or boronic acid esterification reaction, and the produced intermediate is used in the Suzuki coupling reaction, other metalation reactions, and cross-linking via metal species. By performing a coupling reaction (Negishi coupling reaction, Kumada-Tamao coupling reaction, Kosugi-Migita-Stille coupling reaction, etc.), the pyrene compound represented by formula (2) can be produced as appropriate. can. In addition, an intermediate having a substituent such as an alkoxy group such as a methoxy group is produced, and after a demethylation reaction using pyridine hydrochloride or the like to form a -OH form, a reagent such as trifluoromethanesulfonic anhydride is used. The pyrene-based compound represented by the formula (2) can also be produced by forming a sulfonic acid ester and performing a cross-coupling reaction such as Suzuki coupling reaction. Commercially available materials can also be used for these intermediates having halogen, boronic acid, boronic acid ester or sulfonic acid ester. For reference, specific methods for producing the pyrene-based compound are described in Synthesis Examples to be described later.

1-5. Dopant materials suitable for the present invention (boron-containing compounds)
Examples of boron-containing compounds include compounds represented by the following general formula (3) and polymers of compounds having a plurality of structures represented by general formula (3). The compound and its multimer are preferably compounds represented by the following general formula (3′) or multimers of compounds having a plurality of structures represented by the following general formula (3′). In formula (3), "B" of the central atom means a boron atom, and "A" and "C" together with "B" in the ring are symbols indicating the ring structure represented by the ring.

A ring, B ring and C ring in general formula (3) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. This substituent can be substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and amino group with heteroaryl), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy are preferred. When these groups have substituents, the substituents include aryl, heteroaryl, alkyl and cycloalkyl. The aryl ring or heteroaryl ring is a 5-membered or 6-membered ring sharing a bond with the central condensed 2-ring structure of general formula (3) consisting of "B", "X ¹ " and "X ² ". It preferably has a ring.

Here, the “condensed two-ring structure” means that two saturated hydrocarbon rings composed of “B”, “X ¹ ” and “X ² ” shown in the center of the general formula (3) are condensed means a structure that Further, "a 6-membered ring sharing a bond with the condensed 2-ring structure" is, for example, a ring (benzene ring (6-membered ring)) fused to the condensed 2-ring structure as shown in the above general formula (3') means Further, "the aryl ring or heteroaryl ring (which is the A ring) has this 6-membered ring" means that the A ring is formed only by this 6-membered ring, or that the 6-membered ring is included. It means that the A ring is formed by further condensing another ring and the like to this 6-membered ring. In other words, the “aryl ring or heteroaryl ring having a 6-membered ring (which is the A ring)” as used herein means that the 6-membered ring constituting all or part of the A ring is fused to the condensed two-ring structure. means that The same description applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

Ring A (or ring B or ring C) in general formula (3) is ring a in general formula (3′) and its substituents R ¹ to R ³ (or ring b and its substituents R ⁸ to R ¹¹ , c ring and its substituents R ⁴ to R ⁷ ). That is, general formula (3′) corresponds to a structure in which “A to C rings having a 6-membered ring” are selected as A to C rings of general formula (3). In this sense, each ring of general formula (3′) is represented by lower case letters a to c.

In the general formula (3′), adjacent groups among the substituents R ¹ to R ¹¹ of the a ring, the b ring and the c ring are combined to form an aryl ring or a heteroaryl ring together with the a ring, the b ring or the c ring. at least one hydrogen in the formed ring is substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Therefore, the compound represented by the general formula (3') can be represented by the following formulas (3'-1) and (3'-2) depending on the mutual bond form of the substituents on the a ring, b ring and c ring. As shown, the ring structures that make up the compound change. A' ring, B' ring and C' ring in each formula respectively correspond to A ring, B ring and C ring in general formula (3). The definitions of R ¹ to R ¹¹ , a, b, c, X ¹ and X ² in each formula are the same as those in general formula (3′).

The A' ring, B' ring and C' ring in the above formulas (3'-1) and (3'-2) are those of the substituents R ¹ to R ¹¹ when explained in the general formula (3') Adjacent groups among them are bonded together to form an aryl ring or heteroaryl ring formed together with the a ring, the b ring, and the c ring (formed by condensing another ring structure to the a ring, b ring, or c ring). can also be called a condensed ring). Although not shown in the formula, there are compounds in which all of the a-ring, b-ring and c-ring are changed to A'-ring, B'-ring and C'-ring. Further, as can be seen from the above formulas (3′-1) and (3′-2), for example, R ⁸ of the b ring and R ⁷ of the c ring, R ¹¹ of the b ring and R ¹ of the a ring, c R ⁴ of the ring and R ³ of the a ring do not correspond to "adjacent groups" and are not bonded. That is, "adjacent groups" mean groups that are adjacent on the same ring.

The compounds represented by the above formula (3'-1) and formula (3'-2) are, for example, formulas (3-2) to (3-9) listed as specific compounds described later and formula (3- 290) to compounds represented by formulas (3-375). That is, for example, an A' ring (or B') formed by condensing a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, or the like to a benzene ring (or b ring or c ring). ring or C' ring), and the formed condensed ring A' (or condensed ring B' or condensed ring C') is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring. and so on.

X ¹ and X ² in general formula (3) are each independently >O or >NR, and R in >NR is optionally substituted aryl or optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, and R in >NR may be bonded to the B ring and/or C ring through a linking group or a single bond. Often, -O-, -S- or -C(-R) ₂ - is preferred as the linking group. R in the above "-C(-R) ₂ -" is hydrogen, alkyl or cycloalkyl. This explanation is the same for X ¹ and X ² in general formula (3′).

Here, the definition that "R of >N-R is bonded to the A ring, B ring and/or C ring through a linking group or a single bond" in general formula (3) corresponds to general formula (3' ), the definition that "R of >N-R is -O-, -S-, -C(-R) ₂ - or is bonded to the a-ring, b-ring and/or c-ring via a single bond" corresponds to
This definition can be represented by a compound having a ring structure in which X ¹ and X ² are incorporated in condensed ring B' and condensed ring C', represented by the following formula (3'-3-1). That is ^, for example, B' ^ring ( or C' ring). This compound corresponds to, for example, the compounds represented by formulas (3-40) to (3-114) listed below as specific compounds, and is formed by condensed ring B′ (or condensed Ring C') is for example a phenoxazine ring, a phenothiazine ring or an acridine ring.
In addition, the above definition includes a ring structure in which X ¹ and/or X ² is incorporated in a condensed ring A' represented by the following formula (3'-3-2) or (3'-3-3) It can also be expressed as a compound having That is, for example, a compound having an A' ring formed by condensing other rings such that X ¹ (and/or X ² ) is incorporated into the benzene ring, which is the a ring in general formula (3'). be. This compound corresponds to, for example, compounds represented by formulas (3-115) to (3-126) listed as specific compounds described later, and the formed condensed ring A′ is, for example, phenoxazine ring, phenothiazine ring or acridine ring. In the following formulas (3′-3-1), (3′-3-2) and (3′-3-3), R ¹ to R ¹¹ , a, b, c, X ¹ and X The definition of ² is the same as the definition in general formula (3').

The "aryl ring" which is the A ring, B ring and C ring of the general formula (3) includes, for example, an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms. An aryl ring having 6 to 12 carbon atoms is more preferred, and an aryl ring having 6 to 10 carbon atoms is particularly preferred. The “aryl ring” is an aryl ring formed together with the a-ring, b-ring or c-ring by bonding adjacent groups among R ¹ to R ¹¹ defined in general formula (3′). ”, and since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total carbon number of the condensed ring fused with a 5-membered ring is the lower limit of 9 number of carbon atoms.

Specific “aryl rings” include a monocyclic benzene ring, a bicyclic biphenyl ring, a condensed bicyclic naphthalene ring, and a tricyclic terphenyl ring (m-terphenyl, o -terphenyl, p-terphenyl), condensed tricyclic system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic triphenylene ring, pyrene ring, naphthacene ring, condensed pentacyclic ring system A perylene ring, a pentacene ring, and the like can be mentioned.

The "heteroaryl ring" which is the A ring, B ring and C ring of the general formula (3) includes, for example, a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms. , a heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Examples of the "heteroaryl ring" include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms. The “heteroaryl ring” is a hetero ring formed together with the “a ring, b ring or c ring by bonding adjacent groups among R ¹ to R ¹¹ defined in general formula (3′). aryl ring", and since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total carbon number of the condensed ring obtained by condensing a 5-membered ring to this is 6 It becomes the lower limit of the number of carbon atoms.

Specific "heteroaryl rings" include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring , cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, Benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, thianthrene ring, and the like.

At least one hydrogen in the above "aryl ring" or "heteroaryl ring" is the first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or It may be substituted with unsubstituted "alkoxy" or substituted or unsubstituted "aryloxy", but the aryl of "aryl", "heteraryl" or "diarylamino" as the first substituent , the heteroaryl of "diheteroarylamino", the aryl and heteroaryl of "arylheteroarylamino", and the aryl of "aryloxy" are the above-mentioned monovalent groups of "aryl ring" or "heteroaryl ring" can give.

The "alkyl" as the first substituent may be either straight-chain or branched-chain, and examples thereof include straight-chain alkyl having 1 to 24 carbon atoms and branched-chain alkyl having 3 to 24 carbon atoms. . Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and 1 to 6 carbon atoms. (branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methyl Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.

The "cycloalkyl" as the first substituent includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. , cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (especially methyl)-substituted products thereof having 1 to 4 carbon atoms, and bicyclo[1.0 .1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1 .2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

"Alkoxy" as the first substituent includes, for example, straight chain alkoxy having 1 to 24 carbon atoms or branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (branched alkoxy having 3 to 18 carbon atoms) is preferable, alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferable, and 1 carbon atom. ∼6 alkoxy (branched alkoxy with 3 to 6 carbon atoms) is more preferred, and alkoxy with 1 to 4 carbon atoms (branched alkoxy with 3 to 4 carbon atoms) is particularly preferred.

Specific alkoxy includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

The first substituent, substituted or unsubstituted “aryl”, substituted or unsubstituted “heteroaryl”, substituted or unsubstituted “diarylamino”, substituted or unsubstituted “diheteroarylamino”, substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy" are described as substituted or unsubstituted, optionally having at least one hydrogen in them replaced with a second substituent. Examples of the second substituent include aryl, heteroaryl, alkyl, and cycloalkyl, and specific examples thereof include the above-described monovalent group of “aryl ring” or “heteroaryl ring”, and Reference can be made to the description of "alkyl" or "cycloalkyl" as one substituent. In the aryl or heteroaryl as the second substituent, at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), alkyl such as methyl (specific examples are the groups described above), or cyclohexyl A group substituted with cycloalkyl (specific examples are the groups described above) such as is also included in aryl and heteroaryl as the second substituent. For example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl, an alkyl such as methyl, or a cycloalkyl such as cyclohexyl is also a second substituent. heteroaryl as a substituent of

Aryl, heteroaryl, diarylamino aryl, diheteroarylamino heteroaryl, arylheteroarylamino aryl and heteroaryl, or aryloxy aryl for R ¹ to R ¹¹ in general formula (3′) may be A monovalent group of “aryl ring” or “heteroaryl ring” described in formula (3) can be mentioned. For alkyl, cycloalkyl or alkoxy in R ¹ to R ¹¹ , see the description of “alkyl”, “cycloalkyl” and “alkoxy” as the first substituent in the description of general formula (3) above. can do. Furthermore, the same applies to aryl, heteroaryl, alkyl or cycloalkyl as substituents to these groups. Further, when adjacent groups among R ¹ to R ¹¹ are combined to form an aryl ring or heteroaryl ring together with the a ring, the b ring, or the c ring, it is a substituent for these rings. The same applies for heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy and further substituents aryl, heteroaryl, alkyl or cycloalkyl.

>N—R in X ¹ and X ² in general formula (3) is aryl, heteroaryl, alkyl or cycloalkyl optionally substituted with the second substituent described above, and aryl, heteroaryl, At least one hydrogen in alkyl or cycloalkyl may be replaced with, for example, alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl and cycloalkyl include the groups mentioned above. In particular, aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl etc.), heteroaryl having 2 to 15 carbon atoms (eg carbazolyl etc.), alkyl having 1 to 4 carbon atoms (eg methyl, ethyl etc.), 3 to 16 carbon atoms. (eg, bicyclooctyl, adamantyl, etc.) are preferred. This explanation is the same for X ¹ and X ² in general formula (3′).

R in "-C(-R) ₂ -" which is a linking group in general formula (3) is hydrogen, alkyl or cycloalkyl, and examples of alkyl or cycloalkyl include the groups described above. Particularly preferred are alkyls having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.). This explanation is the same for the linking group “—C(—R) ₂ —” in general formula (3′).

Further, the light-emitting layer contains multimers of compounds having a plurality of unit structures represented by general formula (3), preferably multimers of compounds having a plurality of unit structures represented by general formula (3′). may be The multimer is preferably a 2- to 6-mer, more preferably a 2- to 3-mer, and particularly preferably a dimer. The polymer may be in a form having a plurality of the above unit structures in one compound. For example, the unit structure is a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, a connecting group such as a naphthylene group. In addition to a form in which multiple units are bonded, a form in which any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the above unit structure is shared by multiple unit structures. or in a form in which arbitrary rings (A ring, B ring or C ring, a ring, b ring or c ring) included in the above unit structure are condensed and bonded to each other good.

Examples of such multimers include the following formulas (3′-4), formulas (3′-4-1), formulas (3′-4-2), formulas (3′-5-1) to formulas (3'-5-4) or multimeric compounds represented by formula (3'-6). The multimeric compound represented by formula (3'-4) below corresponds to, for example, a compound represented by formula (3-21) described below. That is, in general formula (3′), a multimer compound having a plurality of unit structures represented by general formula (3′) in one compound so as to share a benzene ring which is a ring is. Also, the multimeric compound represented by the following formula (3'-4-1) corresponds to, for example, a compound represented by the formula (3-218) described below. That is, in general formula (3′), a multimer compound having two unit structures represented by general formula (3′) in one compound so as to share the benzene ring which is the a ring is. Further, the multimeric compound represented by formula (3'-4-2) below corresponds to, for example, a compound represented by formula (3-219) described later. That is, in general formula (3′), a polymer compound having three unit structures represented by general formula (3′) in one compound so as to share the benzene ring which is the a ring is. In addition, multimeric compounds represented by the following formulas (3′-5-1) to (3′-5-4) are, for example, the following formulas (3-19), (3-20), formulas ( 3-22) or compounds represented by formula (3-23). That is, in general formula (3′), a plurality of unit structures represented by general formula (3′) are formed in one compound so as to share the benzene ring, which is the b ring (or c ring). is a multimeric compound having Further, the multimeric compound represented by formula (3'-6) below corresponds to, for example, compounds represented by formulas (3-24) to (3-28) described later. That is, in general formula (3′), for example, a benzene ring that is the b ring (or a ring, c ring) of a certain unit structure and a benzene ring that is the b ring (or a ring, c ring) of a certain unit structure It is a polymeric compound having a plurality of unit structures represented by general formula (3′) in one compound such that the rings are condensed. The definition of each symbol in the following structural formula is the same as that in general formula (3').

The multimeric compound is a multimerized form represented by formula (3'-4), formula (3'-4-1) or formula (3'-4-2), and formula (3'-5-1) ~ Formula (3'-5-4) or may be a multimer combined with a multimerized form represented by formula (3'-6), formula (3'-5-1) ~ It may be a multimer that is a combination of a multimerized form represented by any of formulas (3'-5-4) and a multimerized form represented by formula (3'-6), (3′-4), formula (3′-4-1) or multimerized forms represented by formula (3′-4-2) and formulas (3′-5-1) to formulas (3′-5 -4) may be a combination of the multimerized form represented by formula (3'-6) and the multimerized form.

Further, all or part of hydrogen in the chemical structure of the compound represented by general formula (3) or (3') and its multimer may be substituted with halogen, cyano or deuterium. For example, in formula (3), ring A, ring B, ring C (rings A to C are aryl rings or heteroaryl rings), substituents on rings A to C, and X ¹ and X ² > Hydrogens in R (=alkyl, cycloalkyl, aryl) in NR can be replaced with halogen, cyano or deuterium, among which all or part of the hydrogens in aryl or heteroaryl are halogen, cyano or deuterium An aspect substituted with is mentioned. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine.

More specific examples of the compound represented by formula (3) and its multimer include compounds represented by the following structural formulas. In the following structural formulas, "Me" is a methyl group, "tBu" is a tertiary butyl group, "iPr" is an isopropyl group, and "Ph" is a phenyl group.

1-6. Compound Represented by Formula (3) and Method for Producing Multimers Thereof Compounds represented by general formulas (3) and (3′) and their multimers are basically first prepared as A ring (a ring) and An intermediate is produced by bonding the B ring (b ring) and the C ring (c ring) with a bonding group (a group containing X ¹ and X ² ) (first reaction), and then the A ring (a ring), B ring (b ring) and C ring (c ring) with a linking group (group containing the central atom "B" (boron)) to prepare the final product (Second Reaction ). In the first reaction, a general reaction such as the Buchwald-Hartwig reaction can be used as long as it is an amination reaction. Moreover, in the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, hereinafter the same) can be used. In schemes (1) to (13) described later, the cases where X ¹ and X ² are >NR are described, but the same applies to the case of O. Further, the definition of each symbol in the structural formulas in schemes (1) to (13) is the same as in formulas (3) and (3').

In the second reaction, as shown in the following schemes (1) and (2), the central atom "B" (boron) connecting the A ring (a ring), the B ring (b ring) and the C ring (c ring) First, the hydrogen atom between X ¹ and X ² (>NR) is ortho-metallated with n-butyllithium, sec-butyllithium, t-butyllithium or the like. Next, boron trichloride, boron tribromide, or the like is added to carry out metal exchange of lithium-boron, and then a Bronsted base such as N,N-diisopropylethylamine is added to cause a tandem bolus Friedel-Crafts reaction to achieve the desired can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to promote the reaction.

The above schemes (1) and (2) mainly show methods for producing the compounds represented by the general formulas (3) and (3′), but for the multimer, a plurality of A rings ( a ring), B ring (b ring) and C ring (c ring). The details will be described in schemes (3) to (5) below. In this case, the desired product can be obtained by doubling or tripling the amount of reagent such as butyllithium to be used.

In the above scheme, lithium is introduced to the desired position by ortho-metallation. Lithium can be introduced at desired positions.

In addition, regarding the production method of the multimer described in scheme (3), a halogen such as a bromine atom or a chlorine atom is introduced to the position where lithium is to be introduced as in schemes (6) and (7) above, and halogen-metal Lithium can also be introduced to the desired position by exchange (schemes (8), (9) and (10) below).

This method is useful because it can synthesize the desired product even in cases where ortho-metallation is not possible due to the influence of substituents.

Specific examples of the solvent used in the above reaction are t-butylbenzene, xylene, and the like.

A compound having a substituent at a desired position and a polymer thereof can be synthesized by appropriately selecting the above-described synthesis method and appropriately selecting the raw materials to be used.

Further, in the general formula (3′), adjacent groups among the substituents R ¹ to R ¹¹ of the a ring, the b ring and the c ring are bonded together to form an aryl ring or a hetero ring together with the a ring, the b ring or the c ring. An aryl ring may be formed, and at least one hydrogen in the formed ring may be substituted with aryl or heteroaryl. Therefore, the compound represented by the general formula (3') is represented by the formula (3'-1) of the following schemes (11) and (12) depending on the mutual bonding configuration of the substituents on the a ring, b ring and c ring. And as shown in formula (3'-2), the ring structure constituting the compound changes. These compounds can be synthesized by applying the synthesis methods shown in schemes (1) to (10) above to the intermediates shown in schemes (11) and (12) below.

In the above formulas (3′-1) and (3′-2), the A′ ring, B′ ring and C′ ring are bonded with adjacent groups among the substituents R ¹ to R ¹¹ , Each represents an aryl ring or a heteroaryl ring formed together with the a ring, the b ring and the c ring (it can also be said to be a condensed ring formed by condensing the a ring, the b ring or the c ring with another ring structure). Although not shown in the formula, there are compounds in which all of the a-ring, b-ring and c-ring are changed to A'-ring, B'-ring and C'-ring.

In general formula (3′), R of “>NR is —O—, —S—, —C(—R) ₂ — or is bonded to the a ring, b ring and/or c ring through a single bond. The definition of "has" is a ring structure in which X ¹ or X ² is incorporated in condensed ring B' and condensed ring C', represented by formula (3'-3-1) in scheme (13) below and a compound having a ring structure in which X ¹ or X ² is incorporated into a condensed ring A' represented by formula (3'-3-2) or formula (3'-3-3) can do. These compounds can be synthesized by applying the synthesis methods shown in schemes (1) to (10) above to intermediates shown in scheme (13) below.

Further, in the synthesis methods of schemes (1) to (13) above, a hydrogen atom (or a halogen atom) between X ¹ and X ² is replaced with butyl lithium or the like before adding boron trichloride, boron tribromide, or the like. An example of tandem hetero Friedel-Crafts reaction by ortho-metalation was shown, but the reaction proceeded by adding boron trichloride, boron tribromide, etc. without ortho-metalation using butyllithium etc. You can also let

The ortho-metalating reagents used in the above schemes (1) to (13) include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium and t-butyllithium, lithium diisopropylamide, lithium tetramethyl Organic alkali compounds such as piperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide can be mentioned.

The metal-“B” (boron) metal exchange reagents used in schemes (1) to (13) above include boron trifluoride, boron trichloride, boron tribromide, and boron triiodine. boron halides such as boron chlorides, boron aminated halides such as CIPN(NEt ₂ ) ₂ , boron alkoxylates, boron aryloxides, and the like.

The Bronsted bases used in schemes (1) to (13) above include N,N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6 -pentamethylpiperidine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (Ar is aryl such as phenyl) and the like.

Examples of Lewis acids used in schemes (1) to (13) include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , InBr ₃ , In(OTf) ₃ , _SnCl4 , _SnBr4 , AgOTf, _ScCl3 , Sc(OTf) ₃ , ZnCl2 _{, ZnBr2} , Zn(OTf) ₂ , MgCl2 _{, MgBr2} , Mg(OTf) ₂ , LiOTf, NaOTf , KOTf, _Me3SiOTf , Cu(OTf) ₂ , CuCl2 _{, YCl3} , Y(OTf) ₃ , _TiCl4 , _TiBr4 , _ZrCl4 , _ZrBr4 , FeCl3, _FeBr3 , _{CoCl3 ,} CoBr3 _, etc. can give.

In schemes (1)-(13) above, Bronsted bases or Lewis acids may be used to facilitate the tandem hetero Friedel-Crafts reaction. However, when boron halides such as boron trifluoride, boron trichloride, boron tribromide, and boron triiodide are used, hydrogen fluoride, hydrogen fluoride, Since acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced, the use of a Bronsted base that scavenges acids is effective. On the other hand, when aminated halides of boron and alkoxylated boron compounds are used, amines and alcohols are generated as the aromatic electrophilic substitution reaction progresses, so in many cases it is not necessary to use a Bronsted base. However, since the leaving ability of amino groups and alkoxy groups is low, the use of a Lewis acid that promotes their leaving is effective.

Further, the compound represented by the formula (3) and its multimer include compounds in which at least some hydrogen atoms are substituted with deuterium, compounds in which halogen such as fluorine and chlorine or cyano are substituted, and the like. However, such compounds can be synthesized in the same manner as described above by using starting materials deuterated, fluorinated, chlorinated or cyanated at desired sites.

1-7. Dopant material suitable for the present invention (pyrene-based compound)
This pyrene-based compound is a pyrene-based compound different from the pyrene-based compound represented by the general formula (2), and includes a compound represented by the following general formula (4).

In the above formula (4),
R ¹ to R ¹⁰ are each independently hydrogen, diarylamino, diheteroarylamino or arylheteroarylamino, in which at least one hydrogen is substituted with aryl, heteroaryl, alkyl or cycloalkyl well,
At least one hydrogen in the compound represented by formula (4) may be replaced with halogen, cyano or deuterium.

For the definition of the substituents R ¹ to R ¹⁰ in formula (4), the description in general formula (3) or general formula (3′) representing the boron-containing compound as the dopant material can be cited. In addition to the description that can be cited as such, the heteroaryl in the above “diheteroarylamino”, the heteroaryl in the above “arylheteroarylamino”, and the above “heteroaryl” as a substituent thereof are anthracene-based It may be a group represented by the above formula (A), which is one of the substituents in the above general formula (1) representing a compound, and the description thereof can be cited. Further, the substitution position of the above “diarylamino”, “diheteroarylamino” and “arylheteroarylamino” is at least one of R ¹ to R ³ and R ⁶ to R ⁸ in the above formula (4). Two positions of R ¹ and R ⁶ and two positions of R ² and R ⁷ are more preferred, and two positions of R ¹ and R ⁶ are even more preferred.

Specific examples of the compound represented by formula (4) include compounds represented by the following structural formulas. In addition, "iPr" in the following structural formula represents an isopropyl group.

1-8. Method for producing compound represented by formula (4) The compound represented by formula (4) has a structure in which various substituents are bonded to a pyrene skeleton or the like, and can be manufactured using a known method. . For example, it can be produced by referring to the production method described in JP-A-2013-080961 and the synthesis examples in Examples.

2. Organic Electroluminescence Device Hereinafter, the organic EL device according to the present embodiment will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

<Structure of Organic Electroluminescent Device>
The organic EL device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a The hole-transport layer 104 provided, the light-emitting layer 105 provided over the hole-transport layer 104, the electron-transport layer 106 provided over the light-emitting layer 105, and the electron-transport layer 106 provided and a cathode 108 provided on the electron injection layer 107 .

Note that the organic EL element 100 is fabricated in reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107 an electron transport layer 106 provided on the electron transport layer 106; a light emitting layer 105 provided on the electron transport layer 106; a hole transport layer 104 provided on the light emitting layer 105; A structure having a hole-injection layer 103 provided at the bottom and an anode 102 provided on the hole-injection layer 103 may be employed.

All of the above layers are not indispensable, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection Layer 107 is an optional layer. Moreover, each of the above layers may be composed of a single layer, or may be composed of a plurality of layers.

In addition to the configuration of the above-described "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", the layers constituting the organic EL element may include " substrate/anode/hole-transporting layer/luminescent layer/electron-transporting layer/electron-injecting layer/cathode”, “substrate/anode/hole-injecting layer/luminescent layer/electron-transporting layer/electron-injecting layer/cathode”, “substrate/ Anode/Hole Injection Layer/Hole Transport Layer/Light Emitting Layer/Electron Injection Layer/Cathode", "Substrate/Anode/Hole Injection Layer/Hole Transport Layer/Light Emitting Layer/Electron Transport Layer/Cathode", "Substrate/ Anode/light emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron transport layer/cathode", "substrate/anode /Emitting layer/Electron transporting layer/Cathode" or "Substrate/Anode/Emitting layer/Electron injection layer/Cathode".

<Substrate in Organic Electroluminescent Device>
A substrate 101 is a support for the organic EL element 100, and is usually made of quartz, glass, metal, plastic, or the like. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate and polysulfone are preferred. If it is a glass substrate, soda-lime glass, alkali-free glass, or the like is used, and the thickness should be sufficient to maintain the mechanical strength. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. As for the material of the glass, it is preferable to use non-alkali glass because the fewer ions eluted from the glass, the better. However, soda-lime glass with a barrier coating such as SiO ₂ is also available on the market and can be used. can. In addition, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side thereof in order to enhance gas barrier properties. When used, it is preferable to provide a gas barrier film.

<Anode in Organic Electroluminescent Device>
Anode 102 serves to inject holes into light-emitting layer 105 . When the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

Materials for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide metal (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of organic compounds include polythiophenes such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, it can be used by appropriately selecting from materials used as anodes of organic EL elements.

The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but a low resistance is desirable from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω/□ or less functions as an element electrode, but it is now possible to supply a substrate of about 10 Ω/□. It is particularly desirable to use a low resistance product of /□. Although the thickness of ITO can be arbitrarily selected according to the resistance value, it is usually used in the range of 50 to 300 nm.

<Hole Injection Layer and Hole Transport Layer in Organic Electroluminescent Device>
The hole-injecting layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light-emitting layer 105 or the hole-transporting layer 104 . The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105 . The hole injection layer 103 and the hole transport layer 104 are each formed by stacking and mixing one or more kinds of hole injection/transport materials, or by a mixture of a hole injection/transport material and a polymer binder. be done. Also, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form the layer.

As a hole-injecting/transporting substance, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. It is desirable to For this purpose, it is preferable that the ionization potential is low, the hole mobility is high, the stability is excellent, and impurities that become traps are less likely to occur during manufacture and use.

Materials for forming the hole injection layer 103 and the hole transport layer 104 include compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, and hole injection layers of organic EL devices. Any material can be selected and used from known materials used for the hole transport layer and the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine derivatives (aromatic tertiary Polymers with amino in the main chain or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4 ,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4 ,4′-diphenyl-1,1′-diamine, N,N′-dinaphthyl-N,N′-diphenyl-4,4′-diphenyl-1,1′-diamine, N ⁴ ,N ⁴ ′ -diphenyl- N ⁴ ,N ^4′ -bis(9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine, N ⁴ ,N ⁴ ,N ^4′ ,N ^{4 '} -tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, 4,4',4''-tris(3-methylphenyl(phenyl) triphenylamine derivatives such as amino)triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives , quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. Polycarbonate, styrene derivatives, polyvinylcarbazole, polysilane and the like having the above-mentioned monomers in the side chains are preferable for polymer systems, but a thin film necessary for manufacturing a light-emitting device can be formed and holes can be injected from the anode. Further, the compound is not particularly limited as long as it is a compound capable of transporting holes.

It is also known that the conductivity of organic semiconductors is strongly influenced by their doping. Such an organic semiconductor matrix material is composed of a compound with good electron-donating property or a compound with good electron-accepting property. Strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are known for doping electron donors. (For example, M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)” and the literature “J. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731 (1998)"). They generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). The conductivity of the base material varies considerably depending on the number and mobility of holes. As matrix substances having hole-transporting properties, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine ZnPc, etc.) are known (Japanese Unexamined Patent Application Publication No. 2005-167175).

<Light Emitting Layer in Organic Electroluminescent Device>
The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. As a material for forming the light-emitting layer 105, any compound (light-emitting compound) that emits light when excited by recombination of holes and electrons can be used. It is preferably a compound that exhibits strong luminescence (fluorescence) efficiency at . In the light-emitting layer of the present invention, the anthracene-based compound represented by the general formula (1) and the pyrene-based compound represented by the general formula (2) are contained as essential components as host materials, and the dopant material is preferably the above-described boron-containing compound or the above-described A pyrene-based compound different from the pyrene-based compound of general formula (2) can be contained. Details of these are given above, and a general description of the light-emitting layer follows.

The light-emitting layer may be a single layer or a plurality of layers, each of which is formed of a light-emitting layer material (host material, dopant material). The dopant material may be included entirely or partially in the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be mixed with the host material in advance and then vapor-deposited simultaneously.

The amount of host material to be used varies depending on the type of host material, and may be determined according to the properties of the host material. A guideline for the amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the total light-emitting layer material. is.

The amount of dopant material used varies depending on the type of dopant material, and may be determined according to the properties of the dopant material. A guideline for the amount of dopant to be used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight of the total light-emitting layer material. be. The above range is preferable in that, for example, the phenomenon of concentration quenching can be prevented.

<Electron Injection Layer and Electron Transport Layer in Organic Electroluminescent Device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106 . The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105 . The electron transport layer 106 and the electron injection layer 107 are formed by stacking and mixing one or more electron transport/injection materials, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable to use a substance that has high electron affinity, high electron mobility, excellent stability, and does not easily generate trapping impurities during production and use. However, when considering the transport balance of holes and electrons, if the function mainly plays the role of efficiently preventing holes from the anode from flowing to the cathode side without recombination, the electron transport capacity is not so high. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material with a high electron transport ability. Therefore, the electron injection/transport layer in this embodiment may also have the function of a layer capable of efficiently blocking the movement of holes.

Materials (electron transport materials) forming the electron transport layer 106 or the electron injection layer 107 include compounds conventionally used as electron transport compounds in photoconductive materials, and those used in the electron injection layer and electron transport layer of organic EL elements. It can be used by arbitrarily selecting from among the known compounds that are known.

Materials used for the electron transport layer or electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, and pyrrole derivatives. and condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4′-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, and anthraquinone. and quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes. These materials may be used alone, but may be used in combination with different materials.

Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, and oxadiazole. derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazole- 2-yl)benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4′-(2,2′:6′2 "-terpyridinyl)) benzene, etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives , and bis-styryl derivatives.

Metal complexes having electron-accepting nitrogen can also be used, for example, quinolinol-based metal complexes, hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, benzoquinoline metal complexes, and the like. can give.

Although the above materials can be used alone, they may be used in combination with different materials.

Borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metals, among the materials mentioned above. Complexes are preferred.

上記式（ＥＴＭ－１）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｘは、置換されていてもよいアリーレンであり、Ｙは、置換されていてもよい炭素数１６以下のアリール、置換されているボリル、または置換されていてもよいカルバゾリルであり、そして、ｎはそれぞれ独立して０～３の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。 <borane derivative>
The borane derivative is, for example, a compound represented by the following general formula (ETM-1), which is disclosed in detail in JP-A-2007-27587.

In the above formula (ETM-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen-containing at least one of heterocycle and cyano, and R ¹³ to R ¹⁶ are each independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl , X is optionally substituted arylene, Y is optionally substituted aryl having up to 16 carbon atoms, optionally substituted boryl, or optionally substituted carbazolyl, and n are each independently an integer of 0 to 3. Also, substituents in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

式（ＥＴＭ－１－１）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、ｎはそれぞれ独立して０～３の整数であり、そして、ｍはそれぞれ独立して０～４の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。

式（ＥＴＭ－１－２）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、そして、ｎはそれぞれ独立して０～３の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。 Among the compounds represented by the above general formula (ETM-1), compounds represented by the following general formula (ETM-1-1) and compounds represented by the following general formula (ETM-1-2) are preferable.

In formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen at least one of heterocyclic ring-containing or cyano, and R ¹³ to R ¹⁶ are each independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl and R ²¹ and R ²² are each independently at least hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano X ¹ is an optionally substituted arylene having 20 or less carbon atoms, each n is independently an integer of 0 to 3, and each m is independently an integer of 0 to 4 is an integer. Also, substituents in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

In formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen at least one of heterocyclic ring-containing or cyano, and R ¹³ to R ¹⁶ are each independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl , X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and each n is independently an integer of 0 to 3. Also, substituents in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

（各式中、Ｒ^ａは、それぞれ独立してアルキル基、シクロアルキル基または置換されていてもよいフェニル基である。） Specific examples of X ¹ include divalent groups represented by the following formulas (X-1) to (X-9).

(In each formula, R ^a is each independently an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)

Specific examples of this borane derivative include the following compounds.

This borane derivative can be produced using known raw materials and known synthetic methods.

<Pyridine derivative>
The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by formula (ETM-2-1) or (ETM-2-2).

φ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; be.

In the above formula (ETM-2-1), R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).

In the above formula (ETM-2-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R ¹¹ and R ¹² may combine to form a ring.

In each formula, the "pyridine-based substituent" is any one of the following formulas (Py-1) to (Py-15), and the pyridine-based substituents are each independently alkyl having 1 to 4 carbon atoms or carbon It may be substituted with 5 to 10 cycloalkyls. Also, the pyridine-based substituent may be bonded to φ, anthracene ring or fluorene ring in each formula via a phenylene group or naphthylene group.

The pyridine-based substituent is any of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44) is preferred.

At least one hydrogen in each pyridine derivative may be replaced with deuterium, and among the two "pyridine-based substituents" in the above formulas (ETM-2-1) and (ETM-2-2), may be replaced with aryl.

“Alkyl” for R ¹¹ to R ¹⁸ may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms and branched chain alkyl having 3 to 24 carbon atoms. Preferred "alkyl" are alkyls of 1 to 18 carbon atoms (branched alkyls of 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

Specific “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

As the alkyl having 1 to 4 carbon atoms with which the pyridine-based substituent is substituted, the above description of alkyl can be cited.

Examples of "cycloalkyl" for R ¹¹ to R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.
Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the cycloalkyl having 5 to 10 carbon atoms with which the pyridine-based substituent is substituted, the above description of cycloalkyl can be cited.

As “aryl” for R ¹¹ to R ¹⁸ , aryl having 6 to 30 carbon atoms is preferable, aryl having 6 to 18 carbon atoms is more preferable, and aryl having 6 to 14 carbon atoms is more preferable. and particularly preferably aryl having 6 to 12 carbon atoms.

Specific examples of "aryl having 6 to 30 carbon atoms" include monocyclic aryl phenyl, condensed bicyclic aryl (1-,2-) naphthyl, condensed tricyclic aryl acenaphthylene-( 1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -,3-,4-,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthacene-(1- ,2-,5-)yl, condensed pentacyclic aryl perylene-(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl and the like. .

Preferable "aryl having 6 to 30 carbon atoms" includes phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, particularly preferably phenyl, 1 -naphthyl or 2-naphthyl.

R ¹¹ and R ¹² in the above formula (ETM-2-2) may combine to form a ring, and as a result, the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene, indene, and the like may be spiro-bonded.

Specific examples of this pyridine derivative include the following compounds.

This pyridine derivative can be produced using known raw materials and known synthetic methods.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), which is disclosed in detail in WO2010/134352.

In the above formula (ETM-3), X ¹² to X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted represents heteroaryl. Here, examples of substituents when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Specific examples of this fluoranthene derivative include the following compounds.

<BO-based derivative>
The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).

R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Adjacent groups among R ¹ to R ¹¹ may be combined to form an aryl ring or heteroaryl ring together with the a ring, the b ring, or the c ring, and at least one hydrogen atom in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy in which at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.

At least one hydrogen in the compound or structure represented by formula (ETM-4) may be replaced with halogen or deuterium.

For the description of the substituents and ring formation forms in formula (ETM-4), and the multimer formed by combining multiple structures of formula (ETM-4), the above general formula (3) and formula (3′) are shown. A description of the compound and its multimers can be cited.

Specific examples of this BO derivative include the following compounds.

This BO-based derivative can be produced using known raw materials and known synthetic methods.

<Anthracene derivative>
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).

Ar is each independently divalent benzene or naphthalene, R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or carbon atoms 6-20 aryl.

Each Ar can be independently selected as appropriate from divalent benzene or naphthalene, and the two Ars may be different or the same, but from the viewpoint of ease of synthesis of the anthracene derivative, they are the same is preferably Ar is bound to pyridine to form a "site consisting of Ar and pyridine", and this site is, for example, anthracene as a group represented by any of the following formulas (Py-1) to (Py-12). is bound to

Among these groups, a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and a group represented by any one of the above formulas (Py-1) to (Py-6) is more preferred. The two “sites consisting of Ar and pyridine” that bind to anthracene may have the same or different structures, but preferably have the same structure from the viewpoint of ease of synthesis of anthracene derivatives. However, from the viewpoint of device characteristics, it is preferable that the structures of the two “sites consisting of Ar and pyridine” be the same or different.

The alkyl having 1 to 6 carbon atoms in R ¹ to R ⁴ may be straight chain or branched chain. That is, straight chain alkyl of 1 to 6 carbon atoms or branched chain alkyl of 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, or 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl , methyl, ethyl, or t-butyl are more preferred.

Specific examples of cycloalkyl having 3 to 6 carbon atoms for R ¹ to R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl and dimethylcyclohexyl.

The aryl having 6 to 20 carbon atoms in R ¹ to R ⁴ is preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms, and particularly preferably aryl having 6 to 10 carbon atoms.

Specific examples of "aryl having 6 to 20 carbon atoms" include monocyclic aryl phenyl, (o-, m-, p-)tolyl, (2,3-,2,4-,2,5- , 2,6-,3,4-,3,5-)xylyl, mesityl (2,4,6-trimethylphenyl), (o-,m-,p-)cumenyl, bicyclic aryl (2 -,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4 '-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p- terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl, anthracen-(1-,2-,9-)yl, acenaphthylene- (1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-, 2-,3-,4-,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, tetracene-(1 -,2-,5-)yl, and perylene-(1-,2-,3-)yl which is a condensed pentacyclic aryl.

Preferred "aryl having 6 to 20 carbon atoms" is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl, More preferred are phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferred is phenyl.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Each Ar ¹ is independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

Each Ar ² is independently an aryl having 6 to 20 carbon atoms, and the same explanation as for the "aryl having 6 to 20 carbon atoms" in the above formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perylenyl.

R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or aryl having 6 to 20 carbon atoms, and the above formula (ETM-5-1) The description in can be quoted.

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced using known raw materials and known synthetic methods.

<Benzofluorene derivative>
A benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Each Ar ¹ is independently an aryl having 6 to 20 carbon atoms, and the same explanation as for the "aryl having 6 to 20 carbon atoms" in the above formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perylenyl.

Ar ² is each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms) ) and the two Ar ² may be combined to form a ring.

“Alkyl” for Ar ² may be either straight-chain or branched-chain, such as straight-chain alkyl having 1 to 24 carbon atoms or branched-chain alkyl having 3 to 24 carbon atoms. Preferred "alkyl" are alkyls of 1 to 18 carbon atoms (branched alkyls of 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

“Cycloalkyl” for Ar ² includes, for example, cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

The “aryl” for Ar ² is preferably aryl having 6 to 30 carbon atoms, more preferably aryl having 6 to 18 carbon atoms, more preferably aryl having 6 to 14 carbon atoms, and particularly Aryl having 6 to 12 carbon atoms is preferred.

Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl and the like.

Two ^Ar2 may be joined to form a ring, so that the 5-membered ring of the fluorene skeleton is spiro-bonded with cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene, etc. may

Specific examples of this benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced using known raw materials and known synthetic methods.

Ｒ^５は、置換または無置換の、炭素数１～２０のアルキル、炭素数３～２０のシクロアルキル、炭素数６～２０のアリールまたは炭素数５～２０のヘテロアリールであり、
Ｒ^６は、ＣＮ、置換または無置換の、炭素数１～２０のアルキル、炭素数３～２０のシクロアルキル、炭素数１～２０のヘテロアルキル、炭素数６～２０のアリール、炭素数５～２０のヘテロアリール、炭素数１～２０のアルコキシまたは炭素数６～２０のアリールオキシであり、
Ｒ^７およびＲ^８は、それぞれ独立して、置換または無置換の、炭素数６～２０のアリールまたは炭素数５～２０のヘテロアリールであり、
Ｒ^９は酸素または硫黄であり、
ｊは０または１であり、ｋは０または１であり、ｒは０～４の整数であり、ｑは１～３の整数である。
ここで、置換されている場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。 <Phosphine oxide derivative>
A phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/079217.

R ⁵ is substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
R ⁶ is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, aryl having 5 to 20 carbon atoms, 20 heteroaryl, alkoxy having 1 to 20 carbon atoms or aryloxy having 6 to 20 carbon atoms,
R ⁷ and R ⁸ are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
^R9 is oxygen or sulfur,
j is 0 or 1, k is 0 or 1, r is an integer of 0-4, and q is an integer of 1-3.
Here, examples of substituents when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

A phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).

R ¹ to R ³ may be the same or different, hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, arylether group , arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and condensed ring formed between adjacent substituents selected from

Ar ¹ may be the same or different and is an arylene group or a heteroarylene group, and Ar ² may be the same or different and is an aryl group or a heteroaryl group. However, at least one of Ar ¹ and Ar ² has a substituent or forms a condensed ring with an adjacent substituent. n is an integer of 0 to 3. When n is 0, there is no unsaturated structural moiety, and when n is 3, R ¹ does not exist.

Among these substituents, the alkyl group means, for example, a saturated aliphatic hydrocarbon group such as methyl group, ethyl group, propyl group and butyl group, which may be unsubstituted or substituted. When substituted, the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, a heterocyclic group, and the like, and this point is also common to the following description. Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually in the range of 1 to 20 from the standpoint of availability and cost.

The cycloalkyl group is, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl and adamantyl, which may be unsubstituted or substituted. Although the number of carbon atoms in the alkyl group portion is not particularly limited, it is usually in the range of 3-20.

An aralkyl group is, for example, an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. I don't mind. Although the number of carbon atoms in the aliphatic portion is not particularly limited, it is usually in the range of 1-20.

The alkenyl group is, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as vinyl group, allyl group, butadienyl group, etc., which may be unsubstituted or substituted. Although the number of carbon atoms in the alkenyl group is not particularly limited, it is usually in the range of 2-20.

In addition, the cycloalkenyl group is, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexene group, which may be unsubstituted or substituted. I don't mind.

The alkynyl group is, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted. Although the number of carbon atoms in the alkynyl group is not particularly limited, it is usually in the range of 2-20.

An alkoxy group is, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. Although the number of carbon atoms in the alkoxy group is not particularly limited, it is usually in the range of 1-20.

An alkylthio group is a group in which an oxygen atom in an ether bond of an alkoxy group is substituted with a sulfur atom.

A cycloalkylthio group is a group in which an oxygen atom in an ether bond of a cycloalkoxy group is substituted with a sulfur atom.

An aryl ether group is, for example, an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted. Although the number of carbon atoms in the aryl ether group is not particularly limited, it is usually in the range of 6-40.

An arylthioether group is a group in which an oxygen atom in an ether bond of an arylether group is substituted with a sulfur atom.

Further, the aryl group means, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenylyl group, a phenanthryl group, a terphenyl group and a pyrenyl group. An aryl group can be unsubstituted or substituted. Although the number of carbon atoms in the aryl group is not particularly limited, it is usually in the range of 6-40.

In addition, the heterocyclic group refers to, for example, a cyclic structural group having atoms other than carbon atoms such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group, which may be unsubstituted or substituted. I don't mind. Although the number of carbon atoms in the heterocyclic group is not particularly limited, it is usually in the range of 2-30.

Halogen means fluorine, chlorine, bromine and iodine.

Aldehyde groups, carbonyl groups, and amino groups can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like.

Aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic rings may be substituted or unsubstituted.

A silyl group is, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. Although the number of carbon atoms in the silyl group is not particularly limited, it is usually in the range of 3-20. Also, the silicon number is usually 1-6.

Condensed rings formed between adjacent substituents are, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar 2 and R ² , Ar ² and R ³ , R ² and R ³ , Ar ^{1 and} Conjugated or non-conjugated fused ring formed between Ar ² and so on. Here, when n is 1, two R ^1s may form a conjugated or non-conjugated condensed ring. These condensed rings may contain a nitrogen, oxygen or sulfur atom in the ring structure, or may be condensed with another ring.

Specific examples of this phosphine oxide derivative include the following compounds.

This phosphine oxide derivative can be produced using known raw materials and known synthetic methods.

<Pyrimidine Derivative>
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.

Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl. n is an integer of 1-4, preferably an integer of 1-3, more preferably 2 or 3;

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.

Specific “aryl” includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5′-phenyl-m-terphenyl-3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyren-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a condensed pentacyclic aryl )yl, pentacene-(1-,2-,5-,6-)yl, etc.

"Heteroaryl" of "optionally substituted heteroaryl" includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl and the like.

Also, the above aryl and heteroaryl may be substituted, and each may be substituted, for example, by the above aryl or heteroaryl.

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced using known raw materials and known synthetic methods.

<Carbazole derivative>
A carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which multiple such compounds are bonded via single bonds. Details are described in US Publication No. 2014/0197386.

Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl. n is independently an integer of 0-4, preferably an integer of 0-3, more preferably 0 or 1;

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.

Specific “aryl” includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5′-phenyl-m-terphenyl-3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyren-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a condensed pentacyclic aryl )yl, pentacene-(1-,2-,5-,6-)yl, etc.

"Heteroaryl" of "optionally substituted heteroaryl" includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl and the like.

Also, the above aryl and heteroaryl may be substituted, and each may be substituted, for example, by the above aryl or heteroaryl.

The carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded via single bonds or the like. In this case, they may be bonded by an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring) other than a single bond.

Specific examples of this carbazole derivative include the following compounds.

This carbazole derivative can be produced using known starting materials and known synthetic methods.

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/0156013.

Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl. n is an integer of 1-4, preferably an integer of 1-3, more preferably 2 or 3;

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.

Specific “aryl” includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5′-phenyl-m-terphenyl-3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyren-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a condensed pentacyclic aryl )yl, pentacene-(1-,2-,5-,6-)yl, etc.

"Heteroaryl" of "optionally substituted heteroaryl" includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl and the like.

Also, the above aryl and heteroaryl may be substituted, and each may be substituted, for example, by the above aryl or heteroaryl.

Specific examples of this triazine derivative include the following compounds.

This triazine derivative can be produced using known raw materials and known synthetic methods.

<Benzimidazole derivative>
A benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

φ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; , and the "benzimidazole-based substituent" is the pyridyl group in the "pyridine-based substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo It is a substituent substituted for the imidazole group, and at least one hydrogen in the benzimidazole derivative may be replaced with deuterium.

R ¹¹ in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, and the above formula (ETM-2-1) and formula ( The description of R ¹¹ in ETM-2-2) can be cited.

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the above formula (ETM-2-1) or formula (ETM-2-2). R ¹¹ to R ¹⁸ can refer to the groups explained in the above formula (ETM-2-1) or (ETM-2-2). In addition, the above formula (ETM-2-1) or formula (ETM-2-2) is described in a form in which two pyridine-based substituents are bonded, but when replacing these with a benzimidazole-based substituent, both may be replaced with a benzimidazole-based substituent (i.e., n=2), or any one pyridine-based substituent may be replaced with a benzimidazole-based substituent and the other pyridine-based substituent may be replaced by R ¹¹ ~ ^R18 may be substituted (ie n=1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole-based substituent, and the “pyridine-based substituent” may be replaced with R ¹¹ to R ¹⁸ .

Specific examples of this benzimidazole derivative include 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10-( Naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl) -1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole, 1-(4 -(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di(naphthalen-2-yl) anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-2- phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d]imidazole and the like.

This benzimidazole derivative can be produced using known raw materials and known synthetic methods.

<Phenanthroline derivative>
A phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006/021982.

φ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; be.

R ¹¹ to R ¹⁸ in each formula are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon aryl of numbers 6 to 30). Further, in the above formula (ETM-12-1), any one of R ¹¹ to R ¹⁸ is bonded to φ which is an aryl ring.

At least one hydrogen in each phenanthroline derivative may be replaced with deuterium.

As alkyl, cycloalkyl and aryl for R ¹¹ to R ¹⁸ , the description of R ¹¹ to R ¹⁸ in formula (ETM-2) above can be cited. In addition to the structures described above, φ includes, for example, the following structural formulas. In the following structural formulas, each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

Specific examples of this phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di(1,10- phenanthrolin-2-yl)anthracene, 2,6-di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10-phenanthroline-5-yl)benzene, 9,9' -difluoro-bis(1,10-phenanthroline-5-yl), bathocuproine, 1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene, compounds represented by the following structural formulas, etc. can give.

This phenanthroline derivative can be produced using known raw materials and known synthetic methods.

式中、Ｒ^１～Ｒ^６は、それぞれ独立して、水素、フッ素、アルキル、シクロアルキル、アラルキル、アルケニル、シアノ、アルコキシまたはアリールであり、ＭはＬｉ、Ａｌ、Ｇａ、ＢｅまたはＺｎであり、ｎは１～３の整数である。 <Quinolinol-based metal complex>
A quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).

wherein R ¹ to R ⁶ are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl; M is Li, Al, Ga, Be or Zn; n is an integer of 1-3.

Specific examples of quinolinol-based metal complexes include 8-quinolinollithium, tris(8-quinolinolato)aluminum, tris(4-methyl-8-quinolinolato)aluminum, tris(5-methyl-8-quinolinolato)aluminum, tris(3 ,4-dimethyl-8-quinolinolato)aluminum, tris(4,5-dimethyl-8-quinolinolato)aluminum, tris(4,6-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-8-quinolinolato) ( phenolate)aluminum, bis(2-methyl-8-quinolinolato)(2-methylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3-methylphenolate)aluminum, bis(2-methyl-8- quinolinolato)(4-methylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(2-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3-phenylphenolate)aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) ( 2,6-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3,4-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3,5-dimethylphenolate) Aluminum, bis(2-methyl-8-quinolinolato)(3,5-di-t-butylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(2,6-diphenylphenolate)aluminum, bis( 2-methyl-8-quinolinolato)(2,4,6-triphenylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(2,4,6-trimethylphenolate)aluminum, bis(2-methyl -8-quinolinolato)(2,4,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinolato)(2 -naphtholato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(2-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolato) ) (3-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolato)(4-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3,5-dimethylphenolate) lacto)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3,5-di-t-butylphenolate)aluminum, bis(2-methyl-8-quinolinolato)aluminum-μ-oxo-bis(2 -methyl-8-quinolinolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)aluminum, μ-oxo-bis(2,4-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-4-ethyl -8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolato)aluminum, bis(2-methyl-4-methoxy-8-quinolinolato)aluminum-μ-oxo-bis(2 -methyl-4-methoxy-8-quinolinolato)aluminum, bis(2-methyl-5-cyano-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolato)aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum, bis(10-hydroxybenzo[h]quinoline) beryllium, etc.

This quinolinol-based metal complex can be produced using known raw materials and known synthetic methods.

ベンゾチアゾール誘導体は、例えば下記式（ＥＴＭ－１４－２）で表される化合物である。

<Thiazole Derivatives and Benzothiazole Derivatives>
A thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).

A benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).

φ in each formula is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4 is an integer, and the “thiazole-based substituent” or “benzothiazole-based substituent” is the “pyridine-based The pyridyl group in "substituent" is a substituent substituted with the following thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with deuterium.

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the above formula (ETM-2-1) or formula (ETM-2-2). R ¹¹ to R ¹⁸ can refer to the groups explained in the above formula (ETM-2-1) or (ETM-2-2). In addition, the above formula (ETM-2-1) or formula (ETM-2-2) is described in the form of two pyridine-based substituents bonded, but these are thiazole-based substituents (or benzothiazole-based substituents group), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (i.e., n=2), or any one pyridine-based substituent may be replaced with a thiazole-based substituent. (or benzothiazole-based substituents) and the other pyridine-based substituents may be replaced with R ¹¹ to R ¹⁸ (ie n=1). Furthermore, for example, at least one of R ¹¹ to R ¹⁸ in the formula (ETM-2-1) is replaced with a thiazole-based substituent (or a benzothiazole-based substituent) to form a “pyridine-based substituent” of R ¹¹ to R ¹⁸ . can be replaced with

These thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthetic methods.

The electron-transporting layer or electron-injecting layer may further contain a substance capable of reducing the material forming the electron-transporting layer or electron-injecting layer. Various substances are used as the reducing substance as long as they have a certain reducing property. from the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2.95 eV). 9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and materials with a work function of 2.9 eV or less are particularly preferred. Among these, more preferred reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, it is possible to improve the emission luminance and extend the life of the organic EL device. As a reducing substance having a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, particularly a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reduction ability can be efficiently exhibited, and by addition to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL device can be improved and the life of the device can be extended.

<Cathode in Organic Electroluminescent Device>
The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106 .

The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used. Metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloys, magnesium - indium alloys, aluminum-lithium alloys such as lithium fluoride/aluminum, etc.). Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective in increasing the electron injection efficiency and improving the device characteristics. However, these low work function metals are generally unstable in the atmosphere. In order to improve this point, for example, a method of doping an organic layer with a small amount of lithium, cesium, or magnesium to use a highly stable electrode is known. Other dopants can also be inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide. However, it is not limited to these.

Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride A preferable example is lamination of a hydrocarbon-based polymer compound or the like. The method of manufacturing these electrodes is not particularly limited, either by resistance heating, electron beam, sputtering, ion plating, coating, or the like, as long as it is possible to obtain electrical continuity.

<Binder that may be used in each layer>
The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer described above can form each layer alone. Polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and other curable resins. be.

<Method for producing organic electroluminescent element>
Each layer constituting the organic EL element is formed by depositing a material to constitute each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, casting, or coating. can be formed by The thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation film thickness measuring device or the like. When thin film formation is performed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the desired crystal structure and association structure of the film, and the like. The vapor deposition conditions are generally boat heating temperature +50 to +400° C., degree of vacuum 10 ⁻⁶ to 10 ⁻³ Pa, vapor deposition rate 0.01 to 50 nm/sec, substrate temperature −150 to +300° C., film thickness 2 nm to 5 μm. It is preferable to set appropriately within the range.

Next, as an example of a method for producing an organic EL device, an organic EL device comprising an anode/hole injection layer/hole transport layer/light-emitting layer comprising a host material and a dopant material/electron transport layer/electron injection layer/cathode. The manufacturing method of is explained. A thin film of an anode material is formed on a suitable substrate by a vapor deposition method or the like to prepare an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited thereon to form a thin film to form a light-emitting layer, an electron-transporting layer and an electron-injecting layer are formed on the light-emitting layer, and a thin film of a cathode material is formed by vapor deposition or the like. A target organic EL element is obtained by forming the material and using it as a cathode. In the production of the organic EL element described above, the order of production can be reversed to produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. is.

When a DC voltage is applied to the organic EL device thus obtained, it is sufficient to apply the positive polarity to the positive electrode and the negative polarity to the negative electrode. Light emission can be observed from the side (anode or cathode, and both). Further, this organic EL element emits light even when a pulse current or an alternating current is applied. Note that the AC waveform to be applied may be arbitrary.

<Application example of organic electroluminescence device>
The present invention can also be applied to a display device having an organic EL element, a lighting device having an organic EL element, or the like.
A display device or a lighting device including an organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known driving device, and can be manufactured by direct current driving, pulse driving, alternating current driving, or the like. It can be driven by appropriately using a known driving method.

Examples of display devices include panel displays such as color flat panel displays, and flexible displays such as flexible color organic electroluminescence (EL) displays (for example, JP-A-10-335066 and JP-A-2003-321546). (See Japanese Patent Laid-Open No. 2004-281086, etc.). Moreover, the display method of the display includes, for example, a matrix and/or a segment method. Note that matrix display and segment display may coexist in the same panel.

In the matrix, pixels for display are arranged in a two-dimensional pattern such as a grid pattern or a mosaic pattern, and a set of pixels displays characters and images. The shape and size of the pixels are determined by the application. For example, in the image and character display of personal computers, monitors, and televisions, square pixels with a side of 300 μm or less are usually used, and in the case of a large display such as a display panel, a pixel with a side of mm order is used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, pixels of red, green, and blue are displayed side by side. In this case, there are typically delta type and stripe type. As a method for driving this matrix, either a line-sequential driving method or an active matrix method may be used. The line-sequential drive has the advantage of being simpler in structure, but considering the operating characteristics, the active matrix may be superior.

In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined area is illuminated. Examples include time and temperature displays in digital clocks and thermometers, operating state displays in audio equipment and electromagnetic cookers, and panel displays in automobiles.

Examples of lighting devices include lighting devices such as indoor lighting, backlights for liquid crystal display devices, and the like (for example, JP-A-2003-257621, JP-A-2003-277741, JP-A-2004-119211, and the like). etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, clocks, audio devices, automobile panels, display boards, signs, and the like. In particular, as a liquid crystal display device, especially a backlight for a personal computer, for which thinning is a problem, it is difficult to reduce the thickness of the conventional method because it is made of a fluorescent lamp or a light guide plate. The backlight using the light-emitting element according to 1 is characterized by its thinness and light weight.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these. First, synthesis examples of the compounds used in the examples are described below.

化合物（１－１３４－Ｏ）は、国際公開第2014/141725号公報の段落[0106]に記載された方法に準じて合成した。 Synthesis example (1)
Synthesis of compound (1-134-O): 2-(10-phenylanthracen-9-yl)naphtho[2,3-b]benzofuran

Compound (1-134-O) was synthesized according to the method described in paragraph [0106] of WO2014/141725.

化合物（１－１９５）は、特開2016-88927号公報の「合成例３０：化合物（ＣＨ－ＡＰ４１）の合成」に記載された方法に準じて合成した。 Synthesis example (2)
Synthesis of compound (1-195)

Compound (1-195) was synthesized according to the method described in "Synthesis Example 30: Synthesis of compound (CH-AP41)" in JP-A-2016-88927.

化合物（１－１９９）は、特開2012-104806号公報の「式（１－５５）で表される化合物の合成例」に記載された方法に準じて合成した。 Synthesis example (3)
Synthesis of compound (1-199)

Compound (1-199) was synthesized according to the method described in "Synthesis Example of Compound Represented by Formula (1-55)" in JP-A-2012-104806.

Synthesis example (4)
Compound (2-1): Synthesis of 11,11-diphenyl-6-(pyren-1-yl)-11H-benzo[a]fluorene

Under a nitrogen atmosphere, 1-bromo-2-methoxynaphthalene (9.5 g), bis(pinacolato)diboron (12.2 g), potassium acetate (11.8 g), and palladium catalyst (1,1′-bis( Diphenylphosphino)ferrocene)palladium(II) dichloride/dichloromethane complex (0.98 g) and cyclopentyl methyl ether (CPME, 143 mL) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and ethyl acetate was further added for liquid separation and extraction. After separating the organic layer, it was dried, concentrated, and purified with an activated carbon short column (eluent: toluene) to obtain intermediate A (11.3 g).

Under a nitrogen atmosphere, Intermediate A (11.3 g), methyl 2-bromobenzoate (8.6 g), potassium phosphate (16.9 g), tetrakis(triphenylphosphine)palladium (1.4 g) as a palladium catalyst, Toluene (85 mL), ethanol (17 mL) and water (9 mL) were placed in a flask and stirred at reflux temperature for 7 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation and extraction. After separating the organic layer, it was dried and concentrated, and the crude product was purified with a silica gel column (eluent: toluene) to obtain intermediate B (9.1 g).

Intermediate B (9.1 g) and tetrahydrofuran (THF, 21 mL) were placed in a flask under a nitrogen atmosphere, cooled in an ice bath, and then a 1 M phenylmagnesium bromide/THF solution (94 mL) was added dropwise under a nitrogen atmosphere. and stirred at reflux temperature for 3 hours. After cooling, a saturated aqueous solution of ammonium chloride was added to terminate the reaction, and ethyl acetate was added for solvent extraction. After separating the organic layer, it was dried and concentrated, and the crude product was purified with a silica gel column (eluent: toluene) to obtain Intermediate C (12.3 g).

Under a nitrogen atmosphere, Intermediate C (12.3 g) and acetic acid (117 mL) were placed in a flask, one drop of concentrated sulfuric acid was added thereto, and the mixture was stirred at 90° C. for 3 hours under a nitrogen atmosphere. After cooling, water was added, the precipitate was filtered, washed with water and dried to obtain intermediate D (10.6 g).

Under a nitrogen atmosphere, Intermediate D (10.6 g), pyridine hydrochloride (15.4 g) and N-methylpyrrolidone (NMP, 10 mL) were placed in a flask and stirred at 185° C. for 4 hours under a nitrogen atmosphere. After cooling and adding water, the precipitate was filtered, washed with water and dried to give Intermediate E (10.1 g).

Intermediate E (10 g) and pyridine (100 mL) were placed in a flask under a nitrogen atmosphere, cooled in an ice bath, and then trifluoromethanesulfonic anhydride (18.3 g) was added dropwise under a nitrogen atmosphere. After the mixture was stirred as it was for 3 hours, water was added to terminate the reaction. The precipitate was filtered and purified with a silica gel short column (eluent: toluene) to obtain intermediate F (13.4 g).

Intermediate F (3 g), 1-pyreneboronic acid (2.1 g), potassium phosphate (2.5 g), tetrakis(triphenylphosphine)palladium (0.2 g) as a palladium catalyst, 1,2, 4-trimethylbenzene (24 mL), t-butyl alcohol (3 mL) and water (1.5 mL) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation and extraction. After separating the organic layer, it is dried and concentrated, and the crude product is purified with a silica gel column (eluent: toluene/heptane = 3/1 (volume ratio)) and then purified by sublimation to obtain compound (2-1). obtained (1.2 g).

The structure of compound (2-1) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.0 (d, 1H), 6.6 (dt, 1H), 7.0 (dt, 1H), 7.2-7.5 (m, 13H), 7 .9-8.0 (m, 5H), 8.0 (t, 1H), 8.2-8.3 (m, 5H), 8.4 (d, 1H).

Synthesis example (5)
Synthesis of Compound (2-46): 6-(6-(naphthalen-2-yl)pyren-1-yl)-11,11-diphenyl-11H-benzo[a]fluorene

Under a nitrogen atmosphere, 1,6-dibromopyrene (3.5 g), 2-naphthylboronic acid (1.7 g), potassium carbonate (2.7 g), and tetrakis(triphenylphosphine) palladium (0.3 g) as a palladium catalyst. , toluene (35 mL), and water (9 mL) were placed in a flask and stirred at reflux temperature for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation and extraction. After separating the organic layer, it was dried and concentrated, and the crude product was purified with a silica gel column (eluent: toluene/heptane=6/1 (volume ratio)) to obtain intermediate G (2.1 g).

Intermediate F (7 g), bis(pinacolato)diboron (4.1 g), potassium acetate (4.0 g), and (1,1′-bis(diphenylphosphino)ferrocene) palladium(II) as a palladium catalyst under a nitrogen atmosphere. ) dichloride-dichloromethane complex (0.3 g) and cyclopentyl methyl ether (CPME, 67 mL) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and ethyl acetate was further added for liquid separation and extraction. After separating the organic layer, it was dried, concentrated, and purified with an activated carbon short column (eluent: toluene) to obtain intermediate H (4.6 g).

Under nitrogen atmosphere, intermediate G (0.8 g), intermediate H (0.9 g), potassium phosphate (0.9 g), tetrakis(triphenylphosphine) palladium (0.1 g) as palladium catalyst, 1,2 ,4-trimethylbenzene (12 mL), t-butyl alcohol (2 mL) and water (1 mL) were placed in a flask and stirred at reflux temperature for 14 hours under a nitrogen atmosphere. The reaction liquid was cooled to room temperature, water was added, and toluene was further added to carry out liquid separation and extraction. After separating the organic layer, it is dried and concentrated, and the crude product is purified with a silica gel column (eluent: toluene/heptane = 1/3 (volume ratio)) and then purified by sublimation to obtain compound (2-46). obtained (1.0 g).

The structure of compound (2-46) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.0 (d, 1H), 6.6 (dt, 1H), 7.0 (dt, 1H), 7.2-7.6 (m, 15H), 7 .8-8.2 (m, 14H), 8.2-8.3 (m, 2H).

Synthesis example (6)
Synthesis of Compound (2-174): 2-(pyren-1-yl)naphtho[2,3-b]benzofuran

Under a nitrogen atmosphere, 1-pyreneboronic acid (1.0 g) and 2-bromobenzo[b]naphtho[2,3-d]furan (1.1 g) synthesized by the method described in WO 2014/141725. , tetrakis(triphenylphosphine)palladium (0.09 g) as a palladium catalyst, potassium phosphate (1.7 g), xylene (15 mL), t-butyl alcohol (5 mL) and water (3 mL) were placed in a flask and heated to reflux temperature. and stirred for 2 hours. After the reaction, the mixture was cooled, water and ethyl acetate were added to the reaction solution, and the mixture was stirred. The precipitate was filtered, and the crude product was washed with water and methanol. The precipitate was dried, dissolved in chlorobenzene by heating, filtered through a silica gel short column (eluent: toluene), and the solid obtained by concentrating the eluate was further purified by chlorobenzene/reprecipitation. The resulting solid was dried and purified by sublimation to obtain compound (2-174) (1.0 g).

The structure of compound (2-174) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.5 (m, 1H), 7.5-7.6 (m, 1H), 7.7-7.8 (m, 2H), 8.0-8. 3 (m, 13H), 8.5 (s, 1H).

Synthesis example (7)
Synthesis of Compound (2-350): 2-(pyren-1-yl)triphenylene

Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane (3.0 g), 1-bromopyrene (2.2 g) and palladium were placed in a flask. Chlorophenylallyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (25 mg), potassium carbonate (2.2 g), tetrabutylammonium bromide (TBAB, 0.2 g) as a catalyst. 8 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were placed in a flask and heated with stirring at reflux temperature for 2 hours. After the reaction, the mixture was cooled, water was added to the reaction mixture, and the mixture was stirred, and then the precipitate was filtered. After drying the precipitate, it is dissolved in chlorobenzene by heating, filtered through a silica gel short column (eluent: toluene), the solid obtained by concentrating the eluate is filtered, dried and purified by sublimation to obtain a compound. (2-350) was obtained (3.3 g).

The structure of compound (2-350) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.6-7.7 (m, 4H), 7.9 (dd, 1H), 8.0 (m, 2H), 8.1-8.2 (m, 4H), 8.2 (m, 1H), 8.3 (m, 2H), 8.7-8.8 (m, 4H), 8.8 (d, 1H), 8.9 (d, 1H) ).

Synthesis example (8)
Synthesis of Compound (2-356): 2-(pyren-1-yl)dibenzo[g,p]chrysene

Under a nitrogen atmosphere, 3-bromodibenzo[g,p]chrysene (14 g) and tetrahydrofuran (THF, 200 mL) synthesized by the method described in Japanese Patent Publication No. 2011-006397 were placed in a flask and made into a homogeneous solution, followed by drying. After cooling to −78° C. with an ice-acetone bath, 1.6 M n-butyllithium/hexane solution (28 mL) was added dropwise. After stirring at the same temperature for 0.5 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12.8 g) was added. After stirring at the same temperature for 3 hours, the temperature was raised and dilute hydrochloric acid was added to stop the reaction. After adding toluene and extracting, the organic layer was concentrated, and the obtained crude product was purified with a silica gel column (eluent: toluene/heptane = 7/3 (volume ratio)) to obtain intermediate I ( 11.5 g).

Under a nitrogen atmosphere, Intermediate I (1.0 g), 1-bromopyrene (0.59 g), bis(di-t-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (16 mg) as a palladium catalyst, potassium phosphate ( 0.9 g), xylene (10 mL), t-butyl alcohol (3 mL) and water (2 mL) were placed in a flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added, and the mixture was stirred, and the deposited precipitate was filtered. The obtained crude product was purified by a silica gel short column (eluent: toluene), and then purified by reprecipitation with toluene/heptane. The resulting solid was dried and purified by sublimation to obtain compound (2-356) (0.7 g).

The structure of compound (2-356) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.7 (m, 6H), 7.9 (dd, 1H) 8.0-8.1 (m, 2H), 8.1-8.3 (m, 5H) ), 8.3 (d, 1H), 8.4 (d, 1H), 8.7-8.8 (m, 5H), 8.9 (m, 1H), 8.9 (d, 1H) , 9.0(d, 1H).

Synthesis example (9)
Synthesis of Compound (2-359): 1,6-bis(naphtho[2,3-b]benzofuran-2-yl)-3a ¹ ,5a ¹ -dihydropyrene

Under a nitrogen atmosphere, 2-bromobenzo[b]naphtho[2,3-d]furan (10.8 g) and tetrahydrofuran (THF, 200 mL) synthesized by the method described in WO 2014/141725 were placed in a flask. and cooled to −78° C. with a dry ice-acetone bath. A 1.6 M n-butyllithium/heptane solution (25 mL) was added dropwise thereto. After stirring at the same temperature for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10 g) was added. After stirring at the same temperature for 2 hours, the temperature was raised and dilute hydrochloric acid was added to stop the reaction. After adding toluene and extracting, the organic layer was concentrated, and the obtained crude product was purified with a silica gel column (eluent: toluene/heptane = 7/3 (volume ratio)) to obtain intermediate J ( 9.2g).

Under a nitrogen atmosphere, 1,6-dibromopyrene (1.0 g), intermediate J (2.0 g), bis(di-t-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (20 mg) as a palladium catalyst, phosphorus Potassium acid (2.4 g), xylene (15 mL), t-butyl alcohol (3 mL) and water (2 mL) were placed in a flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added, and the mixture was stirred, and the deposited precipitate was filtered. The obtained crude product was purified by a silica gel short column (eluent: toluene), and then washed with hot chlorobenzene for purification. The resulting solid was dried and purified by sublimation to obtain compound (2-359) (1.6 g).

The obtained compound (2-359) was confirmed by LC-MS measurement.
MS (ACPI) m/z = 635 (M+H)

Synthesis example (10)
Synthesis of Compound (2-1001): 3,9-di(pyren-1-yl)spiro[benzo[a]fluorene-11,9′-fluorene]

Under a nitrogen atmosphere, a flask containing pyrene-1-boronic acid (5 g), ethylene glycol (3.8 g) and toluene (30 mL) was stirred at reflux temperature for 3 hours. After the reaction was completed, the mixture was cooled, water was added, the mixture was stirred, the organic layer was separated, and the organic layer was concentrated under reduced pressure to obtain a crude product. After the crude product was passed through a silica gel short column (eluent: toluene), the eluate was concentrated to obtain 2-(pyren-1-yl)-1,3,2-dioxaborolane (4.2 g).

Intermediate K (3.8 g), 2-(pyren-1-yl)-1,3,2-dioxaborolane (3.3 g) synthesized by the method described in Japanese Patent Publication No. 2009-184993 under a nitrogen atmosphere, palladium Chlorophenylallyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (19 mg), potassium carbonate (3.2 g), tetrabutylammonium bromide (TBAB, 0.2 g) as a catalyst. 6 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were placed in a flask and heated with stirring at reflux temperature for 9 hours. After the reaction, the mixture was cooled, water was added to the reaction mixture, and the mixture was stirred, and then the precipitate was filtered. After drying the precipitate, dissolving it in chlorobenzene by heating, filtering through a silica gel short column (eluent: toluene), concentrating the eluate, filtering the resulting solid, drying, and sublimation purification. Compound (2-1001) was obtained (2.2 g).

The structure of compound (2-1001) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.9-7.0 (m, 4H), 7.2 (t, 2H), 7.4 (dd, 1H), 7.4 (dt, 2H), 7 .7 (dd, 1H), 7.8-7.9 (m, 2H), 7.9-8.1 (m, 9H), 8.1-8.2 (m, 13H).

Synthesis example (11)
Synthesis of Compound (2-1080): 3,9-bis(7-(t-butyl)pyren-2-yl)spiro[benzo[a]fluorene-11,9′-fluorene]

Under a nitrogen atmosphere, Intermediate L synthesized by the method described in WO 2015/141608 (1.7 g), 2-bromo-7-(t-butyl)pyrene (2 g), chlorophenylallyl as a palladium catalyst [ 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (9 mg), potassium carbonate (1.6 g), tetrabutylammonium bromide (TBAB, 0.3 g), cyclopentylmethyl Ether (CPME, 20 mL) and water (2 mL) were placed in a flask and heated with stirring at reflux temperature for 4 hours. After the reaction, the mixture was cooled, water was added to the reaction mixture, and the mixture was stirred, and then the precipitate was filtered. After drying the precipitate, it is dissolved in chlorobenzene by heating, filtered through a silica gel short column (eluent: toluene), and the solid obtained by concentrating the eluate is filtered, dried, and purified by sublimation. Compound (2-1080) was obtained (1.6 g).

The structure of the compound (2-1080) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 1.6 (s, 9H), 1.6 (s, 9H), 6.9 (d, 2H), 6.9 (d, 1H), 7.1 (dt , 2H), 7.2 (d, 1H), 7.5 (dt, 2H), 7.6 (dd, 1H), 7.9 (dd, 1H), 8.0-8.2 (m, 19H), 8.3(s, 3H).

化合物（２－１２２３）は、上記合成例（１０）に記載された方法に準じて合成した。 Synthesis example (12)
Synthesis of compound (2-1223)

Compound (2-1223) was synthesized according to the method described in Synthesis Example (10) above.

化合物（３－１３９）は、国際公開第2015/102118号公報の「合成例（３２）」に記載された方法に準じて合成した。 Synthesis example (13)
Compound (3-139): 2,12-di-t-butyl-5,9-bis(4-(t-butyl)phenyl)-7-methyl-5,9-dihydro-5,9-diaza-13b - Synthesis of boranaphtho[3,2,1-de]anthracene

Compound (3-139) was synthesized according to the method described in "Synthesis Example (32)" of WO 2015/102118.

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ=1.47 (s, 36H), 2.17 (s, 3H), 5.97 (s, 2H), 6.68 (d, 2H), 7 .28 (d, 4H), 7.49 (dd, 2H), 7.67 (d, 4H), 8.97 (d, 2H).

化合物（４－１）は、特開2013-080961号公報の「製造例８」に記載された方法に準じて合成した。 Synthesis example (14)
Synthesis of compound (4-1)

Compound (4-1) was synthesized according to the method described in "Production Example 8" of JP-A-2013-080961.

Other compounds of the present invention can be synthesized by methods according to the synthesis examples described above by appropriately changing the starting compounds.

Examples of organic EL devices using the compounds of the present invention are shown below in order to describe the present invention in more detail, but the present invention is not limited to these.

Organic EL devices according to Examples 1 to 7 and Comparative Examples 1 to 11 were produced, and voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency at the time of light emission with specific luminance, respectively (%) was measured. In addition, the time for which a specific luminance is maintained (device life) was also measured.

The quantum efficiency of a light-emitting device includes internal quantum efficiency and external quantum efficiency. The internal quantum efficiency is purely converted from external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting device into photons. indicates the percentage of On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting device, and some of the photons generated in the light-emitting layer continue to be absorbed or reflected inside the light-emitting device. Therefore, the external quantum efficiency is lower than the internal quantum efficiency because the light is not emitted to the outside of the light emitting device.

The method for measuring the external quantum efficiency is as follows. Using a voltage/current generator R6144 manufactured by Advantest, the devices were caused to emit light by applying voltages such that the luminance of the devices was 1000 cd/m ² , 100 cd/m ² and 10 cd/m ² . Using a spectral radiance meter SR-3AR manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light-emitting surface is a perfect diffusion surface, the number of photons at each wavelength is obtained by dividing the measured spectral radiance of each wavelength component by the wavelength energy and multiplying by π. Then, the number of photons in the entire observed wavelength region was integrated to obtain the total number of photons emitted from the device. The external quantum efficiency is obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device, with the value obtained by dividing the applied current value by the elementary charge as the number of carriers injected into the device.

Tables 1 to 4 below show the material structure of each layer and the EL characteristic data of the organic EL devices according to Examples 1 to 7 and Comparative Examples 1 to 11.

In Tables 1-4, "HI" is N ⁴ ,N ^4' -diphenyl-N ⁴ ,N ^4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]- 4,4′-diamine, “HAT-CN” is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, “HT-1” is N-([1,1′ -biphenyl]-4-yl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1′-biphenyl]-4-amine, “HT-2” is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine and “ET- 1” is 4,6,8,10-tetraphenyl[1,4]benzoxaborinino[2,3,4-kl]phenoxaborinine and “ET-2” is 9-{7-[bis (2,4,6-trimethylphenyl)boranyl]-9,9-dimethyl-9H-fluoren-2-yl}-3,6-dimethyl-9H-carbazole and “ET-3” is 3,3′ -((2-phenylanthracene-9,10-diyl)bis(4,1-phenylene))bis(4-methylpyridine) and "ET-4" is 3,3'-[(2-phenylanthracene -9,10-diyl)dibenzene-3,1-diyl]bis(5-methylpyridine). The chemical structure is shown below together with "Liq".

<Example 1>
<Host material: element of compound (2-1001) and compound (1-134-O)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, compound (2-1001), compound (1-134) —O), compounds (3-139), ET-1 and ET-3 respectively, and aluminum nitride evaporation boats containing Liq, magnesium and silver respectively.

As shown in Table 1, the following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN, HT-1 and HT-2 were vapor-deposited in this order to form hole injection layer 1 (film thickness 40 nm), hole injection layer 2 (film thickness 5 nm thick), hole transport layer 1 (thickness 15 nm) and hole transport layer 2 (thickness 10 nm). Next, the compound (2-1001) and the compound (3-139) were simultaneously heated and evaporated to a film thickness of 12.5 nm to form a light-emitting layer 1 . The deposition rate was adjusted so that the mass ratio of compound (2-1001) to compound (3-139) was approximately 98:2. Next, the compound (1-134-O) and the compound (3-139) were simultaneously heated and evaporated to a thickness of 12.5 nm to form a light-emitting layer 2 . The deposition rate was adjusted so that the mass ratio of compound (1-134-O) to compound (3-139) was approximately 98:2. Next, ET-1 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-3 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-3 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. .1%, blue light emission with a wavelength of 464 nm and CIE chromaticity (x, y)=(0.129, 0.106) was obtained. The external quantum efficiency at 100 cd/m ² emission was 7.0%, and the external quantum efficiency at 10 cd/m ² emission was 6.6%. Next, when the fabricated device was subjected to a low current drive test (current density=10 mA/cm ² ), the time for maintaining 90% or more of the initial luminance was 1016 hours.

<Examples 2 to 5>
According to Example 1, each organic EL element was manufactured with the layer structure described in Table 1, and the EL characteristic data was measured (Table 1).

<Example 6>
<Host material: element of compound (2-1080) and compound (1-134-O)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, compound (2-1080), compound (1-134) —O), compounds (3-139), ET-1 and ET-3 respectively, and aluminum nitride evaporation boats containing Liq, magnesium and silver respectively.

As shown in Table 2, the following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN, HT-1 and HT-2 were vapor-deposited in this order to form hole injection layer 1 (film thickness 40 nm), hole injection layer 2 (film thickness 5 nm thick), hole transport layer 1 (thickness 15 nm) and hole transport layer 2 (thickness 10 nm). Next, the compound (2-1080) and the compound (3-139) were heated at the same time and evaporated to a thickness of 5 nm to form a light-emitting layer 1 . The deposition rate was adjusted so that the mass ratio of compound (2-1080) to compound (3-139) was approximately 96:4. Next, the compound (1-134-O) and the compound (3-139) were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer 2 . The deposition rate was adjusted so that the mass ratio of compound (1-134-O) to compound (3-139) was approximately 96:4. Next, ET-1 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-3 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-3 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. 9%, and blue light emission with a wavelength of 463 nm and CIE chromaticity (x, y)=(0.131, 0.091) was obtained. The external quantum efficiency at 100 cd/m ² emission was 7.0%, and the external quantum efficiency at 10 cd/m ² emission was 6.9%.

<Example 7>
<Host material: element of compound (2-1001) and compound (1-199)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, compound (2-1001), compound (1-199), compound ( 3-139), a molybdenum vapor deposition boat containing ET-2 and ET-4, respectively, and an aluminum nitride vapor deposition boat containing Liq, magnesium and silver respectively.

As shown in Table 2, the following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN and HT-1 were vapor-deposited in this order to obtain hole injection layer 1 (thickness: 40 nm), hole injection layer 2 (thickness: 5 nm), and A hole transport layer (thickness: 25 nm) was formed. Next, the compound (2-1001) and the compound (3-139) were simultaneously heated and evaporated to a film thickness of 12.5 nm to form a light-emitting layer 1 . The deposition rate was adjusted so that the mass ratio of compound (2-1001) to compound (3-139) was approximately 98:2. Next, the compound (1-199) and the compound (3-139) were heated at the same time and evaporated to a film thickness of 12.5 nm to form a light-emitting layer 2 . The deposition rate was adjusted so that the mass ratio of compound (1-199) to compound (3-139) was approximately 98:2. Next, ET-2 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-4 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-4 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. .6%, blue light emission with a wavelength of 464 nm and CIE chromaticity (x, y)=(0.129, 0.109) was obtained. The external quantum efficiency at 100 cd/m ² emission was 7.0%, and the external quantum efficiency at 10 cd/m ² emission was 6.4%.

<Comparative Example 1>
<Host material: element of compound (1-134-O)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, compound (1-134-O), compound (3) -139), a molybdenum evaporation boat containing ET-1 and ET-3 respectively, and an aluminum nitride evaporation boat containing Liq, magnesium and silver respectively.

As shown in Table 3, the following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN, HT-1 and HT-2 were vapor-deposited in this order to form hole injection layer 1 (film thickness 40 nm), hole injection layer 2 (film thickness 5 nm thick), hole transport layer 1 (thickness 15 nm) and hole transport layer 2 (thickness 10 nm). Next, the compound (1-134-O) and the compound (3-139) were simultaneously heated and evaporated to a thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of compound (1-134-O) to compound (3-139) was approximately 98:2. Next, ET-1 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-3 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-3 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. .7%, blue light emission with a wavelength of 461 nm and CIE chromaticity (x, y)=(0.131, 0.084) was obtained. The external quantum efficiency at 100 cd/m ² emission was 6.7%, and the external quantum efficiency at 10 cd/m ² emission was 6.0%. Next, when the fabricated device was subjected to a low current drive test (current density=10 mA/cm ² ), the time for maintaining 90% or more of the initial brightness was 501 hours.

<Comparative Examples 2 to 7>
According to Comparative Example 1, each organic EL device was manufactured with the layer structure shown in Table 3, and the EL characteristic data was measured (Table 3).

<Comparative Example 8>
<Host material: element of compound (1-134-O)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, compound (1-134-O), compound (3) -139), a molybdenum evaporation boat containing ET-1 and ET-3 respectively, and an aluminum nitride evaporation boat containing Liq, magnesium and silver respectively.

As shown in Table 4, the following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN, HT-1 and HT-2 were vapor-deposited in this order to form hole injection layer 1 (film thickness 40 nm), hole injection layer 2 (film thickness 5 nm thick), hole transport layer 1 (thickness 15 nm) and hole transport layer 2 (thickness 10 nm). Next, the compound (1-134-O) and the compound (3-139) were simultaneously heated and evaporated to a thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of compound (1-134-O) to compound (3-139) was approximately 96:4. Next, ET-1 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-3 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-3 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. .1%, blue light emission with a wavelength of 462 nm and CIE chromaticity (x, y)=(0.132, 0.085) was obtained. The external quantum efficiency at 100 cd/m ² emission was 6.1%, and the external quantum efficiency at 10 cd/m ² emission was 5.8%.

<Comparative Example 9>
According to Comparative Example 8, an organic EL device was produced with the layer structure shown in Table 4, and EL characteristic data was measured (Table 4).

<Comparative Example 10>
<Host material: element of compound (1-199)>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 180 nm was formed by sputtering and polished to 150 nm. This transparent supporting substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, compound (1-199), compound (3-139), ET- A molybdenum deposition boat containing 2 and ET-4, respectively, and an aluminum nitride deposition boat containing Liq, magnesium, and silver, respectively, were equipped.

As shown in Table 4, the following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 ⁻⁴ Pa, and HI, HAT-CN and HT-1 were vapor-deposited in this order to obtain hole injection layer 1 (thickness: 40 nm), hole injection layer 2 (thickness: 5 nm), and A hole transport layer (thickness: 25 nm) was formed. Next, the compound (1-199) and the compound (3-139) were simultaneously heated and evaporated to a thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of compound (1-199) to compound (3-139) was approximately 98:2. Next, ET-2 was heated and evaporated to a thickness of 5 nm to form an electron transport layer 1 . Next, ET-4 and Liq were heated at the same time and evaporated to a thickness of 25 nm to form an electron transport layer 2 . The deposition rate was adjusted so that the weight ratio of ET-4 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. After that, Liq is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm, and then magnesium and silver are simultaneously heated and vapor-deposited so that the film thickness becomes 100 nm. A cathode was formed to obtain an organic EL device. At this time, the vapor deposition rate was adjusted between 0.1 and 10 nm/sec so that the atomic ratio of magnesium and silver was 10:1.

A DC voltage was applied using the ITO electrode as the anode and the magnesium/silver electrode as the cathode, and the characteristics at the time of light emission of 1000 cd/m ² were measured. .2%, blue light emission with a wavelength of 462 nm and CIE chromaticity (x, y)=(0.131, 0.085) was obtained. Further, the external quantum efficiency at 100 cd/m ² emission was 6.3%, and the external quantum efficiency at 10 cd/m ² emission was 6.4%.

<Comparative Example 11>
According to Comparative Example 10, an organic EL device was produced with the layer structure shown in Table 4, and EL characteristic data was measured (Table 4).

As described above, some of the compounds according to the present invention were evaluated as materials for the light-emitting layer of an organic EL device, and their usefulness was demonstrated. They are compounds having a similar structure as a whole, and those skilled in the art will understand that they are materials for a light-emitting layer similarly having excellent properties.

According to a preferred embodiment of the present invention, in the organic electroluminescent device, by forming a light-emitting layer containing both an anthracene-based compound and a pyrene-based compound as host materials, either device efficiency or device life, particularly preferably Device efficiency and device life can be improved.

REFERENCE SIGNS LIST 100 organic electroluminescent element 101 substrate 102 anode 103 hole injection layer 104 hole transport layer 105 light emitting layer 106 electron transport layer 107 electron injection layer 108 cathode

Claims (11)

An organic electroluminescence device having a pair of electrode layers consisting of an anode layer and a cathode layer and a light-emitting layer disposed between the pair of electrode layers,
The light-emitting layer contains an anthracene-based compound represented by the following general formula (1) and a pyrene-based compound represented by the following general formula (2) as a host material, and further includes a boron-containing compound or the general Including a pyrene-based compound different from the pyrene-based compound represented by formula (2) ,
The light-emitting layer is configured by laminating at least a first light-emitting layer and a second light-emitting layer, the first light-emitting layer contains an anthracene-based compound represented by the general formula (1), and the second light-emitting layer is An organic electroluminescence device containing a pyrene compound represented by the general formula (2) .

(In the above formula (1),
X and Ar ⁴ are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio or optionally substituted silyl, wherein not all X and Ar ⁴ are simultaneously hydrogen,
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, deuterium or optionally substituted heteroaryl. )
(in the above formula (2),
s pyrene moieties and p Ar moieties are bound at any position of * of the pyrene moiety and any position of the Ar moiety,
At least one hydrogen in the pyrene moiety is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms. may be substituted with alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these is independently aryl having 6 to 10 carbon atoms , heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryl having 6 to 30 carbon atoms. optionally substituted with oxy,
Each Ar is independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in these is each independently an aryl having 6 to 10 carbon atoms, substituted with heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms may have been
s and p are each independently an integer of 1 or 2, s and p are not 2 at the same time, and when s is 2, the two pyrene moieties are structurally identical including substituents may be different, and when p is 2, the two Ar moieties may be structurally the same or different, including substituents, and
At least one hydrogen in the compound represented by formula (2) may be independently substituted with halogen, cyano or deuterium. ) 2. The organic electroluminescence device according to claim 1, wherein the anthracene-based compound is an anthracene-based compound represented by the following general formula (1) .

(In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), and naphthylene in formula (1-X1) and formula (1-X2) The site may be condensed with one benzene ring, and the group represented by formula (1-X1), formula (1-X2) or formula (1-X3) is the anthracene ring of formula (1) in *. and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the above formula (A), wherein at least one hydrogen in Ar ³ is further phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or the above optionally substituted with a group represented by formula (A),
Ar ⁴ is each independently hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or silyl substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, deuterium or a group represented by formula (A) above,
In formula (A) above, Y is —O—, —S— or >N—R ²⁹ , and R ²¹ to R ²⁸ are each independently hydrogen, optionally substituted alkyl, optionally substituted optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, tricycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, wherein adjacent groups among R ²¹ to R ²⁸ are bonded together to form a hydrocarbon ring, an aryl ring or a heteroaryl ring; R ²⁹ is hydrogen or optionally substituted aryl, and the group represented by formula (A) in * is a naphthalene ring of formula (1-X1) or formula (1-X2), formula ( 1-X3) single bond, bonded to Ar ³ of formula (1-X3) and also replaces at least one hydrogen in the compound represented by formula (1), and in the structure of formula (A) any are combined with these at the positions of ) 2. The organic electroluminescence device according to claim 1, wherein the anthracene-based compound is an anthracene-based compound represented by the following general formula (1) .

(In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), formula (1-X1), formula (1-X2) or formula The group represented by (1-X3) is bonded to the anthracene ring of formula (1) at *, and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl , terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by any of the above formulas (A-1) to (A-11), wherein at least one hydrogen in Ar ³ is , further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by any of the above formulas (A-1) to (A-11) often,
each Ar ⁴ is independently hydrogen, phenyl, or naphthyl; and
at least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano or deuterium,
In formulas (A-1) to (A-11) above, Y is —O—, —S— or >N—R ²⁹ , R ²⁹ is hydrogen or aryl, and formulas (A-1) to At least one hydrogen in the group represented by formula (A-11) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, tricycloalkylsilyl, diaryl-substituted amino, diheteroaryl optionally substituted with substituted amino, arylheteroaryl substituted amino, halogen, hydroxy or cyano, the groups represented by formulas (A-1) to (A-11) are represented by formula (1-X1) or Naphthalene ring of formula (1-X2), single bond of formula (1-X3), bond to Ar ³ of formula (1-X3), and in the structures of formulas (A-1) to (A-11) Combine with these at any position. ) In the above formula (1),
X is each independently a group represented by the above formula (1-X1), formula (1-X2) or formula (1-X3), formula (1-X1), formula (1-X2) or formula The group represented by (1-X3) is bonded to the anthracene ring of formula (1) at *, and Ar ¹ , Ar ² and Ar ³ are each independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl , terphenylyl, naphthyl, phenanthryl, fluorenyl, or a group represented by any of the above formulas (A-1) to (A-4), wherein at least one hydrogen in Ar ³ is further phenyl, naphthyl, phenanthryl, fluorenyl, or optionally substituted with a group represented by any of the above formulas (A-1) to (A-4),
each Ar ⁴ is independently hydrogen, phenyl, or naphthyl; and
at least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, or deuterium;
The organic electroluminescence device according to claim 3. 2. The organic electroluminescence device according to claim 1, wherein said anthracene-based compound is a compound represented by the following structural formula.

Ar in the general formula (2) is each independently a group represented by the following general formula (Ar-1) or general formula (Ar-2), according to any one of claims 1 to 5 organic electroluminescence device.

In each of the above formulas,
Z is >CR ₂ , >NR, >O or >S;
> Each R in CR ₂ is independently alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and the aryl and at least one hydrogen in heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may combine with each other to form a ring,
>R in NR is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and at least one hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms;
R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ are each independently hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, and 3 to 24 carbon atoms. cycloalkyl, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, wherein at least one hydrogen in these is alkyl having 1 to 6 carbon atoms or 3 to may be substituted with 14 cycloalkyls, adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, The formed rings are each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and 2 to 30 carbon atoms. alkenyl, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, at least one hydrogen in which is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms may be replaced with, and
at least one hydrogen in the group represented by the above formula (Ar-1) or formula (Ar-2) may be independently substituted with halogen, cyano or deuterium,
The group represented by the above formula (Ar-1) or formula (Ar-2) is bonded at any position of the pyrene moiety in *, and the pyrene moiety is the above formula (Ar-1) or formula (Ar-2) It binds at any position in the group represented by. Ar in the general formula (2) is each independently represented by the following general formulas (Ar-1-1) to (Ar-1-12) and general formulas (Ar-2-1) to (Ar- The organic electroluminescence device according to any one of claims 1 to 5, which is a group represented by any one of 2-4).

In each of the above formulas,
Z is >CR ₂ , >NR, >O or >S;
>R in CR ₂ is each independently alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms or aryl having 6 to 12 carbon atoms, and the Rs are bonded to each other to form a ring. may be
>R in NR is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or aryl having 6 to 12 carbon atoms,
At least one hydrogen in the groups represented by the above formulas is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms or 3 to 24 carbon atoms. and optionally substituted with a cycloalkyl of
At least one hydrogen in the groups represented by the above formulas may be independently substituted with halogen, cyano or deuterium,
The group represented by any of the above formulas (Ar-1-1) to (Ar-1-12) and formulas (Ar-2-1) to (Ar-2-4) is the pyrene moiety in * bonded at any position, and the pyrene moiety is any of the above formulas (Ar-1-1) to (Ar-1-12) and formulas (Ar-2-1) to (Ar-2-4) It binds at any position in the group represented by. The organic electroluminescence device according to any one of claims 1 to 5, wherein the pyrene-based compound represented by the general formula (2) is a compound represented by any one of the following structural formulas.

Further, an electron-transporting layer and/or an electron-injecting layer disposed between the cathode layer and the light-emitting layer, wherein at least one of the electron-transporting layer and the electron-injecting layer is a borane derivative, a pyridine derivative, or a fluoranthene Contains at least one selected from the group consisting of derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes The organic electroluminescence device according to any one of claims 1 to 8 . The electron-transporting layer and/or electron-injecting layer may further comprise an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal containing at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes 9. The organic electroluminescence device according to 9 . A display device or lighting device comprising the organic electroluminescence device according to any one of claims 1 to 10 .

Images