JPWO2019235452A1 - Tershally alkyl-substituted polycyclic aromatic compounds - Google Patents

Abstract

By introducing a specific tertiary alkyl group into a novel polycyclic aromatic compound in which a plurality of aromatic rings are linked by a boron atom and an oxygen atom, the choice of materials for organic devices such as materials for organic EL elements is increased. .. Further, by using a novel cycloalkyl-substituted polycyclic aromatic compound as a material for an organic EL device, for example, an organic EL device having excellent luminous efficiency can be provided.

Description

The present invention relates to tertiary alkyl-substituted polycyclic aromatic compounds, organic electroluminescent devices, organic electroluminescent transistors and organic thin-film solar cells using the same, and display devices and lighting devices. In the present specification, the "organic electroluminescent element" may be referred to as an "organic EL element" or simply an "element".

Conventionally, display devices using an electric field-emitting element have been studied in various ways because they can be reduced in power and thickness, and further, an organic electroluminescent element made of an organic material can be easily reduced in weight and size. Therefore, it has been actively examined. In particular, the development of organic materials having emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transporting ability such as holes and electrons (which have the potential to become semiconductors and superconductors). Development has been actively studied regardless of whether it is a high molecular weight compound or a low molecular weight compound.

The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers containing an organic compound, which is arranged between the pair of electrodes. Layers containing organic compounds include light emitting layers and charge transport / injection layers that transport or inject charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

As a material for a light emitting layer, for example, a benzofluorene compound or the like has been developed (International Publication No. 2004/061047). Further, as a hole transport material, for example, a triphenylamine-based compound and the like have been developed (Japanese Patent Laid-Open No. 2001-172232). Further, as an electron transport material, for example, an anthracene compound and the like have been developed (Japanese Patent Laid-Open No. 2005-170911).

Further, in recent years, a material obtained by improving a triphenylamine derivative has been reported as a material used for an organic EL element or an organic thin-film solar cell (International Publication No. 2012/118164). This material was prepared with reference to N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD), which had already been put into practical use. It is a material characterized in that its flatness is improved by connecting aromatic rings constituting triphenylamine. In this document, for example, the charge transport property of a NO-linking compound (Compound 1 on page 63) is evaluated, but a method for producing a material other than the NO-linking compound is not described, and the element to be linked is not described. Since the electronic state of the entire compound is different if they are different, the properties obtained from materials other than the NO-linking compound are not yet known. Other examples of such compounds can be found (International Publication No. 2011/107186). For example, a compound having a conjugated structure having a large triplet exciton energy (T1) is useful as a material for a blue light emitting layer because it can emit phosphorescence having a shorter wavelength. Further, as an electron transporting material or a hole transporting material that sandwiches the light emitting layer, a compound having a novel conjugated structure having a large T1 is required.

The host material of the organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are linked by a single bond or a phosphorus atom or a silicon atom. This is because the large HOMO-LUMO gap (bandgap Eg in the thin film) required for the host material is secured by connecting a large number of relatively small aromatic rings of the conjugated system. In addition, the host material of the organic EL element using a phosphorescent material or a heat activated delayed fluorescent material, high triplet excitation energy (E _T) is also required, the donor or acceptor properties of the aromatic ring and substituents in the molecule by connecting, to localize the SOMO1 and SOMO2 triplet excited state (T1), by reducing the exchange interaction between the two trajectories, it is possible to improve the triplet excitation energy (E _T) Will be. However, the small aromatic ring of the conjugated system does not have sufficient redox stability, and the device using the molecule connecting the existing aromatic ring as the host material does not have a sufficient life. On the other hand, polycyclic aromatic compounds having an extended π conjugated system, generally, but the redox stability is excellent, because HOMO-LUMO gap and triplet excitation energy (band gap Eg of the thin film) (E _T) is low, It has been considered unsuitable for host materials.

International Publication No. 2004/061047 Japanese Unexamined Patent Publication No. 2001-172232 Japanese Patent Application Laid-Open No. 2005-170911 International Publication No. 2012/118164 International Publication No. 2011/107186 International Publication No. 2015/102118

As described above, various materials have been developed as materials used for organic EL devices, but in order to increase the choices of materials for organic EL devices, it is desired to develop a material made of a compound different from the conventional one. There is. In particular, the organic EL properties obtained from materials other than the NO-linking compounds reported in Patent Documents 1 to 4 and the method for producing the same are not yet known.

Further, Patent Document 6 reports a polycyclic aromatic compound containing boron and an organic EL device using the same. However, in order to further improve the device characteristics, light emission efficiency and device life can be improved. There is a demand for layer materials, especially dopant materials.

As a result of diligent studies to solve the above problems, the present inventors have arranged a layer containing a polycyclic aromatic compound having a tertiary alkyl group having a specific structure between a pair of electrodes, for example, an organic EL. We have found that an excellent organic EL element can be obtained by constructing the element, and completed the present invention. That is, the present invention relates to the following tertiary alkyl-substituted polycyclic aromatic compounds or multimers thereof, and further, materials for organic EL devices containing the following tertiary alkyl-substituted polycyclic aromatic compounds or multimers thereof and the like. Provides materials for organic devices.

In addition, although the chemical structure and the substituent may be represented by the number of carbon atoms in the present specification, the number of carbon atoms in the case where the substituent is substituted in the chemical structure or the substituent is further substituted in the substituent is the chemical structure. It means the carbon number of each of the substituents and substituents, and does not mean the total carbon number of the chemical structure and the substituents or the total carbon number of the substituents and the substituents. For example, "substituent B of carbon number Y substituted with substituent A of carbon number X" means that "substituent A of carbon number X" is substituted with "substituent B of carbon number Y". However, the number of carbon atoms Y is not the total number of carbon atoms of the substituent A and the substituent B. Further, for example, "substituent B having a carbon number Y substituted with a substituent A" means that "substituent A (with no limitation on the number of carbon atoms)" is substituted for "substituent B having a carbon number Y". However, the number of carbon atoms Y is not the total number of carbon atoms of the substituent A and the substituent B.

（上記式（１）中、
Ａ環、Ｂ環およびＣ環は、それぞれ独立して、アリール環またはヘテロアリール環であり、これらの環における少なくとも１つの水素は置換されていてもよく、
Ｙ^１は、Ｂ、Ｐ、Ｐ＝Ｏ、Ｐ＝Ｓ、Ａｌ、Ｇａ、Ａｓ、Ｓｉ−ＲまたはＧｅ−Ｒであり、前記Ｓｉ−ＲおよびＧｅ−ＲのＲは、アリール、アルキルまたはシクロアルキルであり、
Ｘ^１およびＸ^２は、それぞれ独立して、＞Ｏ、＞Ｎ−Ｒ、＞Ｃ（−Ｒ）_２、＞Ｓまたは＞Ｓｅであり、前記＞Ｎ−ＲのＲは、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キルまたは置換されていてもよいシクロアルキルであり、前記＞Ｃ（−Ｒ）_２のＲは、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アルキルまたは置換されていてもよいシクロアルキルであり、また、前記＞Ｎ−ＲのＲおよび／または前記＞Ｃ（−Ｒ）_２のＲは連結基または単結合により前記Ａ環、Ｂ環および／またはＣ環と結合していてもよく、
式（１）で表される化合物または構造における少なくとも１つの水素は、重水素、シアノまたはハロゲンで置換されていてもよく、そして、
式（１）で表される化合物または構造における少なくとも１つの水素は上記一般式（ｔＲ）で表される基で置換されており、
上記式（ｔＲ）中、Ｒ^ａは炭素数２〜２４のアルキルであり、Ｒ^ｂおよびＲ^ｃはそれぞれ独立して炭素数１〜２４のアルキルであり、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置換されていてもよく、上記式（ｔＲ）で表される基は＊において上記式（１）で表される化合物または構造における少なくとも１つの水素と置換する。）Item 1.
A multimer of a polycyclic aromatic compound represented by the following general formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).

(In the above formula (1),
Rings A, B, and C are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is aryl, alkyl or cycloalkyl. And
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, even if the R of> N-R is substituted. A good aryl, a heteroaryl which may be substituted, an alkyl which may be substituted or a cycloalkyl which may be substituted, and the R of> C (-R) ₂ is hydrogen, which may be substituted. A good aryl, a optionally substituted alkyl or a optionally substituted cycloalkyl, and the R of> N-R and / or the R of> C (-R) ₂ are linking groups or single bonds. May be bonded to the A ring, B ring and / or C ring.
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound or structure represented by the formula (1) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *. )

Item 2.
The A ring, B ring, and C ring are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings is a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, or a substituted ring. Or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted aryl heteroarylamino, substituted or unsubstituted diarylboryl (two aryls are bonded via a single bond or a linking group). May be substituted), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy, and these rings are Y ¹ , A 5-membered ring or a 6-membered ring that shares a bond with the fused two-ring structure in the center of the above formula composed of ^{X 1} and X ^2.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is aryl, alkyl or cycloalkyl. And
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, and the R of> N-R is alkyl or cycloalkyl, respectively. Heteroaryl, alkyl or cycloalkyl which may be substituted with aryl, alkyl or cycloalkyl which may be substituted, wherein R of> C (-R) ₂ is substituted with hydrogen, alkyl or cycloalkyl. It may be aryl, alkyl or cycloalkyl, and the R of> N-R and / or the R of> C (-R) ₂ is -O-, -S-, -C (-R). _It may be bonded to the A ring, the B ring and / or the C ring by a _{2- or a single bond, and the R of the -C (-R) 2-} is hydrogen, alkyl or cycloalkyl.
At least one hydrogen in the compound or structure represented by the formula (1) may be substituted with deuterium, cyano or halogen.
In the case of a multimer, it is a 2 or trimer having 2 or 3 structures represented by the general formula (1), and
At least one hydrogen in the compound or structure represented by the formula (1) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *.
Item 2. The polycyclic aromatic compound according to Item 1 or a multimer thereof.

（上記式（２）中、
Ｒ^１〜Ｒ^１１は、それぞれ独立して、水素、アリール、ヘテロアリール、ジアリールアミノ、ジヘテロアリールアミノ、アリールヘテロアリールアミノ、ジアリールボリル（２つのアリールは単結合または連結基を介して結合していてもよい）、アルキル、シクロアルキル、アルコキシまたは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、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で置換されていてもよく、また、Ｒ^１〜Ｒ^１１のうちの隣接する基同士が結合してａ環、ｂ環またはｃ環と共に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、形成された環における少なくとも１つの水素は、アリール、ヘテロアリール、ジアリールアミノ、ジヘテロアリールアミノ、アリールヘテロアリールアミノ、ジアリールボリル（２つのアリールは単結合または連結基を介して結合していてもよい）、アルキル、シクロアルキル、アルコキシまたは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、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で置換されていてもよく、
Ｙ^１は、Ｂ、Ｐ、Ｐ＝Ｏ、Ｐ＝Ｓ、Ａｌ、Ｇａ、Ａｓ、Ｓｉ−ＲまたはＧｅ−Ｒであり、前記Ｓｉ−ＲおよびＧｅ−ＲのＲは、炭素数６〜１２のアリール、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あり、
Ｘ^１およびＸ^２は、それぞれ独立して、＞Ｏ、＞Ｎ−Ｒ、＞Ｃ（−Ｒ）_２、＞Ｓまたは＞Ｓｅであり、前記＞Ｎ−ＲのＲは、炭素数６〜１２のアリール、炭素数２〜１５のヘテロアリール、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あり、前記＞Ｃ（−Ｒ）_２のＲは、水素、炭素数６〜１２のアリール、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あり、また、前記＞Ｎ−ＲのＲおよび／または前記＞Ｃ（−Ｒ）_２のＲは−Ｏ−、−Ｓ−、−Ｃ（−Ｒ）_２−または単結合により前記ａ環、ｂ環および／またはｃ環と結合していてもよく、前記−Ｃ（−Ｒ）_２−のＲ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あり、
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、重水素、シアノまたはハロゲンで置換されていてもよく、そして、
式（２）で表される化合物における少なくとも１つの水素は上記一般式（ｔＲ）で表される基で置換されており、
上記式（ｔＲ）中、Ｒ^ａは炭素数２〜２４のアルキルであり、Ｒ^ｂおよびＲ^ｃはそれぞれ独立して炭素数１〜２４のアルキルであり、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置換されていてもよく、上記式（ｔＲ）で表される基は＊において上記式（２）で表される化合物における少なくとも１つの水素と置換する。）Item 3.
Item 2. The polycyclic aromatic compound represented by the following general formula (2).

(In the above formula (2),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diallylboryl (two aryls are bonded via a single bond or a linking group). may be), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in these, aryl, heteroaryl, may be substituted with alkyl or cycloalkyl and, of R ¹ to R ¹¹ Adjacent groups thereof may be bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring or a c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, or diaryl. Amino, diheteroarylamino, arylheteroarylamino, diallylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy. Well, at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R has 6 to 12 carbon atoms. Aryl, alkyl with 1 to 6 carbons or cycloalkyl with 3 to 14 carbons,
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, and R of> N-R has 6 to 12 carbon atoms. Aryl, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and R of> C (-R) ₂ is hydrogen and 6 to 12 carbon atoms. The aryl, the alkyl having 1 to 6 carbon atoms or the cycloalkyl having 3 to 14 carbon atoms, and the R of> N-R and / or the R of> C (-R) ₂ are -O-,-. _{S -, - C (-R)} 2 - or the a ring by a single bond, may be bound to b ring and / or c ring, wherein -C _{(-R) 2} - of R is 1 carbon atoms It is an alkyl of 6 or a cycloalkyl of 3 to 14 carbon atoms.
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *. )

Item 4.
R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, diallyl amino (where aryl is aryl with 6 to 12 carbon atoms), and diallyl boryl (provided that aryl is aryl with 6 to 12 carbon atoms). Aryl is an aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), and can be an alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms. In addition, ^{adjacent groups of R 1 to} R ¹¹ are bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring. At least one hydrogen in the formed ring may be substituted with an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 12 carbon atoms, or a cycloalkyl having 3 to 16 carbon atoms.
Y ¹ is B, P, P = O, P = S or Si-R, and R of the Si-R is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms, or 5 to 5 carbon atoms. 10 cycloalkyl,
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ or> S, and R of> N-R is an aryl having 6 to 10 carbon atoms. It is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, and the R of> C (-R) ₂ is hydrogen, an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms or carbon. It is a cycloalkyl of the number 5 to 10.
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
Item 3. The polycyclic aromatic compound according to Item 3.

Item 5.
R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 20 carbon atoms, diallyl amino (where aryl is aryl with 6 to 10 carbon atoms), and diarylboryl (provided that aryl is 6 to 10 carbon atoms). Aryl is an aryl having 6 to 10 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms. ,
Y ¹ is B, P, P = O or P = S,
X ¹ and X ² are independently>O,> N-R or> C (-R) ₂ , and the R of> N-R is an aryl having 6 to 10 carbon atoms and 1 carbon number. It is an alkyl of ~ 4 or a cycloalkyl having 5 to 10 carbon atoms, and the R of> C (-R) ₂ is hydrogen, an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 4 carbon atoms. It is 10 cycloalkyl, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
Item 3. The polycyclic aromatic compound according to Item 3.

Item 6.
R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 16 carbon atoms, diarylamino (where aryl is aryl with 6 to 10 carbon atoms), and diarylboryl (where aryl is aryl with 6 to 10 carbon atoms). The two aryls may be attached via a single bond or a linking group), and are alkyls having 1 to 12 carbon atoms or cycloalkyls having 3 to 16 carbon atoms.
Y ¹ is B,
Both X ¹ and X ² are> N-R, or X ¹ is> N-R and X ² is> O, and the R of> N-R has 6 to 10 carbon atoms. Aryl, alkyl with 1 to 4 carbons or cycloalkyl with 5 to 10 carbons, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
Item 3. The polycyclic aromatic compound according to Item 3.

Item 7.
A diarylamino group substituted with a group represented by the general formula (tR), a carbazolyl group substituted with a group represented by the general formula (tR), or a group represented by the general formula (tR). Item 2. The polycyclic aromatic compound according to any one of Items 1 to 6, or a multimer thereof, which is substituted with the benzocarbazolyl group.

Item 8.
Item 3 to 6, wherein R ² is a diarylamino group substituted with a group represented by the general formula (tR) or a carbazolyl group substituted with a group represented by the general formula (tR). The polycyclic aromatic compound described in.

Item 9.
Item 2. The polycyclic aromatic compound according to any one of Items 1 to 8, wherein the halogen is fluorine, or a multimer thereof.

（各式中の「ｔＢｕ」はｔ−ブチル基、「ｔＡｍ」はｔ−アミル基である。）Item 10.
Item 2. The polycyclic aromatic compound represented by any of the following structural formulas.

(In each formula, "tBu" is a t-butyl group and "tAm" is a t-amyl group.)

（各式中の「Ｍｅ」はメチル基、「ｔＢｕ」はｔ−ブチル基、「ｔＡｍ」はｔ−アミル基である。）Item 11.
Item 2. The polycyclic aromatic compound represented by any of the following structural formulas.

(In each formula, "Me" is a methyl group, "tBu" is a t-butyl group, and "tAm" is a t-amyl group.)

Item 12.
Item 2. A reactive compound in which a polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof is substituted with a reactive substituent.

Item 13.
A polymer compound obtained by polymerizing the reactive compound according to Item 12 as a monomer, or a polymer crosslinked product obtained by further cross-linking the polymer compound.

Item 14.
A pendant type polymer compound in which the main chain type polymer is substituted with the reactive compound according to Item 12, or a pendant type polymer crosslinked product in which the pendant type polymer compound is further crosslinked.

Item 15.
A material for an organic device containing the polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof.

Item 16.
A material for an organic device containing the reactive compound according to Item 12.

Item 17.
Item 3. A material for an organic device containing the polymer compound or polymer crosslinked product according to Item 13.

Item 18.
A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked body according to Item 14.

Item 19.
Item 2. The material for an organic device according to any one of Items 15 to 18, wherein the material for an organic device is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

Item 20.
Item 2. The material for an organic device according to Item 19, wherein the material for the organic electroluminescent element is a material for a light emitting layer.

Item 21.
An ink composition containing the polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof, and an organic solvent.

Item 22.
An ink composition containing the reactive compound according to Item 12 and an organic solvent.

Item 23.
An ink composition containing a main chain polymer, the reactive compound according to Item 12, and an organic solvent.

Item 24.
An ink composition containing the polymer compound or polymer crosslinked product according to Item 13 and an organic solvent.

Item 25.
An ink composition containing the pendant-type polymer compound or the pendant-type polymer crosslinked product according to Item 14 and an organic solvent.

Item 26.
The polycyclic aromatic compound according to any one of claims 1 to 11 or a polymer thereof, which is arranged between the pair of electrodes composed of an anode and a cathode, and the reactive compound according to item 12. An organic electroluminescent element having an organic layer containing the polymer compound or polymer crosslinked body according to Item 13 or the pendant type polymer compound or pendant type polymer crosslinked body according to Item 14.

Item 27.
Item 13. A polycyclic aromatic compound or a polymer according to any one of Items 1 to 11, a reactive compound according to Item 12, which is arranged between a pair of electrodes composed of an anode and a cathode and the pair of electrodes. An organic electroluminescent element having a light emitting layer containing the polymer compound or polymer crosslinked body according to Item 14 or the pendant type polymer compound or pendant type polymer crosslinked body according to Item 14.

Item 28.
The light emitting layer contains a host and the polycyclic aromatic compound as a dopant, a multimer thereof, a reactive compound, a polymer compound, a polymer crosslinked product, a pendant type polymer compound or a pendant type polymer crosslinked product. 27. The organic field light emitting element according to Item 27.

Item 29.
Item 28. The organic electroluminescent element according to Item 28, wherein the host is an anthracene compound, a fluorene compound, a dibenzochrysene compound or a pyrene compound.

Item 30.
It has an electron transporting layer and / or an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, a fluorentene derivative, or BO. Item 26, which contains at least one selected from the group consisting of system derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol metal complexes. The organic electric field light emitting element according to any one of ~ 29.

Item 31.
The electron transporting layer and / or electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, and an alkaline earth metal. Item 30. Item 30 contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. The organic electric field light emitting element according to.

Item 32.
At least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or a polymer compound. , A polymer crosslinked product obtained by further cross-linking the polymer compound, or a pendant type polymer compound obtained by reacting a low molecular weight compound capable of forming each layer with a main chain type polymer, or the pendant type polymer compound. Item 2. The organic electric field light emitting element according to any one of Items 26 to 31, further comprising a crosslinked pendant type polymer crosslinked body.

Item 33.
A display device or a lighting device including the organic electroluminescent element according to any one of Items 26 to 32.

Item 34.
A composition for forming a light emitting layer for coating and forming a light emitting layer of an organic electroluminescent device.
As the first component, at least one polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof, and
As the second component, at least one host material and
As the third component, at least one organic solvent and
A composition for forming a light emitting layer containing.

Item 35.
An organic electroluminescent device having a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and formed by applying and drying the light emitting layer forming composition according to Item 34.

According to a preferred embodiment of the present invention, it is possible to provide a novel tertiary alkyl-substituted polycyclic aromatic compound that can be used as a material for an organic device such as a material for an organic EL element, and this tertiary alkyl-substituted By using a polycyclic aromatic compound, it is possible to provide an excellent organic device such as an organic EL element.

Specifically, we have found that polycyclic aromatic compounds (basic skeleton portions) in which aromatic rings are linked by heteroelements such as boron, phosphorus, oxygen, nitrogen, and sulfur have a large HOMO-LUMO gap (in a thin film). It was found to have a band gap Eg) and high triplet excitation energy (E _T). This is because the 6-membered ring containing the hetero element has low aromaticity, so that the decrease in the HOMO-LUMO gap due to the expansion of the conjugated system is suppressed, and the triplet excited state (T1) is due to the electronic perturbation of the hetero element. It is considered that the cause is the localization of SOMO1 and SOMO2 in). Further, in the polycyclic aromatic compound (basic skeleton portion) containing a hetero element according to the present invention, the exchange interaction between both orbitals becomes small due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small, and thermally activated delayed fluorescence is exhibited, so that it is also useful as a fluorescent material for organic EL elements. Further, the material having high triplet excitation energy (E _T), is also useful as an electron transport layer and a hole transport layer of an organic EL element utilizing a phosphorescent organic EL device and heat activated delayed fluorescence. Furthermore, since these polycyclic aromatic compounds (basic skeleton portions) can arbitrarily move the energies of HOMO and LUMO by introducing substituents, the ionization potential and electron affinity are optimized according to the peripheral materials. It is possible.

In addition to such characteristics of the basic skeleton portion, the following effects can be obtained by introducing a tertiary alkyl group represented by the above general formula (tR) into the compound of the present invention.

Since the basic skeleton portion of a polycyclic aromatic compound has high molecular flatness and large intermolecular interaction, it is derived from the aggregation of molecules, for example, when used as a dopant material for the light emitting layer of an organic EL element. The luminous efficiency of the element may decrease. Therefore, conventionally, the luminous efficiency has been improved by introducing an alkyl group into the basic skeleton portion to reduce the interaction between molecules.

However, for example, the t-butyl group does not have an alkyl chain length sufficient to enhance the solubility of the compound, and if the solubility of the compound is low, an enormous amount of organic solvent is required for processing such as synthesis and purification, which requires a huge amount of organic solvent, and requires a lot of work and production. It is not preferable because it increases the cost.

As a result of diligent studies in view of these points, by introducing a group represented by the above general formula (tR), agglutination of molecules is relaxed, so that high luminous efficiency is obtained and solubility is further improved. We have found a polycyclic aromatic compound that can be produced at a lower cost. Further, since the introduction of the group represented by the above formula (tR) improves the solubility in an organic solvent, it can be applied to device fabrication using a coating process. However, these effects can be obtained if at least one group represented by the formula (tR) is present in the molecule, and the above-mentioned alkyl chain length is sufficient to enhance the solubility in the molecule. It does not deny the existence of non-substituents (eg, t-butyl groups). The present invention is not particularly limited to these principles.

It is a schematic cross-sectional view which shows the organic EL element which concerns on this embodiment.

1. 1. Polycyclic aromatic compounds substituted with tertiary alkyl and their multimers The present invention has a plurality of polycyclic aromatic compounds represented by the following general formula (1) or a plurality of structures represented by the following general formula (1). It is a multimer of a polycyclic aromatic compound, preferably a polycyclic aromatic compound represented by the following general formula (2), or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2). At least one hydrogen in these compounds or structures is substituted with a group represented by the following general formula (tR).

The A ring, B ring, and C ring in the general formula (1) are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted with a substituent. This substituent can be a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted diheteroarylamino, a substituted or unsubstituted aryl heteroarylamino (with aryl). Amino groups with heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be attached via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl. , Substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy are preferable. Examples of the substituent when these groups have a substituent include aryl, heteroaryl, alkyl and cycloalkyl. Further, the aryl ring or heteroaryl ring may have a 5-membered ring or a 6-membered ring that shares a bond with the condensed two-ring structure in the center of the general formula (1) composed of ^{Y 1} , X ¹ and X ^2. preferable.

Here, the "condensed bicyclic structure" means a structure in which two saturated hydrocarbon rings ^{including Y 1} , X ¹ and X ² shown in the center of the general formula (1) are condensed. .. The "6-membered ring that shares a bond with the condensed 2-ring structure" is, for example, an a-ring (benzene ring (6-membered ring)) condensed into the condensed 2-ring structure as shown in the general formula (2). means. Further, "the aryl ring (which is the A ring) or the heteroaryl ring has the 6-membered ring" means that the A-ring is formed only by the 6-membered ring or includes the 6-membered ring. This means that another ring or the like is further condensed with this 6-membered ring to form an A ring. In other words, the "aryl ring having a 6-membered ring (which is an A ring) or a heteroaryl ring" as used herein means that a 6-membered ring constituting all or a part of the A ring is condensed into the condensed two-ring structure. It means that you are doing it. The same description applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

Ring A (or B ring, C ring) in Formula (1) has the general formula (2) a ring in its substituents ^R 1 to R ³ (or b ring and substituents thereof ^R 8 ^{to R} 11, c ring and corresponding to the substituent ^R 4 ^{~R 7).} That is, the general formula (2) corresponds to a structure in which "A to C rings having a 6-membered ring" is selected as the A to C rings of the general formula (1). In that sense, each ring of the general formula (2) is represented by lowercase letters a to c.

In general formula (2), a ring, a ring adjacent groups are bonded to one of the substituents R ¹ to R ¹¹ of b ring and c rings, with b ring or c ring aryl or heteroaryl ring At least one hydrogen in the formed ring may be formed, and the at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, diarylboryl (two aryls via a single bond or a linking group). , Alkyl, cycloalkyl, alkoxy or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. .. Therefore, the polycyclic aromatic compounds represented by the general formula (2) have the following formulas (2-1) and (2-2) depending on the mutual bonding form of the substituents in the a ring, b ring and c ring. As shown in, the ring structure constituting the compound changes. The A'ring, B'ring and C'ring in each formula correspond to the A ring, B ring and C ring in the general formula (1), respectively.

The formula (2-1) and ring A ', B' in the formula (2-2) ring and C 'ring, will be described in the general formula (2), adjoining of the substituents ^R 1 ^{to R 11} Indicates an aryl ring or a heteroaryl ring formed by bonding a ring, a b ring, and a c ring, respectively (a fused ring formed by condensing another ring structure on the a ring, b ring, or c ring). It can be said that). Although not shown in the formula, there are some 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 equations (2-1) and (2-2), for example, R ⁸ of b ring and R ⁷ of c ring, R ¹¹ of b ring and R ^{1 of} a ring, and c ring. R ⁴ and R ^{3 of the} a ring do not correspond to "adjacent groups", and they do not bond with each other. That is, the "adjacent group" means an adjacent group on the same ring.

The compounds represented by the above formulas (2-1) and (2-2) are, for example, a benzene ring, an indole ring, a pyrrole ring, and a benzofuran ring with respect to a benzene ring which is an a ring (or b ring or c ring). Alternatively, it is a compound having an A'ring (or B'ring or C'ring) formed by condensing a benzothiophene ring, and the formed fused ring A'(or fused ring B'or fused ring C'. ) Are naphthalene rings, carbazole rings, indole rings, dibenzofuran rings or dibenzothiophene rings, respectively.

^{Y 1} in the general formula (1) is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is It is aryl, alkyl or cycloalkyl. In the case of P = O, P = S, Si-R or Ge-R, the atom bonded to the A ring, B ring or C ring is P, Si or Ge. Y ¹ is preferably B, P, P = O, P = S or Si—R, and B is particularly preferable. This explanation is the same for ^{Y 1} in the general formula (2).

^{X 1} and X ² in the general formula (1) are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, and the R of> N-R is , Aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted or cycloalkyl which may be substituted, and R of> C (-R) ₂ is hydrogen. , Aryl which may be substituted, alkyl which may be substituted or cycloalkyl which may be substituted, and R of> N-R and / or R of the above> C (-R) ₂ are linked. It may be bonded to the B ring and / or C ring by a group or a single bond, and the linking group is preferably _{−O−, −S− or −C (−R) 2-.} In addition, R of the said "−C (−R) ₂₋ ” is hydrogen, alkyl or cycloalkyl. This explanation is the same for ^{X 1} and X ² in the general formula (2).

Here, in the general formula (1), "R of> N-R and / or R of said> C (-R) ₂ is bonded to the A ring, B ring and / or C ring by a linking group or a single bond. In the general formula (2), the rule that "is done" is that "R of> N-R and / or R of> C (-R) ₂ is -O-, -S-, -C (-R). ) It corresponds to the provision that "it is bonded to the a ring, b ring and / or c ring by _{2- or a single bond".}

^{This specification can be expressed by a compound having a ring structure in which X 1} and X ² are incorporated into the condensed ring B'and the condensed ring C', which are represented by the following formula (2-3-1). That is, for example, the B'ring (or ring) formed by condensing other rings so as to incorporate ^{X 1} (or X ² ) into the benzene ring which is the b ring (or c ring) in the general formula (2). It is a compound having a C'ring). The formed fused ring B'(or fused ring C') is, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

^{Further, the above specification is a compound having a ring structure in which X 1} and / or X ² is incorporated into the condensed ring A', which is represented by the following formula (2-3-2) or formula (2-3-3). But it can be expressed. That is, for example, it is a compound having an A'ring formed by condensing other rings so as to incorporate ^{X 1} (and / or X ² ) with respect to the benzene ring which is the a ring in the general formula (2). .. The formed fused ring A'is, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

Examples of the "aryl ring" which is the A ring, the B ring and the C ring of the general formula (1) include an aryl ring having 6 to 30 carbon atoms, and an aryl ring having 6 to 16 carbon atoms is preferable. An aryl ring of 6 to 12 is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable. This "aryl ring" is defined by the general formula (2) as " ^{an aryl ring formed by combining adjacent groups of R 1 to} R ¹¹ together with an a ring, a b ring, or a c ring". In addition, since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the carbon having a total carbon number of 9 is the lower limit of the fused ring in which a 5-membered ring is condensed. It becomes a number.

Specific examples of the "aryl ring" include a benzene ring which is a monocyclic system, a biphenyl ring which is a bicyclic system, a naphthalene ring which is a fused bicyclic system, and a terphenyl ring (m-terphenyl, o) which is a tricyclic system. -Terphenyl, p-terphenyl), fused tricyclics, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic triphenylene ring, pyrene ring, naphthalene ring, fused pentacyclic system. Examples include a perylene ring and a pentacene ring.

Examples of the "heteroaryl ring" which is the A ring, B ring and C ring of the general formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, and a heteroaryl ring having 2 to 25 carbon atoms is preferable. , A heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is further preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Examples of the "heteroaryl ring" include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms. In addition, this "heteroaryl ring" is ^{a heteroaryl formed by bonding adjacent groups among "R 1 to} R ¹¹ " defined by the general formula (2) together with an a ring, a b ring or a c ring. Since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total carbon number 6 of the fused ring in which a 5-membered ring is condensed is the lower limit. It becomes the carbon number of.

Specific examples of the "heteroaryl ring" include a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxazole ring, a thiazazole ring, a triazole ring, a tetrazole ring, and a pyrazole ring. Ppyridine 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 , Synnoline ring, quinazoline ring, quinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysine ring, phenoxathione ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indridin ring, Examples thereof include a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a flazan ring, and a thiantolen ring.

At least one hydrogen in the "aryl ring" or "heteroaryl ring" is the first substituent, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted. "Diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl (two aryls via a single bond or a linking group) May be bonded) ", substituted or unsubstituted" alkyl ", substituted or unsubstituted" cycloalkyl ", substituted or unsubstituted" alkoxy ", or substituted or unsubstituted" aryloxy ". As the first substituent, "aryl", "heteroaryl", "diarylamino" aryl, "diheteroarylamino" heteroaryl, and "arylheteroarylamino" aryl Examples of the heteroaryl, the aryl of "diarylboryl", and the aryl of "aryloxy" include the monovalent group of the "aryl ring" or "heteroaryl ring" described above.

The "alkyl" as the first substituent may be either a straight chain or a branched chain, and examples thereof include a linear alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. An alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms is more preferable. (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. As the alkyl having 1 to 4 carbon atoms, a methyl group and a t-butyl group are more preferable, but a t-butyl group is further 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- Examples thereof include tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

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 (particularly methyl) substituents having 1 to 4 carbon atoms, norbornenyl, 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.

Examples of the "alkoxy" as the first substituent include alkoxy having a linear chain having 1 to 24 carbon atoms or a branched chain having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (alkoxy of branched chains having 3 to 18 carbon atoms) is preferable, and alkoxy having 1 to 12 carbon atoms (alkoxy of branched chains having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms is more preferable. Alkoxy (alkoxy of a branched chain having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 4 carbon atoms (alkoxy of a branched chain having 3 to 4 carbon atoms) is particularly preferable.

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

Further, as the "aryl" in the "diarylboryl" of the first substituent, the above-mentioned description of aryl can be cited. Further, the two aryls may be bonded via a single bond or a linking group (for example,> C (-R) ₂ ,>O,> S or> N-R). Here, R of> C (-R) ₂ and> N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (above, the first substituent), and the first is said to be. The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (hereinafter, the second substituent), and specific examples of these groups include aryl and hetero as the first substituent described above. Descriptions of aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy can be cited.

The first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted Or unsubstituted "aryl heteroarylamino", substituted or unsubstituted "diarylboryl (two aryls may be bonded via a single bond or a linking group)", substituted or unsubstituted "alkyl", Substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy" are described as substituted or unsubstituted by at least one hydrogen in them. It may be substituted with a second substituent. Examples of the second substituent include aryl, heteroaryl, alkyl and cycloalkyl, and specific examples thereof include the monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring", and the second substituent. The description of "alkyl" or "cycloalkyl" as the substituent of 1 can be referred to. Further, in aryl and heteroaryl as the second substituent, at least one hydrogen in them is aryl such as phenyl (specific example is the group described above), alkyl such as methyl (specific example is the group described above) or cyclohexyl. A structure substituted with a cycloalkyl (specific example is the group described above) such as, is also included in aryl or heteroaryl as the second substituent. As an example, when the second substituent is a carbazolyl group, the carbazolyl group in which at least one hydrogen at the 9-position is substituted with aryl such as phenyl, alkyl such as methyl or cycloalkyl such as cyclohexyl is also the second. It is contained in heteroaryl as a substituent of.

Aryl, heteroaryl, diarylamino aryl, diheteroarylamino heteroaryl, aryl heteroarylamino aryl and heteroaryl, diarylboryl aryl, or aryloxy aryl in general formulas (2) R ^{1 to} R ¹¹ Examples include the monovalent group of the "aryl ring" or "heteroaryl ring" described in the general formula (1). Further, as the ^{alkyl, cycloalkyl or alkoxy in R 1 to} R ¹¹ , refer to the description of “alkyl”, “cycloalkyl” or “alkoxy” as the first substituent in the above-mentioned explanation of the general formula (1). can do. The same applies to aryl, heteroaryl, alkyl or cycloalkyl as substituents to these groups. Further, when ^{adjacent groups of R 1 to} R ¹¹ are bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring or a c ring, a heteroaryl which is a substituent to these rings. , Diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, and more. The same applies to the substituents aryl, heteroaryl, alkyl or cycloalkyl.

Specifically, the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron attracting property of the structure of the first substituent, and the group is preferably represented by the following structural formula, more preferably. , Methyl, t-Butyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xsilyl, 2,6-xsilyl, 2,4,6-mesityl, diphenylamino, di-p- Trillamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, more preferably methyl, t. -Butyl, phenyl, o-tolyl, 2,6-xsilyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6 -Dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl. From the viewpoint of ease of synthesis, a larger steric hindrance is preferable for selective synthesis, and specifically, t-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5. -Xylyl, 2,6-xsilyl, 2,4,6-mesityl, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, 3,6-dimethylcarbazolyl and 3,6-di -T-Butylcarbazolyl is preferred.

In the following structural formula, "Me" represents methyl and "tBu" represents t-butyl.

^{The R of Si-R and Ge-R in Y 1} of the general formula (1) is aryl, alkyl or cycloalkyl, and examples of the aryl, alkyl or cycloalkyl include the above-mentioned groups. In particular, aryls having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), alkyls having 1 to 4 carbon atoms (eg, methyl, ethyl, t-butyl, etc., especially t-butyl) or cycloalkyls having 5 to 10 carbon atoms (preferably). Is preferably cyclohexyl or adamantyl). This explanation is the same for ^{Y 1} in the general formula (2).

^{The R of> N-R in X 1} and X ² of the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl, which may be substituted with the second substituent described above, and is aryl or hetero. At least one hydrogen in aryl may be substituted with, for example, alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl or cycloalkyl include the groups described above. In particular, aryls having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.), heteroaryls having 2 to 15 carbon atoms (for example, carbazolyl), alkyls having 1 to 4 carbon atoms (for example, methyl, ethyl, t-butyl, etc.), in particular t -Butyl) or cycloalkyl (preferably cyclohexyl or adamantyl) having 5 to 10 carbon atoms is preferable. This explanation is the same for ^{X 1} and X ² in the general formula (2).

> C (-R) ₂ of R in X ¹ and X ² in the general formula (1) is hydrogen, may be substituted with a second substituent described above, aryl, alkyl or cycloalkyl, aryl At least one hydrogen in the above may be substituted with, for example, alkyl or cycloalkyl. Examples of the aryl, alkyl or cycloalkyl include the above-mentioned groups. In particular, aryls having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), alkyls having 1 to 4 carbon atoms (eg, methyl, ethyl, t-butyl, etc., especially t-butyl) or cycloalkyls having 5 to 10 carbon atoms (preferably). Is preferably cyclohexyl or adamantyl). This explanation is the same for ^{X 1} and X ² in the general formula (2).

_{The R of "-C (-R) 2-} " which is a linking group in the general formula (1) is hydrogen, alkyl or cycloalkyl, and examples of the alkyl or cycloalkyl include the above-mentioned groups. In particular, an alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, t-butyl, etc., particularly t-butyl) or a cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl) is preferable. This explanation is the same for _{"-C (-R) 2-} " which is a linking group in the general formula (2).

Further, the present invention is a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). It is a multimer of a compound. The multimer is preferably a 2-hexamer, more preferably a 2-3mer, and particularly preferably a dimer. The multimer may be in the form of having a plurality of the above unit structures in one compound. For example, the multimer may be a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. In addition to the plurally bonded form (linked multimer), any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure is shared by the plurality of unit structures. It may be in a form bonded in this way (ring-shared multimer), or any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure. Although it may be in the form of being bonded so as to condense (ring-condensed multimer), a ring-shared multimer and a ring-condensed multimer are preferable, and a ring-covalent multimer is more preferable.

Examples of such a multimer include the following formulas (2-4), formulas (2-4-1), formulas (2-4-2), formulas (2-5-1) to formulas (2-5). -4) or a multimeric compound represented by the formula (2-6) can be mentioned. The multimeric compound represented by the following formula (2-4) is represented by a plurality of general formulas (2) so as to share the benzene ring which is the a ring, if it is explained by the general formula (2). It is a multimer compound (ring-shared multimer) having a unit structure in one compound. Further, the multimeric compound represented by the following formula (2-4-1) is described by the general formula (2) so as to share the benzene ring which is the a ring, and the two general formulas (2) are shared. It is a multimer compound (ring-shared multimer) having a unit structure represented by (1) in one compound. Further, the multimeric compound represented by the following formula (2-4-2) is described by the general formula (2) so as to share the benzene ring which is the a ring, and the three general formulas (2). It is a multimer compound (ring-shared multimer) having a unit structure represented by (1) in one compound. Further, the multimeric compound represented by the following formulas (2-5-1) to (2-5-4) is a benzene ring which is a b ring (or c ring) according to the general formula (2). It is a multimer compound (ring-shared multimer) having a unit structure represented by a plurality of general formulas (2) in one compound so as to share the above. Further, the multimeric compound represented by the following formula (2-6) is described by the general formula (2), for example, a benzene ring which is a b ring (or a ring or c ring) of a certain unit structure and a certain unit. A multimeric compound (ring condensation) having a unit structure represented by a plurality of general formulas (2) in one compound so as to be condensed with a benzene ring which is a b ring (or a ring or c ring) of the structure. Type multimer).

The multimeric compound has a quantified form represented by the formula (2-4), the formula (2-4-1) or the formula (2-4-2), and the formulas (2-5-1) to (2). It may be a multimer in combination with any of −5-4) or the quantified form represented by the formula (2-6), and formulas (2-5-1) to (2-5-). It may be a multimer in which the quantifier form represented by any one of 4) and the quantifier form represented by the formula (2-6) are combined, and the formulas (2-4) and (2) may be used. 4-1) or the quantified form represented by the formula (2-4-2) and the quantified form represented by any of the formulas (2-5-1) to (2-5-4). It may be a multimer in combination with the quantifier form represented by the formula (2-6).

Further, the hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer may be deuterium, cyano or halogen in whole or in part. For example, in the formula (1), A ring, B ring, C ring (A to C rings are aryl rings or heteroaryl rings), substituents to A to C rings, Y ¹ is Si-R or Ge-R. In R (= alkyl, cycloalkyl, aryl) when, and in R (= alkyl, cycloalkyl, aryl) when X ¹ and X ² are> N-R or> C (-R) ₂ . Hydrogen can be substituted with dear hydrogen, cyano or halogen, among which all or some of the hydrogen in aryls and heteroaryls may be substituted with deuterium, cyano or halogen. The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Further, the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent device, an organic field effect transistor, and an organic thin film solar cell. In particular, in an organic electroluminescent element, as the dopant material of the light emitting layer, Y ¹ is B, X ¹ and X ² are> N-R compounds, Y ¹ is B, X ¹ is> O, and X ² is>. Compounds of N-R, compounds in which Y ¹ is B, X ¹ and X ^{2 are> O are preferable, and Y 1} is B, X ¹ is> O, and X ² is> N- as the host material of the light emitting layer. A compound having R, a compound having Y ¹ being B, X ¹ and X ² being> O is preferable, and as an electron transporting material, a compound having Y ¹ being B, X ¹ and X ² being> O, and Y ¹ being P. Compounds in which = O, X ¹ and X ² are> O are preferably used.

Further, at least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer is substituted with a group represented by the following general formula (tR). , All hydrogen or some hydrogen may be a group represented by the following formula (tR).

In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) or the above formula (2) in *.

^{The "alkyl having 2 to 24 carbon atoms" of Ra} may be either a straight chain or a branched chain, for example, a linear alkyl having 2 to 24 carbon atoms, a branched alkyl having 3 to 24 carbon atoms, or 2 carbon atoms. Alkyl of ~ 18 (branched chain alkyl of 3 to 18 carbons), alkyl of 2 to 12 carbons (branched chain alkyl of 3 to 12 carbons), alkyl of 2 to 6 carbons (branch of 3 to 6 carbons) Chain alkyl) and alkyl having 2 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) can be mentioned.

The "alkyl having 1 to 24 carbon atoms" of R ^b and R ^c may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms or a branched alkyl chain having 3 to 24 carbon atoms. Alkyl with 1 to 18 carbon atoms (branched chain alkyl with 3 to 18 carbon atoms), alkyl with 1 to 12 carbon atoms (branched chain alkyl with 3 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms (3 to 6 carbon atoms) 6 branched chain alkyl) and alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) can be mentioned.

^{The total number of carbon atoms of Ra} , R ^b, and R ^c in the formula (tR) of the general formula (1) is preferably 4 to 20 carbon atoms, and particularly preferably 4 to 10 carbon atoms.

Specific alkyls of R ^a , R ^b and R ^{c include methyl (excluding Ra} ), ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, etc. 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, n-Tridecyl, 1-Hexylheptyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl, n-Eicosyl and the like.

Examples of the group represented by the formula (tR) include t-amyl group, 1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group and 1-ethyl-1. -Methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,1,4-trimethylpentyl group, 1,1,2-trimethylpropyl group, 1,1-dimethyloctyl group, 1,1-dimethyl Pentyl group, 1,1-dimethylheptyl group, 1,1,5-trimethylhexyl group, 1-ethyl-1-methylhexyl group, 1-ethyl-1,3-dimethylbutyl group, 1,1,2,2 -Tetramethylpropyl group, 1-butyl-1-methylpentyl group, 1,1-diethylbutyl group, 1-ethyl-1-methylpentyl group, 1,1,3-trimethylbutyl group, 1-propyl-1- Examples thereof include methylpentyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1,2,2-trimethylpropyl group, 1-propyl-1-methylbutyl group and 1,1-dimethylhexyl group.

As another form of the tertiary alkyl substitution of the present invention, a polycyclic aromatic compound represented by the general formula (1) or (2) and a multimer thereof are substituted with, for example, a group of the formula (tR). Examples thereof include a diarylamino group, a carbazolyl group substituted with a group of formula (tR), or a benzocarbazolyl group substituted with a group of formula (tR). Examples of the "diarylamino group" include the groups described as the "first substituent" above. As a substitution form of a group of the formula (tR) with a diarylamino group, a carbazolyl group and a benzocarbazolyl group, a part or all of hydrogen of the aryl ring or the benzene ring in these groups is a group of the formula (tR). Examples include replacements.

Further, as a more specific example, the polycyclic aromatic compound represented by the general formula (2) and R ² in the multimer thereof are substituted with a group of the formula (tR) to form a diarylamino group or a formula (tR). ) Is an example of a carbazolyl group substituted with a group.

An example of this is a polycyclic aromatic compound represented by the following general formula (2-A) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2-A). .. tR is an integer of 1 to 5 (preferably 1) independently of the base of the formula (tR), and the definition of each code in the structural formula is the same as the definition of each code in the general formula (2). Is.

Further, as a specific example of the tertiary alkyl-substituted polycyclic aromatic compound of the present invention and its multimer, at least one hydrogen in one or more aromatic rings in the compound is one or more. Examples thereof include compounds substituted with a group of the formula (tR), for example, a compound substituted with a group of one or two formulas (tR).

Specific examples thereof include compounds represented by the following formulas (1-1-1 tR) to (1-4401-tR). Each of n in the following formula is 0 to 2 independently (however, not all n becomes 0), preferably 1. In the following structural formula, "tR" represents a group represented by the formula (tR), "OPh" represents a phenoxy group, and "Me" represents a methyl group.

As a more specific example of the tertiary alkyl-substituted polycyclic aromatic compound of the present invention, a compound represented by the following structural formula can be mentioned. In the following structural formula, "D" is deuterium, "Me" is a methyl group, "Et" is an ethyl group, "Pr" is a propyl group, "Hep" is a heptyl group, and "tBu" is a t-butyl group. , "TAm" indicates a t-amyl group.

The polycyclic aromatic compound represented by the general formula (1) and its multimer according to the present invention are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted therein as a monomer (this high polymer compound). The monomer for obtaining a molecular compound has a polymerizable substituent) or a polymer crosslinked product obtained by further cross-linking the polymer compound (the polymer compound for obtaining this polymer crosslinked product has a crosslinkable substituent). (Having), or a pendant type polymer compound obtained by reacting a main chain type polymer with the above-mentioned reactive compound (the above-mentioned reactive compound for obtaining this pendant type polymer compound has a reactive substituent). Alternatively, the pendant type polymer crosslinked product obtained by further cross-linking the pendant type polymer compound (the pendant type polymer compound for obtaining this pendant type polymer crosslinked product has a crosslinkable substituent) can also be used for organic devices. It can be used as a material, for example, a material for an organic field light emitting element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

As the above-mentioned reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant type polymer, hereinafter, also simply referred to as “reactive substituent”). , The substituent capable of increasing the molecular weight of the polycyclic aromatic compound or its multimer, the substituent capable of further cross-linking the polymer compound thus obtained, and the substituent capable of pendant reaction with the main chain type polymer. The group is not particularly limited as long as it is a group, but a substituent having the following structure is preferable. * In each structural formula indicates the bonding position.

L is a single bond, −O−, −S−,> C = O, −OC (= O) −, alkylene having 1 to 12 carbon atoms, and oxyalkylene having 1 to 12 carbon atoms, respectively. And a polyoxyalkylene having 1 to 12 carbon atoms. Among the above substituents, it is represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10) or the formula (XLS-17). The group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.

Details of the use of such a polymer compound, a polymer crosslinked body, a pendant type polymer compound and a pendant type polymer crosslinked body (hereinafter, also simply referred to as “polymer compound and polymer crosslinked body”) will be described later.

2. Method for producing tertiary alkyl-substituted polycyclic aromatic compounds and their multimers The polycyclic aromatic compounds represented by the general formulas (1) and (2) and their multimers are described in, for example, International Publication No. 2015/102118. It can be synthesized by applying the method disclosed in the publication. Basically, an intermediate is produced by ^first binding the A ring (a ring), 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), followed by binding A ring (a ring), B ring (b ring) and C ring (c ring) with a binding group ( ^{group containing Y 1} ) to produce the final product. Can be (second reaction). In addition, somewhere in these reaction steps, a step of using a raw material substituted with a tertiary alkyl group represented by the formula (tR) or introducing a tertiary alkyl group represented by the formula (tR) is added. By doing so, the compound of the present invention in which the desired position is substituted with a tertiary alkyl can be produced.

In the first reaction, for example, in the case of an etherification reaction, a general reaction such as a nucleophilic substitution reaction or an Ullmann reaction can be used, and in the case of an amination reaction, a general reaction such as a Buchwald-Hartwig reaction can be used. Further, in the second reaction, a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used.

The second reaction, as shown in the following scheme (1) or (2), A ring (a ring), B ring (b ring) and C rings (c ring) be the reaction of introducing a ^{Y 1} to bind As an example, the case where Y ¹ is a boron atom and X ¹ and X ² are oxygen atoms is shown below. First, ^{the hydrogen atom between X 1} and X ² is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Next, boron trichloride, boron tribromide, etc. are added, metal exchange of lithium-boron is performed, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem Bora Friedel-Crafts reaction. You can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. The definitions of the symbols in the following schemes (1) and (2) and in the subsequent schemes (3) to (5) are the same as the definitions described above.

The above schemes (1) and (2) mainly show methods for producing polycyclic aromatic compounds represented by the general formulas (1) and (2), but there are a plurality of multimers thereof. It can be produced by using an intermediate having an A ring (a ring), a B ring (b ring) and a C ring (c ring). Details will be described in the following schemes (3) to (5). In this case, the target product can be obtained by doubling or trebling the amount of the reagent such as butyllithium to be used.

In the above scheme, lithium was introduced to the desired position by orthometalation, but halogen such as a bromine atom can be introduced at the position where lithium is to be introduced, and lithium can be introduced to the desired position by halogen-metal exchange. can.

In addition, for the polycyclic aromatic compound represented by the general formula (2-A), an intermediate substituted with a tertiary alkyl group represented by the formula (tR) is synthesized as in the following scheme (6). Then, by cyclizing it, a polycyclic aromatic compound in which the desired position is substituted with a tertiary alkyl can be synthesized. In scheme (6), X represents halogen or hydrogen, and the definitions of other codes are the same as the definitions of codes in the general formula (2).

The pre-cyclization intermediate in scheme (6) can also be synthesized by the method shown in scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining a Buchwald-Hartwig reaction, a Suzuki coupling reaction, an etherification reaction by a nucleophilic substitution reaction, an Ullmann reaction, or the like. In these reactions, commercially available products can also be used as raw materials to be precursors substituted with tertiary alkyl.

The compound of the general formula (2-A) having a tertiary alkyl-substituted diphenylamino group can also be synthesized by, for example, the following method. That is, after introducing a tertiary alkyl-substituted diphenylamino group of tertiary alkyl-substituted bromobenzene and trihalogenated aniline by an amination reaction such as Buchwald-Hartwig reaction, X ¹ and X ² are N-R. at some case amination reaction such as Buchwald-Hartwig ^reaction, when X 1, ^{X 2} is O is guided to the intermediate member by etherification with phenol (M-3), then, For example, tandem bora by acting a metallizing reagent such as butyllithium to transmetallate, then reacting with a boron halide such as boron tribromide, and then acting with a blended base such as diethylisopropylamine. The compound of the general formula (2-A) can be synthesized by the Friedelcrafts reaction. These reactions can also be applied to other tertiary alkyl substituted compounds.

3. 3. Organic Devices The tertiary alkyl-substituted polycyclic aromatic compounds according to the present invention can be used as materials for organic devices. Examples of the organic device include an organic electroluminescent device, an organic field effect transistor, and an organic thin film solar cell.

3-1. Organic electroluminescent device The organic EL device according to this embodiment will be described in detail below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL device according to the present embodiment.

<Structure of organic electroluminescent device>
The organic EL element 100 shown in FIG. 1 is placed on a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. The hole transport layer 104 is provided, the light emitting layer 105 is provided on the hole transport layer 104, the electron transport layer 106 is provided on the light emitting layer 105, and the electron transport layer 106 is provided. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

The organic EL element 100 is manufactured in the 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. Above the electron transport layer 106 provided on the electron transport layer 106, the light emitting layer 105 provided on the electron transport layer 106, the hole transport layer 104 provided on the light emitting layer 105, and the hole transport layer 104. The hole injection layer 103 provided in the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be provided.

Not all of the above layers are required, 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. The layer 107 is an arbitrarily provided layer. Further, each of the above layers may be composed of a single layer or a plurality of layers.

As the mode of the layer constituting the organic EL element, in addition to the above-mentioned "board / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", " Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection 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 / Anode", "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" The configuration may be "/ light emitting layer / electron transporting layer / cathode" or "substrate / anode / light emitting layer / electron injection layer / cathode".

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic EL element 100, and usually quartz, glass, metal, plastic, or the like is used. 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, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. As for the glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness may be sufficient to maintain the mechanical strength. Therefore, for example, 0.2 mm or more may be used. 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, non-alkali glass is preferable because it is better that there are few elution ions from the glass, but _{soda lime glass with a barrier coat such as SiO 2} is also commercially available, so this can be used. can. Further, in order to enhance the gas barrier property, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side, and a synthetic resin plate, film or sheet having a particularly low gas barrier property may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these. ..

Examples of the material forming the anode 102 include an inorganic compound and an organic compound. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxidation, etc.). (IZO, etc.), metals halide (copper iodide, etc.), copper sulfide, carbon black, ITO glass, nesa glass, etc. Examples of the organic compound include polythiophene such as poly (3-methylthiophene) and conductive polymers such as polypyrrole and polyaniline. In addition, it can be appropriately selected and used from the substances used as the anode of the organic EL element.

The resistance of the transparent electrode is not limited as long as a sufficient current can be supplied to emit light from the light emitting element, but it is desirable that the resistance is low 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 since it is now possible to supply a substrate of about 10 Ω / □, for example, 100 to 5 Ω / □, preferably 50 to 5 Ω. It is especially desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but 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 injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport 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 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more of the hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder, respectively. Will be done. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

As a hole injection / transporting substance, it is necessary to efficiently inject / transport holes from the positive electrode between electrodes to which an electric field is applied, and the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. For that purpose, it is preferable that the substance has a small ionization potential, a large hole mobility, excellent stability, and is less likely to generate trap impurities during production and use.

As the material for forming the hole injection layer 103 and the hole transport layer 104, in the photoconductive material, a compound conventionally used as a hole charge transport material, a p-type semiconductor, and a hole injection layer of an organic EL element. And any compound can be selected and used from the known compounds used for 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), and triarylamine derivatives (aromatic tertiary). Polymers with amino in the main or side chains, 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, starburstamine derivatives, etc.), stillben derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives , Kinoxalin derivatives (eg, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivative having the monomer as a side chain, polyvinylcarbazole, polysilane, or the like is preferable, but a thin film necessary for producing a light emitting element can be formed and holes can be injected from the anode. Further, the compound is not particularly limited as long as it can transport holes.

It is also known that the conductivity of organic semiconductors is strongly affected by its doping. Such an organic semiconductor matrix substance is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping electron donors. (For example, the document "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (22), 3202-3204 (1998)" and the document "J. Blochwitz, M." See .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-transporting material). Depending on the number of holes and the mobility, the conductivity of the base material changes considerably. As the matrix substance having hole transporting properties, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA or the like), or a specific metal phthalocyanine (particularly, zinc phthalocyanine (ZnPc) or the like) is known ( Japanese Unexamined Patent Publication No. 2005-167175).

The above-mentioned materials for the hole injection layer and the material for the hole transport layer are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a polymer crosslinked product thereof. A pendant type polymer compound obtained by reacting a main chain type polymer with the above-mentioned reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for a hole layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Light emitting layer in organic electroluminescent device>
The light emitting layer 105 is a layer that emits light by recombining the holes injected from the anode 102 and the electrons injected from the cathode 108 between the electrodes to which an electric field is applied. The material for forming the light emitting layer 105 may be a compound (light emitting compound) that is excited by recombination of holes and electrons to emit light, and can form a stable thin film shape and is in a solid state. It is preferable that the compound exhibits a strong emission (fluorescence) efficiency. In the present invention, as the material for the light emitting layer, a host material and, for example, a polycyclic aromatic compound represented by the above general formula (1) as a dopant material can be used.

The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). The host material and the dopant material may be one kind or a combination of two or more. The dopant material may be included in the entire host material, partially, or in any part. As a doping method, it can be formed by a co-evaporation method with a host material, but it can be produced by a wet film formation method after being mixed with the host material in advance and then vapor-deposited at the same time, or mixed with an organic solvent in advance with the host material. It may be filmed.

The amount of the host material used depends on the type of host material and may be determined according to the characteristics of the host material. The guideline for the amount of the host material used is preferably 50 to 99.99% by weight, more preferably 80 to 99.95% by weight, and further preferably 90 to 99.9% by weight of the entire material for the light emitting layer. Is.

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

Host materials include fused ring derivatives such as anthracene, pyrene, dibenzoglycene or fluorene, which have long been known as luminescent materials, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. And so on. In particular, anthracene-based compounds, fluorene-based compounds or dibenzochrysene-based compounds are preferable.

<Anthracene compounds>
The anthracene-based compound as a host is, for example, a compound represented by the following general formula (3).

In equation (3),
X and Ar ⁴ are independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, respectively. Aryl heteroarylamino which may be substituted, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted, alkoxy which may be substituted, which may be substituted. Aryloxy, optionally substituted arylthio or optionally substituted silyl, all X and Ar ⁴ are not hydrogenated at the same time.
At least one hydrogen in the compound represented by the formula (3) may be substituted with a halogen, cyano, deuterium or a heteroaryl which may be substituted.

Further, a multimer (preferably a dimer) may be formed by using the structure represented by the formula (3) as a unit structure. In this case, for example, a form in which the unit structures represented by the formula (3) are bonded to each other via X can be mentioned, and the X includes a single bond, an arylene (phenylene, biphenylene, naphthylene, etc.) and a heteroarylene (pyridine ring, etc.). A group in which a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, a phenyl-substituted carbazole ring, etc. have a divalent bond value) and the like can be mentioned.

Details of the above aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl will be described in the section of preferred embodiments below. Examples of the substituents thereof include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, silyl, and the like. Details will also be described in the section of preferred embodiments below.

Preferred embodiments of the anthracene-based compound will be described below. The definition of the code in the structure below is the same as the definition described above.

In the general formula (3), X is a group independently represented by the above formula (3-X1), the formula (3-X2) or the formula (3-X3), and the formula (3-X1) and the formula (3-X1). The group represented by (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3) in *. Preferably, the two Xs do not simultaneously form a group represented by the formula (3-X3). More preferably, the two Xs do not simultaneously become a group represented by the formula (3-X2).

Further, a multimer (preferably a dimer) may be formed by using the structure represented by the formula (3) as a unit structure. In this case, for example, a form in which the unit structures represented by the formula (3) are bonded to each other via X can be mentioned, and the X includes a single bond, an arylene (phenylene, biphenylene, naphthylene, etc.) and a heteroarylene (pyridine ring, etc.). A group in which a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, a phenyl-substituted carbazole ring, etc. have a divalent bond value) and the like can be mentioned.

The naphthalene moiety in the formulas (3-X1) and (3-X2) may be condensed with one benzene ring. The structure condensed in this way is as follows.

Ar ¹ and Ar ² are independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or in the above formula (A). The group represented (including carbazolyl group, benzocarbazolyl group and phenyl-substituted carbazolyl group). When Ar ¹ or Ar ² is a group represented by the formula (A), the group represented by the formula (A) is in the formula (3-X1) or the formula (3-X2) in the *. It binds to the naphthalene ring.

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

Further, Ar ³ may have a substituent, and ^{at least one hydrogen in Ar 3} is further an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, phenyl, biphenylyl, terphenylyl, naphthyl and phenanthryl. , Fluolenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group) may be substituted. When the ^{substituent contained in Ar 3} is a group represented by the formula (A), the group represented by the formula (A) is bonded to ^{Ar 3 in the formula (3-X3) in the *.}

Ar ⁴ is independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or an alkyl having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and / or a cycloalkyl having 5 to 10 carbon atoms. Cyril has been.

Examples of alkyl having 1 to 4 carbon atoms to be substituted with silyl include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc., and the three hydrogens in silyl are independent of each other. , Substituted with these alkyls.

Specific examples of "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, and 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, methyldii-propylsilyl, ethyldii-propylsilyl, Examples thereof include butyl di-propyl silyl, sec-butyl di-propyl silyl and t-butyl di-propyl silyl.

Cycloalkyls having 5 to 10 carbon atoms to be substituted with silyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, 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, decahydro Azulenyl and the like are mentioned, and the three hydrogens in silyl are independently substituted with these cycloalkyls.

Specific examples of the "silyl substituted with cycloalkyl having 5 to 10 carbon atoms" include tricyclopentyl silyl and tricyclohexyl silyl.

Substituted silyls include dialkylcycloalkylsilyls substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyls substituted with one alkyl and two cycloalkyls, which are substituted alkyls and cycloalkyls. As a specific example of, the above-mentioned group can be mentioned.

Further, hydrogen in the chemical structure of the anthracene-based compound represented by the general formula (3) may be substituted with the group represented by the above formula (A). When substituted with a group represented by the formula (A), the group represented by the formula (A) is substituted with at least one hydrogen in the compound represented by the formula (3) in the *.

The group represented by the formula (A) is one of the substituents that the anthracene-based compound represented by the formula (3) can have.

In the above formula (A), Y is -O-, -S- or> N-R ²⁹ , and R ^{21 to} R ²⁸ are independently hydrogen, optionally substituted alkyl, and optionally substituted, respectively. Good cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, Tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, the ^{adjacent groups of R 21-} R ²⁸ are bonded to each other to form a hydrocarbon ring. , may form an aryl or heteroaryl ring, R ²⁹ is aryl which may be hydrogen or substituted.

The "alkyl" of the "optionally substituted alkyl" in R ^21- R ²⁸ may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms or a linear alkyl having 3 to 24 carbon atoms. Branched chain alkyl can be mentioned. An alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms is more preferable. (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" includes 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 thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicocil.

The "cycloalkyl" of the "optionally substituted cycloalkyl" in R ^{21 to} R ²⁸ includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, and 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, cycloalkyl having 5 carbon atoms and the like.

Specific "cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (particularly methyl) substituents having 1 to 4 carbon atoms, norbornenyl, 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] Hexil, Bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like can be mentioned.

Examples of the "aryl" of the "optionally substituted aryl" in R ^{21 to} R ²⁸ include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 16 carbon atoms, and 6 to 12 carbon atoms. Aryl is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of "aryl" include phenyl, which is a monocyclic system, biphenylyl, which is a bicyclic system, naphthyl, which is a condensed bicyclic system, and terfenylyl, which is a tricyclic system (m-terphenylyl, o-terphenylyl, p-terphenylyl). , Condensed tricyclics such as acenaftyrenyl, fluorenyl, phenylenyl, phenylentrenyl, condensed tetracyclics triphenylenyl, pyrenyl, naphthacenyl, condensed pentacyclics perylenyl, pentasenyl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" in R ^{21 to} R ²⁸ include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and carbon. Heteroaryls having a number of 2 to 20 are more preferable, heteroaryls having 2 to 15 carbon atoms are further preferable, and heteroaryls having 2 to 10 carbon atoms are particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific "heteroaryl" includes, for example, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, indrill, isoindrill, 1H-. Indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl, pteridinyl, carbazolyl, acridinyl, phenoxatinyl, phenoxadinyl, phenoxadinyl Examples thereof include phenazinyl, indridinyl, frill, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo [b] thienyl, dibenzothienyl, frazanyl, oxadiazolyl, thiantranyl, naphthobenzofuranyl and naphthobenzothienyl.

Examples of the “alkoxy” of the “optionally substituted alkoxy” in R ^{21 to} R ²⁸ include a straight-chain alkoxy having 1 to 24 carbon atoms or a branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (alkoxy of branched chains having 3 to 18 carbon atoms) is preferable, and alkoxy having 1 to 12 carbon atoms (alkoxy of branched chains having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms is more preferable. Alkoxy (alkoxy of a branched chain having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 4 carbon atoms (alkoxy of a branched chain having 3 to 4 carbon atoms) is particularly preferable.

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 the "optionally substituted aryloxy" in R ^{21 to} R ²⁸ is a group in which the hydrogen of the -OH group is substituted with an aryl, and this aryl is used in R ^{21 to} R ²⁸ described above. The group described as "aryl" can be cited.

The "arylthio" of the "optionally substituted arylthio" in R ^{21 to} R ²⁸ is a group in which the hydrogen of the -SH group is substituted with an aryl, and this aryl is the "aryl" in ^{R 21 to} R ^{28 described above.} Can be quoted as the group described as.

Examples of the "trialkylsilyl" in R ^{21 to R 28} include groups in which the three hydrogens in the silyl group are independently substituted with alkyl, and this alkyl is referred to as the "alkyl" in ^{R 21 to} R ^{28 described above.} The groups described can be quoted. The alkyl preferred for substitution is an alkyl having 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl and cyclobutyl.

Specific "trialkylsilyl" includes trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl. Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropyl silyl, ethyl dipropyl silyl, butyl dipropyl silyl, sec-butyl dipropyl silyl, t-butyl dipropyl silyl, methyl di-propyl silyl, ethyl di-propyl silyl, butyl di-propyl silyl, sec-butyl di i -Propylsilyl, t-butyldii-propylsilyl and the like can be mentioned.

Examples of the "tricycloalkylsilyl" in R ^{21 to R 28} include groups in which the three hydrogens in the silyl group are independently substituted with cycloalkyl, and this cycloalkyl is the above-mentioned "tricycloalkylsilyl" in R ^{21 to} R ²⁸ . The group described as "cycloalkyl" can be cited. 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] Hexil, Bicyclo [2.1.2] Heptyl, Bicyclo [2.2.2] Octyl, Adamantyl, Examples thereof include decahydronaphthalenyl and decahydroazurenyl.

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

Specific examples of the dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and the alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls are selected from the specific alkyls and cycloalkyls described above. Examples thereof include silyl in which the group to be substituted is substituted.

Examples of the "substituted amino" of the "optionally substituted amino" in R ^{21 to} R ^{28 include an amino group in which two hydrogens are substituted with aryl or heteroaryl.} Aminos in which two hydrogens are substituted with aryls are diaryl substituted aminos, aminos in which two hydrogens are substituted with heteroaryls are diheteroaryl substituted aminos, and aminos in which two hydrogens are substituted with aryls and heteroaryls. Is an aryl heteroaryl substituted amino. As the aryl or heteroaryl, the groups described as "aryl" or "heteroaryl" in ^{R 21 to} R ^{28 described above can be cited.}

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

Examples of the "halogen" in R ^{21 to} R ²⁸ include fluorine, chlorine, bromine and iodine.

Among the groups described as R ^{21 to} R ²⁸ , some may be substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl or heteroaryl. The alkyl, cycloalkyl, aryl or heteroaryl can be cited as the groups described above as "alkyl", "cycloalkyl", "aryl" or "heteroaryl" in ^{R 21-} R ^28.

R ²⁹ in the "> N-R ^29" as Y is hydrogen or aryl which may be substituted, be cited a group described as the "aryl" in R ²¹ to R ²⁸ described above as the aryl As the substituent, the group described as the substituent for ^{R 21 to} R ^{28 can be cited.}

Adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. The case where the ring is not formed is the group represented by the following formula (A-1), and the case where the ring is formed is, for example, the group represented by the following formulas (A-2) to (A-14). Be done. In addition, at least one hydrogen in the group represented by any of formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl,. It may be substituted with tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl substituted amino, diheteroaryl substituted amino, aryl heteroaryl substituted amino, halogen, hydroxy or cyano.

Examples of the ring formed by bonding adjacent groups to each other include a cyclohexane ring in the case of a hydrocarbon ring, and "aryl" and "heteroaryl" in ^{R 21 to} R ^{28 described above as an aryl ring and a heteroaryl ring.} , And these rings are formed so as to condense 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 of the above formulas (A-1) to (A-14), and the above formulas (A-1) to (A-14). −5) and the group represented by any of the formulas (A-12) to (A-14) are preferable, and the group represented by any of the above formulas (A-1) to (A-4) is preferable. Is more preferable, and the group represented by any one of the above formula (A-1), the formula (A-3) and the above formula (A-4) is further preferable, and the group represented by the above formula (A-1) is more preferable. Especially preferable.

The group represented by the formula (A) is a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), and a formula in * in the formula (A). ^{As described above, it binds to Ar 3} in (3-X3) and replaces it with at least one hydrogen in the compound represented by the formula (3), but among these binding forms, the formula (3-X1) Alternatively, a form in which the naphthalene ring in the formula (3-X2), the single bond in the formula (3-X3) and / or the Ar ³ in the formula (3-X3) is bonded is preferable.

Further, in the structure of the group represented by the formula (A), the naphthalene ring in the formula (3-X1) or the formula (3-X2), the single bond in the formula (3-X3), and the formula (3-X3). ) Ar ³ is bonded position in, also, the formula (in the structure of groups in represented by a), substituted position with at least one hydrogen in the compound represented by formula (3) has the formula (a) It may be at any position in the structure of, for example, any of the two benzene rings in the structure of formula (A) or adjacent groups ^{of R 21 to} R ^{28 in the structure of formula (A).} It can be bonded at any ring formed by bonding with each other or at any position in R ^{29 in "> N-R 29" as Y in the structure of the formula (A).}

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

Further, all or part of the hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be deuterium.

Specific examples of the anthracene-based compound include compounds represented by the following formulas (3-1) to (3-72). In the following structural formula, "Me" indicates a methyl group, "D" indicates a deuterium, and "tBu" indicates a t-butyl group.

The anthracene-based compound represented by the formula (3) includes a compound having a reactive group at a desired position in the anthracene skeleton and a compound having a reactive group in a partial structure such as the structure of ^{X, Ar 4 and the formula (A).} Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using the above as a starting material. Examples of the reactive group of these reactive compounds include halogen and boronic acid. As a specific production method, for example, the synthesis method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 can be referred to.

<Fluorene compounds>
The compound represented by the general formula (4) basically functions as a host.

In the above formula (4),
R ¹ to R ¹⁰ are independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the above formula (4) via a linking group), diarylamino, and dihetero. Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
In addition, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are independently combined. It may form a fused ring or a spiro ring, and at least one hydrogen in the formed ring may be aryl or heteroaryl (the heteroaryl may be bonded to the formed ring via a linking group). ), Diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen is aryl, heteroaryl, alkyl or cycloalkyl. May be replaced with, and
At least one hydrogen in the compound represented by the formula (4) may be substituted with halogen, cyano or deuterium.

For the details of each group in the definition of the above formula (4), the above-mentioned description of the polycyclic aromatic compound of the formula (1) can be cited.

Examples of the alkenyl in R ¹ to R ¹⁰ include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and having 2 to 6 carbon atoms. Alkenyl is more preferable, and alkenyl having 2 to 4 carbon atoms is particularly preferable. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl.

式（４−Ａｒ１）から式（４−Ａｒ５）中、Ｙ^１は、それぞれ独立して、Ｏ、ＳまたはＮ−Ｒであり、Ｒはフェニル、ビフェニリル、ナフチル、アントラセニルまたは水素であり、
上記式（４−Ａｒ１）から式（４−Ａｒ５）の構造における少なくとも１つの水素はフェニル、ビフェニリル、ナフチル、アントラセニル、フェナントレニル、メチル、エチル、プロピル、または、ブチルで置換されていてもよい。As a specific example of the heteroaryl, any one from the compounds of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) A monovalent group represented by excluding one hydrogen atom can also be mentioned.

Wherein (4-Ar5) from equation (4-Ar1), ^{Y 1} are each independently, O, S or N-R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structure of the above formulas (4-Ar1) to (4-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.

These heteroaryls may be bound to the fluorene skeleton in the above formula (4) via a linking group. That is, not only the fluorene skeleton in the formula (4) and the heteroaryl may be directly bonded, but also they may be bonded via a linking group. Examples of the linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, and -OCH ₂ CH ₂ O-.

^{Further, R 1} and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ or R ⁷ and R ⁸ in the equation (4) are independently combined. The fused ring may ^{be bonded to R 9} and R ¹⁰ to form a spiro ring. The ^{condensed ring formed by R 1} to R ⁸ is a ring condensed with the benzene ring in the formula (4), and is an aliphatic ring or an aromatic ring. It is preferably an aromatic ring, and examples of the structure including the benzene ring in the formula (4) include a naphthalene ring and a phenanthrene ring. The ^{spiro ring formed by R 9} and R ¹⁰ is a ring spiro-bonded to the 5-membered ring in the formula (4), and is an aliphatic ring or an aromatic ring. It is preferably an aromatic ring, and examples thereof include a fluorene ring.

The compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2) or formula (4-3), and each of them is represented by the general formula (4). ), The compound in which the benzene ring formed by combining ^{R 1} and R ^{2 is condensed, the compound in which the benzene ring formed by combining R 3} and R ⁴ in the general formula (4) is condensed, and the general formula (4). a compound either is not bound from R ¹ R ⁸ is in).

^{The definitions of R 1} to R ¹⁰ in Eqs. (4-1), Eq. (4-2) and Eq. (4-3) are the same as the ^{corresponding R 1} to R ¹⁰ in Eq. (4), and Eq. (4-4). ^{The definitions of R 11} to R ¹⁴ in 1) and equation (4-2) are the same as those ^{of R 1} to R ¹⁰ in equation (4).

The compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A) or formula (4-3A), respectively. -1), in formula (4-1) or formula (4-3), R ⁹ and R ¹⁰ are combined to form a spiro-fluorene ring.

^{The definitions of R 2} to R ^{7 in} the formula (4-1A), the formula (4-2A) and the formula (4-3A) are in the formula (4-1), the formula (4-2) and the formula (4-3). corresponding the same from ^{R 2} and ^{R 7, R} in the formula also defined formula (4-1) of the ^{R 14} from ^{R 11} in (4-1A) and (4-2A) and (4-2) ¹¹ from is the same as ^{R 14.}

Further, the hydrogen in the compound represented by the formula (4) may be entirely or partially substituted with halogen, cyano or deuterium.

<Dibenzochrysene compounds>
The dibenzochrysene compound as a host is, for example, a compound represented by the following general formula (5).

In the above formula (5),
R ¹ to R ¹⁶ are independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzoglycene skeleton in the above formula (5) via a linking group), diarylamino, and di. Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
Further, ^{adjacent groups of R 1} to R ¹⁶ may be bonded to each other to form a fused ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl is via a linking group). It may be attached to the formed ring), and may be substituted with diallylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, at least in these. One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound represented by the formula (5) may be substituted with halogen, cyano or deuterium.

For the details of each group in the definition of the above formula (5), the above-mentioned description of the polycyclic aromatic compound of the formula (1) can be cited.

Examples of the alkenyl in the definition of the above formula (5) include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to 2 carbon atoms. The alkenyl of 6 is more preferable, and the alkenyl having 2 to 4 carbon atoms is particularly preferable. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl.

式（５−Ａｒ１）から式（５−Ａｒ５）中、Ｙ^１は、それぞれ独立して、Ｏ、ＳまたはＮ−Ｒであり、Ｒはフェニル、ビフェニリル、ナフチル、アントラセニルまたは水素であり、
上記式（５−Ａｒ１）から式（５−Ａｒ５）の構造における少なくとも１つの水素はフェニル、ビフェニリル、ナフチル、アントラセニル、フェナントレニル、メチル、エチル、プロピル、または、ブチルで置換されていてもよい。As a specific example of the heteroaryl, any one from the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) A monovalent group represented by excluding one hydrogen atom can also be mentioned.

Wherein (5-Ar5) from equation (5-Ar1), ^{Y 1} are each independently, O, S or N-R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structure of the above formulas (5-Ar1) to (5-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.

These heteroaryls may be attached to the dibenzochrysene skeleton in the above formula (5) via a linking group. That is, not only the dibenzochrysene skeleton in the formula (5) and the heteroaryl may be directly bonded, but also they may be bonded via a linking group. Examples of the linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, and -OCH ₂ CH ₂ O-.

The compound represented by the general formula (5) is preferably R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ are hydrogen. ^{In this case, R 2} , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in the formula (5) are independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl and phenanthrenyl, respectively. , A monovalent group having the structure of the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (1 having the structure). The valence group is phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O- via the above formula (5). (May be bound to the dibenzoglycene skeleton in), methyl, ethyl, propyl, or butyl is preferred.

The compounds represented by the general formula (5) are more preferably R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R. ¹⁶ is hydrogen. In this case, at least one (preferably one or two, more preferably one) ^{of R 3} , R ⁶ , R ¹¹ and R ^{14 in the formula (5) is a single bond, phenylene, biphenylene, naphthylene,.} The above formulas (5-Ar1), formulas (5-Ar2), and formulas via anthrasenylene, methylene, ethylene, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, or -OCH ₂ CH _{2 O-.} (5-Ar3), a monovalent group having the structure of formula (5-Ar4) or formula (5-Ar5).
Other than the at least one (that is, other than the position where the monovalent group having the structure is substituted) is hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, and at least one of these. Hydrogen may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.

Further, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in the formula (5) are represented by the above formulas (5-Ar1) to (5-Ar5). When a monovalent group having such a structure is selected, at least one hydrogen in the structure ^{may be bonded to any of R 1} to R ^{16 in} the formula (5) to form a single bond. ..

<Pyrene compound>
The pyrene-based compound as a host is, for example, a compound represented by the following general formula (6).

In the above formula (6),
The s pyrene portions and the p Ar portions are combined at any position of * and any position of the Ar portion of the pyrene portion.
At least one hydrogen in the pyrene moiety is independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, and a carbon number of carbon atoms. It may be substituted with 2 to 30 alkenyl, 1 to 30 carbon alkoxy or 6 to 30 carbon aryloxy, in which at least one hydrogen is independently an aryl with 6 to 10 carbons. , Heteroaryl with 2 to 11 carbon atoms, alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 24 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms or aryl with 6 to 30 carbon atoms. May be replaced with oxy
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 independently an aryl having 6 to 10 carbon atoms and having 6 to 10 carbon atoms. Replaced with 2-11 heteroaryl, 1-30 carbon alkyl, 3-24 carbon cycloalkyl, 2-30 carbon alkenyl, 1-30 carbon alkoxy or 6-30 carbon aryloxy May have been
s and p are independently integers of 1 or 2, s and p cannot be 2 at the same time, and when s is 2, the two pyrene moieties are structurally identical, including substituents. Or different, and if p is 2, the two Ar moieties may be structurally identical or different, including the substituents, and
At least one hydrogen in the compound represented by the formula (6) may be independently substituted with halogen, cyano or deuterium.

For the details of each group in the definition of the above formula (6), the above-mentioned description of the polycyclic aromatic compound of the formula (1) can be cited.

Examples of the alkenyl include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and further preferably alkenyl having 2 to 6 carbon atoms. , Alkenyl having 2 to 4 carbon atoms is particularly preferable. Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl.

式（６−Ａｒ１）から式（６−Ａｒ５）中、Ｙ^１は、それぞれ独立して、＞Ｏ、＞Ｓまたは＞Ｎ−Ｒであり、当該Ｒはフェニル、ビフェニリル、ナフチル、アントラセニルまたは水素であり、
上記式（６−Ａｒ１）から式（６−Ａｒ５）の構造における少なくとも１つの水素はフェニル、ビフェニリル、ナフチル、アントラセニル、フェナントレニル、メチル、エチル、プロピル、または、ブチルで置換されていてもよい。As a specific example of the heteroaryl, a monovalent having the structure of the following formula (6-Ar1), formula (6-Ar2), formula (6-Ar3), formula (6-Ar4) or formula (6-Ar5). The basis of is also given.

Wherein (6-Ar1) from equation (6-Ar5), ^{Y 1} are each independently>O,> S or> N-R, the R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen can be,
At least one hydrogen in the structure of the above formulas (6-Ar1) to (6-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.

These heteroaryls may be bonded to the pyrene moiety in the above formula (6) via a linking group. That is, not only the pyrene moiety in the formula (6) and the heteroaryl may be directly bonded, but also they may be bonded via a linking group. Examples of the linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, and -OCH ₂ CH ₂ O-.

The above-mentioned materials for the light emitting layer (host material and dopant material) are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a main chain. A pendant type polymer compound obtained by reacting a type polymer with the above-mentioned reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for a light emitting layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Example of polymer host material>

In the formula (SPH-1)
MU is an independently divalent aromatic compound, EC is an independently monovalent aromatic compound, two hydrogens in the MU are replaced with EC or MU, and k is an integer of 2 to 50,000. be.

More specifically
The MUs are arylene, heteroarylene, dialylene arylamino, dialylene arylboryl, oxaborin-diyl, and azaborin-diyl, respectively.
ECs are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, respectively.
At least one hydrogen in MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl and cycloalkyl.
k is an integer of 2 to 50,000.
k is preferably an integer of 20 to 50,000, and more preferably an integer of 100 to 50,000.

At least one hydrogen in MU and EC in the formula (SPH-1) may be substituted with an alkyl having 1 to 24 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, a halogen or deuterium, and further described above. arbitrary -CH ₂ in the alkyl - is -O- or -Si _{(CH 3) 2} - may be substituted with the formula in the alkyl (SPH-1) -CH connected directly to the EC of ₂ - Any −CH ₂ − except for may be substituted with an arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.

Examples of the MU include a divalent group represented by removing any two hydrogen atoms from any of the following compounds.

More specifically, a divalent group represented by any of the following structures can be mentioned. In these, the MU binds to another MU or EC at *.

Further, as the EC, for example, a monovalent group represented by any of the following structures can be mentioned. In these, EC binds to MU at *.

The compound represented by the formula (SPH-1) has an alkyl having 1 to 24 carbon atoms in which 10 to 100% of the total number of MUs (k) in the molecule has an alkyl having 1 to 24 carbon atoms from the viewpoint of solubility and coating film forming property. More preferably, 30 to 100% of the total number of MUs (k) in the molecule has an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms), and the total number of MUs in the molecule ( It is more preferable that 50 to 100% of MU of k) has an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10 to 100% of the total number of MUs (k) in the molecule has an alkyl having 7 to 24 carbon atoms, and the total number of MUs in the molecule (k). ), It is more preferable that 30 to 100% of the MU has an alkyl having 7 to 24 carbon atoms (branched chain alkyl having 7 to 24 carbon atoms).

Details of the uses of such polymer compounds and crosslinked polymers will be described later.

The polycyclic aromatic compound represented by the general formula (1) can also be used as a composition for forming a light emitting layer together with an organic solvent. The composition contains at least one polycyclic aromatic compound as the first component, at least one host material as the second component, and at least one organic solvent as the third component. The first component functions as a dopant component of the light emitting layer obtained from the composition, and the second component functions as a host component of the light emitting layer. The third component functions as a solvent that dissolves the first component and the second component in the composition, and at the time of application, the third component itself gives a smooth and uniform surface shape by the controlled evaporation rate of the third component itself.

<Organic solvent>
The composition for forming a light emitting layer contains at least one kind of organic solvent as a third component. By controlling the evaporation rate of the organic solvent at the time of film formation, it is possible to control and improve the film forming property, the presence or absence of defects in the coating film, the surface roughness, and the smoothness. Further, at the time of film formation using the inkjet method, the meniscus stability at the pinhole of the inkjet head can be controlled, and the ejection property can be controlled / improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and life of the organic EL device having the light emitting layer obtained from the light emitting layer forming composition can be improved. Can be done.

(1) Physical Properties of Organic Solvent In the third component, the boiling point of at least one organic solvent is 130 ° C. to 300 ° C., more preferably 140 ° C. to 270 ° C., still more preferably 150 ° C. to 250 ° C. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of inkjet ejection property. Further, when the boiling point is lower than 300 ° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent and smoothness. The third component is more preferably composed of two or more kinds of organic solvents from the viewpoint of good inkjet ejection property, film forming property, smoothness and low residual solvent. On the other hand, in some cases, the composition may be in a solid state by removing the solvent from the composition for forming a light emitting layer in consideration of transportability and the like.

Further, the third component comprises a good solvent (GS) and poor solvent (PS) for the host material of the second component, the good boiling _{(BP PS} solvent boiling (GS) _{(BP GS)} is a poor solvent (PS) ) Is lower, the configuration is particularly preferred.
By adding the poor solvent having a high boiling point, the good solvent having a low boiling point volatilizes first at the time of film formation, and the concentration of the inclusion in the composition and the concentration of the poor solvent increase, and rapid film formation is promoted. As a result, a coating film having few defects, a small surface roughness, and high smoothness can be obtained.

Differential solubility _(S GS _{-S PS)} is preferably 1% or more, more preferably 3% or more, more preferably 5% or more. The difference in boiling points (BP _PS- BP _GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably 50 ° C. or higher.

After the film formation, the organic solvent is removed from the coating film by a drying step such as vacuum, reduced pressure, and heating. When heating is performed, it is preferable to perform it at the glass transition temperature (Tg) of the first component + 30 ° C. or lower from the viewpoint of improving the coating film forming property. From the viewpoint of reducing the residual solvent, it is preferable to heat the first component at the glass transition point (Tg) of −30 ° C. or higher. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(2) Specific Examples of Organic Solvents Examples of the organic solvent used in the composition for forming a light emitting layer include an alkylbenzene solvent, a phenyl ether solvent, an alkyl ether solvent, a cyclic ketone solvent, an aliphatic ketone solvent, and a monocyclic solvent. Examples thereof include a ketone solvent, a solvent having a diester skeleton, and a fluorine-containing solvent. Specific examples thereof include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, and the like. Heptane-2-ol, octane-2-ol, decan-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol Dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene , O-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoro Anisol, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mecitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Anisol, phenetol, benzodioxol, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methyl Anisole, Simene, 1,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, Decalin (decahydronaphthalene), neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, benzoic acid Methyl, isopentylbenzene, 3,4-dimethylanisole, o-tornitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene , 1-Methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-bitril, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydro Benzofuran, 1-methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) ) Benzene, 1-methyl-4- (heptyloxymethyl) benzenebenzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether and the like, but are not limited thereto. Further, the solvent may be used alone or may be mixed.

<Arbitrary ingredient>
The composition for forming a light emitting layer may contain an arbitrary component as long as its properties are not impaired. Examples of the optional component include a binder, a surfactant and the like.

(1) Binder The composition for forming a light emitting layer may contain a binder. The binder forms a film at the time of film formation and joins the obtained film to the substrate. It also plays a role in dissolving, dispersing and binding other components in the light emitting layer forming composition.

Examples of the binder used in the composition for forming a light emitting layer include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, and the like. Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile -Styrene copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymers of the above resins and polymers, but are not limited thereto.

The binder used in the composition for forming a light emitting layer may be only one kind or a mixture of a plurality of kinds may be used.

(2) Surfactant The light-emitting layer-forming composition contains, for example, a surfactant for controlling the film surface uniformity, the solvent-like property and the liquid-repellent property of the film surface of the light-emitting layer-forming composition. May be good. Surfactants are classified into ionic and nonionic based on the structure of hydrophilic groups, and further classified into alkyl-based, silicon-based and fluorine-based based on the structure of hydrophobic groups. Further, from the molecular structure, it is classified into a monomolecular system having a relatively small molecular weight and a simple structure and a polymer system having a large molecular weight and having side chains and branches. Further, it is classified into a single system, a mixed system in which two or more kinds of surfactants and a base material are mixed, according to the composition. As the surfactant that can be used in the light emitting layer forming composition, all kinds of surfactants can be used.

Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181 and Disperbake. Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Futagent 222F, Futergent 251 and FTX-218 (trade name) Product name, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Product name, manufactured by Mitsubishi Materials Co., Ltd.), Megafuck F- 470, Mega Fuck F-471, Mega Fuck F-475, Mega Fuck R-08, Mega Fuck F-477, Mega Fuck F-479, Mega Fuck F-553, Mega Fuck F-554 (trade name, DIC Co., Ltd.) ), Fluoroalkylbenzene sulfonate, Fluoralkyl carboxylate, Fluoroalkyl polyoxyethylene ether, Fluoroalkyl ammonium iodide, Fluoroalkyl betaine, Fluoroalkyl sulfonate, Diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether) ), Fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Steerate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polio Examples thereof include xyethylene naphthyl ether, alkylbenzene sulfonate and alkyldiphenyl ether disulfonate.

Further, the surfactant may be used alone or in combination of two or more.

<Composition and physical properties of composition for forming a light emitting layer>
The content of each component in the light emitting layer forming composition is obtained from the good solubility, storage stability and film forming property of each component in the light emitting layer forming composition, and the light emitting layer forming composition. Good film quality of the coating film, good ejection property when the inkjet method is used, and good electrical characteristics, light emission characteristics, efficiency, and life of an organic EL element having a light emitting layer produced by using the composition. From the viewpoint of, the first component is 0.0001% by weight to 2.0% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. It is preferably 0.0999% by weight to 8.0% by weight, and the third component is 90.0% by weight to 99.9% by weight with respect to the total weight of the composition for forming a light emitting layer.

More preferably, the first component is 0.005% by weight to 1.0% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The third component is 0.095% by weight to 4.0% by weight, and the third component is 95.0% by weight to 99.9% by weight based on the total weight of the composition for forming a light emitting layer. More preferably, the first component is 0.05% by weight to 0.5% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The third component is 0.25% by weight to 2.5% by weight, and the third component is 97.0% by weight to 99.7% by weight based on the total weight of the composition for forming a light emitting layer.

The composition for forming a light emitting layer can be produced by appropriately selecting the above-mentioned components by a known method such as stirring, mixing, heating, cooling, dissolving, and dispersing. Further, after the preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment and the like may be appropriately selected.

As the viscosity of the light emitting layer forming composition, the higher the viscosity, the better the film forming property and the good ejection property when the inkjet method is used. On the other hand, the lower the viscosity, the easier it is to form a thin film. From this, the viscosity of the light emitting layer forming composition is preferably 0.3 mPa · s to 3 mPa · s at 25 ° C., and more preferably 1 mPa · s to 3 mPa · s. In the present invention, the viscosity is a value measured using a conical flat plate type rotational viscometer (cone plate type).

The lower the surface tension of the light emitting layer forming composition, the better the film forming property and the coating film without defects. On the other hand, the higher the value, the better the inkjet ejection property. From this, the viscosity of the light emitting layer forming composition preferably has a surface tension of 20 mN / m to 40 mN / m at 25 ° C., and more preferably 20 mN / m to 30 mN / m. In the present invention, the surface tension is a value measured by using the suspension method.

<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 the electrons injected from the cathode 108 or the 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 laminating and mixing one or more of the electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder, respectively.

The electron injection / transport layer is a layer in which electrons are injected from the cathode and is in charge of further transporting electrons, and it is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For that purpose, it is preferable that the substance has a high electron affinity, a high electron mobility, excellent stability, and is less likely to generate trap impurities during production and use. However, when considering the transport balance between holes and electrons, the electron transport capacity is so high when it mainly plays a role of efficiently blocking the holes from the anode from flowing to the cathode side without recombination. Even if it is not high, it has the same effect of improving luminous efficiency as a material having high electron transport capacity. Therefore, the electron injection / transport layer in the present embodiment may also include a layer function that can efficiently block the movement of holes.

As the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, it is used for a compound conventionally used as an electron transfer compound in a photoconductive material, an electron injection layer and an electron transport layer of an organic EL element. It can be arbitrarily selected and used from the known compounds known.

The material used for the electron transport layer or the electron injection layer is a compound composed of an aromatic ring or a complex aromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus. It preferably contains at least one selected from a pyrrole derivative, a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, fused ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives typified by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , Kinone derivatives such as anthraquinone and diphenoquinone, phosphoroxide derivatives, carbazole derivatives and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, flavonol metal complex and benzoquinoline metal complex. These materials may be used alone, but may be mixed 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 oxadiasols. 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.), thiazazole derivatives, oxine derivative metal complexes, quinolinol-based metal complexes, quinoxalin derivatives, quinoxalin derivative polymers, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorophenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinolins Derivatives (2,2'-bis (benzo [h] quinoline-2-yl) -9,9'-spirobifluorene, etc.), imidazole pyridine derivatives, borane derivatives, benzoimidazole derivatives (tris (N-phenylbenzoimidazole-) 2-yl) benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as telpyridine, bipyridine derivatives, telpyridine derivatives (1,3-bis (4'-(2,2': 6'2)) "-Terpyridinyl)) benzene, etc.), naphthylidine derivatives (bis (1-naphthyl) -4- (1,8-naphthylidine-2-yl) phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indol derivatives, phosphoroxide derivatives , Bistylyl derivatives and the like.

Further, a metal complex having electron-accepting nitrogen can also be used. For example, hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinolin metal complexes can be used. can give.

The above-mentioned materials may be used alone, but may be mixed with different materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol metals Derivatives 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), and is disclosed in detail in JP-A-2007-27587.

In the above formula (ETM-1), R ¹¹ and R ¹² each independently contain hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, and optionally substituted nitrogen. At least one of the heterocycle or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. Yes, X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boron, or an optionally substituted carbazolyl, and n is an independently integer of 0 to 3. In addition, examples of the substituent in the case of "may be 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), the compound represented by the following general formula (ETM-1-1) and the compound represented by the following general formula (ETM-1-2) are preferable.

In formula (ETM-1-1), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. At least one of the containing heterocycles, or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. R ²¹ and R ²² are independently of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. At least one, X ¹ is an arylene having 20 or less carbon atoms which may be substituted, n is an integer of 0 to 3 independently, and m is 0 to 4 independently. Is an integer of. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

In formula (ETM-1-2), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. At least one of the contained heterocycles, or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. X ¹ is an arylene having 20 or less carbon atoms which may be substituted, and n is an integer of 0 to 3 independently. In addition, examples of the substituent in the case of "may be 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 any of the following formulas (X-1) to (X-9).

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

Specific examples of this borane derivative include the following compounds.

This borane derivative can be produced by using a known raw material and a known synthesis method.

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

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

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

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

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

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

The "alkyl" in R ^{11 to} R ¹⁸ may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

Specific "alkyl" includes 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 thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicocil.

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

Examples of the "cycloalkyl" in 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. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms.
Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the ^{"aryl" in R 11 to} R ¹⁸ , the preferred aryl is an aryl having 6 to 30 carbon atoms, the more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms. Yes, particularly preferably an aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, which is a monocyclic aryl, (1-, 2-) naphthyl, which is a fused dicyclic aryl, and acenaphthylene- (which is a condensed tricyclic aryl). 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2) -, 3-, 4-, 9-) phenanthryl, triphenylene- (1-, 2-) yl, which is a fused tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 1-) , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl and the like. ..

Preferred "aryls having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl, triphenylenyl and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, and particularly preferably phenyl, 1 -Naphtyl or 2-naphthyl can be mentioned.

^{R 11} and R ¹² in the above formula (ETM-2-2) may be combined to form a ring, and as a result, the 5-membered ring of the fluorene skeleton has cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, etc. 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 by using a known raw material and a known synthesis method.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

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 a heteroaryl. Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Specific examples of this fluoranthene derivative include the following compounds.

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

R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these. May be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, ^{adjacent groups of R 1 to} R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen 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.

Further, at least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.

Regarding the description of the substituent and the form of ring formation in the formula (ETM-4), the description of the polycyclic aromatic compound represented by the general formula (1) and its multimer can be cited.

Specific examples of this BO-based derivative include the following compounds.

This BO-based derivative can be produced by using a known raw material and a known synthesis method.

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

Ar is independently divalent benzene or naphthalene, and R ^{1 to} R ⁴ are independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or carbon number of carbons, respectively. 6 to 20 aryls.

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

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

The alkyl having 1 to 6 carbon atoms in R ^{1 to} R ⁴ may be either a straight chain or a branched chain. That is, it is a straight chain alkyl having 1 to 6 carbon atoms or a branched chain alkyl having 3 to 6 carbon atoms. More preferably, it is an alkyl having 1 to 4 carbon atoms (branched chain 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, Examples thereof include 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. , Methyl, ethyl, or t-butyl is more preferred.

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

Regarding the aryl having 6 to 20 carbon atoms in R ^{1 to} R ^4, the aryl having 6 to 16 carbon atoms is preferable, the aryl having 6 to 12 carbon atoms is more preferable, and the aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of "aryls having 6 to 20 carbon atoms" include phenyl, which is a monocyclic aryl, (o-, m-, p-) trill, and (2,3-,2,4-,2,5-). , 2,6-, 3,4-, 3,5-) xsilyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2) -, 3-, 4-) Biphenylyl, fused bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) '-Il, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -Il, 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, anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) aryl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-) 2-, 3-, 4-, 9-) phenanthryl, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1) -, 2-, 5-) yl, perylene- (1-, 2-, 3-) yl, which is a fused pentacyclic aryl, and the like can be mentioned.

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

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

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

Ar ² is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphtylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

R ^{1 to} R ⁴ are independently hydrogen, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 20 carbon atoms, respectively, according to the above formula (ETM-5-1). The explanation 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>
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Ar ¹ is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphtylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

Ar ² is 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 form a ring.

The "alkyl" in Ar ² 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. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific "alkyl" includes 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 can be mentioned.

Examples of the "cycloalkyl" in Ar ² include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms. Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As ^{the "aryl" in Ar 2} , the preferred aryl is an aryl having 6 to 30 carbon atoms, the more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms, particularly. It is preferably an aryl having 6 to 12 carbon atoms.

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

Two Ar ² may form a ring, as a result, the 5-membered ring of the fluorene skeleton, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-linked You may.

Specific examples of this benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced by using a known raw material and a known synthetic method.

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３〜１６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３〜１６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>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/07927.

R ⁵ is a substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl, heteroaryl aryl or 5 to 20 carbon atoms of 6 to 20 carbon atoms 3 to 16 carbon atoms,
R ⁶ is CN, substituted or unsubstituted, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and 5 to 5 carbon atoms. 20 heteroaryl, alkoxy with 1 to 20 carbons or aryloxy with 6 to 20 carbons.
R ⁷ and R ⁸ are independently substituted or unsubstituted aryls having 6 to 20 carbon atoms or heteroaryls having 5 to 20 carbon atoms, respectively.
R ⁹ is oxygen or sulfur
j is 0 or 1, k is 0 or 1, r is an integer from 0 to 4, and q is an integer from 1 to 3.
Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

The 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, and 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 in the fused ring formed between adjacent substituents. Is selected from.

Ar ¹ may be the same or different and is an arylene or heteroarylene group. 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 fused ring with an adjacent substituent. n is an integer from 0 to 3, and when n is 0, the unsaturated structure portion does not exist, and when n is 3, R ¹ does not exist.

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

Further, the cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may be unsubstituted or substituted. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is usually in the range of 3 to 20.

Further, the aralkyl group indicates 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 are substituted without substitution. It doesn't matter. The carbon number of the aliphatic portion is not particularly limited, but is usually in the range of 1 to 20.

The alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may be unsubstituted or substituted. The carbon number of the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.

Further, the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexene group, etc., which may be unsubstituted or substituted. It doesn't matter.

Further, the alkynyl group refers to an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted. The carbon number of the alkynyl group is not particularly limited, but is usually in the range of 2 to 20.

Further, the alkoxy group indicates, 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. The number of carbon atoms of the alkoxy group is not particularly limited, but is usually in the range of 1 to 20.

The alkylthio group is a group in which the oxygen atom of the ether bond of the alkoxy group is replaced with a sulfur atom.

The cycloalkylthio group is a group in which the oxygen atom of the ether bond of the cycloalkoxy group is replaced with a sulfur atom.

Further, the aryl ether group indicates, 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. The number of carbon atoms of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

The arylthioether group is a group in which the oxygen atom of the ether bond of the arylether group is replaced with a sulfur atom.

Further, the aryl group indicates, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group and a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbon atoms of the aryl group is not particularly limited, but is usually in the range of 6 to 40.

Further, the heterocyclic group indicates a cyclic structural group having an atom other than carbon such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group and a carbazolyl group, which are substituted even if they are not substituted. It doesn't matter. The number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen refers to fluorine, chlorine, bromine, and iodine.

The aldehyde group, carbonyl group, and amino group can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

Further, the aliphatic hydrocarbon, the alicyclic hydrocarbon, the aromatic hydrocarbon, and the heterocycle may be substituted or substituted.

The silyl group refers to a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The carbon number of the silyl group is not particularly limited, but is usually in the range of 3 to 20. The number of silicon is usually 1 to 6.

The fused rings formed between the 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 , and Ar ¹ . It is a conjugated or non-conjugated fused ring formed between Ar ^{2 and the like.} Here, when n is 1, may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These fused rings may contain nitrogen, oxygen, and sulfur atoms 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 by using a known raw material and a known synthetic method.

<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.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific "aryls" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , 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 aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (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), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl. ) Il, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include 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 preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of the heteroaryl include frill, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and may be substituted with, for example, the above-mentioned aryl and heteroaryl, respectively.

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced by using a known raw material and a known synthetic method.

<Carbazole derivative>
The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which a plurality of the compounds are bound by a single bond or the like. Details are described in US Publication No. 2014/0197386.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific "aryl" includes phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , 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, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1 -, 2-) Il, (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), triphenylene- (1-, 2), which is a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include 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 preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthilidinyl, prynyl , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantrenyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and may be substituted with, for example, the above-mentioned aryl and heteroaryl, respectively.

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

Specific examples of this carbazole derivative include the following compounds.

This carbazole derivative can be produced by using a known raw material and a known synthetic method.

<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. 2011/015601.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 1-3, preferably 2 or 3.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific "aryls" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , 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 aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (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), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl. ) Il, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include 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 preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of the heteroaryl include frill, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and may be substituted with, for example, the above-mentioned aryl and heteroaryl, respectively.

Specific examples of this triazine derivative include the following compounds.

This triazine derivative can be produced by using a known raw material and a known synthesis method.

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

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzfluorene ring, phenylene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. In the "benzimidazole-based substituent", 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 that replaces the imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with dehydrogen.

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

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the above formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but when these are replaced with benzoimidazole-based substituents, both are used. The pyridine-based substituent of the above may be replaced with a benzoimidazole-based substituent (that is, n = 2), any one of the pyridine-based substituents may be replaced with a benzoimidazole-based substituent, and the other pyridine-based substituent may be replaced with R ^11. It may be replaced with ~ R ¹⁸ (that is, 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, for example, 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (10-). Naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl-1H-benzazole, 1- (4) -(10- (naphthalen-2-yl) anthracene-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- Examples thereof include phenyl-1H-benzo [d] imidazole and 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole.

This benzimidazole derivative can be produced by using a known raw material and a known synthetic method.

<Phenanthroline derivative>
The 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 an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. be.

^{R 11 to} R ¹⁸ of each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon number 3 to 12). The number 6 to 30 aryl). 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 substituted with deuterium.

Alkyl in R ¹¹ to R ^18, cycloalkyl and aryl may be cited to the description of ^R 11 ^{to R 18} in the formula (ETM-2). Further, in addition to the above-mentioned example, φ can be given, for example, the following structural formula. In addition, R in the following structural formulas is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

Specific examples of this phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-). Phenanthroline-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-bi (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 by using a known raw material and a known synthetic method.

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。<Kinolinol-based metal complex>
The quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).

In the formula, R ^{1 to} R ⁶ are independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, Ga, Be or Zn. n is an integer of 1-3.

Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, and tris (3). , 4-Dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) ( Phenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenorate) aluminum, bis (2-methyl-8- Kinolinolate) (4-methylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-Methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) ( 2,6-Dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,4-dimethylphenorate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-di-t-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) Aluminum, bis ( 2-Methyl-8-quinolinolate) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl -8-quinolinolate) (2,4,5,6-tetramethylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2) -Naftrat) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenylate) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) Latte) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis (2) -Methyl-8-quinolinolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-4-ethyl) -8-Kinolinolate) Aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolate) Aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) Aluminum-μ-oxo-bis (2) -Methyl-4-methoxy-8-quinolinolate) aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2-Methyl-5-trifluoromethyl-8-quinolinolate) Aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) Aluminum, bis (10-hydroxybenzo [h] quinolinate) Berylium and the like can be mentioned.

This quinolinol-based metal complex can be produced by using a known raw material and a known synthesis method.

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 derivative and benzothiazole derivative>
The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).

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

Φ of each formula is an n-valent aryl ring (preferably an 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 The "thiazole-based substituent" and "benzothiazole-based substituent" are the "pyridine-based" in the above formulas (ETM-2), (ETM-2-1) and (ETM-2-2). The pyridyl group in the "substituent" is a substituent in which the following thiazole group or benzothiazole group is replaced, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with dehydrogen.

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the above formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but these are described as thiazole-based substituents (or benzothiazole-based substituents). When substituting with (group), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (that is, n = 2), or any one of the pyridine-based substituents may be replaced with thiazole-based substituents. It may be replaced with a group (or a benzothiazole-based substituent) and the other pyridine-based substituent ^{may be replaced with R 11 to} R ¹⁸ (that is, n = 1). ^{Further, for example, at least one of R 11 to} R ¹⁸ in the above formula (ETM-2-1) is replaced with a thiazole-based substituent (or a benzothiazole-based substituent) to replace the "pyridine-based substituent" with R ^{11 to} R ^18. May be replaced with.

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

The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances are used as long as they have a certain reducing property. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali. 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). Examples thereof include alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) and Ba (2.52 eV), and a substance having a work function of 2.9 eV or less is particularly preferable. Of these, the more preferable reducing substance is an alkali metal 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, the emission brightness and the life of the organic EL device can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more kinds of alkali metals is also preferable, and in particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be improved.

The above-mentioned material for the electron transport injection layer and the material for the electron transport layer are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a main component thereof. A pendant type polymer compound obtained by reacting a chain type polymer with the above-mentioned reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for an electronic layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Cathode in organic electroluminescent device>
The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injecting layer 107 and the electron transporting layer 106.

The material for forming the cathode 108 is not particularly limited as long as it is a substance capable of efficiently injecting electrons into the organic layer, but a material similar to the material for forming the anode 102 can be used. Among them, 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 alloy, magnesium). -Indium alloy, aluminum-lithium alloy such as lithium fluoride / aluminum, etc.) are preferable. In order to improve the electron injection efficiency and the device characteristics, an alloy containing lithium, sodium, potassium, cesium, calcium, magnesium or these low-work function metals is effective. However, these low work function metals are generally often unstable in the atmosphere. In order to improve this point, for example, a method of doping an organic layer with a trace amount of lithium, cesium or magnesium and using a highly stable electrode is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used. However, it is not limited to these.

In addition, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium for electrode protection, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride. , Laminating a hydrocarbon-based polymer compound or the like is given as a preferable example. The method for producing these electrodes is also not particularly limited as long as conduction can be obtained, such as resistance heating, electron beam deposition, sputtering, ion plating and coating.

<Binder that may be used in each layer>
The materials used for the above-mentioned hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer independently, but as a polymer binder, polyvinyl chloride, polycarbonate, etc. Polystyrene, poly (N-vinylcarbazole), polymethylmethacrylate, polybutylmethacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It is also possible to disperse and use it in solvent-soluble resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and curable resin such as silicone resin. be.

<Method of manufacturing organic electroluminescent device>
Each layer constituting the organic EL element is made of a thin film by a method such as a vapor deposition method, a resistance heating vapor deposition, an electron beam vapor deposition, a sputtering, a molecular lamination method, a printing method, a spin coating method or a casting method, or a coating method. By setting, it can be formed. The film 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 type film thickness measuring device or the like. When a thin film is formed by using a thin film deposition method, the vapor deposition conditions differ depending on the type of material, the target crystal structure and association structure of the film, and the like. The vapor deposition conditions are generally: boat heating temperature +50 to + 400 ° C., vacuum degree ^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.

When a DC voltage is applied to the organic EL element thus obtained, the anode may be applied with a positive polarity and the cathode may be applied with a negative polarity, and when a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Emission can be observed from the side (anode or cathode, or both). The organic EL element also emits light when a pulse current or an AC current is applied. The waveform of the alternating current to be applied may be arbitrary.

Next, as an example of a method for producing an organic EL device, an organic EL device composed of an anode / hole injection layer / hole transport layer / light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. The manufacturing method of the above will be described.

<Thin-film deposition method>
A thin film of an anode material is formed on an appropriate 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 on this to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like. By forming the cathode into a cathode, the desired organic EL element can be obtained. In the above-mentioned production of the organic EL element, the production order can be reversed, and 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 can be manufactured in this order. Is.

<Wet film formation method>
The wet film forming method is carried out by preparing a low molecular weight compound capable of forming each organic layer of an organic EL device as a liquid organic layer forming composition and using the same. If there is no suitable organic solvent to dissolve this low molecular weight compound, it is high together with other monomers having a soluble function as a reactive compound in which the low molecular weight compound is substituted with a reactive substituent and a main chain type polymer. A composition for forming an organic layer may be prepared from a molecularized polymer compound or the like.

In the wet film forming method, a coating film is generally formed by a coating step of applying an organic layer forming composition to a substrate and a drying step of removing a solvent from the applied organic layer forming composition. When the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound), it is further crosslinked by this drying step to form a crosslinked polymer. Depending on the difference in the coating process, the method using a spin coater is the spin coating method, the method using the slit coater is the slit coating method, the method using the plate is gravure, offset, reverse offset, the flexographic printing method, and the method using the inkjet printer is the inkjet method. , The method of spraying in the form of mist is called the spray method. The drying step includes methods such as air drying, heating, and vacuum drying. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, different methods may be used in combination, for example, firing under reduced pressure.

The wet film forming method is a film forming method using a solution, and is, for example, a partial printing method (inkjet method), a spin coating method or a casting method, a coating method, or the like. Unlike the vacuum vapor deposition method, the wet film deposition method does not require the use of an expensive vacuum vapor deposition apparatus and can form a film under atmospheric pressure. In addition, the wet film formation method enables a large area and continuous production, leading to a reduction in manufacturing cost.

On the other hand, when compared with the vacuum vapor deposition method, the wet film deposition method may be difficult to laminate. When forming a laminated film using the wet film formation method, it is necessary to prevent the lower layer from being dissolved by the upper layer composition, and the composition with controlled solubility, the lower layer cross-linking and the orthogonal solvent (Orthogonal solvent) dissolve each other. No solvent) etc. are used. However, even if these techniques are used, it may be difficult to use the wet film forming method for coating all the films.

Therefore, in general, a method is adopted in which only a few layers are formed by a wet film forming method and the rest are formed by a vacuum vapor deposition method to produce an organic EL device.

For example, the procedure for manufacturing an organic EL device by partially applying the wet film forming method is shown below.
(Procedure 1) Film formation by vacuum vapor deposition method of anode (Procedure 2) Film formation by wet film formation method of composition for forming hole injection layer containing material for hole injection layer (Procedure 3) Material for hole transport layer Formation of a composition for forming a hole transport layer containing (Procedure 4) Formation of a composition for forming a light emitting layer containing a host material and a dopant material by a wet film formation method (Procedure 5) Electron transport layer (Procedure 6) Film formation by vacuum vapor deposition method of electron injection layer (Procedure 7) Film formation by vacuum vapor deposition method of cathode By going through this procedure, anode / hole injection layer / hole transport An organic EL element composed of a light emitting layer / electron transport layer / electron injection layer / cathode composed of a layer / host material and a dopant material can be obtained.
Of course, there is a means for preventing the dissolution of the light emitting layer of the lower layer, or by using a means for forming a film from the cathode side contrary to the above procedure, a layer including a material for an electron transport layer and a material for an electron injection layer is formed. It can be prepared as a composition for use and deposited by a wet film forming method.

<Other film formation methods>
A laser heating drawing method (LITI) can be used to form a film of the composition for forming an organic layer. LITI is a method in which a compound adhered to a base material is heated and vapor-deposited with a laser, and an organic layer forming composition can be used as a material to be applied to the base material.

<Arbitrary process>
Appropriate treatment steps, cleaning steps, and drying steps may be appropriately added before and after each step of film formation. Examples of the treatment step include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, heat treatment and the like. Furthermore, a series of steps for producing a bank can also be mentioned.

Photolithography technology can be used to create the bank. As the bank material that can be used for photolithography, a positive type resist material and a negative type resist material can be used. Further, a patternable printing method such as an inkjet method, a gravure offset printing, a reverse offset printing, and a screen printing can also be used. In that case, a permanent resist material can also be used.

Materials used for banks include polysaccharides and their derivatives, homopolymers and copolymers of ethylenic monomers with hydroxyls, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, polyetherimides. , Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer polymer (ABS), silicone resin, polyvinyl chloride, chlorine Fluoropolymers such as polyethylene chemicals, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene, fluoroolefin-hydrocarbon olefin copolymer polymer, fluorocarbon polymer, etc. However, it is not limited to that.

<Composition for forming an organic layer used in a wet film formation method>
The composition for forming an organic layer is obtained by dissolving a low molecular weight compound capable of forming each organic layer of an organic EL element or a high molecular weight compound obtained by polymerizing the low molecular weight compound in an organic solvent. For example, the composition for forming a light emitting layer includes a polycyclic aromatic compound (or a polymer compound thereof) which is at least one type of dopant material as a first component, at least one kind of host material as a second component, and a third component. It contains at least one organic solvent as a component. The first component functions as a dopant component of the light emitting layer obtained from the composition, and the second component functions as a host component of the light emitting layer. The third component functions as a solvent that dissolves the first component and the second component in the composition, and at the time of application, the third component itself gives a smooth and uniform surface shape by the controlled evaporation rate of the third component itself.

<Organic solvent>
The composition for forming an organic layer contains at least one kind of organic solvent. By controlling the evaporation rate of the organic solvent at the time of film formation, it is possible to control and improve the film forming property, the presence or absence of defects in the coating film, the surface roughness, and the smoothness. Further, at the time of film formation using the inkjet method, the meniscus stability at the pinhole of the inkjet head can be controlled, and the ejection property can be controlled / improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and life of the organic EL device having the organic layer obtained from the composition for forming the organic layer can be improved. Can be done.

(1) Physical Properties of Organic Solvent The boiling point of at least one organic solvent is 130 ° C. to 300 ° C., more preferably 140 ° C. to 270 ° C., and even more preferably 150 ° C. to 250 ° C. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of inkjet ejection property. Further, when the boiling point is lower than 300 ° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent and smoothness. The organic solvent is more preferably configured to contain two or more kinds of organic solvents from the viewpoint of good inkjet ejection property, film forming property, smoothness and low residual solvent. On the other hand, in some cases, the composition may be in a solid state by removing the solvent from the composition for forming an organic layer in consideration of transportability and the like.

Further, the organic solvent contains a good solvent (GS) and a poor solvent (PS) for at least one of the solutes, and the boiling point (BP _GS ) of the good solvent (GS) is higher than _{the boiling point (BP PS} ) of the poor solvent (PS). Also low, configuration is particularly preferred.
By adding the poor solvent having a high boiling point, the good solvent having a low boiling point volatilizes first at the time of film formation, and the concentration of the inclusion in the composition and the concentration of the poor solvent increase, and rapid film formation is promoted. As a result, a coating film having few defects, a small surface roughness, and high smoothness can be obtained.

Differential solubility _(S GS _{-S PS)} is preferably 1% or more, more preferably 3% or more, more preferably 5% or more. The difference in boiling points (BP _PS- BP _GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably 50 ° C. or higher.

After the film formation, the organic solvent is removed from the coating film by a drying step such as vacuum, reduced pressure, and heating. When heating is performed, it is preferable to perform heating at a glass transition temperature (Tg) of at least one of the solutes + 30 ° C. or lower from the viewpoint of improving the coating film-forming property. From the viewpoint of reducing the residual solvent, it is preferable to heat the solute at at least one glass transition point (Tg) of −30 ° C. or higher. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(2) Specific Examples of Organic Solvents Examples of the organic solvent used in the composition for forming an organic layer include an alkylbenzene solvent, a phenyl ether solvent, an alkyl ether solvent, a cyclic ketone solvent, an aliphatic ketone solvent, and a monocyclic solvent. Examples thereof include a ketone solvent, a solvent having a diester skeleton, and a fluorine-containing solvent. Specific examples thereof include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, and the like. Heptane-2-ol, octane-2-ol, decan-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol Dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene , O-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoro Anisol, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mecitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Anisol, phenetol, benzodioxol, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methyl Anisole, Simene, 1,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, Decalin (decahydronaphthalene), neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, benzoic acid Methyl, isopentylbenzene, 3,4-dimethylanisole, o-tornitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene , 1-Methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-bitril, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydro Benzofuran, 1-methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) ) Benzene, 1-methyl-4- (heptyloxymethyl) benzene benzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether and the like, but are not limited thereto. Further, the solvent may be used alone or may be mixed.

<Arbitrary ingredient>
The composition for forming an organic layer may contain an arbitrary component as long as its properties are not impaired. Examples of the optional component include a binder, a surfactant and the like.

(1) Binder The composition for forming an organic layer may contain a binder. The binder forms a film at the time of film formation and joins the obtained film to the substrate. It also plays a role in dissolving, dispersing and binding other components in the composition for forming an organic layer.

Examples of the binder used in the composition for forming an organic layer include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, and the like. Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile -Stylite copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymers of the above resins and polymers, but are not limited thereto.

The binder used in the composition for forming an organic layer may be only one kind or a mixture of a plurality of kinds may be used.

(2) Surfactant The composition for forming an organic layer contains, for example, a surfactant for controlling the film surface uniformity, the solvent-like property and the liquid repellency of the film surface of the composition for forming an organic layer. May be good. Surfactants are classified into ionic and nonionic based on the structure of hydrophilic groups, and further classified into alkyl-based, silicon-based and fluorine-based based on the structure of hydrophobic groups. Further, from the molecular structure, it is classified into a monomolecular system having a relatively small molecular weight and a simple structure and a polymer system having a large molecular weight and having side chains and branches. Further, it is classified into a single system, a mixed system in which two or more kinds of surfactants and a base material are mixed, according to the composition. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.

Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181 and Disperbake. Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Futagent 222F, Futergent 251 and FTX-218 (trade name) Product name, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Product name, manufactured by Mitsubishi Materials Co., Ltd.), Megafuck F- 470, Mega Fuck F-471, Mega Fuck F-475, Mega Fuck R-08, Mega Fuck F-477, Mega Fuck F-479, Mega Fuck F-553, Mega Fuck F-554 (trade name, DIC Co., Ltd.) ), Fluoroalkylbenzene sulfonate, Fluoralkyl carboxylate, Fluoroalkyl polyoxyethylene ether, Fluoroalkyl ammonium iodide, Fluoroalkyl betaine, Fluoroalkyl sulfonate, Diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether) ), Fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Steerate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polio Examples thereof include xyethylene naphthyl ether, alkylbenzene sulfonate and alkyldiphenyl ether disulfonate.

Further, the surfactant may be used alone or in combination of two or more.

<Composition and physical properties of composition for forming organic layer>
The content of each component in the composition for forming an organic layer is obtained from the good solubility, storage stability and film forming property of each component in the composition for forming an organic layer, and the composition for forming an organic layer. Good film quality of the coating film, good ejection property when the inkjet method is used, and good electrical characteristics, light emission characteristics, efficiency, and life of the organic EL element having an organic layer produced by using the composition. It is decided in consideration of the viewpoint of. For example, in the case of a composition for forming a light emitting layer, the first component is 0.0001% by weight to 2.0% by weight based on the total weight of the composition for forming a light emitting layer, and the second component is for forming a light emitting layer. 0.0999% by weight to 8.0% by weight based on the total weight of the composition, and 90.0% by weight to 99.9% by weight of the third component based on the total weight of the composition for forming a light emitting layer. preferable.

More preferably, the first component is 0.005% by weight to 1.0% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The third component is 0.095% by weight to 4.0% by weight, and the third component is 95.0% by weight to 99.9% by weight based on the total weight of the composition for forming a light emitting layer. More preferably, the first component is 0.05% by weight to 0.5% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The third component is 0.25% by weight to 2.5% by weight, and the third component is 97.0% by weight to 99.7% by weight based on the total weight of the composition for forming a light emitting layer.

The composition for forming an organic layer can be produced by appropriately selecting the above-mentioned components by a known method such as stirring, mixing, heating, cooling, dissolving, and dispersing. Further, after the preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment and the like may be appropriately selected.

As the viscosity of the composition for forming an organic layer, the higher the viscosity, the better the film forming property and the good ejection property when the inkjet method is used. On the other hand, the lower the viscosity, the easier it is to form a thin film. From this, the viscosity of the composition for forming an organic layer is preferably 0.3 to 3 mPa · s at 25 ° C., and more preferably 1 to 3 mPa · s. In the present invention, the viscosity is a value measured using a conical flat plate type rotational viscometer (cone plate type).

The lower the surface tension of the composition for forming an organic layer, the better the film-forming property and the coating film without defects. On the other hand, the higher the value, the better the inkjet ejection property. From this, the viscosity of the composition for forming an organic layer is preferably 20 to 40 mN / m and more preferably 20 to 30 mN / m in surface tension at 25 ° C. In the present invention, the surface tension is a value measured by using the suspension method.

式（ＸＬＰ−１）において、
ＭＵｘ、ＥＣｘおよびｋは上記式（ＳＰＨ−１）におけるＭＵ、ＥＣおよびｋと同定義であり、ただし、式（ＸＬＰ−１）で表される化合物は少なくとも１つの架橋性置換基（ＸＬＳ）を有し、好ましくは架橋性置換基を有する１価または２価の芳香族化合物の含有量は、分子中０．１〜８０重量％である。<Crosslinkable polymer compound: Compound represented by the general formula (XLP-1)>
Next, a case where the above-mentioned polymer compound has a crosslinkable substituent will be described. Such a crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).

In formula (XLP-1)
MUx, ECx and k have the same definition as MU, EC and k in the above formula (SPH-1), except that the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS). The content of the monovalent or divalent aromatic compound having, preferably having a crosslinkable substituent is 0.1 to 80% by weight in the molecule.

The content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight.

The crosslinkable substituent (XLS) is not particularly limited as long as it is a group capable of further crosslinking the above-mentioned polymer compound, but a substituent having the following structure is preferable. * In each structural formula indicates the bonding position.

L is a single bond, −O−, −S−,> C = O, −OC (= O) −, alkylene having 1 to 12 carbon atoms, and oxyalkylene having 1 to 12 carbon atoms, respectively. And a polyoxyalkylene having 1 to 12 carbon atoms. Among the above substituents, it is represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10) or the formula (XLS-17). The group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.

Examples of the divalent aromatic compound having a crosslinkable substituent include a compound having the following partial structure.

<Manufacturing method of polymer compound and crosslinkable polymer compound>
The method for producing the polymer compound and the crosslinkable polymer compound will be described by taking the compound represented by the above formula (SPH-1) and the compound represented by (XLP-1) as examples. These compounds can be synthesized by appropriately combining known production methods.

Examples of the solvent used in the reaction include aromatic solvents, saturated / unsaturated hydrocarbon solvents, alcohol solvents, ether solvents and the like, and examples thereof include dimethoxyethane, 2- (2-methoxyethoxy) ethane, and 2- (2). -Ethoxyethoxy) ethane and the like.

Moreover, the reaction may be carried out in a two-phase system. When the reaction is carried out in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.

When the compound of the formula (SPH-1) and the compound of (XLP-1) are produced, they may be produced in one step or in multiple steps. Further, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are put in the reaction vessel, or it may be carried out by a dropping polymerization method in which the raw materials are dropped and added to the reaction vessel, and the product proceeds in the reaction. It may be carried out by a precipitation polymerization method in which the mixture precipitates, and these can be combined and synthesized as appropriate. For example, when the compound represented by the formula (SPH-1) is synthesized in one step, the desired product is obtained by carrying out the reaction with the monomer unit (MU) and the end cap unit (EC) added to the reaction vessel. .. Further, when synthesizing a compound represented by the general formula (SPH-1) in multiple stages, the purpose is to polymerize the monomer unit (MU) to the desired molecular weight and then add the end cap unit (EC) to react. Get things. By adding different types of monomer units (MUs) in multiple stages and carrying out the reaction, it is possible to prepare a polymer having a concentration gradient in the structure of the monomer units. In addition, after preparing the precursor polymer, the target polymer can be obtained by a subsequent reaction.

Moreover, the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in 1 to 3 of the synthesis scheme, it is possible to synthesize a polymer having a random primary structure (synthesis scheme 1), a polymer having a regular primary structure (synthesis schemes 2 and 3), and the like. Therefore, it can be used in combination as appropriate according to the target product. Furthermore, hyperbranched polymers and dendrimers can be synthesized by using a monomer unit having three or more polymerizable groups.

Examples of the monomer unit that can be used in the present invention include JP-A-2010-189630, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, and International Publication No. 2011/049241. No., International Publication No. 2013/146806, International Publication No. 2005/049546, International Publication No. 2015/145871, Japanese Patent Application Laid-Open No. 2010-215886, Japanese Patent Application Laid-Open No. 2008-106241, Japanese Patent Application Laid-Open No. 2010-215886, International It can be synthesized according to the methods described in Publication No. 2016/031639, Japanese Patent Application Laid-Open No. 2011-174062, International Publication No. 2016/031639, International Publication No. 2016/031639, and International Publication No. 2002/045184. ..

For specific polymer synthesis procedures, see JP2012-036388, International Publication No. 2015/008851, JP2012-36381, JP2012-144722, and International Publication No. 2015/194448. , International Publication No. 2013/146806, International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, International Publication No. 2016/031639, International Publication No. 2016/031639, International It can be synthesized according to the method described in Publication No. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049241 and Japanese Patent Application Laid-Open No. 2012-144722.

<Application example of organic electroluminescent device>
The present invention can also be applied to a display device provided with an organic EL element, a lighting device provided with an organic EL element, and the like.
A display device or a lighting device provided with an organic EL element can be manufactured by a known method such as connecting an organic EL element according to the present embodiment to a known drive device, and can be manufactured by a known method such as DC drive, pulse drive, AC drive, or the like. It can be driven by using a known driving method as appropriate.

Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescent (EL) display (for example, JP-A-10-335066, JP-A-2003-321546). See Japanese Patent Publication No. 2004-281086, etc.). Further, as the display method of the display, for example, a matrix and / or a segment method can be mentioned. The matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are arranged two-dimensionally such as in a grid pattern or a mosaic pattern, and characters and images are displayed as a set of pixels. The shape and size of the pixels are determined by the application. For example, for displaying images and characters on a personal computer, monitor, or television, quadrangular 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, pixels with a side on the order of mm should be used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. Then, as the driving method of this matrix, either a line sequential driving method or an active matrix may be used. Line sequential drive has the advantage of a simpler structure, but when considering operating characteristics, the active matrix may be superior, so it is also necessary to use it properly depending on the application.

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

Examples of the lighting device include a lighting device such as indoor lighting and a backlight of a liquid crystal display device (for example, JP-A-2003-257621, JP-A-2003-277741, JP-A-2004-119211). Etc.). The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light by itself, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, as a backlight for a liquid crystal display device, especially for a personal computer for which thinning is an issue, considering that it is difficult to thin the backlight because the conventional method consists of a fluorescent lamp and a light guide plate, the present embodiment The backlight using the light emitting element according to the above is characterized by being thin and lightweight.

3-2. Other Organic Devices The polycyclic aromatic compounds according to the present invention can be used for producing organic electroluminescent transistors, organic thin-film solar cells, and the like, in addition to the above-mentioned organic electroluminescent devices.

The organic field effect transistor is a transistor that controls a current by an electric field generated by a voltage input, and is provided with a gate electrode in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. The field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.

The structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed by using the polycyclic aromatic compound according to the present invention, and further in contact with the organic semiconductor active layer. It suffices if the gate electrode is provided so as to sandwich the insulating layer (dielectric layer). Examples of the element structure include the following structures.
(1) Substrate / Gate electrode / Insulator layer / Source electrode / Drain electrode / Organic semiconductor active layer (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode / Drain electrode (3) Substrate / Organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) Substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode It can be applied as a pixel-driven switching element of an active matrix-driven liquid crystal display or an organic electroluminescence display.

The organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound according to the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical characteristics. The polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. In addition to the above, the organic thin film solar cell may appropriately include a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like. For the organic thin film solar cell, known materials used for the organic thin film solar cell can be appropriately selected and used in combination.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. First, an example of synthesizing a polycyclic aromatic compound will be described below.

Synthesis example (1): Synthesis of compound (1-151)

4- (T-Amil) aniline (15.0 g) was dissolved in acetonitrile (150 ml) under a nitrogen atmosphere, bromine (22.5 g) was added dropwise thereto under ice-cooling, and the mixture was stirred for 0.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give the intermediate (IA) (20.0 g).

Under a nitrogen atmosphere, copper (10.1 g) chloride and intermediate (IA) (20.0 g) were dissolved in acetonitrile (100 ml), and t-butyl nitrite (50 ml) was dissolved therein. 9.6 g) was added dropwise at 60 ° C., and the mixture was stirred at the same temperature for 0.5 hours. After the reaction, dilute hydrochloric acid and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel short column (eluent: toluene / heptane = 1/4 (volume ratio)) to obtain an intermediate (IB) (19.0 g).

Under a nitrogen atmosphere, intermediate (IB) (10.0 g), bis (4-t-butylphenyl) amine (18.2 g), dichlorobis [(di-t-butyl (4-dimethylaminophenyl)) as a palladium catalyst ) Phosphino) Palladium (Pd-132, 0.21 g), sodium-t-butoxide (NaOtBu, 7.1 g) and xylene (100 ml) were placed in a flask and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IC) (18.0 g).

In a flask containing the intermediate (IC) (18.0 g) and t-butylbenzene (500 ml), add a 1.56 M t-butyllithium pentane solution (28.9 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (11.3 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (5.8 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The obtained crude product was recrystallized from chlorobenzene to obtain compound (1-151) (7.1 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.49 (t, 3H), 0.92 (s, 6H), 1.28 (q, 2H), 1.46 (s, 18H), 1.47 (S, 18H), 6.05 (s, 2H), 6.77 (d, 2H), 7.28 (m, 4H), 7.50 (m, 2H), 7.67 (m, 4H) , 8.97 (d, 2H).

Synthesis example (2): Synthesis of compound (1-147)

Under a nitrogen atmosphere, 2,3-dichloroaniline (15.0 g), 1-bromo-4-t-amylbenzene (52.6 g), Pd-132 (1.32 g) as a palladium catalyst, NaOtBu (22.0 g) And xylene (150 ml) were placed in a flask and heated at 130 ° C. for 4 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel short column (eluent: toluene / heptane = 1/1 (volume ratio)) to obtain an intermediate (ID) (38.0 g).

Under a nitrogen atmosphere, intermediate (ID) (15.0 g), bis (4-t-butylphenyl) amine (8.4 g), Pd-132 (0.21 g) as a palladium catalyst, NaOtBu (4.3 g) ) And xylene (60 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IE) (15.0 g).

In a flask containing the intermediate (IE) (15.0 g) and t-butylbenzene (120 ml), add a 1.56 M t-butyllithium pentane solution (27.5 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (10.7 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (5.5 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-147) (6.5 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.76 (t, 3H), 0.82 (t, 3H), 1.41 (s, 6H), 1.44 (s, 6H), 1.46 (S, 9H), 1.47 (s, 9H), 1.76 (q, 4H), 6.13 (dd, 2H), 6.73 (d, 1H), 6.75 (d, 1H) , 7.28 (m, 5H), 7.45 (dd, 1H), 7.52 (dd, 1H), 7.61 (d, 2H), 7.67 (d, 2H), 8.91 ( d, 1H), 8.97 (d, 1H).

Synthesis example (3): Synthesis of compound (1-142)

Under a nitrogen atmosphere, intermediate (ID) (15.0 g), bis (4-t-amylphenyl) amine (9.3 g), Pd-132 (0.21 g) as a palladium catalyst, NaOtBu (4.3 g) ) And xylene (60 ml) were placed in a flask and heated at 120 ° C. for 1.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IF) (14.5 g).

In a flask containing the intermediate (IF) (14.5 g) and t-butylbenzene (120 ml), add a 1.56 M t-butyllithium pentane solution (25.6 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (10.0 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (5.1 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-142) (5.7 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.76 (t, 6H), 0.82 (t, 6H), 1.42 (s, 12H), 1.44 (s, 12H), 1.76 (M, 8H), 6.12 (d, 2H), 6.73 (d, 2H), 7.23 (t, 1H), 7.30 (d, 4H), 7.44 (dd, 2H) , 7.61 (d, 4H), 8.89 (d, 2H).

Synthesis example (4): Synthesis of compound (1-401)

Under a nitrogen atmosphere, intermediate (IB) (7.0 g), bis (4-tert-amylphenyl) amine (14.0 g), Pd-132 (0.15 g) as a palladium catalyst, NaOtBu (4.9 g) And xylene (80 ml) was placed in a flask and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IG) (9.8 g).

In a flask containing the intermediate (IG) (9.8 g) and t-butylbenzene (80 ml), add a 1.56 M t-butyllithium pentane solution (15.8 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (6.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (3.2 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-401) (4.9 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.48 (t, 3H), 0.75 (m, 12H), 0.90 (s, 6H), 1.27 (q, 2H), 1.42 (S, 12H), 1.44 (s, 12H), 1.76 (m, 8H), 6.03 (s, 2H), 6.80 (d, 2H), 7.29 (d, 4H) , 7.43 (dd, 2H), 7.61 (d, 4H), 8.88 (d, 2H).

Synthesis example (5): Synthesis of compound (1-171)

Under a nitrogen atmosphere, 3,4,5-trichloroaniline (15.0 g), iodobenzene (46.7 g), Pd-132 (0.54 g) as a palladium catalyst, NaOtBu (18.3 g) and xylene (150 ml). It was placed in a flask and heated at 120 ° C. for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IH) (49.7 g).

Under a nitrogen atmosphere, intermediate (IH) (10.0 g), bis (4-tert amylphenyl) amine (19.5 g), bis (dibenzylideneacetone) palladium (0) (Pd (dba)) as a palladium catalyst ₂ , 0.33 g), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (Spos, 0.59 g), NaOtBu (6.9 g) and xylene (80 ml) are placed in a flask and placed at 100 ° C. for 1 hour. It was heated. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give the intermediate (I-I) (16.0 g).

In a flask containing the intermediate (I-I) (16.0 g) and t-butylbenzene (100 ml), add a 1.56 M t-butyllithium pentane solution (22.1 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (9.0 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (4.6 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-171) (8.5 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.62 (t, 6H), 0.75 (t, 6H), 1.29 (s, 12H), 1.43 (s, 12H), 1.62 (Q, 4H), 1.75 (q, 4H), 5.63 (s, 2H), 6.70 (d, 2H), 6.86 (m, 2H), 6.92 (d, 4H) , 7.05 (m, 4H), 7.14 (d, 4H), 7.38 (m, 6H), 8.85 (d, 2H).

Synthesis example (6): Synthesis of compound (1-141)

Under a nitrogen atmosphere, 1,3-dibromo-5-t-butyl-2-chlorobenzene (10.0 g), bis (4-tert-amylphenyl) amine (20.9 g), Pd-132 (0.22 g) as a palladium catalyst ), NaOtBu (7.4 g) and xylene (100 ml) were placed in a flask and heated at 100 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IJ) (20.0 g).

In a flask containing the intermediate (IJ) (20.0 g) and t-butylbenzene (100 ml), add a 1.56 M t-butyllithium pentane solution (32.7 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (12.8 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (6.6 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-141) (9.1 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.75 (m, 12H), 0.96 (s, 9H), 1.42 (s, 12H), 1.44 (s, 12H), 1.75 (M, 8H), 6.08 (s, 2H), 6.78 (d, 2H), 7.29 (d, 4H), 7.43 (dd, 2H), 7.61 (d, 4H) , 8.88 (d, 2H).

Synthesis example (7): Synthesis of compound (1-406)

Under a nitrogen atmosphere, intermediate (I-K) (15.0 g), bis (4-t-amylphenyl) amine (8.0 g), Pd-132 (0.19 g) as a palladium catalyst, NaOtBu (3.9 g) ) And xylene (60 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IL) (15.2 g).

In a flask containing the intermediate (IL) (15.0 g) and t-butylbenzene (120 ml), add a 1.56 M t-butyllithium pentane solution (27.0 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (10.5 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (5.4 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-406) (6.9 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.75 (t, 3H), 0.81 (t, 3H), 1.43 (s, 12H), 1.47 (s, 18H), 1.76 (Quin, 4H), 2.16 (s, 3H), 5.95 (d, 2H), 6.68 (d, 2H), 7.28 (m, 4H), 7.42 (dd, 1H) , 7.49 (dd, 1H), 7.61 (d, 2H), 7.67 (d, 2H), 8.89 (d, 1H), 8.95 (d, 1H).

Synthesis example (8): Synthesis of compound (1-146)

Under a nitrogen atmosphere, 2,3-dichloro-5-methylaniline (7.0 g), 1-bromo-4-t-amylbenzene (19.9 g), Pd-132 (0.28 g) as a palladium catalyst, NaOtBu ( 9.6 g) and xylene (70 ml) were placed in a flask and heated at 120 ° C. for 3 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IM) (12.0 g).

Under a nitrogen atmosphere, intermediate (IM) (11.0 g), bis (4-t-amylphenyl) amine (6.1 g), Pd-132 (0.17 g) as a palladium catalyst, NaOtBu (3.4 g) ) And xylene (50 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IN) (12.5 g).

In a flask containing the intermediate (IN) (12.5 g) and t-butylbenzene (100 ml), add a 1.56 M t-butyllithium pentane solution (21.6 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (8.4 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (4.4 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-146) (6.9 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.75 (t, 6H), 0.81 (t, 6H), 1.42 (s, 12H), 1.43 (s, 12H), 1.76 (Quin, 8H), 2.15 (s, 3H), 5.93 (s, 2H), 6.68 (d, 2H), 7.28 (m, 4H), 7.42 (dd, 2H) , 7.61 (d, 4H), 8.88 (d, 2H).

Synthesis example (9): Synthesis of compound (1-403)

Under a nitrogen atmosphere, intermediate (IK) (8.0 g), bis (4-t-octylphenyl) amine (6.5 g), Pd-132 (0.13 g) as a palladium catalyst, NaOtBu (2.6 g) ) And xylene (40 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IO) (11.5 g).

In a flask containing the intermediate (IO) (11.5 g) and t-butylbenzene (90 ml), add a 1.56 M t-butyllithium pentane solution (18.5 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (7.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-403) (4.6 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.74 (s, 9H), 0.84 (s, 9H), 1.46 (s, 9H), 1.47 (s, 9H), 1.51 (S, 6H), 1.54 (s, 6H), 1.82 (s, 2H), 1.86 (s, 2H), 2.12 (s, 3H), 5.94 (d, 2H) , 6.68 (d, 1H), 6.74 (d, 1H), 7.28 (m, 4H), 7.45 (dd, 1H), 7.49 (dd, 1H), 7.68 ( m, 4H), 8.93 (d, 1H), 8.97 (d, 1H).

Synthesis example (10): Synthesis of compound (1-502)

Under a nitrogen atmosphere, 4- (t-amyl) phenol (24.3 g), 2-bromo-5-chloro-1,3-difluorobenzene (16.0 g), potassium carbonate (29.2 g) and N-methyl- 2-Pyrrolidone (NMP, 80 ml) was placed in a flask and heated at 180 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then toluene were added to separate the solutions. After the reaction, water and heptane were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel short column (eluent: toluene / heptane = 1/2 (volume ratio)) to obtain an intermediate (IP) (27 g).

Tetrahydrofuran solution of intermediate (IP) (17.5 g) in a flask containing 1.3 M isopropylmagnesium chloride-lithium chloride complex solution (33 ml) and tetrahydrofuran (THF, 50 ml) under a nitrogen atmosphere at 0 ° C. (70 ml) was added. After completion of the dropping, the temperature was raised to room temperature and the mixture was stirred for 2 hours. After cooling to 0 ° C., add a tetrahydrofuran solution (15 ml) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.8 g), and raise the temperature to room temperature 2 Stirred for hours. Toluene and saturated aqueous ammonium chloride solution were added to the reaction mixture, and the mixture was stirred, and then the organic layer was separated and washed with water. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene) to obtain an intermediate (IQ) (17.1 g).

N, N-diisopropylethylamine (3.9 g) was added to a flask containing boron tribromide (25 g) and toluene (25 ml) under a nitrogen atmosphere. Then, a toluene solution (35 ml) of the intermediate (IQ) (5.6 g) was added, and the mixture was stirred under heating under reflux for 6 hours. After the reaction, water and heptane were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The obtained crude product was reprecipitated with heptane to give an intermediate (IR) (3.0 g).

Under a nitrogen atmosphere, Intermediate (IR) (11.0 g), 9,10-dihydro-9,9-dimethylacridin (1.0 g), tri-t-butylphosphonium tetrafluoroborate ([(t-) Bu) ₃ PH] BF ₄ , 0.1 g), Pd (dba) ₂ (0.05 g) as a palladium catalyst, NaOtBu (0.65 g) and toluene (40 ml) were placed in a flask and heated under reflux for 2 hours. did. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene / heptane = 1/1 (volume ratio)). The resulting crude product was reprecipitated with heptane to give compound (1-502) (2.2 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.79 (t, 6H), 1.48 (s, 12H), 1.72 (s, 6H), 1.80 (quin, 4H), 6.49. (D, 2H), 6.94-7.01 (m, 4H), 7.22 (s, 2H), 7.48-7.50 (m, 4H), 7.73 (dd, 2H), 8.71 (d, 2H).

Synthesis example (11): Synthesis of compound (1-163)

Under a nitrogen atmosphere, 3,4,5-trichloroaniline (20.0 g), 1-bromo-4-t-amylbenzene (48.6 g), Pd-132 (2.88 g) as a palladium catalyst, NaOtBu (24. 5 g) and xylene (200 ml) were placed in a flask and heated at 120 ° C. for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IS) (49.7 g).

Under a nitrogen atmosphere, intermediate (IS) (22.4 g), bis (4-tert-amylphenyl) amine (28.4 g), [(t-Bu) ₃ PH] BF ₄ (0.53 g), palladium Pd (dba) ₂ (0.84 g), NaOtBu (11.0 g) and xylene (225 ml) were placed in a flask as a catalyst and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IT) (31.2 g).

In a flask containing the intermediate (IT) (22.0 g) and t-butylbenzene (100 ml), add a 1.56 M t-butyllithium pentane solution (25.0 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (10.1 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (5.2 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-163) (8.5 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.63 (t, 6H), 0.69 (t, 6H), 0.74 (t, 6H), 1.22 (s, 12H), 1.28 (S, 12H), 1.43 (s, 12H), 1.56 (q, 4H), 1.62 (q, 4H), 1.74 (q, 4H), 5.84 (br, 2H) , 6.63 (d, 2H), 6.79 (d, 4H), 6.99 (d, 4H), 7.14 (d, 4H), 7.37 (m, 6H), 8.83 ( d, 2H).

Synthesis example (12): Synthesis of compound (1-412)

Under a nitrogen atmosphere, intermediate (IU) (8.0 g), bis (4-t-octylphenyl) amine (7.0 g), Pd-132 (0.13 g) as a palladium catalyst, NaOtBu (2.6 g) ) And xylene (40 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, and the mixture was stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified on a silica gel short column (eluent: toluene) to give an intermediate (IV) (10.5 g).

In a flask containing the intermediate (IV) (10.5 g) and t-butylbenzene (80 ml), add a 1.56 M t-butyllithium pentane solution (17.5 ml) at 0 ° C. under a nitrogen atmosphere. added. After completion of the dropping, the temperature was raised to 70 ° C. and the mixture was stirred for 0.5 hours, and then components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50 ° C., boron tribromide (6.7 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hours. Then, the mixture was cooled to 0 ° C. again, N, N-diisopropylethylamine (3.5 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then the temperature was raised to 100 ° C. and the mixture was heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the solutions. After concentrating the organic layer, it was purified by a silica gel short column (eluent: toluene). The resulting crude product was reprecipitated with heptane to give compound (1-412) (4.2 g).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (CDCl ₃ ): δ = 0.75 (s, 9H), 0.86 (s, 9H), 1.45 (s, 9H), 1.48 (s, 9H), 1.50 (S, 6H), 1.54 (s, 6H), 1.83 (s, 2H), 1.87 (s, 2H), 6.13 (t, 2H), 6.72 (d, 1H) , 6.74 (d, 1H), 7.22 (t, 1H), 7.28 (m, 4H), 7.45 (dd, 1H), 7.52 (dd, 1H), 7.68 ( m, 4H), 8.94 (d, 1H), 8.98 (d, 1H).

By appropriately changing the raw material compound, the other polycyclic aromatic compound of the present invention can be synthesized by a method according to the above-mentioned synthesis example.

Next, in order to explain the present invention in more detail, examples of an organic EL device using the compound of the present invention will be shown, but the present invention is not limited thereto.

<Evaluation of organic EL elements>
The organic EL elements according to Examples 1-1 to 1-8 were produced, and the voltage (V), emission wavelength (nm), and external quantum efficiency (%), which are the characteristics at the time of ^{1000 cd / m 2 emission, were measured.} ..

The quantum efficiency of the light emitting element includes the internal quantum efficiency and the external quantum efficiency. In the internal quantum efficiency, the external energy injected as electrons (or holes) into the light emitting layer of the light emitting element is converted into pure photons. The ratio is shown. On the other hand, the external quantum efficiency is calculated based on the amount of these photons emitted to the outside of the light emitting element, and a part of the photons generated in the light emitting layer is continuously absorbed or reflected inside the light emitting element. Therefore, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.

The method for measuring the external quantum efficiency is as follows. A voltage / current generator R6144 manufactured by Advantest Co., Ltd. was used ^{to apply a voltage at which the brightness of the element became 1000 cd / m 2} to cause the element to emit light. The spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a completely diffused surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons was integrated over the entire observed wavelength region to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

The material composition and EL characteristic data of each layer in the produced organic EL device according to Examples 1-1 to 1-8 are shown in Tables 1A and 1B below.

In Table 1A, "HI" is N ⁴ , N ^4' -diphenyl-N ⁴ , N ^4' -bis (9-phenyl-9H-carbazole-3-yl)-[1,1'-biphenyl] -4, It is 4'-diamine, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, and "HT-1" is N- ([1,1'-biphenyl]. ] -4-yl-9,9-dimethyl-N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl) -9H-fluoren-2-amine [1,1'-biphenyl] -4 -Amine, "HT-2" is N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1': 4', 1 "-terphenyl] It is a -4-amine, "BH-1" is 2- (10-phenylanthracene-9-yl) naphtho [2,3-b] benzofuran, and "ET-1" is 4,6,8,10. -Tetraphenyl [1,4] benzoxabolinino [2,3,4-kl] phenoxabolinine, "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl) ) Bis (4,1-phenylene)) Bis (4-methylpyridine). The chemical structure is shown below together with "Liq".

<Example 1-1>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by polishing ITO formed to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available thin film deposition apparatus (manufactured by Choshu Industry Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-151), ET. A tantalum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum, respectively, were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is ^{depressurized to 5 × 10 -4} Pa, and HI is first heated to be vapor-deposited to a film thickness of 40 nm, and then HAT-CN is heated to be vapor-deposited to a film thickness of 5 nm. Next, HT-1 is heated to be vapor-deposited to a thickness of 45 nm, and then HT-2 is heated to be vapor-deposited to a thickness of 10 nm to form a hole layer consisting of four layers. did. Next, BH-1 and the compound (1-151) were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-151) was approximately 98: 2. Further, ET-1 is heated and vapor-deposited to a film thickness of 5 nm, and then ET-2 and Liq are simultaneously heated and vapor-deposited to a film thickness of 25 nm to form an electronic layer composed of two layers. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 and Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm, and then aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. Then, an organic EL element was obtained.

When a DC voltage was applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode and ^{the characteristics at the time of 1000 cd / m 2} emission were measured, blue emission with a wavelength of 465 nm was obtained, the drive voltage was 3.66 V, and the external quantum efficiency. Was 8.73%.

<Examples 1-2 to 1-8>
An organic EL device was produced by a method according to Example 1-1 (Table 1A), and EL characteristics were measured (Table 1B).

<Example 2>
Next, a dissolution test of the compound was conducted. After 1 g of the test compound was placed in 30 ml of toluene at 100 ° C. and stirred, it was verified whether or not the test compound was dissolved. The results are shown in Table 2.

<Evaluation of coating type organic EL element>
Next, an organic EL device obtained by coating and forming an organic layer will be described.

<Polymer host compound: Synthesis of SPH-101>
SPH-101 was synthesized according to the method described in WO 2015/008851. A copolymer in which M2 or M3 is bonded is obtained next to M1, and it is estimated from the charging ratio that each unit has a 50:26:24 (molar ratio).

<Polymer hole transport compound: Synthesis of XLP-101>
XLP-101 was synthesized according to the method described in JP-A-2018-61028. A copolymer in which M2 or M3 is bonded is obtained next to M7, and it is estimated from the charging ratio that each unit is 40:10:50 (molar ratio).

<Examples 3 to 10>
A coating solution of the material forming each layer is prepared to prepare a coating type organic EL device.

<Manufacturing of Organic EL Devices of Examples 3 to 5>
Table 3 shows the material composition of each layer in the organic EL device.

The structure of "ET1" in Table 3 is shown below.

<Preparation of composition (1) for forming a light emitting layer>
The composition for forming a light emitting layer (1) is prepared by stirring the following components until a uniform solution is obtained. The prepared composition for forming a light emitting layer is spin-coated on a glass substrate and dried by heating under reduced pressure to obtain a coating film having no film defects and excellent smoothness.
Compound (A) 0.04% by weight
SPH-101 1.96% by weight
Xylene 69.00% by weight
Decalin 29.00% by weight

The compound (A) is a monomer of a polycyclic aromatic compound represented by the general formula (1), a multimer thereof, the polycyclic aromatic compound or a multimer thereof (that is, the monomer has a reactive substituent). ), Or a polymer crosslinked product obtained by further cross-linking the polymer compound. The polymer compound for obtaining a polymer crosslinked product has a crosslinkable substituent.

<PEDOT: PSS solution>
A commercially available PEDOT: PSS solution (Clevios (TM) P VP AI4083, PEDOT: PSS aqueous dispersion, manufactured by Heraeus Holdings) is used.

<Preparation of OTPD solution>
OTPD (LT-N159, manufactured by Luminescence Technology Corp) and IK-2 (photocationic polymerization initiator, manufactured by San Apro) were dissolved in toluene, and the OTPD concentration was 0.7% by weight and the IK-2 concentration was 0.007% by weight. OTPD solution is prepared.

<Preparation of XLP-101 solution>
XLP-101 is dissolved in xylene at a concentration of 0.6% by weight to prepare a 0.7% by weight XLP-101 solution.

<Preparation of PCz solution>
PCz (polyvinylcarbazole) is dissolved in dichlorobenzene to prepare a 0.7 wt% PCz solution.

<Example 3>
A PEDOT: PSS film having a film thickness of 40 nm is formed by spin-coating a PEDOT: PSS solution on a glass substrate on which ITO is deposited to a thickness of 150 nm and firing it on a hot plate at 200 ° C. for 1 hour. (Hole injection layer). Next, the OTPD solution was spin-coated, dried on a hot plate at 80 ° C. for 10 minutes, exposed to an exposure intensity of 100 mJ / cm ² with an exposure machine, and baked on a hot plate at 100 ° C. for 1 hour to obtain the solution. An OTPD film having a film thickness of 30 nm, which is insoluble in the solution, is formed (hole transport layer). Next, the composition for forming a light emitting layer (1) is spin-coated and fired on a hot plate at 120 ° C. for 1 hour to form a light emitting layer having a film thickness of 20 nm.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, ET1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Example 4>
An organic EL device is obtained in the same manner as in Example 2. The hole transport layer is formed by spin-coating an XLP-101 solution and firing it on a hot plate at 200 ° C. for 1 hour to form a film having a film thickness of 30 nm.

<Example 5>
An organic EL device is obtained in the same manner as in Example 2. The hole transport layer is spin-coated with a PCz solution and fired on a hot plate at 120 ° C. for 1 hour to form a film having a film thickness of 30 nm.

<Manufacturing of Organic EL Devices of Examples 6 to 8>
Table 4 shows the material composition of each layer in the organic EL device.

<Preparation of compositions (2) to (4) for forming a light emitting layer>
The composition for forming a light emitting layer (2) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
mCBP 1.98% by weight
Toluene 98.00% by weight

The composition for forming a light emitting layer (3) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
SPH-101 1.98% by weight
Xylene 98.00% by weight

The composition for forming a light emitting layer (4) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
DOBNA 1.98% by weight
Toluene 98.00% by weight

In Table 4, "mCBP" is 3,3'-bis (N-carbazolyl) -1,1'-biphenyl and "DOBNA" is 3,11-di-o-tolyl-5,9-dioxa-. It is 13b-boranaft [3,2,1-de] anthracene and "TSPO1" is a diphenyl [4- (triphenylsilyl) phenyl] phosphine oxide. The chemical structure is shown below.

<Example 6>
An ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) solution is spin-coated on a glass substrate on which ITO is formed to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further at 230 ° C., 15 By heating for a minute, an ND-3202 film having a film thickness of 50 nm is formed (hole injection layer). Next, the XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a film thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (2) is spin-coated and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, TSPO1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Examples 7 and 8>
Using the light emitting layer forming composition (3) or (4), an organic EL device is obtained in the same manner as in Example 6.

<Manufacturing of Organic EL Devices of Examples 9 to 11>
Table 5 shows the material composition of each layer in the organic EL device.

<Preparation of compositions (5) to (7) for forming a light emitting layer>
A composition for forming a light emitting layer is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
mCBP 1.80% by weight
Toluene 98.00% by weight

A composition for forming a light emitting layer is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
SPH-101 1.80% by weight
Xylene 98.00% by weight

A composition for forming a light emitting layer is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
DOBNA 1.80% by weight
Toluene 98.00% by weight

In Table 5, "2PXZ-TAZ" is 10,10'-((4-phenyl-4H-1,2,4-triazole-3,5-diyl) bis (4,1-phenyl)) bis ( 10H-phenoxazine). The chemical structure is shown below.

<Example 9>
An ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) solution is spin-coated on a glass substrate on which ITO is formed to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further at 230 ° C., 15 By heating for a minute, an ND-3202 film having a film thickness of 50 nm is formed (hole injection layer). Next, the XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a film thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (5) is spin-coated and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, TSPO1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Examples 10 and 11>
Using the light emitting layer forming composition (6) or (7), an organic EL device is obtained in the same manner as in Example 9.

In the present invention, by providing a novel tertiary alkyl-substituted polycyclic aromatic compound, it is possible to increase the choice of materials for organic devices such as materials for organic EL devices. Further, by using a novel tertiary alkyl-substituted polycyclic aromatic compound as a material for an organic EL device, for example, an organic EL device having excellent luminous efficiency, a display device equipped with the organic EL device, a lighting device equipped with the organic EL device, and the like are provided. can do.

100 Organic electroluminescent device 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 (35)

A multimer of a polycyclic aromatic compound represented by the following general formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).

(In the above formula (1),
Rings A, B, and C are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings may be substituted.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is aryl, alkyl or cycloalkyl. And
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, even if the R of> N-R is substituted. A good aryl, a heteroaryl which may be substituted, an alkyl which may be substituted or a cycloalkyl which may be substituted, and the R of> C (-R) ₂ is hydrogen, which may be substituted. A good aryl, a optionally substituted alkyl or a optionally substituted cycloalkyl, and the R of> N-R and / or the R of> C (-R) ₂ are linking groups or single bonds. May be bonded to the A ring, B ring and / or C ring.
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound or structure represented by the formula (1) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *. ) The A ring, B ring, and C ring are independently aryl rings or heteroaryl rings, and at least one hydrogen in these rings is a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, or a substituted ring. Or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted aryl heteroarylamino, substituted or unsubstituted diarylboryl (two aryls are bonded via a single bond or a linking group). May be substituted), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy, and these rings are Y ¹ , A 5-membered ring or a 6-membered ring that shares a bond with the fused two-ring structure in the center of the above formula composed of ^{X 1} and X ^2.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is aryl, alkyl or cycloalkyl. And
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, and the R of> N-R is alkyl or cycloalkyl, respectively. Heteroaryl, alkyl or cycloalkyl which may be substituted with aryl, alkyl or cycloalkyl which may be substituted, wherein R of> C (-R) ₂ is substituted with hydrogen, alkyl or cycloalkyl. It may be aryl, alkyl or cycloalkyl, and the R of> N-R and / or the R of> C (-R) ₂ is -O-, -S-, -C (-R). _It may be bonded to the A ring, the B ring and / or the C ring by a _{2- or a single bond, and the R of the -C (-R) 2-} is hydrogen, alkyl or cycloalkyl.
At least one hydrogen in the compound or structure represented by the formula (1) may be substituted with deuterium, cyano or halogen.
In the case of a multimer, it is a 2 or trimer having 2 or 3 structures represented by the general formula (1), and
At least one hydrogen in the compound or structure represented by the formula (1) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *.
The polycyclic aromatic compound according to claim 1 or a multimer thereof. The polycyclic aromatic compound according to claim 1, which is represented by the following general formula (2).

(In the above formula (2),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diallylboryl (two aryls are bonded via a single bond or a linking group). may be), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in these, aryl, heteroaryl, may be substituted with alkyl or cycloalkyl and, of R ¹ to R ¹¹ Adjacent groups thereof may be bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring or a c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, or diaryl. Amino, diheteroarylamino, arylheteroarylamino, diallylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy. Well, at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
Y ¹ is B, P, P = O, P = S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R has 6 to 12 carbon atoms. Aryl, alkyl with 1 to 6 carbons or cycloalkyl with 3 to 14 carbons,
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ ,> S or> Se, and R of> N-R has 6 to 12 carbon atoms. Aryl, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and R of> C (-R) ₂ is hydrogen and 6 to 12 carbon atoms. The aryl, the alkyl having 1 to 6 carbon atoms or the cycloalkyl having 3 to 14 carbon atoms, and the R of> N-R and / or the R of> C (-R) ₂ are -O-,-. _{S -, - C (-R)} 2 - or the a ring by a single bond, may be bound to b ring and / or c ring, wherein -C _{(-R) 2} - of R is 1 carbon atoms It is an alkyl of 6 or a cycloalkyl of 3 to 14 carbon atoms.
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *. ) R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, diallyl amino (where aryl is aryl with 6 to 12 carbon atoms), and diallyl boryl (provided that aryl is aryl with 6 to 12 carbon atoms). Aryl is an aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), and can be an alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms. In addition, ^{adjacent groups of R 1 to} R ¹¹ are bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring. At least one hydrogen in the formed ring may be substituted with an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 12 carbon atoms, or a cycloalkyl having 3 to 16 carbon atoms.
Y ¹ is B, P, P = O, P = S or Si-R, and R of the Si-R is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms, or 5 to 5 carbon atoms. 10 cycloalkyl,
X ¹ and X ² are independently>O,>N-R,> C (-R) ₂ or> S, and R of> N-R is an aryl having 6 to 10 carbon atoms. It is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, and the R of> C (-R) ₂ is hydrogen, an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms or carbon. It is a cycloalkyl of the number 5 to 10.
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
The polycyclic aromatic compound according to claim 3. R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 20 carbon atoms, diallyl amino (where aryl is aryl with 6 to 10 carbon atoms), and diarylboryl (provided that aryl is 6 to 10 carbon atoms). Aryl is an aryl having 6 to 10 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms. ,
Y ¹ is B, P, P = O or P = S,
X ¹ and X ² are independently>O,> N-R or> C (-R) ₂ , and the R of> N-R is an aryl having 6 to 10 carbon atoms and 1 carbon number. It is an alkyl of ~ 4 or a cycloalkyl having 5 to 10 carbon atoms, and the R of> C (-R) ₂ is hydrogen, an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 4 carbon atoms. It is 10 cycloalkyl, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
The polycyclic aromatic compound according to claim 3. R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 16 carbon atoms, diarylamino (where aryl is aryl with 6 to 10 carbon atoms), and diarylboryl (where aryl is aryl with 6 to 10 carbon atoms). The two aryls may be attached via a single bond or a linking group), and are alkyls having 1 to 12 carbon atoms or cycloalkyls having 3 to 16 carbon atoms.
Y ¹ is B,
Both X ¹ and X ² are> N-R, or X ¹ is> N-R and X ² is> O, and the R of> N-R has 6 to 10 carbon atoms. Aryl, alkyl with 1 to 4 carbons or cycloalkyl with 5 to 10 carbons, and
At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the above general formula (tR).
In the above formula (tR), ^Ra is an alkyl having 2 to 24 carbon atoms, R ^b and R ^c are independently alkyls having 1 to 24 carbon atoms, and any −CH ₂ − in the alkyl is It may be substituted with −O−, and the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
The polycyclic aromatic compound according to claim 3. A diarylamino group substituted with a group represented by the general formula (tR), a carbazolyl group substituted with a group represented by the general formula (tR), or a group represented by the general formula (tR). The polycyclic aromatic compound according to any one of claims 1 to 6, or a multimer thereof, which is substituted with the benzocarbazolyl group. R ² is a carbazolyl group substituted with a group represented by the general formula (tR) substituted by a group represented by the diarylamino group or the general formula (tR), any claim 3-6 Polycyclic aromatic compounds described in. The polycyclic aromatic compound or a multimer thereof according to any one of claims 1 to 8, wherein the halogen is fluorine. The polycyclic aromatic compound according to claim 1, which is represented by any of the following structural formulas.

(In each formula, "tBu" is a t-butyl group and "tAm" is a t-amyl group.) The polycyclic aromatic compound according to claim 1, which is represented by any of the following structural formulas.

(In each formula, "Me" is a methyl group, "tBu" is a t-butyl group, and "tAm" is a t-amyl group.) A reactive compound in which a polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof is substituted with a reactive substituent. A polymer compound obtained by polymerizing the reactive compound according to claim 12 as a monomer, or a polymer cross-linked product obtained by further cross-linking the polymer compound. A pendant type polymer compound in which the main chain type polymer is substituted with the reactive compound according to claim 12, or a pendant type polymer crosslinked product in which the pendant type polymer compound is further crosslinked. A material for an organic device containing the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof. A material for an organic device containing the reactive compound according to claim 12. A material for an organic device containing the polymer compound or polymer crosslinked product according to claim 13. A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked product according to claim 14. The material for an organic device according to any one of claims 15 to 18, wherein the material for an organic device is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell. The material for an organic device according to claim 19, wherein the material for the organic electroluminescent element is a material for a light emitting layer. An ink composition containing the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof, and an organic solvent. An ink composition containing the reactive compound according to claim 12 and an organic solvent. An ink composition containing a main chain polymer, the reactive compound according to claim 12, and an organic solvent. An ink composition containing the polymer compound or the crosslinked polymer according to claim 13 and an organic solvent. An ink composition containing the pendant-type polymer compound or the pendant-type polymer crosslinked product according to claim 14 and an organic solvent. A polycyclic aromatic compound according to any one of claims 1 to 11, or a polymer thereof, a reactive compound according to claim 12, which is arranged between a pair of electrodes composed of an anode and a cathode and the pair of electrodes. An organic electroluminescent element having an organic layer containing the polymer compound or polymer crosslinked body according to claim 13 or the pendant type polymer compound or pendant type polymer crosslinked body according to claim 14. A polycyclic aromatic compound or a polymer according to any one of claims 1 to 11, which is arranged between a pair of electrodes composed of an anode and a cathode, and a reactive compound according to claim 12. An organic electroluminescent element having a light emitting layer containing the polymer compound or polymer crosslinked body according to claim 13 or the pendant type polymer compound or pendant type polymer crosslinked body according to claim 14. The light emitting layer contains a host and the polycyclic aromatic compound as a dopant, a multimer thereof, a reactive compound, a polymer compound, a polymer crosslinked product, a pendant type polymer compound or a pendant type polymer crosslinked product. 27. The organic field light emitting element according to claim 27. 28. The organic electroluminescent element according to claim 28, wherein the host is an anthracene compound, a fluorene compound, a dibenzochrysene compound or a pyrene compound. It has an electron transporting layer and / or an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, a fluorentene derivative, or BO. Claim that contains at least one selected from the group consisting of system derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol metal complexes. The organic electric field light emitting element according to any one of 26 to 29. The electron transporting layer and / or electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, and an alkaline earth metal. Claim that it contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. 30. The organic electric field light emitting element. At least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or a polymer compound. , A polymer crosslinked product obtained by further cross-linking the polymer compound, or a pendant type polymer compound obtained by reacting a low molecular weight compound capable of forming each layer with a main chain type polymer, or the pendant type polymer compound. The organic electroluminescent element according to any one of claims 26 to 31, further comprising a crosslinked pendant type polymer crosslinked body. A display device or a lighting device including the organic electroluminescent element according to any one of claims 26 to 32. A composition for forming a light emitting layer for coating and forming a light emitting layer of an organic electroluminescent device.
As the first component, at least one polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof, and
As the second component, at least one host material and
As the third component, at least one organic solvent and
A composition for forming a light emitting layer containing. An organic electroluminescent device having a pair of electrodes composed of an anode and a cathode, and a light emitting layer arranged between the pair of electrodes and formed by applying and drying the light emitting layer forming composition according to claim 34.

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