JP2022032441A - Polycyclic aromatic compound - Google Patents

Abstract

To provide a new compound that is useful as a material for organic devices, in particular, as a material for luminescent layers, which is to form luminescent layers of organic EL elements.SOLUTION: The present invention discloses a polycyclic aromatic compound represented by, for example, formula (1-161).SELECTED DRAWING: None

Description

The present invention relates to polycyclic aromatic compounds. The present invention also relates to materials for organic devices containing the above polycyclic aromatic compounds, organic electroluminescent devices, and display devices and lighting devices.

Conventionally, display devices using a light emitting element that emits electric field light 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 (“organic EL element” in the present specification. "Or simply referred to as" element ".) Has been actively studied because it is easy to reduce the weight and increase the size. In particular, the development of organic materials with emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials with 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 consisting of an anode and a cathode, and one layer or a plurality of layers arranged between the pair of electrodes and containing an organic compound. Layers containing organic compounds include light emitting layers and charge transport / injection layers that transport or inject charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

Among them, Patent Document 1 discloses that a polycyclic aromatic compound in which an aromatic ring is linked with a hetero element such as boron, phosphorus, oxygen, nitrogen, or sulfur is useful as a material for an organic electric field light emitting element or the like. Has been done. This polycyclic aromatic compound has a large HOMO-LUMO gap and high triplet excitation energy ( _ET ), and exhibits thermally activated delayed fluorescence, so that it is particularly useful as a fluorescent material for organic electroluminescent devices. It has been reported.

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. An object of the present invention is to provide a novel material useful as a material for an organic device such as an organic EL element.

The present inventors have diligently studied to solve the above problems and succeeded in producing a new compound as a polycyclic aromatic compound in which an aromatic ring is linked with a hetero element such as boron, phosphorus, oxygen, nitrogen and sulfur. .. Further, they have found that an excellent organic EL element can be obtained by arranging a layer containing this polycyclic aromatic compound between a pair of electrodes to form an organic EL element, and completed the present invention. That is, the present invention provides a polycyclic aromatic compound such as the following, and a material for an organic device containing the following polycyclic aromatic compound.

式（１Ａ）および式（１Ｂ）中、
Ａ環およびＢ環は、それぞれ独立して、置換されていてもよいアリール環または置換されていてもよいヘテロアリール環であり、
Ｒ^XD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、破線が－Ｘ－または単結合となってＡ環またはＢ環の少なくとも１つと結合していてもよく、
Ａ環、Ｂ環またはＲ^XDの少なくとも１つにおける前記アリール環またはヘテロアリール環は式（１Ｂ）で表される部分構造に結合しており、
式（１Ｂ）で表される部分構造は２つの＊の位置で前記アリール環またはヘテロアリール環の環上で隣接する２つの原子にそれぞれ結合し、
Ｃ環は、それぞれ独立して、置換されていてもよいアリール環または置換されていてもよいヘテロアリール環であり、
Ｒ^XE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、破線が－Ｘ－または単結合となってＣ環と結合していてもよく、また、破線が－Ｘ－または単結合となって式（１Ｂ）で表される部分構造が結合している環と（＊）の位置で結合していてもよく、
Ｙは、それぞれ独立して、Ｂ、Ｐ、Ｐ＝ＯまたはＰ＝Ｓであり、
Ｘは、それぞれ独立して、＞Ｃ（－Ｒ）₂、＞Ｎ－Ｒ、＞Ｏ、＞Ｓｉ（－Ｒ）₂または＞Ｓ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および＞Ｓｉ（－Ｒ）₂のＲは、それぞれ独立して、水素、置換されていてもよいアリール、置換されていてもよい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、また連結基によって互いに結合していてもよく、また、前記＞Ｎ－Ｒ、前記＞Ｃ（－Ｒ）₂、および前記＞Ｓｉ（－Ｒ）₂のＲの少なくとも１つは連結基または単結合によりＡ環、Ｂ環、Ｃ環、Ｒ^XD、またはＲ^XEの少なくとも１つと結合していてもよく、
Ｘは、少なくとも１つが＞Ｎ－Ｒであり、＞Ｎ－ＲであるＸの少なくとも１つにおけるＲは前記Ａ環、Ｂ環、Ｃ環、Ｒ^XD、またはＲ^XEの１つと結合して式（Ａ１０）で表される部分構造を形成しており、式（Ａ１０）中、Ｒ^A1～Ｒ^A4はそれぞれ独立して、水素、置換されていてもよいアルキルまたは置換されていてもよいシクロアルキルであり、Ｒ^A1～Ｒ^A4の任意の２～４個は連結基または単結合により互いに結合していてもよく、式（Ａ１０）で表される部分構造は、２つの＊の位置で一方の環に、＊＊の位置で他方の環に結合しており、
前記多環芳香族化合物におけるアリール環およびヘテロアリール環からなる群より選択される少なくとも１つは、少なくとも１つのシクロアルカンで縮合されていてもよく、当該シクロアルカン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、当該シクロアルカンにおける少なくとも１つの－ＣＨ₂－は－Ｏ－で置換されていてもよく、
前記多環芳香族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い。 <1> A polycyclic aromatic compound composed of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B);

In formula (1A) and formula (1B),
Rings A and B are independently optionally substituted aryl rings or optionally substituted heteroaryl rings, respectively.
R ^XD is an aryl that may be substituted, a heteroaryl that may be substituted, an alkyl that may be substituted or a cycloalkyl that may be substituted, and the dashed line is -X- or a single bond. It may be bonded to at least one of the A ring or the B ring.
The aryl ring or heteroaryl ring in at least one of the A ring, the B ring or the ^RXD is bonded to the partial structure represented by the formula (1B).
The partial structure represented by the formula (1B) is bonded to two adjacent atoms on the ring of the aryl ring or the heteroaryl ring at two * positions, respectively.
The C ring is an aryl ring which may be substituted or a heteroaryl ring which may be substituted, respectively.
R ^XE is an aryl that may be substituted, a heteroaryl that may be substituted, an alkyl that may be substituted or a cycloalkyl that may be substituted, and the dashed line is -X- or a single bond. It may be bonded to the C ring, and the broken line is -X- or a single bond and is bonded to the ring to which the partial structure represented by the equation (1B) is bonded at the position (*). May be
Y is B, P, P = O or P = S independently of each other.
X is independently> C (-R) ₂ ,>N-R,>O,> Si (-R) ₂ or> S, and R in> N-R is substituted. _{R _} Are independently hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and may be attached to each other by a linking group. At least one of the above> N-R, the above> C (-R) ₂ , and the above> Si (-R) ₂ R is an A ring, a B ring, a C ring, an R ^XD , or an A ring by a linking group or a single bond. May be combined with at least one of R ^XE ,
X is an expression in which at least one of X is> N-R and R in at least one of X is> N-R combined with one of the A ring, B ring, C ring, R ^XD , or R ^XE . A partial structure represented by (A10) is formed, and in the formula (A10), ^{RA1 to RA4 are} independently hydrogen, substituted alkyl or substituted cycloalkyl, respectively. Any 2 to 4 of ^RA1 to ^RA4 may be bonded to each other by a linking group or a single bond, and the partial structure represented by the formula (A10) is one at two * positions. It is attached to the ring at the position of ** and is attached to the other ring.
At least one selected from the group consisting of an aryl ring and a heteroaryl ring in the polycyclic aromatic compound may be condensed with at least one cycloalkane, and at least one hydrogen in the cycloalkane is substituted. Alternatively, at least one -CH _2- in the cycloalkane may be substituted with -O-.
At least one hydrogen in the polycyclic aromatic compound may be substituted with deuterium, cyano or halogen.

<2> Even if R ^XD is an aryl that may be substituted or a heteroaryl that may be substituted, the broken line becomes −X− and is bonded to the A ring, and R ^XE is substituted. The polycyclic aromatic compound according to <1>, which is a good aryl or a heteroaryl which may be substituted, and is bonded to the C ring with a broken line of −X—.
<3> The polycyclic aromatic compound according to <1> or <2>, wherein ^RA1 and ^RA4 are bonded to each other, and ^RA2 and ^RA3 are alkyls which may be independently hydrogenated or substituted, respectively. ..
<4> The polycycle according to <1> or <2>, wherein ^{RA1 and RA4 are} bonded to each other to form − (CH ₂ ) _4- , and ^RA2 and ^RA3 are both methyl. Aromatic compounds.
<5> Substituents when the A ring, B ring and C ring are substituted aryl rings or substituted heteroaryl rings and aryls or substituted heteros in which R ^XD and R ^XE are substituted. All substituents, when aryl, are 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 attached via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or no substituted. Selected from the group consisting of substituted alkoxy, substituted or unsubstituted aryloxy, substituted silyl and -L-Ak.
L is>N-R,> O or> S, where R in> N-R is an aryl optionally substituted, a heteroaryl optionally substituted, an alkyl optionally substituted or substituted. The cycloalkyl may be such that the> N-R R may be attached to Ak by a linking group or a single bond.
Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and at least one hydrogen in the alkyl and cycloalkyl may be substituted and at least one in the alkyl and cycloalkyl. -CH ₂ -may be substituted with -O- and -S-, and may be substituted.
A ring, B ring, C ring, R ^XD and R ^XE are any of <1> to <4> bonded to any X and Y in a 5-membered ring or a 6-membered ring. The polycyclic aromatic compound described in.

式（３－１－１）、式（３－１－２）、式（３－２－１）中、
Ｘ¹は、それぞれ独立して、＞Ｃ（－Ｒ）2、＞Ｎ－Ｒ、＞Ｏ、＞Ｓｉ（－Ｒ）₂または＞Ｓであり、前記＞Ｎ－ＲのＲは、炭素数１～６のアルキルもしくは炭素数３～１４のシクロアルキルで置換されていてもよい炭素数６～１２のアリール、炭素数１～６のアルキルもしくは炭素数３～１４のシクロアルキルで置換されていてもよい炭素数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および＞Ｓｉ（－Ｒ）₂のＲは、それぞれ独立して、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、
Ｙは、それぞれ独立して、Ｂ、Ｐ、Ｐ＝ＯまたはＰ＝Ｓであり、
Ｚは、それぞれ独立して、－Ｃ（－Ｒ^Z）＝または－Ｎ＝であり、隣り合う２つのＺは、－Ｃ（－Ｒ^Z）₂－、－Ｓｉ（－Ｒ^Z）₂－、－Ｎ（－Ｒ^Z）－、－Ｏ－、または－Ｓ－に置き換えられてもよく、
Ｒ^Z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、アリールオキシ、置換シリルまたは－Ｌ－Ａｋ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^Zのうちの隣接する基同士が結合してａ環、ｃ環、ｄ環またはｅ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、アリールオキシ、置換シリルまたは－Ｌ－Ａｋ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、
Ｌは＞Ｎ－Ｒ、＞Ｏまたは＞Ｓ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＞Ｎ－ＲのＲは連結基または単結合によりＡｋと結合していてもよく、
Ａｋは水素、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、当該アルキルおよびシクロアルキル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、当該アルキルおよびシクロアルキルにおける少なくとも１つの－ＣＨ₂－は－Ｏ－および－Ｓ－で置換されていてもよく、
式（３－１－１）、式（３－１－２）、式（３－２－１）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い。 <6> The polycyclic aromatic compound according to <1>, which is represented by any of the following formulas (3-1-1), formula (3-1-2), and formula (3-2-1);

In Eqs. (3-1-1), Eqs. (3-1-2), Eqs. (3-2-1),
X ¹ is independently> C (-R) 2,>N-R,>O,> Si (-R) ₂ or> S, and R of> N-R has 1 carbon atom. May be substituted with an alkyl of ~ 6 or a cycloalkyl of 3-14 carbons. Even if substituted with an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms. A good heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms, and the R of> C (-R) ₂ and> Si (-R) ₂ described above are each. Independently, it is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms.
Y is B, P, P = O or P = S independently of each other.
Z is -C (-R ^Z ) = or -N = independently of each other, and two adjacent Zs are -C (-R ^Z ) _2- , -Si (-R ^Z ) _2- , It may be replaced with -N (-R ^Z )-, -O-, or -S-.
R ^Z may be independently bonded to hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be attached via a single bond or a linking group). ), Alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl or -L-Ak, wherein at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and R. Adjacent groups of ^Z may be bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a c ring, a d ring or an e ring, and at least one hydrogen in the formed ring is aryl. , Heteroaryl, Diarylamino, Diheteroarylamino, Arylheteroarylamino, Diarylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, Substituted Cyril or —L—Ak may be substituted, at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
L is>N-R,> O or> S, where R in> N-R is an aryl optionally substituted, a heteroaryl optionally substituted, an alkyl optionally substituted or substituted. The cycloalkyl may be such that the> N-R R may be attached to Ak by a linking group or a single bond.
Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and at least one hydrogen in the alkyl and cycloalkyl may be substituted and at least one in the alkyl and cycloalkyl. -CH ₂ -may be substituted with -O- and -S-, and may be substituted.
Even if at least one hydrogen in the compound represented by the formula (3-1-1), the formula (3-1-2), and the formula (3-2-1) is substituted with deuterium, cyano or halogen. good.

<7> Y is B,
Z are independently -C (-R ^Z ) = or -N =, where o- or p-position Z with respect to Y is -C (-R ^Z ) =, <6> The polycyclic aromatic compound.
<8> The polycyclic aromatic compound according to <7>, wherein Z is -C (-R ^Z ) =.
<9> A reactive compound in which a reactive substituent is substituted on the polycyclic aromatic compound according to any one of <1> to <8>.
<10> A polymer compound obtained by polymerizing the reactive compound according to <9> as a monomer, or a polymer crosslinked product obtained by further cross-linking the polymer compound.

<11> A pendant type polymer compound in which the main chain type polymer is substituted with the reactive compound described in <9>, or a pendant type polymer crosslinked body in which the pendant type polymer compound is further crosslinked.
<12> A material for an organic device containing the polycyclic aromatic compound according to any one of <1> to <8>.
<13> A material for an organic device containing the reactive compound according to <9>.
<14> A material for an organic device containing the polymer compound or polymer crosslinked body according to <10>.
<15> A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked body according to <11>.
<16> The material for an organic device according to any one of <12> to <15>, wherein the material for the organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell. ..
<17> The material for an organic device according to <16>, wherein the material for the organic electroluminescent element is a material for a light emitting layer.
<18> A composition comprising the polycyclic aromatic compound according to any one of <1> to <8> and an organic solvent.
<19> A composition comprising the reactive compound according to <9> and an organic solvent.
<20> A composition comprising a main chain polymer, the reactive compound according to <9>, and an organic solvent.

<21> A composition comprising the polymer compound or polymer crosslinked body according to <10> and an organic solvent.
<22> A composition comprising the pendant-type polymer compound or the pendant-type polymer crosslinked product according to <11> and an organic solvent.
<23> The polycyclic aromatic compound according to any one of <1> to <8>, and the reactive compound according to <9>, which are arranged between a pair of electrodes composed of an anode and a cathode and the pair of electrodes. , An organic field light emitting element having an organic layer containing the polymer compound or polymer crosslinked body according to <10>, or the pendant type polymer compound or pendant type polymer crosslinked body according to <11>.
<24> The organic electroluminescent device according to <23>, wherein the organic layer is a light emitting layer.
<25> The light emitting layer contains a host and the polycyclic aromatic compound, a reactive compound, a polymer compound, a polymer crosslinked body, a pendant type polymer compound or a pendant type polymer crosslinked body as a dopant. The organic field light emitting element according to <24>.

<26> The organic electroluminescent element according to <25>, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzochrysene-based compound.
<27> It has at least one layer of an electron transport layer and an electron injection layer arranged between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a borane derivative, pyridine. At least one selected from the group consisting of derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphinoxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol-based metal complexes. The organic electric field light emitting element according to any one of <24> to <26>, which contains one.
<28> At least one of the electron transport layer and the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, and an alkaline earth metal oxide. , 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 from the group. The organic electric field light emitting element according to <27>.
<29> A polymer obtained by polymerizing at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer as a monomer of a low molecular weight compound capable of forming each layer. A 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 height. The organic electric field light emitting element according to any one of <24> to <28>, which comprises a pendant type polymer crosslinked body in which a molecular compound is further crosslinked.
<30> A display device or a lighting device provided with the organic electroluminescent element according to any one of <23> to <29>.

INDUSTRIAL APPLICABILITY The present invention provides a novel polycyclic aromatic compound. The polycyclic aromatic compound of the present invention is useful as a material for an organic device, particularly a material for a light emitting layer for forming a light emitting layer of an organic electroluminescent element.

It is a schematic sectional drawing which shows the example of the organic EL element. It is a figure explaining the method of manufacturing the organic EL element by the inkjet method on the substrate which has a bank.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range represented by using "-" in this specification means the range including the numerical values before and after "-" as the lower limit value and the upper limit value. Further, in the present specification, "hydrogen" in the description of the structural formula means "hydrogen atom (H)".

In the present specification, the chemical structure or substituent may be represented by the number of carbon atoms, but the number of carbon atoms when the chemical structure is substituted with a substituent or when the substituent is further substituted with a substituent is the chemical structure or substitution. It means the carbon number of each group, and does not mean the total carbon number of the chemical structure and the substituent, or the total carbon number of the substituent and the substituent. 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 of carbon number Y substituted with substituent A" means that "substituent A (with no limitation on carbon number)" is substituted with "substituent B having 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.

1. 1. Polycyclic Aromatic Compound The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having a partial structure represented by the following formula (1A) and a partial structure represented by at least one formula (1B).

In the formula (1A) and the formula (1B), "A", "B", and "C" are symbols indicating a ring structure. Further, in the formula (1A) and the formula (1B), the broken line indicates that the rings or groups at both ends of the broken line may or may not be bonded to each other. In the formula (1A) and the formula (1B), * indicates a position, but in the formula (1B), the (*) at one end of the broken line indicates that the position may or may not exist. ..

In the polycyclic aromatic compound of the present invention, at least one of X connecting the ring structure and the ring structure is> N-R, and this R may be substituted alkyl or substituted. It is a good cycloalkyl and has a structure linked to an aryl ring or a heteroaryl ring in at least one of the A ring, B ring, C ring, ^RXD , or ^RXE by a linking group or a single bond.
Specifically, the polycyclic aromatic compound of the present invention has the following partial structure (A10) by the above-mentioned linkage.

In formula (A10), ^{RA1 to RA4 are} each independently hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and any 2 to 4 of ^RA1 to ^RA4 . May be attached to each other by a linking group or a single bond, to one ring of the two rings to which X is attached at the two * positions, and to the other ring at the ** position. That is, N in the formula (A10) is N of> NR when X is> NR. The atoms on the ring bonded at the two * positions may be atoms adjacent to each other (preferably carbon atoms).
The partial structure represented by the formula (A10) contains an NC bond having a weak bond dissociation energy (BDE), but the presence of another bond forming a ring causes a reverse reaction even when the NC bond is cleaved (A10). Since the recombination reaction) is promoted, the polycyclic aromatic compound of the present invention has a more stable structure. Therefore, it is expected that the organic EL device manufactured by using the polycyclic aromatic compound of the present invention has a long device life.
The number of the partial structures represented by the above-mentioned linkage formula (A10) contained in the polycyclic aromatic compound of the present invention is 1 to "the number of X", and is preferably 1 or 2.

In formula (A10), ^{RA1 to RA4 are} hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and any 2 to 4 of ^{RA1 to RA4 are} each other by a linking group. It may be connected.
RA1 to ^RA4 can be any two ( ^RA1 and ^RA4 , ^{RA1 and RA4 and RA1} and ^RA4 , ^RA1 and ^RA2 , ^RA3 and ^RA4 , ^RA1 and ^RA4 and ^{RA1 )} . ^{And RA4} ) are preferably bonded to each other by a linking group or a single bond, and more preferably ^{RA1 and RA4 are} bonded to each other by a linking group or a single bond. Examples of the divalent group formed by bonding with each other include alkylene. At least one hydrogen in the alkylene may be substituted with alkyl or cycloalkyl, and at least one (preferably one) -CH _2- in the alkane is substituted with -O- and -S-. May be good. As the linking group, a linear alkylene having 2 to 5 carbon atoms is preferable, a linear alkylene having 3 or 4 carbon atoms is more preferable, and a linear alkylene having 4 carbon atoms (-(CH ₂ ) _4- ) is further preferable. It is particularly preferable that the linear alkylene (-(CH ₂ ) _4- ) having 4 carbon atoms is unsubstituted.

The remaining ^{RA1 to RA4 that} are not involved in the linkage by the linking group are preferably hydrogen or an optionally substituted alkyl, respectively, and may be substituted with 1 to 6 carbon atoms. It is more preferably alkyl, more preferably unsubstituted alkyl having 1 to 6 carbon atoms, and most preferably methyl.
That is, as the partial structure represented by the formula (A10), the structure represented by the following formula (A11) is preferable.

式（Ａ１１）中、Ｍｅはメチルであり、２つの＊の位置でＸが結合する２つの環の一方の環に、＊＊の位置で他方の環に結合している。

In formula (A11), Me is methyl and is attached to one ring of the two rings to which X is attached at the two * positions and to the other ring at the ** position.

In formulas (1A) and (1B), the A ring and the B ring and the C ring are aryl rings which may be independently substituted or heteroaryl rings which may be substituted, respectively.
In formula (1A), R ^XD is an aryl that may be substituted, a heteroaryl that may be substituted, an alkyl that may be substituted, or a cycloalkyl that may be substituted. The R ^XD may be bonded to at least one of the A ring or the B ring with the dashed line being -X- or a single bond. R ^XD is preferably an aryl that may be substituted or a heteroaryl that may be substituted. Further, it is preferable that the broken line of R ^XD is −X— and is bonded to the A ring. In formula (1B), R ^XE are independently substituted aryl, substituted heteroaryl, substituted alkyl or optionally substituted cycloalkyl, respectively. .. In R ^XE , the broken line may be -X- or a single bond and is bonded to the C ring, and the broken line may be -X- or a single bond and the partial structure represented by the formula (1B) is bonded. It may be bonded to the ring at the position of (*). R ^XE is preferably an aryl that may be substituted or a heteroaryl that may be substituted. Further, it is preferable that the broken line of R ^XE is −X— and is bonded to the C ring.
That is, the formula (1A) is preferably the following formula (2A), and the formula (1B) is preferably the following formula (2B).

In the formula (2A), the aryl ring or the heteroaryl ring in at least one of the A ring, the B ring or the D ring is bonded to the partial structure represented by the formula (2B).
The partial structure represented by the formula (2B) is bonded to two adjacent atoms on the ring of the aryl ring or the heteroaryl ring at two positions *.
In formula (2A), the same symbols as in formula (1A) are synonymous with each in formula (1A). “D” is a code indicating a ring structure and is an aspect of R ^XD of the formula (1A). In formula (2B), the same symbols as in formula (1B) are synonymous with each in formula (1B). "E" is a code indicating a ring structure and is an aspect of R ^XE in the formula (1B).

The A ring, B ring, C ring, R ^XD and R ^XE in the formula (1A) and the formula (1B) are (A ring, B ring, C ring, D ring and E in the formula (2A) and the formula (2B). The ring) is preferably bonded to any of X and Y in the 5-membered ring or the 6-membered ring. Here, "in a 5-membered ring or a 6-membered ring, it is bonded to any X and Y" means that the ring is formed only by the 5-membered ring or the 6-membered ring, or the 5-membered ring is formed. Other rings and the like are condensed to include a ring or a 6-membered ring to form an aryl ring or a heteroaryl ring in A ring, B ring, C ring, R ^XD or R ^XE , of which a 5-membered ring or a 6-membered ring is formed. It means that it is bonded to any X or Y at the ring-constituting atom on the member ring.

The A, B, and C rings in formulas (1A) and (1B) and the A, B, C, D, and E rings in formulas (2A) and (2B) are independent of each other. , May be substituted aryl ring or optionally substituted heteroaryl ring.

In the A ring, B ring, C ring, R ^XD and R ^XE in the formula (1A) and the formula (1B), and in the A ring, B ring, C ring, D ring and E ring in the formula (2A) and the formula (2B). Examples of the "aryl ring" include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, more preferably an aryl ring having 6 to 12 carbon atoms, and having 6 to 10 carbon atoms. Aryl rings are particularly preferred.

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, an inden ring, which is a fused dicyclic system, and a terphenyl ring (m-tel), which is a tricyclic system. (Phenyl, o-terphenyl, p-terphenyl), acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, anthracene ring, fused tetracyclic system, triphenylene ring, pyrene ring, naphthalene ring, Examples thereof include a chrysene ring, a perylene ring which is a condensed pentacene ring, and a pentacene ring. Further, the fluorene ring, the benzofluorene ring, and the indene ring also include a structure in which a fluorene ring, a benzofluorene ring, a cyclopentane ring, and the like are spiro-bonded, respectively. In the fluorene ring, benzofluorene ring, and indene ring, two of the two hydrogens of methylene are substituted with an alkyl such as methyl as the first substituent described later, respectively, and the dimethylfluorene ring and the dimethylbenzofluorene ring are substituted. And those with a dimethylindene ring are also included.

In the A ring, B ring, C ring, R ^XD and R ^XE in the formula (1A) and the formula (1B), and in the A ring, B ring, C ring, D ring and E ring in the formula (2A) and the formula (2B). Examples of the "heteroaryl ring" include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, and more preferably a heteroaryl ring having 2 to 20 carbon atoms. A heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Further, 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.

Specific "heteroaryl rings" include, for example, a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxaziazole ring, a thiadiazol ring, a triazole ring, a tetrazole ring, a pyrazole ring, and the like. Ppyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring. , Cinnoline ring, quinazoline ring, quinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indolidin ring, Fran ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazan ring, thiantolen ring, indolocarbazole ring, benzoindorocarbazole ring, benzobenzoindorocarbazole ring, naphthobenzofuran ring, Examples thereof include a dioxine ring, a dihydroaclydin ring, a xanthene ring, a thioxanthene ring, and a dibenzodioxine ring. Further, in the dihydroacridine ring, xanthene ring, and thioxanthene ring, two of the two hydrogens of methylene are substituted with an alkyl such as methyl as the first substituent described later, respectively, and the dimethyldihydroacridine ring and dimethyl are substituted. Those having a xanthene ring, a dimethylthioxanthene ring, or the like are also preferable. Further, a bicyclic bipyridine ring, a phenylpyridine ring, a pyridylphenyl ring, a tricyclic terpyridyl ring, a bispyridylphenyl ring, and a pyridylbiphenyl ring are also mentioned as "heteroaryl rings". Further, the "heteroaryl ring" shall also include a pyran ring.

When at least one hydrogen in the above aryl ring or heteroaryl ring is substituted with a substituent, the substituent is a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino. , Substituted or unsubstituted diheteroarylamino, substituted or unsubstituted aryl heteroarylamino (amino having aryl and heteroaryl), 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, substituted or unsubstituted aryloxy, substituted silyl, or -L-Ak are preferable. When these groups have substituents, the substituents include aryl, heteroaryl, alkyl or cycloalkyl, or diarylamino.

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 ”, substituted or unsubstituted“ aryloxy ”, substituted“ It may be substituted with "silyl" or -L-Ak. The first substituents are "aryl" and "heteroaryl", "diarylamino" aryl, "diheteroarylamino" heteroaryl, "aryl heteroarylamino" aryl and heteroaryl, and "diarylboryl". As the aryl of "aryloxy", the monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring" can be mentioned.

Specifically, examples of the "aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and aryls having 6 to 16 carbon atoms. Is more preferable, aryl having 6 to 12 carbon atoms is particularly preferable, and aryl having 6 to 10 carbon atoms is most preferable.

Specific examples of the aryl include phenyl, which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl, which is a bicyclic aryl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , (2-, 3-, 4-, 5-, 6-, 7-) indenyl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-4'-yl, which is a tricyclic aryl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-telphenyl-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 -Il, p-terphenyl-3-yl, p-terphenyl-4-yl), acenaphtylene- (1-, 3-, 4-, 5-) yl, which is a fused tricyclic aryl, fluoren- ( 1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl Quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m -Quaterphenylyl), triphenylene- (1-, 2-) yl, which is a fused tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) ) Ill, perylene- (1-, 2-, 3-) yl, which is a fused pentacyclic aryl, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" include heteroaryls having 2 to 30 carbon atoms, preferably heteroaryls having 2 to 25 carbon atoms, more preferably heteroaryls having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. A heteroaryl of 15 is more preferred, and a heteroaryl having 2 to 10 carbon atoms is particularly preferred. 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, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, and the like. Isobenzofuranyl, dibenzofuranyl, benzo [b] thienyl, dibenzothienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, Examples thereof include quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl, pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazine, phenazinyl, phenoxatinyl, thiantrenyl, indolidinyl and the like.

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 8 carbon atoms is more preferable. (Branch chain alkyl having 3 to 8 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms) is particularly preferable, and an alkyl having 1 to 5 carbon atoms (3 to 5 carbon atoms) is particularly preferable. Branched chain alkyl) is most preferred.

Specific alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n-. Hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3) -Tetramethylbutyl), 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, etc. can give.

Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1,1,2- Trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3- Dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1 -Propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl and the like can also be mentioned.

As the substituent containing the above "alkyl", the tertiary-alkyl represented by the following formula (tR) is substituted when at least one hydrogen in the above aryl ring or heteroaryl ring is substituted with a substituent. As a base, it is one of the particularly preferable ones. This is because such a bulky substituent increases the intramolecular distance and thus the emission quantum yield (PLQY) is improved. Further, a substituent in which the tertiary-alkyl represented by the formula (tR) is substituted with another substituent as the second substituent is also preferable. Specifically, it is a tertiary-alkyl substituted diarylamino represented by (tR), a tertiary-alkyl substituted carbazolyl represented by (tR) (preferably N-carbazolyl) or (tR). Examples thereof include benzocarbazolyl (preferably N-benzocarbazolyl) substituted with the represented tertiary-alkyl. Examples of the "diarylamino" include groups described below as the "first substituent". As a form of substitution of a group of the formula (tR) with diarylamino, carbazolyl and benzocarbazolyl, a part or all of hydrogen of the aryl ring or the benzene ring in these groups was substituted with the group of the formula (tR). For example.

In the formula (tR), R ^a , R ^b , and R ^c are independently alkyls having 1 to 24 carbon atoms, and any -CH _2- in the alkyl may be substituted with -O-. , The group represented by the formula (tR) is replaced with at least one hydrogen in the compound consisting of the partial structure represented by the formula (1A) and the partial structure represented by at least one formula (1B) in *.

The "alkyl having 1 to 24 carbon atoms" of R ^a , 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 branch having 3 to 24 carbon atoms. Chain alkyl, 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 (carbon) Examples thereof include a branched chain alkyl having 3 to 6 carbon atoms and an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

The total number of carbon atoms of R ^a , R ^b , and R ^c in the formula (tR) is preferably 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms.

Specific alkyls of R ^a , R ^b , and R ^c include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t. -Pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1- Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, Examples thereof include 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

Examples of the group represented by the formula (tR) include t-butyl, t-amyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl and 1-ethyl-1-. Methylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,4-trimethylpentyl, 1,1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1- Dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3-dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1- Methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1-propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl- Examples thereof include 1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl and 1,1-dimethylhexyl. Of these, t-butyl and t-amyl are preferred.

Examples of the "cycloalkyl" as the first substituent include 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. Examples thereof include cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.

Specific cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (particularly methyl) substituents having 1 to 5 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, Adamanthyl, Diamantyl, Decahydronaphthalenyl, Decahydroazurenyl and the like.

Further, as the "alkoxy" as the first substituent, for example, an alkoxy having a linear chain having 1 to 24 carbon atoms or a branched chain having 3 to 24 carbon atoms can be mentioned. Alkoxy having 1 to 18 carbon atoms (alkoxy of a branched chain having 3 to 18 carbon atoms) is preferable, and alkoxy having 1 to 12 carbon atoms (alkoxy of a branched chain 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 5 carbon atoms (alkoxy of a branched chain having 3 to 5 carbon atoms) is particularly preferable.

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

Examples of the "substituted silyl" as the first substituent include silyls substituted with three substituents selected from the group consisting of alkyl, cycloalkyl, and aryl. For example, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, triarylsilyl, dialkylarylsilyl, and alkyldiarylsilyl.

The "trialkylsilyl" includes a group in which each of the three hydrogens in the silyl group is independently substituted with an alkyl, and this alkyl cites the group described as "alkyl" in the first substituent described above. be able to. Preferred alkyls for substitution are alkyls having 1 to 5 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl and t-amyl.

Specific examples of the trialkylsilyl include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, trit-amylsilyl, ethyldimethylsilyl, and propyldimethylsilyl. i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, t-amyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethyl Cyril, t-butyldiethylsilyl, t-amyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, t-amyldipropylsilyl, Examples thereof include methyldi i-propyl silyl, ethyl di-propyl silyl, butyl di-propyl silyl, sec-butyl di-propyl silyl, t-butyl di-propyl silyl, and t-amyldi i-propyl silyl.

Examples of the "tricycloalkylsilyl" include groups in which the three hydrogens in the silyl group are independently substituted with cycloalkyl, and this cycloalkyl has been described as "cycloalkyl" in the first substituent described above. The group can be quoted. 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. Examples include decahydronaphthalenyl and decahydroazurenyl.

Specific examples of the tricycloalkylsilyl include tricyclopentylsilyl and tricyclohexylsilyl.

Specific examples of the dialkyl cycloalkylsilyl 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 Cyril in which the group to be substituted is substituted.

Specific examples of the dialkylarylsilyl substituted with two alkyls and one aryl, the alkyldiarylsilyl substituted with one alkyl and two aryls, and the triarylsilyl substituted with three aryls are the specific alkyls described above. And silyl substituted with a group selected from aryl. Specific examples of triarylsilyl include triphenylsilyl.

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 (hereinafter, the first substituent), and the first is said. 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.

In -L-Ak of the first substituent, L is> N-R,> O or> S, and R of> N-R may be substituted, aryl, or substituted. Heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl. Further, R of> NR may be bonded to Ak by a linking group or a single bond.

Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and at least one hydrogen in the alkyl and cycloalkyl may be substituted and at least one in the alkyl and cycloalkyl. -CH _2- may be substituted with -O- and -S-.

L is preferably> N-R.
When L is> N—R, R is preferably an aryl substituted with alkyl or cycloalkyl, a heteroaryl optionally substituted with alkyl or cycloalkyl, alkyl or cycloalkyl, preferably alkyl. It is more preferably an aryl optionally substituted with, a heteroaryl optionally substituted with alkyl, alkyl or cycloalkyl, even more preferably an aryl optionally substituted with alkyl and substituted with methyl. It is particularly preferable that it is a phenyl which may be used.

Ak is preferably an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms, preferably an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 3 to 8 carbon atoms, and has 1 to 8 carbon atoms. It is more preferably an alkyl of 4, and even more preferably methyl.

When L is> N—R, R may be attached to Ak by a linking group or a single bond. Examples of the linking group at this time include>O,> S or> Si (-R) ₂ . > R of Si (−R) ₂ is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms. The following is an example of a structure in which R of> NR is bonded to Ak by a linking group or a single bond.

In each of the above formulas, Me is methyl and is bonded to the ring-constituting atom of the aryl ring or heteroaryl ring in the A ring, B ring, C ring, R ^XD or R ^XE at the position of *.

The first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted Alternatively, an unsubstituted "aryl heteroarylamino", a substituted or unsubstituted "diarylboryl (two aryls may be bonded via a single bond or a linking group)", a substituted or unsubstituted "alkyl", Substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", substituted or unsubstituted "aryloxy", or substituted "silyl" are described as substituted or unsubstituted. At least one hydrogen in the above 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 also. A description of "alkyl" or "cycloalkyl" as the first substituent can be referred to. Further, in aryls and heteroaryls as the second substituent, at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), methyl, t-butyl and the like (specific examples are described above). Aryl or heteroaryl as a second substituent is also included in the structure substituted with a cycloalkyl (specific example is the group described above) such as (the group described above) or cyclohexyl. As an example, when the second substituent is carbazolyl, carbazolyl 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. Included in heteroaryl as a substituent.

The emission wavelength can be adjusted by the steric hindrance, electron donating property and electron withdrawing property of the structure of the first substituent. It is preferably a group represented by the following structural formula, and more preferably methyl, t-butyl, t-amyl, t-octyl, neopentyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2,4-. Xylyl, 2,5-xylyl, 2,6-xsilyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl (particularly N- Carbazolyl), 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, more preferably methyl, t-butyl, t-amyl, t-octyl, neopentyl, adamantyl. , Phenyl, o-tolyl, 2,6-xysilyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethyl Carbazolyl and 3,6-di-t-butylcarbazolyl. From the viewpoint of ease of synthesis, the one with a large steric hindrance is preferable for selective synthesis, and specifically, t-butyl, t-amyl, t-octyl, adamantyl, o-tolyl, and p-tolyl. , 2,4-Xylylyl, 2,5-Xylylyl, 2,6-xylyl, 2,4,6-methityl, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, 3,6- Dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl are preferred.

In the following structural formula, "Me" is methyl, "tBu" is t-butyl, "tAm" is t-amyl, "toct" is t-octyl, and * represents a binding position.

In the formula (1A) and the formula (1B), Y is B, P, P = O or P = S, respectively, and B or P = O is preferable, and B is more preferable. This description applies similarly to Y in equations (2A) and (2B).

X in the formula (1A) and the formula (1B) are independently> C (-R) 2,>N-R,>O,> Si (-R) ₂ or> S, and the above-mentioned> N. R of —R is an aryl optionally substituted, a heteroaryl optionally substituted, an alkyl optionally substituted or a cycloalkyl optionally substituted, said> C (—R) ₂ . And> R of Si (-R) ₂ are independently hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and by linking groups. They may be attached to each other, and at least one of the Rs of> N-R, said> C (-R) ₂ , and said> Si (-R) ₂ is the A ring by a linking group or a single bond. , B ring, C ring, R ^XD , or R ^XE . And, as mentioned above, X is> N-R, at least one of which is an alkyl optionally substituted or a cycloalkyl optionally substituted with R, and is a linking group or a single bond via R. By bonding, it is linked to an aryl ring or a heteroaryl ring in at least one of A ring, B ring, C ring, ^RXD , or ^RXE . The description of X in the formulas (1A) and (1B) and the description of the following preferable range and the like also apply to X in the formulas (2A) and (2B). In addition, "at least one of A ring, B ring, C ring, R ^XD , or R ^XE " is "A ring, B ring, C ring, D ring or E ring" in the formula (2A) and the formula (2B). At least one selected from the group consisting of ".

The X of formula (1A) and formula (1B)> R of Si (-R) ₂ is aryl, heteroaryl, alkyl or cycloalkyl, which may be substituted with the second substituent described above. .. Examples of the aryl, heteroaryl, alkyl or cycloalkyl include the above-mentioned groups. In particular, aryls with 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), heteroaryls with 2 to 15 carbon atoms (eg, carbazolyl, etc.), alkyls with 1 to 5 carbon atoms (eg, methyl, ethyl, etc.) or 5 to 10 carbon atoms. Cycloalkyl (preferably cyclohexyl or adamantyl) is preferred. This description also applies to R of> Si (-R) ₂ in X in formula (2A) and formula (2B).

The R of> C (-R) ₂ , which is X of formula (1A) and formula (1B), may be substituted with hydrogen, the second substituent described above, aryl, heteroaryl, alkyl or cycloalkyl. Is. Examples of the aryl, heteroaryl, alkyl or cycloalkyl include the above-mentioned groups. In particular, aryls with 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), heteroaryls with 2 to 15 carbon atoms (eg, carbazolyl, etc.), alkyls with 1 to 5 carbon atoms (eg, methyl, ethyl, etc.) or 5 to 10 carbon atoms. Cycloalkyl (preferably cyclohexyl or adamantyl) is preferred. This description applies similarly to R of> C (-R) ₂ in X in equations (2A) and (2B).

It is preferable that at least one of the Xs in the formulas (1A) and (1B) is> N-R described above, and the other Xs are independently> O or> N-R, respectively. It is more preferable that one or more are> NR, and it is further preferable that all of them are> NR.

For aryls, heteroaryls, alkyls and cycloalkyls in R> X> N-R, their description as the first substituents above can be referred to. The R of> N—R in X is preferably an aryl that may be substituted, a heteroaryl that may be substituted, or a cycloalkyl that may be substituted, and is an aryl that may be substituted. Is more preferable. Here, as the aryl, phenyl, biphenylyl (particularly 2-biphenylyl), and terphenylyl (particularly terphenyl-2'-yl) are preferable, and phenyl and biphenylyl are more preferable. When aryl is substituted, methyl or tertiary-alkyl represented by the above formula (tR) is preferable as the substituent. The number of substituents in the aryl is preferably 0 to 3, more preferably 1 to 2.

As R of> N—R of X, unsubstituted phenyl, phenyl having methyl bonded to the ortho-position or para-position, and phenyl having methyl bonded to one or two ortho positions are particularly preferable.

R in at least one of>N-R,> Si (-R) ₂ and> C (-R) ₂ which is X is A ring, B ring, C ring, R ^XD , or R by a linking group or a single bond. It may be attached to at least one ring in ^XE . The linking group is preferably —O—, —S—, or —C (—R) _2- . The R of the above-mentioned "-C (-R) _2- " is hydrogen, alkyl or cycloalkyl. Specific examples of such a structure include the structure represented by the above formula (A10). In addition, more generally, a compound having a ring structure in which X is incorporated into the condensed ring B', which is represented by the following formula (1-3-1), and a compound represented by the following formula (1-3-2). Examples thereof include compounds having a ring structure in which X is incorporated into the fused ring A'. The formed fused ring B'(or fused ring A') is, for example, a carbazole ring, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

When X in the formulas (1A) and (1B) is bound to at least one ring in the A ring, the B ring, the C ring, the R ^XD , or the R ^XE , the linking group includes, for example, -O-, -S-. , -C (-R) _2- or single bond, etc., in which the R of "-C (-R) _2- " is hydrogen, alkyl, or cycloalkyl, which is alkyl or cyclo. Examples of the alkyl include the above-mentioned groups. In particular, an alkyl having 1 to 5 carbon atoms (for example, methyl, ethyl, etc.) or a cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl) is preferable. This description describes the linking group "-C (" when X in formula (2A) and formula (2B) is attached to at least one ring of at least one ring in the A ring, B ring, C ring, D ring or E ring. -R) _2- "also applies in the same way.

At least one selected from the group consisting of an aryl ring and a heteroaryl ring in a compound consisting of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) is at least one cyclo. It may be condensed with an alkane, at least one hydrogen in the cycloalkane may be substituted, and at least one —CH ₂ − in the cycloalkane may be substituted with —O—. This description also applies to compounds where formulas (1A) and (1B) are formulas (2A) and (2B), respectively.

The "cycloalkane" includes cycloalkane having 3 to 24 carbon atoms, cycloalkane having 3 to 20 carbon atoms, cycloalkane having 3 to 16 carbon atoms, cycloalkane having 3 to 14 carbon atoms, and cycloalkane having 5 to 10 carbon atoms. Examples thereof include an alkane, a cycloalkane having 5 to 8 carbon atoms, a cycloalkane having 5 to 6 carbon atoms, and a cycloalkane having 5 carbon atoms.

Specific cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornen, bicyclo [1.0.1] butane, bicyclo [1.1.1] pentane, and so on. Bicyclo [2.0.1] pentane, bicyclo [1.2.1] hexane, bicyclo [3.0.1] hexane, bicyclo [2.1.2] heptane, bicyclo [2.2.2] octane, Examples thereof include adamantane, diamantane, decahydronaphthalene and decahydroazulene, as well as alkyl (particularly methyl) substituents, halogen (particularly fluorine) substitutes and dehydrogenated substitutes having 1 to 5 carbon atoms thereof.

Among these, a structure in which at least one hydrogen is substituted in the carbon at the α-position of cycloalkane (the carbon at the position adjacent to the carbon at the condensation site in the cycloalkyl condensed on the aryl ring or the heteroaryl ring) is preferable, and the structure at the α-position is preferable. A structure in which two hydrogens are substituted in the carbon of 2 is more preferable, and a structure in which a total of 4 hydrogens are substituted in the carbon at the 2 α-position is further preferable. Examples of this substituent include an alkyl (particularly methyl) substituted product having 1 to 5 carbon atoms, a halogen (particularly fluorine) substituted product, and a deuterium substituted product. In particular, it is preferable that the aryl ring or the heteroaryl ring has a structure in which a partial structure represented by the following formula (B10) is bonded to adjacent carbon atoms.

式（Ｂ１０）中、Ｍｅはメチルを示し、＊は結合位置を示す。

In formula (B10), Me indicates methyl and * indicates the binding position.

All or part of the hydrogen in the chemical structure of the polycyclic aromatic compound consisting of the partial structure represented by the formula (1A) and the partial structure represented by at least one formula (1B) is deuterium, cyano, and the like. Alternatively, it may be substituted with halogen. For example, in a polycyclic aromatic compound consisting of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B), the A ring, the B ring, the C ring, the ^RXD , or the R ring. Aryl or heteroaryl rings in ^XE , substituents on these rings, and R (= alkyl) when X is>N-R,> C (-R) ₂ , or> Si (-R) ₂ . , Cycloalkyl, aryl) can be replaced with dehydrogen, cyano or halogen, of which all or part of the hydrogen in aryl or heteroaryl is substituted with dehydrogen, cyano or halogen. Will be. The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, even more preferably fluorine. From the viewpoint of durability, hydrogen in the chemical structure of the polycyclic aromatic compound having a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) is all or one of them. It is also preferable that the portion is deuterated. This description also applies to compounds where formulas (1A) and (1B) are formulas (2A) and (2B), respectively.

Any of the following formulas (3-1) to (3-4) is an example of a polycyclic aromatic compound having a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B). Examples thereof include polycyclic aromatic compounds represented by.

In the formulas (3-1) to (3-4), the same symbols as in the formulas (1A) and (1B) are synonymous with the respective formulas (1A) and (1B), and the preferable ranges are also the same. Is. The A ring, B ring, C ring, R ^XD and R ^XE in the formula (1A) and the formula (1B) are a ring, b ring, c ring, d ring and e ring or a ring and b ring, respectively. , C ring (c'ring), d ring, e ring (e'ring).
In equations (3-1) to (3-4), Z is independently -C (-R ^Z ) = or -N =, and two adjacent Zs are -C (-R). ^Z ) _2- , -Si (-R ^Z ) _2- , -N (-R ^Z )-, -O-, or -S- may be replaced. As a structure in which two adjacent Zs are replaced with -C (-R ^Z ) _2- , -Si (-R ^Z ) _2- , -N (-R ^Z )-, -O-, or -S- Examples include a cyclopentadiene ring, a pyrrole ring, a furan ring, a thiophene ring, a thiazole ring, and an oxazole ring.

In equations (3-1) to (3-4), Z is independently -C (-R ^Z ) = or -N =, and two adjacent Zs are -C (-R). ^Z ) _2- , -Si (-R ^Z ) _2- , -N (-R ^Z )-, -O-, or -S- is preferably not replaced. At this time, it is preferable that Z in the o (ortho) position or the p (para) position with respect to Y is −C ( ^−RZ ) =. Further, in a ring (single ring) containing Z in which -N =, it is preferable that one or two of the plurality of Z's are -N =, and when two are -N =, two -N are used. = Is preferably not adjacent to each other. When the 6-membered ring is a ring containing Z with −N =, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, or a 1,2,3-triazine ring is preferable, and a pyridine ring, a pyrazine ring, or a pyrimidine is preferable. Rings are more preferred. The number of rings (single ring) containing Z with −N = is preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, and 0 to 1. Is particularly preferable.

Specifically, it is preferable that Z is -C (-R ^Z ) =, that is, it is a benzene ring in which any ring may have a substituent. Further, in the equations (3-1) and (3-2), in addition to -C (-R ^Z ) =, any one or more of Z in the b ring is -N =. It is also preferable that each of the other Zs is -C (-R ^Z ) = independently.

R ^Z may be independently bonded to hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be attached via a single bond or a linking group). ), Alkyl, cycloalkyl, alkoxy, aryloxy or substituted silyls, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and adjacent to R ^Z. The groups are bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a c ring, a d ring and an e ring or an a ring, a c ring, a d ring, an e ring, a c'ring and an e'ring. Often, at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls bonded via a single bond or a linking group). May be substituted with alkyl, cycloalkyl, alkoxy, aryloxy, or substituted silyls, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. ..

For details of R ^Z and a preferable range, the above description of the first substituent and the second substituent can be referred to.

In the formulas (3-1) to (3-4), when Z is -C (-R ^Z ) =, R ^Z is independently hydrogen, an aryl having 6 to 30 carbon atoms, and a carbon number of carbon atoms. 2-30 heteroaryls, diarylamino (where aryls are 6-12 carbons), diarylboryls (where aryls are 6-12 carbons, the two aryls are single-bonded or via a linking group. Can be bonded), alkyl with 1 to 24 carbons, cycloalkyl with 3 to 24 carbons, triarylsilyl (where aryl is aryl with 6 to 12 carbons), or trialkylsilyl (where alkyl is carbon). (Alkyl of number 1 to 6) is preferable, however, adjacent ^RZs are bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl having 6 to 15 carbon atoms together with an a ring, a b ring or a c ring. A ring may be formed, and at least one hydrogen in the formed ring is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 12 carbon atoms, a cycloalkyl having 3 to 16 carbon atoms, and a triarylsilyl (provided to be a triarylsilyl). The aryl may be substituted with an aryl having 6 to 12 carbon atoms) or a trialkylsilyl (where the alkyl is an alkyl having 1 to 5 carbon atoms).
Independently, hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 20 carbon atoms, diarylamino (where aryl is aryl with 6 to 10 carbon atoms), alkyl with 1 to 12 carbon atoms or 3 carbon atoms. More preferably, it is a cycloalkyl of ~ 16.
Independently, they can be hydrogen, aryls with 6 to 16 carbon atoms, diallylamino (where aryls are aryls with 6 to 10 carbon atoms), alkyls with 1 to 12 carbon atoms or cycloalkyls with 3 to 16 carbon atoms. More preferred.

In the a ring, b ring, c ring (c'ring), d ring, and e ring (e'ring) in each of the formulas (3-1) to (3-4), the R ^Z in each ring is 0 to 0 to It is preferable that two are substituents other than hydrogen and the other is hydrogen, and more preferably 0 to 1 are substituents other than hydrogen and the other is hydrogen.
Of the a ring, b ring, c ring (c'ring), d ring, and e ring (e'ring) in each of the formulas (3-1) to (3-4), X> NR. In the ring which is bonded to R and forms the structure represented by the above formula (A10), Z other than the bonded portion is preferably CH.

In each of the formulas (3-1) to (3-4), the R ^Zs bonded to the adjacent C (carbon atom) are bonded to each other to form an a ring, a b ring, a c ring (c'ring), a d ring, or a ring. An aryl ring or a heteroaryl ring may be formed together with the e-ring (e'ring).
An example of the compound represented by the formula (3-1) is represented by the following formula (3-1-a) as a structure in which R ^Zs are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring. As a structure, a structure represented by the following formula (3-1-b) can be mentioned as a structure in which R ^Zs are bonded to each other to form an aryl ring or a heteroaryl ring in which R ^Zs are bonded to each other to form an aryl ring or a heteroaryl ring together with an e ring. .. The A'ring, D'ring and E'ring in each formula correspond to the a ring, d ring and e ring in the formula (3-1), respectively. Further, the definitions of Z, a, b, c, d, e, Y, X and Z in each equation are the same as the definitions in the equation (3-1).

The A'ring, D'ring and E'in the formula (3-1-a) and the formula (3-1-b) are in the adjacent C (carbon atom) according to the formula (3-1). The R ^Zs to be bonded are bonded to each other to show an aryl ring or a heteroaryl ring formed together with the a ring, the b ring and the e ring, respectively (the a ring, the b ring and the e ring were formed by condensation of other ring structures. It can also be called a fused ring). Although not shown in the formula, a compound in which the b ring and the c ring are changed to the B'ring and the C'ring, and the a ring, the b ring, the c ring (c'ring), the d ring, or the e ring ( Some compounds have all of the e'rings changed to A'rings, B'rings, C'rings, D'rings and E'rings.

For example, a benzene ring, an indene ring, a pyrrole ring, a furan ring, and a thiophene with respect to a benzene ring which is an a ring (or a b ring, a c ring (c'ring), a d ring, or an e ring (e'ring)). Each fused ring is an A'ring (or B'ring, C'ring, D'and E'ring) formed by condensing a ring, a benzofuran ring, a benzothiophene ring, a cyclopentadiene ring, or an indene ring. It is a naphthalene ring, a carbazole ring, an indene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, an indene ring, or a fluorene ring.

Further, for example, the cyclopentadiene ring, the pyrrole ring, the furan ring, and the thiophene ring, which are the a ring (or the b ring, the c ring (c'ring), the d ring, or the e ring (e'ring)), are adjacent to each other. Examples of the fused ring in the case where the R ^Z bonded to C are bonded to each other to form a ring to form a benzene ring are an indene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.

Preferred examples of the polycyclic aromatic compound represented by any of the formulas (3-1) to (3-4) include the formula (3-1-1), the formula (3-1-2), and the formula (3-1). Examples thereof include polycyclic aromatic compounds represented by any of 3-2-1).

In the formula (3-1-1), the formula (3-1-2), and the formula (3-2-1), the same symbols as the formulas (3-1) to the formula (3-4) are the formulas (3-1). ) To each of the equations (3-4), and the preferred range is also the same.
In the formula (3-1-1), the formula (3-1-2), and the formula (3-2-1), X ¹ is independently represented by> C (-R) 2,> N-R, respectively. >O,> Si (-R) ₂ or> S, and R of> N-R may be substituted with an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms. An aryl of 6 to 12, an alkyl of 1 to 6 carbons or a heteroaryl of 2 to 15 carbons which may be substituted with a cycloalkyl of 3 to 14 carbons, an alkyl of 1 to 6 carbons or 3 to 3 carbons. It is a cycloalkyl of 14, and the R of> C (-R) ₂ and> Si (-R) ₂ is independently hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms, or an alkyl having 1 to 6 carbon atoms. It is a cycloalkyl having 3 to 14 carbon atoms. As the preferable range of X ¹ , the preferable range of X in the formula (1A) and the formula (1B) can be referred to, but specifically, it is preferably> NR or> O, and at this time. ,> R of N-R may be substituted with an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms and having 2 to 15 carbon atoms. It is preferably a heteroaryl of, more preferably an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 6 carbon atoms, and phenyl which may be substituted with methyl or t-butyl. Is more preferable.

As an example of a polycyclic aromatic compound composed of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B), a more specific example is represented by any of the following formulas. Examples include polycyclic aromatic compounds.

The hydrogen bonded to the benzene ring in each of the above structural formulas may be substituted with methyl or t-butyl, and the continuous hydrogen may be substituted with the partial structure represented by the above formula (B10). good.

A more specific example of the polycyclic aromatic compound of the present invention is a compound represented by the following structural formula. In the following structural formula, "Me" indicates methyl and "tBu" indicates t-butyl.

The polycyclic aromatic compound having a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) is a polymer having a reactive compound substituted with a reactive substituent as a monomer. Polymerized polymer compound (the monomer for obtaining this polymer compound has a polymerizable substituent) or a polymer crosslinked product obtained by further cross-linking the polymer compound (for obtaining this polymer crosslinked product). The polymer compound has a crosslinkable substituent) 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) or a 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 is a crosslinkable substituent). Can be used as a material for an organic device, 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 cross-linking 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, 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. Not particularly limited, but alkenyl, alkynyl, unsaturated compounds of cycloalkyl (eg cyclobutenyl), groups in which at least one -CH _2- in cycloalkyl is substituted with -O- (eg epoxy), non-condensed cycloalkane. Examples thereof include saturated substances (for example, condensed cyclobutene), and substituents having the following structures are preferable. * In each structural formula indicates the bonding position.

L is a single bond, -O-, -S-,> C = O, -OC (= O)-, an alkylene having 1 to 12 carbon atoms, and an 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 is preferable, and 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. 2. Method for Producing Polycyclic Aromatic Compounds A polycyclic aromatic compound composed of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) is basically a ring A (1A). a ring), B ring (b ring), C ring (c ring), R ^XD (D ring, d ring), R ^XE (E ring, e ring) are bonded with a bonding group (group containing X). (First reaction), followed by A ring (a ring), B ring (b ring), C ring (c ring), R ^XD (D ring, d ring), R ^XE (E ring). The final product can be produced by attaching a ring (ring, e-ring) with a binding group (a group containing Y) (second reaction). 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. For these manufacturing methods, the methods described in prior art such as International Publication No. 2015/102118 can be referred to. By using a raw material having a partial structure represented by the formula (A10) somewhere in the reaction step, or by adding a step of introducing the partial structure represented by the formula (A10), the formula (A10) can be used. A compound having a partial structure represented by the above can be produced. The partial structure represented by the formula (A10) can be synthesized by using Fischer's indole synthesis and addition reaction.

3. 3. Organic Devices The 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, an organic thin film solar cell, and the like.

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 element according to the present embodiment.

3-1-1. Structure of Organic Electroluminescent Element The organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and holes. The hole transport layer 104 provided on the injection layer 103, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer. It has an electron injection layer 107 provided on the electron injection layer 106 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. May have a configuration having a hole injection layer 103 provided in the hole injection layer 103 and an anode 102 provided on the hole injection layer 103.

Not all of the above layers are indispensable, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. 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" configuration mode, " 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 / Anodic / 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 / "Anodic / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer / electron" Transport layer / cathode ”,“ substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / light emitting layer / electron transport layer / cathode ”,“ substrate / anode ” The configuration may be "/ light emitting layer / electron transport layer / cathode" or "substrate / anode / light emitting layer / electron injection layer / cathode".

3-1-2. The substrate substrate 101 in the organic electroluminescent element 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 to have less elution ions from the glass, but soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it is possible to use this. 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 surface, 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.

3-1-3. The anode-anode 102 in the organic electroluminescent device serves to inject holes into the light-emitting layer 105. If 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 via 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.), metal halides (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.

3-1-4. The hole injection layer and the hole transport layer in the organic electroluminescent device The hole injection layer 103 has a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. Fulfill. The hole transport layer 104 serves to efficiently transport the holes injected from the anode 102 or the 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 / transport material, 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. Is desirable. 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.

The material forming the hole injection layer 103 and the hole transport layer 104 is a compound, a p-type semiconductor, or a hole injection layer of an organic EL device that has been conventionally used as a hole charge transport material in a photoconductive material. 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, N4, ^N4' -diphenyl- N ⁴ , N ^4' -bis (9-phenyl-9H-carbazole-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) Amino) triphenylamine, N- ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole-3-yl) phenyl)- 9H-fluoren-2-amine, N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1': 4', 1 "-terphenyl] -4- Triphenylamine derivatives such as amines, starburstamine derivatives, etc.), stillben derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives and thiophene derivatives, oxadiazole derivatives, quinoxalin derivatives (kinoxalin derivatives) For example, 1,4,5,8,9,12-hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilane, and the like. In the polymer system, polycarbonate or styrene derivative having the monomer in the side chain, polyvinylcarbazole, polysilane, etc. are preferable, but a thin film necessary for producing a light emitting element can be formed, holes can be injected from the anode, and holes can be further injected. It is not particularly limited as long as it is a compound capable of transporting.

It is also known that the conductivity of organic semiconductors is strongly affected by doping. The organic semiconductor matrix material 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." .Pfeiffer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (6), 729-731 (1998) "). They generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material changes considerably. Known matrix materials having hole transport properties include, for example, benzidine derivatives (such as TPD) or starburst amine derivatives (such as TDATA), or specific metallic phthalocyanines (particularly zinc phthalocyanines (ZnPc)) (such as zinc phthalocyanines). 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 cross-linked compound 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 a polycyclic aromatic compound having a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

3-1-5. The light emitting layer light emitting layer 105 in the organic electroluminescent element 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. A compound showing a strong emission (fluorescence) efficiency is preferable. 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 either one type or a plurality of combinations. For example, an emitting dopant and an assisting dopant may be used as the dopant material. The dopant material may be contained in the whole host material, partially contained in the host material, or may be partially contained. As a doping method, it can be formed by a co-deposited method with a host material, but it may be mixed with the host material in advance and then vapor-deposited at the same time. Further, the light emitting layer can also be formed by a wet film forming method using a composition for forming a light emitting layer prepared by dissolving a material in an organic solvent.

The polycyclic aromatic compound of the present invention can be preferably used as a material for forming a light emitting layer of an organic electroluminescent element. The polycyclic aromatic compound of the present invention is more preferably used as an emitting dopant or an assisting dopant in the light emitting layer, and further preferably used as an emitting dopant.

The light emitting layer containing the polycyclic aromatic compound of the present invention may contain a host compound. Here, the host compound may be one kind or two or more kinds.
Further, the light emitting layer may be either a single layer or a plurality of layers. Further, the host compound, the emitting dopant material, and the assisting dopant material may be contained in the same layer, or at least one component may be contained in each of a plurality of layers. The host compound and the dopant material (emitting dopant or assisting dopant) contained in the light emitting layer may be one kind or a plurality of combinations. The assisting dopant and the emitting dopant may be contained entirely or partially in the host compound as a matrix.

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 mass, more preferably 80 to 99.95% by mass, and further preferably 90 to 99.9% by mass of the entire light emitting layer material. 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 mass, more preferably 0.05 to 20% by mass, and further preferably 0.1 to 10% by mass of the entire light emitting layer material. be. Within the above range, for example, it is preferable in that the density quenching phenomenon can be prevented.

On the other hand, in an organic electroluminescent device using a TADF material as a dopant material, it is preferable that the amount of the dopant material used is low because the concentration dimming phenomenon can be prevented, but the amount of the dopant material used is high. One is preferable from the viewpoint of the efficiency of the thermally activated delayed fluorescence mechanism. Furthermore, in an organic electroluminescent device using a TADF material as an assisting dopant, the emtiting dopant is used compared to the amount of the assisting dopant used in terms of the efficiency of the thermally activated delayed fluorescence mechanism of the assisting dopant. The amount is preferably low.

When the assisting dopant material is used, the guideline for the amount of the host material, the emitting dopant and the assisting dopant used is 40 to 99.99% by mass, 59 to 1% by mass and 59 to 1% by mass of the entire light emitting layer material, respectively. It is 20 to 0.001% by mass, preferably 60 to 99.99% by mass, 39 to 5% by mass, and 10 to 0.01% by mass, more preferably 70 to 99.95% by mass, 29. It is ~ 10% by mass and 5 ~ 0.05% by mass.

3-1-5-1. Host compounds Host materials include fused ring derivatives such as anthracene and pyrene, which have long been known as illuminants, bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, and fluorene derivatives. , Benzofluorene derivatives and the like.

The T1 energy of the host material is preferably higher than the T1 energy of the dopant having the highest T1 energy in the light emitting layer or the assisting dopant from the viewpoint of promoting the generation of TADF in the light emitting layer without inhibiting it. Specifically, the T1 energy of the host is preferably 0.01 eV or more, more preferably 0.03 eV or more, and even more preferably 0.1 eV or more.
Further, a TADF active compound may be used as the host material.

Examples of the host material include a compound represented by the following formula (H1), a compound represented by the following formula (H2), a compound represented by the following formula (H3), and a structure represented by the following formula (H4). Examples thereof include a compound represented by the following formula (H5), a compound represented by the following formula (H6), and a compound represented by the following formula (H6).

3-1-5-1-1. The compound represented by the formula (H1)

In the formula (H1), L ¹ is an arylene having 6 to 24 carbon atoms, preferably an arylene having 6 to 16 carbon atoms, more preferably an arylene having 6 to 12 carbon atoms, and particularly preferably an arylene having 6 to 10 carbon atoms. Specifically, divalent such as benzene ring, biphenyl ring, naphthalene ring, terphenyl ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, triphenylene ring, pyrene ring, naphthacene ring, perylene ring and pentacene ring. The basis can be raised.
At least one hydrogen in the compound represented by the formula (H1) may be substituted with an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, cyano, a halogen or deuterium.

3-1-5-1-2. Compound represented by formula (H2)

In formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms. As the aryl, an aryl having 6 to 24 carbon atoms is preferable, an aryl having 6 to 16 carbon atoms is more preferable, an aryl having 6 to 12 carbon atoms is further preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable, specifically. Examples include monovalent groups such as a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthalene ring, a perylene ring and a pentasen ring. .. As the heteroaryl, a heteroaryl having 2 to 25 carbon atoms is preferable, a heteroaryl having 2 to 20 carbon atoms is more preferable, a heteroaryl having 2 to 15 carbon atoms is further preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Preferably, specifically, a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxazole ring, a thiazylazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, and the like. Pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring. , Kinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indridin ring, furan ring, benzofuran ring, isobenzofuran ring. , Dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazan ring, oxazazole ring, thiantolene ring and the like.
At least one hydrogen in the compound represented by the formula (H2) may be substituted with an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, cyano, a halogen or deuterium.

3-1-5-1-3. Compound represented by formula (H3)

In formula (H3)
MU is an independently divalent aromatic group, EC is an independently monovalent aromatic group, and k is an integer of 2 to 50,000.

More specifically
The MUs are arylene, heteroarylene, dialylene arylamino, dialylene arylboryl, oxaborin-diyl, and azaborin-diyl, respectively, independently of each other.
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 from 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 (H3) 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 in the alkyl. Any —CH ₂ − may be substituted with —O— or —Si (CH ₃ ) ₂ −, except for —CH ₂ −, which is directly linked to EC in formula (H3) in the alkyl. -CH _2- may be substituted with an arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.

The MU is, for example, a divalent derivative having the following structure (for example, a divalent group represented by removing any two hydrogen atoms from any compound having the following structure, or a compound having the following structure. A divalent group composed of two or more combinations of divalent groups represented by excluding any two hydrogen atoms from, and a divalent group in which at least one of the hydrogens in those groups is substituted with an alkyl or the like. Group etc.).

More specifically, a divalent group having 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 group represented by the following formula can be mentioned. In these, EC binds to MU at *.

From the viewpoint of solubility and coating film forming property, the compound represented by the formula (H3) preferably 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. It is more preferable that 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 (k). It is more preferable that 50 to 100% of the MU 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 MU of 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).

3-1-5-1-4. A compound containing a structure represented by the formula (H4) The compound containing a structure represented by the formula (H4) has a plurality of structures represented by the formula (H4), preferably 1 to 5, more preferably 1. It contains ~ 3, more preferably 1-2, most preferably one, and when a plurality of the structures are contained, the structures are directly bonded to each other by a single bond or bonded by a specific linking group.

In the formula (H4), G is "= C (-H)-" or "= N-", and H in the above "= C (-H)-" is a substituent or another formula (H4). It may be replaced by the structure represented.

As the compound containing the structure represented by the formula (H4), for example, the compounds described in International Publication No. 2012/153780 and International Publication No. 2013/038650 can be used, and the methods described in the above-mentioned documents can be used. Can be manufactured according to.

Examples of the substituent when H in "= C (-H)-" which is G is substituted include aryl, heteroaryl, substituted silyl, substituted phosphine oxide group, substituted carboxy and the like.

Specific examples of the substituent "aryl" include phenyl, tolyl, xylyl, naphthyl, phenanthryl, pyrenyl, chrysenyl, benzo [c] phenanthril, benzo [g] chrysenyl, benzoanthril, triphenylenyl, fluorenyl, 9,9. -Includes dimethylfluorenyl, benzofluorenyl, dibenzofluorenyl, biphenylyl, terphenylyl, quaterphenylyl, fluoranthenyl and the like, preferably phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, triphenylenyl and Phenylolenyl etc. can be given. Examples of the aryl having a substituent include tolyl, xylyl, 9,9-dimethylfluorenyl and the like. As the specific example shows, aryl includes both condensed aryl and non-condensed aryl.

Specific examples of the substituent "heteroaryl" include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridadinyl, pyridyl, triazinyl, indrill, isoindrill, imidazolyl, benzoimidazolyl, indazolyl, imidazole [1,2-a] pyridinyl, frill, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, azadibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyldinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, feline Examples thereof include nantrolinyl, phenazinyl, phenothiazinyl, phenoxadinyl, oxazolyl, oxadiazolyl, frazanyl, benzoxazolyl, thiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, tetrazolyl, and preferably dibenzofuranyl, dibenzothienyl, carbazolyl, pyridyl, and the like. Examples thereof include pyrimidinyl, triazinyl, azadibenzofuranyl and azadibenzothienyl. Further preferred are dibenzofuranyl, dibenzothienyl, azadibenzofuranyl or azadibenzothienyl.

The substituent "substituted silyl" is also preferably a group selected from the group consisting of substituted or unsubstituted trialkylsilyls, substituted or unsubstituted arylalkylsilyls, and substituted or unsubstituted triarylsilyls. ..

Specific examples of substituted or unsubstituted trialkylsilyls include trimethylsilyl and triethylsilyl. Specific examples of the substituted or unsubstituted arylalkylsilyl include diphenylmethylsilyl, ditrilmethylsilyl, phenyldimethylsilyl and the like. Specific examples of the substituted or unsubstituted triarylsilyl include triphenylsilyl and tritrylsilyl.

The "substituted phosphine oxide group" which is a substituent is also preferably a substituted or unsubstituted diarylphosphine oxide group. Specific examples of the substituted or unsubstituted diarylphosphine oxide group include diphenylphosphine oxide and ditrilphosphine oxide.

Examples of the "substituted carboxy" as a substituent include benzoyloxy and the like.

Examples of the linking group that binds a plurality of structures represented by the formula (H4) include the above-mentioned divalent to tetravalent to tetravalent, bivalent to trivalent, or divalent derivatives of aryls and heteroaryls.

Specific examples of the compound containing the structure represented by the formula (H4) are shown below.

3-1-5-1-5. The compound represented by the formula (H5) and the compound represented by the formula (H6).
3-1-5-1-5-1. Compound represented by formula (H5)

In formula (H5), R ¹ to R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, and at least one hydrogen in these is Further, it may be substituted with aryl, heteroaryl or diarylamino, and may be substituted.
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 an a ring, a b ring, or a c ring, and at least one hydrogen in the formed ring is a hydrogen. It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, in which at least one hydrogen may be further substituted with aryl, heteroaryl or diarylamino. ..
Further, any at least one (preferably 1 to 3) -C (R ⁿ ) = (n is 1 to 11) in the formula (H5) may be replaced with -N =.
Further, at least one hydrogen in the compound represented by the formula (H5) is a group represented by the formula (FG-1), a group represented by the formula (FG-2), or an alkyl having 1 to 24 carbon atoms. Further, any −CH ₂ − in the alkyl may be substituted with —O— or —Si (CH ₃ ) ₂ −, and is represented by the formula (H5) in the alkyl. Any -CH ₂ -except for -CH _2- , which is directly linked to the compound, may be substituted with an arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine. ..
Further, at least one hydrogen in the compound represented by the formula (H5) may be substituted with a halogen or deuterium.

^In formula (H5), adjacent groups among the substituents ^R1 to R11 of the a ring, the b ring and the c ring are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, the b ring or the c ring. At least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, and at least one hydrogen in these. May be further substituted with aryl, heteroaryl or diarylamino. However, here, "adjacent groups" represent adjacent groups on the same ring, and "adjacent groups 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". Corresponds to, for example, a compound represented by the formulas (H5-2) to (H5-17) listed as specific compounds described later. That is, for example, it is a compound formed by condensing a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring or a benzothiophene ring with an a ring (or b ring or c ring), and the formed fused ring is They are a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

3-1-5-1-5-2. Compound represented by formula (H6)

In formula (H6), R ¹ to R ¹⁶ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, and at least one hydrogen in these is Further, it may be substituted with aryl, heteroaryl or diarylamino, and may be substituted.
Adjacent groups of R ¹ to R ¹⁶ may be bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring, a c ring or a d ring, and at least one in the formed ring. Hydrogens may be substituted with aryls, heteroaryls, diarylaminos, diheteroarylaminos, arylheteroarylaminos or aryloxys, wherein at least one hydrogen in these is further substituted with aryls, heteroaryls or diarylaminos. May be.
Further, at least one hydrogen in the compound represented by the formula (H-6) is a group represented by the formula (FG-1), a group represented by the formula (FG-2), or a carbon number of 1 to 24. Can be substituted with an alkyl of the above, and any —CH ₂ − in the alkyl may be substituted with —O— or —Si (CH ₃ ) ₂ −, according to formula (H6) in the alkyl. Any -CH ₂ -except for -CH _2- directly linked to the represented compound may be substituted with an arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl is substituted with fluorine. May be good.
Further, at least one hydrogen in the compound represented by the formula (H6) may be substituted with a halogen or deuterium.

^In formula (H6), adjacent groups among the substituents ^R1 to R16 of the a ring, b ring, c ring and d ring are bonded to each other to form an aryl ring together with the a ring, b ring, c ring or c ring. Alternatively, a heteroaryl ring may be formed, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy. At least one hydrogen in these may be further substituted with aryl, heteroaryl or diarylamino. However, here, the "adjacent group" represents an adjacent group on the same ring, and "adjacent groups are bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring, a c ring or a d ring. The compound described above can be described with reference to, for example, the compounds represented by the formulas (H6-2) to (H6-5) listed as specific compounds of the formula (H6) described later. That is, it is a compound formed by condensing, for example, a ring (or b ring, c ring, or d ring) with a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, or a benzothiophene ring. The fused ring is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

3-1-5-1-5-3. " ^R1 to R11 in equation (H5) " and " ^R1 to ^R16 in equation (H6 ⁾ "
"R ¹ to R ¹¹ in the formula (H5)" and "R ¹ to R ¹⁶ in the formula (H6)" are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, and arylheteroaryl, respectively. Amino or aryloxy, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, diarylamino (amino having two aryls with 6 to 30 carbon atoms), diheteroarylamino (two carbons). Aryls having 2 to 30 heteroaryls), aryl heteroarylaminos (aminos having aryls having 6 to 30 carbon atoms and heteroaryls having 2 to 30 carbon atoms) or aryloxys having 6 to 30 carbon atoms are preferable.

Examples of the aryl of "aryl", "diarylamino", the aryl of "arylheteroarylamino", and the aryl of "aryloxy" include a benzene ring which is a monocyclic system, a biphenyl ring which is a bicyclic system, and condensation. Naphthalene ring which is a bicyclic system, terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl) which is a tricyclic system, acenaphthalene ring, fluorene ring, phenanthrene ring, phenanthrene which is a fused tricyclic system. Examples thereof include a ring, a triphenylene ring which is a fused tetracyclic system, a pyrene ring, a naphthalene ring, a perylene ring which is a fused pentacyclic system, and a pentacene ring. Further, as will be described later, those aryls substituted with the heteroaryls defined below are also defined as aryls in the formulas (H5) and (H6).

Examples of the heteroaryl of "heteraryl", "diheteroarylamino", and the heteroaryl of "arylheteroarylamino" include a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, and an imidazole ring. , Oxazole ring, thiazazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzo Oxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, acylidine ring, phenoxatiin ring. , Phenoxazine ring, phenothiazine ring, phenazine ring, indridin ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazane ring, oxadiazole ring, thiantolen ring and Examples thereof include monovalent groups such as the heteroaryl substituted with N-aryl. Further, as will be described later, those heteroaryls substituted with the aryls defined above are also defined as heteroaryls in the formulas (H5) and (H6).

Further, the aryls, heteroaryls, diarylaminos, diheteroarylaminos, arylheteroarylaminos or ^aryloxys described as ^R1 to R11 in the formula (H5) and ^R1 to ^R16 in the formula (H6) are these. At least one hydrogen in the above may be further substituted with aryl, heteroaryl or diarylamino. Examples of the aryl, heteroaryl or diarylamino thus substituted include those described in the columns of R ¹ to R ¹¹ and R ¹ to R ¹⁶ .

Specific examples of R ¹ to R ¹¹ and R ¹ to R ¹⁶ include groups represented by the following formulas (RG-1) to (RG-10). The groups represented by the following formulas (RG-1) to (RG-10) are bonded to the formula (H5) and the formula (H6) in *.

The "aryl" and "heteroaryl" defined in the formulas (H5) and (H6) will be described with reference to the specific groups described above. (RG-7) is an aryl, the formula (RG-2), the formula (RG-3) and the formula (RG-6) are heteroaryls, and the formula (RG-9) is a heteroaryl substituted with a heteroaryl. The formula (RG-10) is a heteroaryl substituted aryl. The formula (RG-5) is an aryl (phenyl) substituted with diarylamino (diphenylamino), and the formula (RG-8) is diarylamino (diphenylamino).

3-1-5-1-5-4. In formula (H5), a ring formed by bonding adjacent groups of a ring, b ring or c ring, and in formula (H6), adjacent groups of a ring, b ring, c ring or d ring. In the ring formula (H5) formed by bonding with each other, "an aryl ring formed by bonding adjacent groups among R ¹ to R ¹¹ together with an a ring, a b ring, or a c ring", and the formula ( As the "aryl ring formed by bonding adjacent groups of R ¹ to R ¹⁶ together with an a ring, a b ring, a c ring or a d ring" in H6), for example, an aryl having 6 to 30 carbon atoms. The ring is mentioned, and an aryl ring having 6 to 16 carbon atoms is preferable, an aryl ring having 6 to 12 carbon atoms is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable. However, the carbon number of the formed aryl ring includes 6 carbon atoms of the a ring, the b ring, the c ring or the d ring.

Specific examples of the formed aryl ring include naphthalene ring, which is a fused dicyclic system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, and triphenylene ring, which is a fused tetracyclic system. Examples thereof include a pyrene ring, a naphthalene ring, a perylene ring which is a fused pentacene ring, and a pentacene ring.

"A heteroaryl ring formed by bonding adjacent groups of R ¹ to R ¹¹ together with a ring, b ring or c ring" in the formula (H5), and "R ¹ to R 1 to R 6" in the formula (H6). Examples of the "aryl ring formed by bonding adjacent groups of R ¹⁶ together with an a ring, a b ring, a c ring, or a d ring" include a heteroaryl ring having 6 to 30 carbon atoms, which includes carbon. A heteroaryl ring having 6 to 25 carbon atoms is preferable, a heteroaryl ring having 6 to 20 carbon atoms is more preferable, a heteroaryl ring having 6 to 15 carbon atoms is further preferable, and a heteroaryl ring having 6 to 10 carbon atoms is particularly preferable. Further, 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. However, the carbon number of the formed heteroaryl ring includes the carbon number 6 of the a ring, the b ring, the c ring or the d ring.

Specific examples of the formed heteroaryl ring include, for example, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, and an isoquinoline ring. Cinnoline ring, quinazoline ring, quinoxalin ring, phthalazine ring, carbazole ring, aclysine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, benzothiophene ring, dibenzothiophene ring , Cinnoline ring, etc.

At least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, and at least one hydrogen in these is further aryl, hetero. It may be substituted with aryl or diarylamino. For this explanation, the explanations in ^R1 to ^R11 of the equation (H5) and ^R1 to ^R16 of the equation (H6) can be quoted.

3-1-5-1-5-5. Specific Examples of Compounds The following shows more specific structures of the compounds represented by the formula (H5) or the formula (H6).
The specific structure of the compound represented by the following formula (H5) or formula (H6) may be substituted with an alkyl having 1 to 24 carbon atoms.

3-1-5-1-5-6. Method for producing a compound represented by the formula (H5) or the formula (H6) For the compound represented by the formula (H5), an intermediate is first produced by binding rings a to c with a bonding group (—O—). (First reaction), and then the rings a to c are bonded with a binding group (group containing B) to produce the final product (second reaction). Further, in the compound represented by the formula (H6), an intermediate is first produced by binding the a to d rings with a bonding group (> NH or a single bond) (first reaction), and then a to d. The final product can be produced by attaching the rings with a binding group (a group containing B) (second reaction). 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.

<Production method: Example of the second reaction of the compound represented by the formula (H5)>
The second reaction is a reaction for introducing B (boron) that binds the a ring, the b ring, and the c ring as shown in the following scheme (1), and is, for example, in the case of a compound represented by the formula (H5). Is shown below. First, the hydrogen atom between the two O's is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium or the like. Next, boron trichloride, boron tribromide, etc. were added, metal exchange of lithium-boron was performed, and then Bronsted bases such as N, N-diisopropylethylamine were added to cause a tandem Bora Friedel-Crafts reaction. You can get things. In the second reaction, Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

In the above scheme, lithium was introduced to the desired position by orthometalation, but as in scheme (2) below, a bromine atom or the like is introduced at the position where lithium is to be introduced, and the halogen-metal exchange is also performed to the desired position. Lithium can be introduced.

By appropriately selecting the above-mentioned synthesis method and appropriately selecting the raw material to be used, a compound having a substituent at a desired position and represented by the formula (H-5) can be synthesized.

<Manufacturing method: Example of manufacturing method of the compound represented by the formula (H6)>
As for the method for producing the compound represented by the formula (H6), the first reaction and the second reaction in the method for producing the compound represented by the above-mentioned formula (H5) can be applied. That is, the second reaction is a reaction for introducing B (boron) that bonds NH to the c ring and d ring, and the hydrogen atom of NH is orthometal with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. After conversion, boron tribromide, boron tribromide, etc. are added to perform metal exchange of lithium-boron, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem borafreedelcraft reaction. You can get the object. Again, in the second reaction, Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

3-1-5-2. The TADF material light emitting layer also preferably contains a TADF material.
As used herein, the TADF material means a material that is a "thermally activated delayed fluorescent substance." In a "thermally activated delayed fluorescent substance", by reducing the energy difference between the excited singlet state and the excited triplet state, the reverse energy transfer from the excited triplet state, which normally has a low transition probability, to the excited singlet state is high. Generated with efficiency, emission from singlet (thermally activated delayed fluorescence, TADF) is expressed. In normal fluorescence emission, 75% of triplet excitons generated by current excitation cannot be extracted as fluorescence because they pass through a heat deactivation path. On the other hand, in TADF, all excitons can be used for fluorescent emission, and a highly efficient organic EL device can be realized.

TADF materials use electron-donating substituents called donors and electron-accepting substituents called acceptors to localize intramolecular HOMOs and LUMOs for efficient reverse intersystem crossing. ) Is preferably a donor-acceptor type TADF compound (DA type TADF compound) designed to cause this.

Here, the term "electron-donating substituent" (donor) as used herein means a substituent and a partial structure in which the HOMO orbital is localized in the TADF compound molecule, and is an "electron-accepting substituent". (Acceptor) means a substituent and a partial structure in which the LUMO orbital is localized in the TADF compound molecule.

In general, TADF compounds using donors and acceptors have a large spin-orbit coupling (SOC) due to their structure, a small exchange interaction between HOMO and LUMO, and a small ΔE (ST). In addition, a very fast intersystem crossing speed is obtained. On the other hand, TADF compounds using donors and acceptors have greater structural relaxation in the excited state (for some molecules, the stable structure differs between the ground state and the excited state, so conversion from the ground state to the excited state by an external stimulus is performed. When this occurs, the structure changes to a stable structure in the excited state), and since it gives a wide emission spectrum, it may reduce the color purity when used as a light emitting material.

However, by simultaneously using the polycyclic aromatic compound of the present invention, the polycyclic aromatic compound of the present invention functions as an emerging dopant and the TADF material functions as an assisting dopant, and high color purity can be imparted. The TADF material may be a compound whose emission spectrum partially overlaps with the absorption spectrum of the polycyclic aromatic compound of the present invention. Both the polycyclic aromatic compound of the present invention and the TADF material may be contained in the same layer, or may be contained in adjacent layers.

Examples of the TADF material that can be used for such a purpose include a compound represented by the following formula (H7) or a compound having the following formula (H7) as a partial structure.

In formula (H7), ED is an electron donating group, Ln is a linking group, and EA is an electron accepting group, which is triplet with the singlet energy (S ¹ ) of the compound represented by the formula (H7). The energy difference (ΔS ¹ T ¹ ) of the term energy (T ¹ ) is 0.2 eV or less (Hiroki Uoyama, Kenichi Goushi, Katsuyuki Shizu, Hiroko Nomura, Chihaya Adachi, Nature, 492, 234-238 (2012)). The energy difference (ΔS ¹ T ¹ ) is preferably 0.15 eV or less, more preferably 0.10 eV or less, and further preferably 0.08 eV or less.

As the electron donating group (donor structure) and the electron acceptor group (acceptor structure) used in the TADF material, for example, the structures described in Chemistry of Materials, 2017, 29, 1946-1963 may be used. can. Examples of the ED include functional groups containing sp ³ nitrogen, and more specifically, carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, and benzothieno. Carbazole, phenyldihydroindrocarbazole, phenylbicarbazole, bicarbazole, turcarbazole, diphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis (tert-butyl) Examples include groups derived from phenyl) amines, (diphenylamino) phenyl) diphenylbenzenediamine, dimethyltetraphenyldihydroacridindiamine, tetramethyl-dihydro-indenoaclydin and diphenyl-dihydrodibenzoazacillin. Examples of EA include sp ² nitrogen-containing aromatic rings, CN-substituted aromatic rings, rings having ketones and cyano, and more specifically, sulfonyldibenzene, benzophenone, phenylenebis (phenylmethanone), and benzo. Nitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, triazole, oxazole, thiadiazol, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzoimidazole, dibenzoquinoxalin, heptaaza Phenalene, thioxanthonedioxide, dimethylanthrasenone, anthracendione, pyridine, cycloheptabipyridine, benzenetricarbonitrile, fullorangecarbonitrile, pyrazinedicarbonitrile, pyridinedicarbonitrile, dibenzoquinoxalin dicarbonitrile, pyrimidine, phenylpyrimidine , Methylpyrimidine, Triazine, Triphenyltriazine, Bis (phenylsulfonyl) benzene, Dimethylthioxanthene dioxide, Thianslentetraoxide and Tris (dimethylphenyl) borane and the like. Examples of Ln include single bond and arylene, and more specifically, phenylene, biphenylene, naphthylene and the like. Further, hydrogen may be substituted with alkyl, cycloalkyl and aryl in any structure. In particular, at least one selected from carbazole, phenoxazine, aclysine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole and benzophenone as partial structures. It is preferably a compound having one.
In formula (H7), the linking group Ln functions as a spacer structure that separates the donor substructure and the acceptor substructure.

The compound represented by the formula (H7) may be more specifically a compound represented by any of the formula (H7-1), the formula (H7-2) and the formula (H7-3).

In the formula (H7-1), the formula (H7-2) and the formula (H7-3),
M are independently single-bonded, -O-,> N-Ar or> C (-Ar) ₂ , respectively, and the HOMO depth and excited singlet energy level and excited triplet of the substructure to be formed. From the standpoint of high energy level, it is preferably singlet, —O— or> N—Ar.
J is a linking group corresponding to Ln in the formula (H7), is an arylene having 6 to 18 carbon atoms independently, and has a magnitude of conjugate that exudes from the donor-like partial structure and the acceptor-like partial structure. From the viewpoint of the above, arylene having 6 to 12 carbon atoms is preferable, and more specifically, phenylene, methylphenylene and dimethylphenylene can be mentioned.
Q is independently = C (-H)-or = N-, and is a viewpoint of the shallowness of LUMO and the height of the excited singlet energy level and the excited triplet energy level of the formed partial structure. Therefore, preferably = N-,
Ar is a partial structure formed independently of hydrogen, an aryl having 6 to 24 carbon atoms, a heteroaryl having 2 to 24 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 18 carbon atoms. From the viewpoint of the depth of HOMO and the height of the excited single-term energy level and the excited triple-term energy level, hydrogen, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 14 carbon atoms, and a carbon number of carbon atoms are preferable. It is an alkyl of 1 to 4 or a cycloalkyl of 6 to 10 carbon atoms, more preferably hydrogen, phenyl, trill, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazil, carbazolyl, dimethylcarbazolyl, di-tert-. Butylcarbazolyl, benzoimidazole or phenylbenzoimidazole, more preferably hydrogen, phenyl or carbazolyl.
m is 1 or 2 and
n is an integer of 2 to (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance.
Further, at least one hydrogen in the compound represented by each of the above formulas may be substituted with halogen or deuterium.

Examples of the compound represented by the formula (H7) include a compound represented by the following structure. In the structural formula, * indicates the bond position, “Me” indicates methyl, and “tBu” indicates t-butyl.

Among the above-mentioned specific compounds, the compound represented by the formula (H7) includes PIC-TRZ, TXO-TPA, TXO-PhCz, PXZD SO2, ACRD SO2, DTC-DBT, DTAO, 4CzBN, 4CzBN-Ph. , 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, Cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTrz, spiroAC-TRZ, Ac -HPM, Ac-PPM, Ac-MPM, TCzTrz, TmCzTrz and DCzmCzTrz are preferred.

3-1-5-3. Dopant material The polycyclic aromatic compound of the present invention is preferably used as a dopant material.
The dopant material that can be used other than the polycyclic aromatic compound of the present invention is not particularly limited, and a known compound can be used, and it can be selected from various materials according to a desired emission color. can. Specifically, for example, fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysen, benzoxazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxasols. Bistylyl derivatives such as derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazol derivatives, triazole derivatives, pyrazoline derivatives, stilben derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives. (Japanese Patent Laid-Open No. 1-245087), bisstyrylallylene derivative (Japanese Patent Laid-Open No. 2-247278), diazaindacene derivative, furan derivative, benzofuran derivative, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) Isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran and other isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7- Cmarin derivatives such as methoxycoumarin derivative, 7-acetoxycmarin derivative, 3-benzothiazolyl coumarin derivative, 3-benzoimidazolyl coumarin derivative, 3-benzoxazolyl coumarin derivative, dicyanomethylenepyrine derivative, dicyanomethylenethiopyran derivative, polymethine Derivatives, cyanine derivatives, oxobenzoanthrasene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostylyl derivatives, acridin derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrolopyridine derivatives, flopyridine derivatives, Examples thereof include 1,2,5-thiadiazolopylene derivatives, pyrromethene derivatives, perinone derivatives, pyrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives.

To exemplify each coloring light, examples of the blue to blue-green dopant material include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, inden, and chrysen and their derivatives, furan, pyrrole, and thiophene. Aromatic complexes such as silol, 9-silafluolene, 9,9'-spirobisilafluolene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthylidine, quinoxalin, pyrrolpyridine, thioxanthene. Aromatic derivatives such as ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stylben derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazol, carbazole, oxazole, oxadiazol, triazole and their metal complexes and N. , N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine and other aromatic amine derivatives.

Examples of the green to yellow dopant material include a coumarin derivative, a phthalimide derivative, a naphthalimide derivative, a perinone derivative, a pyrrolopyrrole derivative, a cyclopentadiene derivative, an acridone derivative, a quinacridone derivative, a naphthacene derivative such as rubrene, and the like. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the compound exemplified as the blue-green dopant material.

Further, as the orange to red dopant material, naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acidimide, perinone derivatives, rare earth complexes such as Eu complex having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone. Examples thereof include derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrolopyridine derivatives, squarylium derivatives, biolantron derivatives, phenazine derivatives, phenoxazone derivatives and thiathiazolopylene derivatives, and are further exemplified as the above-mentioned blue-blue-green and green-yellow dopant materials. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the above-mentioned compound.

In addition, as the dopant, it can be appropriately selected and used from the compounds described in the June 2004 issue of Chemical Industry, page 13, and the references mentioned therein.

Among the above-mentioned dopant materials, amines, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyrane derivatives or pyrene derivatives having a stillben structure are particularly preferable.

当該式中、Ａｒ¹は炭素数６～３０のアリールに由来するｍ価の基であり、Ａｒ²およびＡｒ³は、それぞれ独立して炭素数６～３０のアリールであるが、Ａｒ¹～Ａｒ³の少なくとも１つはスチルベン構造を有し、Ａｒ¹～Ａｒ³は、アリール、ヘテロアリール、アルキル、シクロアルキル、トリ置換シリル（アリール、アルキルおよび／またはシクロアルキルでトリ置換されたシリル）またはシアノで置換されていてもよく、そして、ｍは１～４の整数である。 The amine having a stilbene structure is represented by, for example, the following formula.

In the formula, Ar ¹ is an m-valent group derived from an aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, but Ar ¹ to Ar are respectively. At least one of ³ has a stilben structure, where Ar ¹ to Ar ³ are aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with aryl, alkyl and / or cycloalkyl) or cyano. May be replaced with, and m is an integer from 1 to 4.

当該式中、Ａｒ²およびＡｒ³は、それぞれ独立して炭素数６～３０のアリールであり、Ａｒ²およびＡｒ³は、アリール、ヘテロアリール、アルキル、シクロアルキル、トリ置換シリル（アリール、アルキルおよび／またはシクロアルキルでトリ置換されたシリル）またはシアノで置換されていてもよい。 As the amine having a stilbene structure, diaminostilbene represented by the following formula is more preferable.

In the formula, Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, and Ar ² and Ar ³ are aryl, heteroaryl, alkyl, cycloalkyl, and trisubstituted silyls (aryl, alkyl and tri-substituted silyls). / Or silyl substituted with cycloalkyl) or may be substituted with cyano.

Specific examples of aryls having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthalsenyl, perylenyl, stillbenyl, distyrylphenyl, and distyrylbiphenylyl. , Distyryl fluorenyl, etc.

Specific examples of amines having a stilbene structure include N, N, N', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, N, N, N', N'-tetra (1-naphthyl). ) -4,4'-Diaminostilbene, N, N, N', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N'-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthril) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) stilbene] -biphenyl, 1,4-bis [4'-bis (diphenylamino) stilbene] -benzene, 2,7-bis [4'-bis (diphenylamino) stilbene] -9,9-dimethyl Examples thereof include fluorene, 4,4'-bis (9-ethyl-3-carbazovinylene) -biphenyl, 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl and the like.
Further, amines having a stilbene structure described in JP-A-2003-347056 and JP-A-2001-307884 may be used.

Examples of the perylene derivative include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, and 3,4-. Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene , 3- (9'-anthril) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di (t-butyl) perylenel) and the like.
In addition, JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267878, JP-A-2001-267076, Perylene derivatives described in JP-A-2000-34234, JP-A-2001-267075, JP-A-2001-217777 and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimethylboryl) anthracene, 9-phenyl-10- (dimethylboryl) anthracene, 4- (9'-anthril) dimethylborylnaphthalene, 4- (10'). -Phenyl-9'-anthryl) dimethylboryl naphthalene, 9- (dimethylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimethylboryl) anthracene, 9- (4'-(N-carbazolyl) phenyl) -10- (Dimethylboryl) Anthracene and the like.
Further, the borane derivative described in International Publication No. 2000/40586 or the like may be used.

当該式中、Ａｒ⁴は炭素数６～３０のアリールに由来するｎ価の基であり、Ａｒ⁵およびＡｒ⁶はそれぞれ独立して炭素数６～３０のアリールであり、Ａｒ⁴～Ａｒ⁶は、アリール、ヘテロアリール、アルキル、シクロアルキル、トリ置換シリル（アリール、アルキルおよび／またはシクロアルキルでトリ置換されたシリル）またはシアノで置換されていてもよく、そして、ｎは１～４の整数である。 The aromatic amine derivative is represented by, for example, the following formula.

In the formula, Ar ⁴ is an n-valent group derived from an aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are independently aryls having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ are independent aryls having 6 to 30 carbon atoms. , Aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with aryl, alkyl and / or cycloalkyl) or cyano, where n is an integer from 1 to 4. be.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene, Ar ⁵ and Ar ⁶ are independently aryls having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ are respectively. May be aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with aryl, alkyl and / or cycloalkyl) or cyano, and n is 2, aromatic. Group amine derivatives are more preferred.

Specific examples of aryls having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthalenyl, perylenyl, pentasenyl and the like.

As the aromatic amine derivative, as a chrysen system, for example, N, N, N', N'-tetraphenylcrisen-6,12-diamine, N, N, N', N'-tetra (p-tolyl) Chrysen-6,12-diamine, N, N, N', N'-tetra (m-tolyl) chrysen-6,12-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) chrysen -6,12-diamine, N, N, N', N'-tetra (naphthalen-2-yl) chrysen-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis ( 4-isopropylphenyl) lysene-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) lysene-6,12-diamine, N, N'-bis (4) -Isopropylphenyl) -N, N'-di (p-tolyl) chrysen-6,12-diamine and the like can be mentioned.

The pyrene system includes, for example, N, N, N', N'-tetraphenylpyrene-1,6-diamine, N, N, N', N'-tetra (p-tolyl) pyrene-1,6. -Diamine, N, N, N', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N', N'-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) pyrene-1 , 6-Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) Pyrene-1,6-diamine, N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (3,4-dimethylphenyl) -3,8-diphenylpyrene-1,6 -Diamine, N, N, N, N-Tetraphenylpyrene-1,8-diamine, N, N'-bis (biphenyl-4-yl) -N, N'-diphenylpyrene-1,8-diamine, N ¹ , N ⁶ -diphenyl-N ¹ , N ⁶ -bis- (4-trimethylsilanyl-phenyl) -1H, 8H-pyrene-1,6-diamine and the like can be mentioned.

The anthracene system includes, for example, N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N', N'-tetra (p-tolyl) anthracene-9,10-diamine. , N, N, N', N'-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene- 9,10-Diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) anthracene-9,10-diamine, N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N, N', N'-tetra (p-tolyl) anthracene-9,10-diamine , 2,6-di-t-butyl-N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N'-bis (4-isopropylphenyl) -N , N'-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N'-bis (4-isopropylphenyl) -N, N'-bis (4-t-butylphenyl) ) Anthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis (4-di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4) -Di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-) Examples thereof include 1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene and the like.

In addition, [4- (4-diphenylamino-phenyl) naphthalene-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalene-2-yl] -diphenylamine, 4,4'. -Bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-Terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl and the like.
Further, the aromatic amine derivative described in JP-A-2006-156888 may be used.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Further, the coumarin derivative described in JP-A-2004-43646, JP-A-2001-76876, JP-A-6-298758, etc. may be used.

また、特開２００５－１２６３９９号公報、特開２００５－０９７２８３号公報、特開２００２－２３４８９２号公報、特開２００１－２２０５７７号公報、特開２００１－０８１０９０号公報、および特開２００１－０５２８６９号公報などに記載されたピラン誘導体を用いてもよい。 Examples of the pyran derivative include the following DCM and DCJTB.

Further, JP-A-2005-126399, JP-A-2005-097283, JP-A-2002-234892, JP-A-2001-220757, JP-A-2001-081090, and JP-A-2001-052869. The pyran derivative described in the above may be used.

3-1-6. The electron injection layer and the electron transport layer electron injection layer 107 in the organic electroluminescent device play 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 serves to efficiently transport 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 kinds of electron transport / injection materials or a mixture of an electron transport / injection material and a polymer binder, respectively.

The electron injection / transport layer is a layer that controls the electron injection from the cathode and further transports the 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, the effect of improving the luminous efficiency is equivalent to that of a material having a 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 known known compounds.

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 is preferable to contain at least one selected from a pyrrole derivative, a fused 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. , Quinone derivatives such as anthraquinone and diphenoquinone, phosphoroxide derivatives, arylnitrile 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, benzofluorene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, and perylene derivatives. , Oxaziazole derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1, etc.) 3,4-Triazole, etc.), thiazazole derivative, metal complex of oxine derivative, quinolinol metal complex, quinoxalin derivative, polymer of quinoxalin derivative, benzazole compound, gallium complex, pyrazole derivative, perfluorofluorinated phenylene derivative, triazine derivative, pyrazine Derivatives, benzoquinoline 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 derivative, benzothiazole derivative, quinoline derivative, oligopyridine derivative such as telpyridine, bipyridine derivative, telpyridine derivative (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, arylnitrile derivatives, indols, etc. Examples thereof include derivatives, phosphine oxide derivatives, and bisstyryl derivatives.

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, azomethin complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline 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 derivative, pyridine derivative, fluorentene derivative, BO derivative, anthracene derivative, benzofluorene derivative, phosphinoxide derivative, pyrimidine derivative, arylnitrile derivative, triazine derivative, benzoimidazole derivative, phenanthroline derivative, and quinolinol derivative. Metal complexes are preferred.

式（ＥＴＭ－１）中、Ｒ¹¹およびＲ¹²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１つであり、Ｒ¹³～Ｒ¹⁶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 formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.

In formula (ETM-1), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, and optionally substituted nitrogen-containing heterocycles, respectively. At least one of a ring, or cyano, R ¹³ to R ¹⁶ are independently substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. , X are optionally substituted arylene, Y is optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazolyl, and n. Are independently integers from 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、Ｒ¹¹およびＲ¹²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１つであり、Ｒ¹³～Ｒ¹⁶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、Ｒ²¹およびＲ²²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１つであり、Ｘ¹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、Ｒ¹¹およびＲ¹²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１つであり、Ｒ¹³～Ｒ¹⁶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、Ｘ¹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 formula (ETM-1), the compound represented by the following formula (ETM-1-1) and the compound represented by the following 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 contained heterocycles, or cyano, R ¹³ to R ¹⁶ are independently substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. And R ²¹ and R ²² are independently 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 independently integer of 0 to 3, and m is an independently of 0 to 4. 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 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 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.

（各式中、Ｒ^aは、それぞれ独立してアルキル、シクロアルキルまたは置換されていてもよいフェニルであり、＊は結合位置を表す。） 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 ^a phenyl that may be independently alkyl, cycloalkyl or substituted, and * represents the bond position.)

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 formula (ETM-2-1), R ¹¹ to R ¹⁸ are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). ) Or aryl (preferably aryl with 6 to 30 carbon atoms).

In the formula (ETM-2-2), R ¹¹ and R ¹² are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms), respectively. ) Or aryl (preferably aryl having 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) (* in the formula represents a bonding position), and the pyridine-based substituent is Each may be independently substituted with an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl and the like, with methyl being preferred. Further, the pyridine-based substituent may be bonded to the φ, anthracene ring or fluorene ring in each formula via phenylene or naphthylene.

The pyridine-based substituent is any of the formulas (Py-1) to (Py-15) (* in the formula represents the bonding position), and among these, the following formula (Py-21) It is preferably any of the formulas (Py-44).

At least one hydrogen in each pyridine derivative may be substituted with deuterium, and of the two "pyridine-based substituents" in formula (ETM-2-1) and formula (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 linear alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. The 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 , a preferable aryl is an aryl having 6 to 30 carbon atoms, a more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms. Yes, and 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-) il, (1-, 2) -, 3-, 4-, 9-) Phenantril, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-) , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl, which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl, etc. ..

Preferred "aryls having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, 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 formula (ETM-2-2) may be bonded to form a ring, and as a result, the 5-membered ring of the fluorene skeleton has cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, or cyclohexane. , Fluorene, inden, etc. 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 formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

In 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 hetero. Represents aryl. 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, arylheteroarylamino, 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 an a ring, a b ring or a 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, wherein at least one hydrogen thereof 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.

For 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 formula (1A) and the formula (1B) can be referred to.

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).

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

Ar ² is independently an aryl having 6 to 20 carbon atoms, preferably an aryl having 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms. .. 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- Telphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused tricyclic aryls, anthracene- (1-, 2-, 9-) yl, acenaphtylene- (1-, 3-, 4-, 5-) aryl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenylen- (1-, 2-) yl, (1-, 2-) yl, 2-,3-,4-,9-) Phenantril, 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. Specific examples of the "aryl having 6 to 10 carbon atoms" include phenyl, biphenylyl, naphthyl, terphenylyl, anthrasenyl, acenaphthylenyl, 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.
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 linear 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 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, dimethylcyclohexyl and the like.

As for 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. As a specific example of "aryl having 6 to 20 carbon atoms", a specific example of "aryl having 6 to 20 carbon atoms" in Ar ² can be cited. Preferred "aryl of 6-20 carbons" 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.

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced by 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 Ar ² of the formula (ETM-5) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl with 6 to 12 carbon atoms is more preferable, and aryl with 6 to 10 carbon atoms is particularly preferable. Specific examples thereof include phenyl, biphenylyl, naphthyl, terphenylyl, anthrasenyl, acenaphthylenyl, 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 be combined to form a ring.

The "alkyl" in Ar ² may be either a straight chain or a branched chain, and examples thereof include a linear alkyl having 1 to 24 carbon atoms or a branched chain alkyl having 3 to 24 carbon atoms. The 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 , a preferable aryl is an aryl having 6 to 30 carbon atoms, a 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, naphthalenyl, perylenyl, pentasenyl and the like.

The two Ar ^2s may be bonded to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-bonded to the 5-membered ring of the fluorene skeleton. 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.

<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 and International Publication No. 2013/079678.

R ⁵ is a substituted or unsubstituted alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 16 carbon atoms, an aryl having 6 to 20 carbon atoms or a heteroaryl having 5 to 20 carbon atoms.
R ⁶ is CN, substituted or unsubstituted, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 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, 1 to 20 carbon alkoxy or 6 to 20 carbon aryloxy.
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 of 0 to 4, and q is an integer of 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, hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether (aryl ether group), aryl thio ether (aryl). It is selected from a fused ring formed between a thioether group), an aryl, a heterocyclic group, a halogen, a cyano, an aldehyde, a carbonyl, a carboxyl, an amino, a nitro, a silyl, and an adjacent substituent.

Ar ¹ may be the same or different and may be an arylen or a heteroarylene. Ar ² may be the same or different and is aryl or heteroaryl. 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 of 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.

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

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

Further, aralkyl indicates an aromatic hydrocarbon group mediated by an aliphatic hydrocarbon such as benzyl or phenylethyl, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be substituted or substituted. do not have. The carbon number of the aliphatic portion is not particularly limited, but is usually in the range of 1 to 20.

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

Further, the cycloalkenyl indicates an unsaturated alicyclic hydrocarbon group containing a double bond such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be substituted or substituted.

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

Further, the alkoxy indicates an aliphatic hydrocarbon group via an ether bond such as methoxy, and the aliphatic hydrocarbon group may be substituted or substituted. The number of carbon atoms of the alkoxy is not particularly limited, but is usually in the range of 1 to 20.

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

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

Further, the aryl ether indicates an aromatic hydrocarbon group via an ether bond such as phenoxy, and the aromatic hydrocarbon group may be substituted or substituted. The carbon number of the aryl ether is not particularly limited, but is usually in the range of 6 to 40.

Further, the arylthio ether is a group in which the oxygen atom of the ether bond of the aryl ether is replaced with a sulfur atom.

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

Further, the heterocyclic group refers to a cyclic structural group having an atom other than carbon such as furanyl, thienyl, oxazolyl, pyridyl, quinolinyl, and carbazolyl, which may be substituted or substituted. The number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen means fluorine, chlorine, bromine and iodine.

Aldehydes, carbonyls and aminos 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 refers to a silicon compound group such as trimethylsilyl, which may be unsubstituted or substituted. The number of carbon atoms of Cyril 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 , a conjugated or non-conjugated fused ring may be formed between the two R1s. These fused rings may contain nitrogen, oxygen, and sulfur atoms in the ring structure, or may be fused 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, (2-, 3-, 4-) biphenylyl, which is a bicyclic aryl, 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-Il, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Fused tricyclic aryls, acenaphtylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenylene- (1) -, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-Phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl. -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-) aryl, a fused pentacyclic aryl. ) Il, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a 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, and the like. Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazine, 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.

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.

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

Ar _ni preferably has a large number of carbon atoms from the viewpoint of fast electron transportability, and preferably has a small number of carbon atoms from the viewpoint of high T1. Specifically, Ar _ni is preferably a high T1 for use in a layer adjacent to the light emitting layer, is an aryl having 6 to 20 carbon atoms, and is preferably an aryl having 6 to 14 carbon atoms, more preferably. It is an aryl having 6 to 10 carbon atoms. Further, the number of substitutions n of the nitrile group is preferably large from the viewpoint of high T1 and preferably small from the viewpoint of high S1. The number of substitutions n of the nitrile group is specifically an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. From the viewpoint of high S1 and high T1, donor heteroaryl is preferable, and since it is used as an electron transport layer, it is preferable that the donor heteroaryl is small. From the viewpoint of charge transportability, aryls or heteroaryls having a large number of carbon atoms are preferable, and aryls having a large number of substituents are preferable. Specifically, the number of substitutions m of Ar is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 to 2.

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, (2-, 3-, 4-) biphenylyl, which is a bicyclic aryl, 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-Il, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Fused tricyclic aryls, acenaphtylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenylene- (1) -, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-Phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl. -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-) aryl, a fused pentacyclic aryl. ) Il, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a 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, and the like. Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazine, 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 arylnitrile derivative may be a multimer in which a plurality of compounds represented by the 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 arylnitrile derivative include the following compounds.

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

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 Patent Application Publication No. 2011/0156013.

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 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, (2-, 3-, 4-) biphenylyl, which is a bicyclic aryl, 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-Il, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Fused tricyclic aryls, acenaphtylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenylene- (1) -, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-Phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl. -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-) aryl, a fused pentacyclic aryl. ) Il, pentasen- (1-, 2-, 5-, 6-) yl and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a 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, and the like. Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl. , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazine, 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.

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 synthetic 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, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. Yes, in the "benzimidazole-based substituent", the pyridyl in the "pyridine-based substituent" in the formula (ETM-2), the formula (ETM-2-1) and the formula (ETM-2-2) is replaced with benzimidazolyl. At least one hydrogen in the benzimidazole derivative may be substituted with fluorene.

R ¹¹ in the benzoimidazolyl 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 of the formula (ETM-2-1) and the formula (ETM-2). The explanation of R ¹¹ in -2) can be quoted.

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the description in the formula (ETM-2-1) or the formula (ETM-2-2), and each formula can be quoted. In R ¹¹ to R ¹⁸ , the explanation in the formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, in the formula (ETM-2-1) or the formula (ETM-2-2), two pyridine-based substituents are described in a bound form, but when these are replaced with benzoimidazole-based substituents, both are described. The pyridine-based substituent 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 to. 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 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 benzoimidazole derivative include, for example, 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (10-). Naphthalene-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-benzo [d] imidazole, 1- (4) -(10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalen-2-yl)) Anthracene-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracene-2-yl) phenyl) -2- Examples thereof include phenyl-1H-benzo [d] imidazole and 5- (9,10-di (naphthalen-2-yl) anthracene-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). Aryl of number 6-30). Further, in the formula (ETM-12-1), any one of R ¹¹ to R ¹⁸ is a bond with φ which is an aryl ring.

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

As the alkyl, cycloalkyl and aryl in R ¹¹ to R ¹⁸ , the description of R ¹¹ to R ¹⁸ in the formula (ETM-2) can be cited. 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 formula is hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terfenylyl independently, and * represents a binding position.

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 and compounds represented by the following structural formulas can give.

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

式中、Ｒ¹～Ｒ⁶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 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. Yes, n is an integer of 1 to 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 (4,6-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-quinolinorate) (2-phenylphenolate) Aluminum, bis (2-methyl-8-quinolinorate) (3-phenylphenorate) Aluminum, bis (2-Methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,3-dimethylphenorate) 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-phenylphenolate) 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) Lat) 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] quinoline) Berylium and the like can be mentioned.

This quinolinol-based metal complex can be produced by using a known raw material and a known synthetic 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 "Thiazole-based substituent" and "benzothiazole-based substituent" are integers of, and "pyridine-based substituent" in the formula (ETM-2), the formula (ETM-2-1) and the formula (ETM-2-2). The pyridyl in the "group" is a substituent in which the following thiazolyl or benzothiazolyl 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 description in the formula (ETM-2-1) or the formula (ETM-2-2), and each formula can be quoted. In R ¹¹ to R ¹⁸ , the explanation in the formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, although the formula (ETM-2-1) or the formula (ETM-2-2) describes the form in which two pyridine-based substituents are bonded, these are described as a thiazole-based substituent (or a benzothiazole-based substituent). ), Both pyridine-based substituents may be replaced with a thiazole-based substituent (or benzothiazole-based substituent) (that is, n = 2), and any one of the pyridine-based substituents may be replaced with a thiazole-based substituent. It may be replaced with (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 formula (ETM-2-1) is replaced with a thiazole-based substituent (or a benzothiazole-based substituent), and the "pyridine-based substituent" is replaced with R ¹¹ to R ¹⁸ . It may be replaced.

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

<Siror derivative>
The siror derivative is, for example, a compound represented by the following formula (ETM-15). Details are described in Japanese Patent Application Laid-Open No. 9-194487.

X and Y are independently alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, heteroaryl, which may be substituted. For details of these groups, the description in formulas (1A) and (1B), as well as the description in formula (ETM-7-2) can be cited. In addition, alkenyloxy and alkynyloxy are groups in which the alkyl moiety in alkoxy is replaced with alkenyl or alkynyl, respectively, and the details of these alkenyl and alkynyl can be referred to in the formula (ETM-7-2).
Further, X and Y, which are both alkyls, may be bonded to form a ring.

R ¹ to R ⁴ are independently hydrogen, halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, azo group, alkylcarbonyloxy, arylcarbonyl, respectively. Oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, sulfinyl, sulfonyl, sulfanyl, silyl, carbamoyl, aryl, heteroaryl, alkenyl, alkynyl, nitro, formyl, nitroso, formyloxy, isocyano, cyanate group, isocyanate group, thiocyanate group, It is an isothiocyanate group or a cyano, which may be substituted with an alkyl, cycloalkyl, aryl or halogen and may form a fused ring with an adjacent substituent.

For details of halogens, alkyls, cycloalkyls, alkoxys, aryloxys, aminos, aryls, heteroaryls, alkenyls and alkynyls in R ¹ to R ⁴ , the description in formulas (1A) and (1B) can be cited.

The details of alkyl, aryl and alkoxy in alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy and aryloxycarbonyloxy in R ¹ to R ⁴ are also given in the formula. The explanations in (1A) and equation (1B) can be quoted.

Examples of the silyl include a silyl group and a group in which at least one of the three hydrogens of the silyl group is independently substituted with aryl, alkyl or cycloalkyl, and trisubstituted silyl is preferable. Examples thereof include trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl and alkyldicycloalkylsilyl. For details of aryl, alkyl and cycloalkyl in these, the explanations in formulas (1A) and (1B) can be cited.

The fused ring formed between the adjacent substituents is, for example, a conjugated or non-conjugated fused ring formed between R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and the like. .. These fused rings may contain nitrogen, oxygen, and sulfur atoms in the ring structure, or may be fused with another ring.

However, preferably, when R ¹ and R ⁴ are phenyl, X and Y are not alkyl or phenyl. Also, preferably, when R ¹ and R ⁴ are thienyl groups, X and Y are alkyl, and R ² and R ³ are alkyl, aryl, alkenyl or R ² and R ³ are bonded to form a ring. It is a structure that does not satisfy cycloalkyl at the same time. Also, preferably, when R ¹ and R ⁴ are silyl groups, R ² , R ³ , X and Y are independently hydrogen or not an alkyl having 1 to 6 carbon atoms. Also, preferably, in the case of a structure in which benzene rings are condensed at R ¹ and R ² , X and Y are not alkyl and phenyl.

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

<Azolin derivative>
The azoline derivative is, for example, a compound represented by the following formula (ETM-16). Details are described in International Publication No. 2017/014226.

In the formula (ETM-16),
φ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocycle having 2 to 40 carbon atoms, and at least one hydrogen of φ has 1 carbon atom. It may be substituted with an alkyl of up to 6; a cycloalkyl of 3 to 14 carbons, an aryl of 6 to 18 carbons or a heteroaryl of 2 to 18 carbons.
Y is independently -O-, -S- or> N-Ar, and Ar is an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms, and at least one hydrogen of Ar. May be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms, and R ¹ to R ⁵ are independent of each other. And hydrogen, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, however, any one of Ar and R ¹ to R ⁵ in the above> N-Ar is bonded to L. It is a part to be
L is independently selected from the group consisting of a divalent group represented by the following formula (L-1) and a divalent group represented by the following formula (L-2).

In equation (L-1), X ¹ to X ⁶ are independently = CR ⁶ − or = N −, and at least two of X ¹ to X ⁶ are = CR ⁶ −, and X ¹ R ⁶ in 2 of ~ X ⁶ = CR ⁶ − is a site that binds to φ or an azoline ring, and R ⁶ in the other = CR ⁶ − is hydrogen.
In equation (L-2), X ⁷ to X ¹⁴ are independently = CR ⁶ − or = N −, and at least two of X ⁷ to X ¹⁴ are = CR ⁶ −, and X ⁷ R ⁶ in 2 = CR ⁶ − of ~ X ¹⁴ is a site that binds to φ or an azoline ring, and R ⁶ in the other = CR ⁶ − is hydrogen.
At least one hydrogen of L may be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 10 carbon atoms or a heteroaryl having 2 to 10 carbon atoms.
m is an integer of 1 to 4, and when m is 2 to 4, the groups formed by the azoline ring and L may be the same or different, and
At least one hydrogen in the compound represented by the formula (ETM-16) may be substituted with deuterium.

The specific azoline derivative is a compound represented by the following formula (ETM-16-1) or formula (ETM-16-2).

In the formula (ETM-16-1) and the formula (ETM-16-2),
φ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocycle having 2 to 40 carbon atoms, and at least one hydrogen of φ has 1 carbon atom. It may be substituted with an alkyl of up to 6; a cycloalkyl of 3 to 14 carbons, an aryl of 6 to 18 carbons or a heteroaryl of 2 to 18 carbons.
In the formula (ETM-16-1), Y is independently -O-, -S- or> N-Ar, and Ar is an aryl having 6 to 12 carbon atoms or a hetero with 2 to 12 carbon atoms. It is aryl, even if at least one hydrogen of Ar is substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms. Often,
In the formula (ETM-16-1), R ¹ to R ⁴ are independently hydrogen, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, respectively, except that R ¹ and R ² are the same. And R ³ and R ⁴ are the same,
In the formula (ETM-16-2), R ¹ to R ⁵ are independently hydrogen, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, respectively, except that R ¹ and R ² are the same. And R ³ and R ⁴ are the same,
In the formula (ETM-16-1) and the formula (ETM-16-2),
L is independently selected from the group consisting of a divalent group represented by the following formula (L-1) and a divalent group represented by the following formula (L-2).

式（Ｌ－１）中、Ｘ¹～Ｘ⁶はそれぞれ独立して＝ＣＲ⁶－または＝Ｎ－であり、Ｘ¹～Ｘ⁶のうちの少なくとも２つは＝ＣＲ⁶－であり、Ｘ¹～Ｘ⁶のうちの２つの＝ＣＲ⁶－におけるＲ⁶はφまたはアゾリン環と結合する部位であり、それ以外の＝ＣＲ⁶－におけるＲ⁶は水素であり、
式（Ｌ－２）中、Ｘ⁷～Ｘ¹⁴はそれぞれ独立して＝ＣＲ⁶－または＝Ｎ－であり、Ｘ⁷～Ｘ¹⁴のうちの少なくとも２つは＝ＣＲ⁶－であり、Ｘ⁷～Ｘ¹⁴のうちの２つの＝ＣＲ⁶－におけるＲ⁶はφまたはアゾリン環と結合する部位であり、それ以外の＝ＣＲ⁶－におけるＲ⁶は水素であり、
Ｌの少なくとも１つの水素は炭素数１～４のアルキル、炭素数５～１０のシクロアルキル、炭素数６～１０のアリールまたは炭素数２～１０のヘテロアリールで置換されていてもよく、
ｍは１～４の整数であり、ｍが２～４であるとき、アゾリン環とＬとで形成される基は同一であっても異なっていてもよく、そして、
式（ＥＴＭ－１６－１）または式（ＥＴＭ－１６－２）で表される化合物中の少なくとも１つの水素は重水素で置換されていてもよい。

In equation (L-1), X ¹ to X ⁶ are independently = CR ⁶ − or = N −, and at least two of X ¹ to X ⁶ are = CR ⁶ −, and X ¹ R ⁶ in 2 of ~ X ⁶ = CR ⁶ − is a site that binds to φ or an azoline ring, and R ⁶ in the other = CR ⁶ − is hydrogen.
In equation (L-2), X ⁷ to X ¹⁴ are independently = CR ⁶ − or = N −, and at least two of X ⁷ to X ¹⁴ are = CR ⁶ −, and X ⁷ R ⁶ in 2 = CR ⁶ − of ~ X ¹⁴ is a site that binds to φ or an azoline ring, and R ⁶ in the other = CR ⁶ − is hydrogen.
At least one hydrogen of L may be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 10 carbon atoms or a heteroaryl having 2 to 10 carbon atoms.
m is an integer of 1 to 4, and when m is 2 to 4, the groups formed by the azoline ring and L may be the same or different, and
At least one hydrogen in the compound represented by the formula (ETM-16-1) or the formula (ETM-16-2) may be substituted with deuterium.

Preferably, φ is a monovalent group represented by the following formulas (φ1-1) to (φ1-18) and a divalent group represented by the following formulas (φ2-1) to (φ2-34). It consists of a trivalent group represented by the following formulas (φ3-1) to (φ3-3) and a tetravalent group represented by the following formulas (φ4-1) to formula (φ4-2). Selected from the group, at least one hydrogen of φ is substituted with an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, an aryl having 6 to 18 carbon atoms or a heteroaryl having 2 to 18 carbon atoms. May be good.

Z in the formula is> CR ₂ ,>N-Ar,> N-L, -O- or -S-, and R in> CR ₂ is an alkyl having 1 to 4 carbon atoms, respectively. It is a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms, and R may be bonded to each other to form a ring, and Ar in> N—Ar is It is an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms, and L in> NL is the formula (ETM-16), the formula (ETM-16-1) or the formula (ETM-16-2). Is L in. * In the formula represents the connection position.

Preferably, L is a divalent group of rings selected from the group consisting of benzene, naphthalene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthylidine, phthalazine, quinoxaline, quinazoline, cinnoline, and pteridine. At least one hydrogen of L may be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 10 carbon atoms or a heteroaryl having 2 to 10 carbon atoms.

Preferably, Ar in> N-Ar as Y or Z consists of the group consisting of phenyl, naphthyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridadinyl, triazinyl, quinolinyl, isoquinolinyl, naphthyldinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, and pteridinyl. Selected, at least one hydrogen of Ar in> N—Ar as Y may be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms or an aryl having 6 to 10 carbon atoms.

Preferably, R ¹ to R ⁴ are independently hydrogen, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, where R ¹ and R ² are the same, and R ³ and R are R. ⁴ is the same, and not all of R ¹ to R ⁴ are hydrogen at the same time, and when m is 1 or 2 and m is 2, the group formed by the azoline ring and L. Are the same.

Specific examples of the azoline derivative include the following compounds. In addition, "Me" in the structural formula represents methyl.

More preferably, φ is a divalent group represented by the following formula (φ2-1), formula (φ2-31), formula (φ2-32), formula (φ2-33) and formula (φ2-34). Selected from the group consisting of, at least one hydrogen of φ may be substituted with an aryl having 6 to 18 carbon atoms.

L is a divalent group of a ring selected from the group consisting of benzene, pyridine, pyrazine, pyrimidine, pyridazine, and triazine, and at least one hydrogen of L is an alkyl having 1 to 4 carbon atoms and 5 to 5 carbon atoms. It may be substituted with 10 cycloalkyl, an aryl having 6 to 10 carbon atoms or a heteroaryl having 2 to 14 carbon atoms.
Ar in> N-Ar as Y is selected from the group consisting of phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridadinyl, and triazinyl, and at least one hydrogen of the Ar is an alkyl having 1 to 4 carbon atoms and 5 to 5 carbon atoms. It may be substituted with 10 cycloalkyl or an aryl with 6 to 10 carbon atoms.
R ¹ to R ⁴ are independently hydrogen, an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, where R ¹ and R ² are the same and R ³ and R ⁴ are the same. And not all of R ¹ to R ⁴ become hydrogen at the same time, and
m is 2, and the groups formed by the azoline ring and L are the same.

Other specific examples of the azoline derivative include, for example, the following compounds. In addition, "Me" in the structural formula represents methyl.

For details of alkyl, cycloalkyl, aryl or heteroaryl in each of the above formulas defining this azoline derivative, the description in formula (1A) and formula (1B) can be cited.

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

<Reducing substance>
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 (2.15 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 improved. 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 materials for the electron injection layer and 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 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 an electronic layer. As the reactive substituent in this case, the description of a polycyclic aromatic compound having a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

3-1-7. The cathode and cathode 108 in the organic electroluminescent device serves to inject electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material for forming the cathode 108 is not particularly limited as long as it is a substance capable of efficiently injecting electrons into the organic layer, but the same material as 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 such as lithium fluoride / aluminum-lithium alloy, etc.) are preferable. Alloys containing lithium, sodium, potassium, cesium, calcium, magnesium or these low work function metals are effective for increasing electron injection efficiency and improving device characteristics. 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.

3-1-8. The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which are higher than the binder that may be used in each layer, can form each layer independently. Polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethylmethacrylate, polybutylmethacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, as a coating agent. Solvent-soluble resins such as vinyl acetate resin, ABS resin and polyurethane resin, curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin and silicone resin. It is also possible to disperse and use it.

3-1-9. Method for manufacturing organic electroluminescent device For each layer constituting an organic EL device, the material to be formed of each layer is vapor-filmed, resistance-heated vapor-deposited, electron beam vapor-deposited, sputtering, molecular lamination method, printing method, spin-coating method or casting method. It can be formed by forming a thin film by a method such as a coating method. 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 by a crystal oscillation type film thickness measuring device or the like. When thinning using a thin film method, the thin film 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 as + and the cathode as negative polarities, and when a voltage of about 2 to 40 V is applied, a transparent or translucent electrode may be applied. Light 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 alternating current is applied. The waveform of the alternating current to be applied may be arbitrary.

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

<Evaporation 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 device, it is also possible to reverse the production order and manufacture the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. Is.

<Wet film formation method>
The wet film forming method is carried out by preparing a small molecule 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 highly compatible 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 coat method, the method using the slit coater is the slit coat method, the method using the plate is gravure, offset, reverse offset, the flexo printing method, and the method using the inkjet printer is the inkjet method. , The method of spraying in the form of a mist is called the spray method.

As an example, a method of forming a coating film on a substrate having a bank by an inkjet method will be described with reference to FIG. 2. First, the bank (200) is provided on the electrode (120) on the substrate (110). In this case, the coating film (130) can be produced by dropping ink droplets (310) between the banks (200) from the inkjet head (300) and drying the ink droplets (310). By repeating this process to prepare the next coating film (140) and further to the light emitting layer (150), and forming an electron transport layer, an electron injection layer and an electrode by a vacuum vapor deposition method, the light emitting part is separated by a bank material. It is possible to manufacture an organic EL element.

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, which leads 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 stack. When the laminated film is prepared by the wet film forming method, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer, and the composition having controlled solubility, the cross-linking of the lower layer and the orthogonal solvent (Orthogonal solvent) are dissolved with 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 an organic EL element is manufactured by a wet film forming method for only a few layers and a vacuum vapor deposition method for the rest.

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 a hole by a wet film formation method (Procedure 4) Film 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, which is the opposite of 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 film formation and can be 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 substrate is heated and vapor-deposited by a laser, and an organic layer forming composition can be used as a material to be applied to the substrate.

<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. Further, a series of steps for forming a bank can be mentioned.

Photolithography technology can be used to create the bank. As the bank material that can be used for photolithography, a positive resist material and a negative 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 derivatives thereof, homopolymers and copolymers of ethylenically monomer having hydroxyl, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, and 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, chlorinated polypropylene, polyacetate, polynorbornen, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene, fluoroolefin-hydrocarbon olefin copolymer, and fluorocarbon polymer. However, it is not limited to that.

<Composition for forming an organic layer used in a wet film forming 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 dopant material as a first component, at least one 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 for dissolving 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, during the film formation using the inkjet method, the meniscus stability in the pinhole of the inkjet head can be controlled, and the ejection property can be controlled and improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecule, 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 defects of the coating film, 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 content 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.

The difference in solubility ( _SGS - _SPS ) is preferably 1% or more, more preferably 3% or more, still 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. Further, 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-based solvent, a phenyl ether-based solvent, an alkyl ether-based solvent, a cyclic ketone-based solvent, an aliphatic ketone-based solvent, and a monocyclic solvent. Examples thereof include a ketone solvent, a solvent having a diester skeleton and a fluorine-containing solvent, and 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, decane-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 isopropylmethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butylmethyl 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, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Anisol, Fenetol, 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, diphenylether, 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 an organic layer may contain an arbitrary component as long as the 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 include, but are not limited to.

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-friendly solvent 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 the hydrophilic group, and further classified into alkyl-based, silicon-based and fluorine-based based on the structure of the hydrophobic group. 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 Disper. 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.), Futergent 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, Mitsubishi Material 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, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylammonium iodide, Fluoroalkylbetaine, Fluoroalkylsulfonate, Diglycerin tetrakis (Fluoroalkylpolyoxyethylene ether) , Fluoroalkyltrimethylammonium salt, Fluoroalkylaminosulfonate, Polyoxyethylene nonylphenyl ether, Polyoxyethylene octylphenyl ether, Polyoxyethylene alkyl ether, Polyoxyethylene laurate, Polyoxyethylene oleate, Polyoxyethylene steer Rate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, poly Oxyethylene sorbitan oleate, polyo 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 the composition for forming an 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 mass to 2.0% by mass with respect to the total mass of the composition for forming a light emitting layer, and the second component is for forming a light emitting layer. 0.0999% by mass to 8.0% by mass with respect to the total mass of the composition, and 90.0% by mass to 99.9% by mass with respect to the total mass of the composition for forming the light emitting layer as the third component. preferable.

More preferably, the first component is 0.005% by mass to 1.0% by mass with respect to the total mass of the light emitting layer forming composition, and the second component is based on the total mass of the light emitting layer forming composition. It is 0.095% by mass to 4.0% by mass, and the third component is 95.0% by mass to 99.9% by mass with respect to the total mass of the composition for forming a light emitting layer. More preferably, the first component is 0.05% by mass to 0.5% by mass with respect to the total mass of the light emitting layer forming composition, and the second component is based on the total mass of the light emitting layer forming composition. The third component is 0.25% by mass to 2.5% by mass, and the third component is 97.0% by mass to 99.7% by mass with respect to the total mass 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, dissolution, and dispersion. Further, after the preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas substitution / 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 can be obtained. 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.

<Crosslinkable polymer compound: compound represented by the 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 formula (XLP-1).

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

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

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)-, an alkylene having 1 to 12 carbon atoms, and an 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 is preferable, and 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 a polymer compound and a crosslinkable polymer compound will be described by taking as an example the compound represented by the above formula (SPH-1) and the compound represented by (XLP-1). 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 advances the reaction. It may be carried out by a precipitation polymerization method in which precipitation is accompanied, 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, a monomer having a polymerizable group bonded to a monomer unit (MU) and a monomer having a polymerizable group bonded to an end cap unit (EC) are used. The desired product is obtained by carrying out the reaction in the state of being added to the reaction vessel. Further, when the compound represented by the formula (SPH-1) is synthesized in multiple stages, the monomer having the polymerizable group bonded to the monomer unit (MU) is polymerized to the desired molecular weight, and then the end cap unit (EC) is formed. The desired product is obtained by adding a monomer to which a polymerizable group is bonded and reacting. By adding a monomer having a polymerizable group bonded to a different type of monomer unit (MU) in multiple steps and carrying out a reaction, a polymer having a concentration gradient with respect to the structure of the monomer unit can be produced. Further, after preparing the precursor polymer, the target polymer can be obtained by a post-reaction.

In addition, the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer. 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 having three or more polymerizable groups.

Examples of the monomers that can be used in the present invention include JP-A-2010-189630, International Publication No. 2012/086671, International Publication No. 2013/1191088, International Publication No. 2002/045184, and International Publication No. 2011/094241. , International Publication No. 2013/146806, International Publication No. 2005/0495446, International Publication No. 2015/145871, JP-A-2010-215886, JP-A-2008-106241, JP-A-2010-215886, International Publication No. It can be synthesized according to the methods described in 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.

Further, regarding specific polymer synthesis procedures, Japanese Patent Application Laid-Open No. 2012-036388, International Publication No. 2015/008851, Japanese Patent Application Laid-Open No. 2012-36381, Japanese Patent Application Laid-Open No. 2012-144722, 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 methods described in Publication No. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049421 and JP-A-2012-144722.

3-1-10. 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.). In addition, examples of the display method of the display include a matrix and / or a segment method. 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. The line sequential drive has the advantage that the structure is simpler, but when considering the 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. For example, a time and temperature display in a digital clock or a thermometer, an operating state display of an audio device or an electromagnetic cooker, a panel display of an automobile, and the like can be mentioned.

Examples of the lighting device include a lighting device such as an indoor lighting device, a backlight of a liquid crystal display device, and the like (for example, JP-A-2003-257621, JP-A-2003-277471, 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 a personal computer for which thinning is an issue, the present embodiment is considered to be difficult to thin because the conventional method consists of a fluorescent lamp and a light guide plate. 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 compound according to the present invention can be used for producing an organic field effect transistor, an organic thin film solar cell, or the like, in addition to the above-mentioned organic field light emitting device.

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 dammed 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. As 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): Compound (1-161)

3.24 g (2.5 mmol) of compound (Int-1-161) was placed in a reaction vessel, and after nitrogen substitution, 20 mL of 1,2-dichlorobenzene was added. 3.13 g of boron tribromide (BBr ₃ ) was added dropwise from the dropping funnel, and the mixture was refluxed at 145 ° C. for 4.5 hours. The reaction was stopped with an aqueous sodium acetate solution, and the mixture was extracted with dichloromethane. The solvent was distilled off and the obtained residue was purified by silica gel short column chromatography (eluent: toluene). Compound (1-161) was obtained by heating under reflux washing with heptane (1.02 g, yield 31%).
The target compound (1-161) was confirmed at m / z = 1311.73 by LC-MS.

Synthesis example (2): Compound (1-180)

2.98 g (2.5 mmol) of compound (Int-1-180) was placed in a reaction vessel, and after nitrogen substitution, 20 mL of 1,2-dichlorobenzene was added. 3.13 g of boron tribromide (BBr ₃ ) was added dropwise from the dropping funnel, and the mixture was refluxed at 145 ° C. for 12 hours. The reaction was stopped with an aqueous sodium acetate solution, and the mixture was extracted with dichloromethane. The solvent was distilled off and the obtained residue was purified by silica gel short column chromatography (eluent: toluene / heptane = 1/1 (volume ratio)). Compound (1-180) was obtained by heating under reflux washing with heptane (0.75 g, yield 25%).
The target compound (1-180) was confirmed at m / z = 1207.65 by LC-MS.

Synthesis example (3): Compound (1-256)

2.56 g (2.5 mmol) of compound (Int-1-256) was placed in a reaction vessel, and after nitrogen substitution, 20 mL of 1,2-dichlorobenzene was added. 3.13 g of boron tribromide (BBr ₃ ) was added dropwise from the dropping funnel, and the mixture was refluxed at 145 ° C. for 14 hours. The reaction was stopped with an aqueous sodium acetate solution, and the mixture was extracted with dichloromethane. The solvent was distilled off and the obtained residue was purified by silica gel short column chromatography (eluent: toluene). Compound (1-256) was obtained by heating under reflux washing with heptane (0.38 g, yield 14%).
The target compound (1-256) was confirmed at m / z = 1076.61 by LC-MS.

Next, the evaluation of the basic physical properties of the compound of the present invention and the production and evaluation of an organic EL device using the compound of the present invention will be described.

(1) Fabrication and evaluation of thin-film deposition type organic EL element The organic EL element according to Examples and Comparative Examples is manufactured, and a voltage is applied to measure current density, luminance, chromaticity, external quantum efficiency and the like. The following configurations A (Table 1) and B (Table 2) are selected and evaluated as the configurations of the produced organic EL elements. However, the application of the compound of the present invention is not limited to these configurations, and the film thickness and constituent materials of each layer can be appropriately changed depending on the basic physical properties of the compound of the present invention.

<< Element configuration and evaluation of configuration A >>

In Table 1,
"NPD" is N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl,
"TcTa" is a 4,4', 4 "-tris (N-carbazolyl) triphenylamine,
"MCP" is 1,3-bis (N-carbazolyl) benzene,
"2CzBN" is 3,4-dicarbazolylbenzonitrile and "BPy-TP2" is 2,7-di ([2,2'-bipyridine] -5-yl) triphenylene.
Together with "BH-1", "RBD-1", "RBD-2" and "RBD-3", the chemical structure is shown below.

<Example 1>
<Structure A: Element using compound (1-161) as a dopant>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available thin-film deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and NPD, TcTa, mCP, BH-1, compound (1-161), 2CzBN and BPy-TP2 were added, respectively. A molybdenum vapor deposition boat and a tungsten vapor deposition boat containing LiF and aluminum were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa, and first, the NPD was heated and vapor-deposited to a film thickness of 40 nm to form a hole injection layer. Next, TcTa was heated and vapor-deposited to a film thickness of 15 nm to form a hole transport layer. Next, the mCP was heated and vapor-deposited to a film thickness of 15 nm to form an electron blocking layer. Next, BH-1 and compound (1-161) were simultaneously heated and vapor-deposited to a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-161) was approximately 99: 1. Next, 2CzBN was heated and vapor-filmed to a film thickness of 10 nm, and then BPy-TP2 was heated and vapor-filmed to a film thickness of 20 nm to form an electron transport layer composed of two layers. The vapor deposition rate of each layer was 0.01 to 1 nm / sec. After that, LiF is heated and vapor-deposited to a film thickness of 1 nm at a vapor deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to be vapor-deposited to a film thickness of 100 nm to form a cathode. Then, an organic EL element was obtained. At this time, the vapor deposition rate of aluminum was adjusted to 1 to 10 nm / sec.

<Examples 2 and 3, Comparative Examples 1 to 3>
The compound (1-161), which is the dopant of Example 1, was changed to the dopant shown in Table 1 to prepare an element.

<Evaluation>
A DC voltage is applied to the manufactured element with the ITO electrode as the anode and the aluminum electrode as the cathode, and the emission wavelength, half-value width, drive voltage, current density, external quantum efficiency (EQE), and LT50 at a brightness of 500 cd / m ² . (Time until it reaches 250 cd / m ² when continuously driven at a current density at an initial brightness of 500 cd / m ² ) was measured. The evaluation results are shown in Table 1.

<< Element configuration and evaluation of configuration B >>

In Table 2,
"HI-1" is N ⁴ , N ^4' -diphenyl-N ⁴ , N ^4' -bis (9-phenyl-9H-carbazole-3-yl)-[1,1'-biphenyl] -4,4' -Diamine
"HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile.
"HT-1" is N- ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole-3-yl) phenyl)- It is 9H-fluorene-2-amine, and "HT-2" is N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1': 4', 1 "-Terphenyl] -4-amine,
"BH-2" is 9-phenyl-10- (4-phenylnaphthalene-1-yl) anthracene,
"BH-3" is 2- (10-phenylanthracene-9-yl) dibenzo [b, d] furan and "ET-1" is 4,6,8,10-tetraphenyl [1,4] benzoki. Sabolinino [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 4>
<Structure B: Element using compound (1-256) as a dopant>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 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 Showa Vacuum Co., Ltd.), and HI-1, HAT-CN, HT-1, HT-2, BH-2, compound (1-256). , ET-1, ET-2 and Liq, respectively, and a tungsten vapor deposition boat containing 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-1 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. , A hole injection layer consisting of two layers was formed. Next, HT-1 was heated and vapor-filmed to a film thickness of 15 nm, and HT-2 was further heated and vapor-filmed to a film thickness of 10 nm to form a hole transport layer composed of two layers. Next, BH-2 and the compound (1-256) 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-2 to compound (1-256) was approximately 99: 1. Next, ET-1 is heated and vapor-filmed to a film thickness of 5 nm, and ET-2 and Liq are heated and vapor-deposited to a film thickness of 25 nm to form a two-layer electron transport layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 and Liq was approximately 1: 1. The vapor deposition rate of each layer is 0.01 to 1 nm / sec. After that, LiF is heated and vapor-deposited to a film thickness of 1 nm at a vapor deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to be vapor-deposited to a film thickness of 100 nm to form a cathode. Then, an organic EL element was obtained. At this time, the vapor deposition rate of aluminum was adjusted to 1 to 10 nm / sec.

<Example 5, Comparative Examples 4 and 5>
The dopant and host of Example 4 were changed to the dopant or host shown in Table 2 to prepare an element.

<Evaluation>
A DC voltage is applied to the manufactured element with the ITO electrode as the anode and the aluminum electrode as the cathode, and the emission wavelength, half-value width, drive voltage, external quantum efficiency, and LT97 (current density 20 mA / cm) at a current density of 20 mA / cm ² are applied. The time until it became 97% of the initial brightness when continuously driven in ² ) was measured. The evaluation results are shown in Table 2.

The polycyclic aromatic compound of the present invention is useful as a material for an organic device, particularly a material for a light emitting layer for forming a light emitting layer of an organic electroluminescent element.

100 Organic electroluminescent element 101 substrate 102 anode 103 hole injection layer 104 hole transport layer 105 light emitting layer 106 electron transport layer 107 electron injection layer 108 cathode 110 substrate 120 electrode 130 coating film 140 coating film 150 light emitting layer 200 bank 300 inkjet head 310 Ink droplets

Claims (30)

A polycyclic aromatic compound consisting of a partial structure represented by the formula (1A) and a partial structure represented by at least one formula (1B);

In formula (1A) and formula (1B),
Rings A and B are independently optionally substituted aryl rings or optionally substituted heteroaryl rings, respectively.
R ^XD is an aryl that may be substituted, a heteroaryl that may be substituted, an alkyl that may be substituted or a cycloalkyl that may be substituted, and the dashed line is -X- or a single bond. It may be bonded to at least one of the A ring or the B ring.
The aryl ring or heteroaryl ring in at least one of the A ring, the B ring or the ^RXD is bonded to the partial structure represented by the formula (1B).
The partial structure represented by the formula (1B) is bonded to two adjacent atoms on the ring of the aryl ring or the heteroaryl ring at two * positions, respectively.
The C ring is an aryl ring which may be substituted or a heteroaryl ring which may be substituted, respectively.
R ^XE is an aryl that may be substituted, a heteroaryl that may be substituted, an alkyl that may be substituted or a cycloalkyl that may be substituted, and the dashed line is -X- or a single bond. It may be bonded to the C ring, and the broken line is -X- or a single bond and is bonded to the ring to which the partial structure represented by the equation (1B) is bonded at the position (*). May be
Y is B, P, P = O or P = S independently of each other.
X is independently> C (-R) 2,>N-R,>O,> Si (-R) ₂ or> S, and R in> N-R is substituted. _{R _} Are independently hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and may be attached to each other by a linking group. At least one of the above> N-R, the above> C (-R) ₂ , and the above> Si (-R) ₂ R is an A ring, a B ring, a C ring, an R ^XD , or an A ring by a linking group or a single bond. May be combined with at least one of R ^XE ,
X is an expression in which at least one of X is> N-R and R in at least one of X is> N-R combined with one of the A ring, B ring, C ring, R ^XD , or R ^XE . A partial structure represented by (A10) is formed, and in the formula (A10), ^{RA1 to RA4 are} independently hydrogen, substituted alkyl or substituted cycloalkyl, respectively. Any 2 to 4 of ^RA1 to ^RA4 may be bonded to each other by a linking group or a single bond, and the partial structure represented by the formula (A10) is one at two * positions. It is attached to the ring at the position of ** and is attached to the other ring.
At least one selected from the group consisting of an aryl ring and a heteroaryl ring in the polycyclic aromatic compound may be condensed with at least one cycloalkane, and at least one hydrogen in the cycloalkane is substituted. Alternatively, at least one -CH _2- in the cycloalkane may be substituted with -O-.
At least one hydrogen in the polycyclic aromatic compound may be substituted with deuterium, cyano or halogen. R ^XD may be substituted or substituted aryl or heteroaryl which may be substituted, and the dashed line becomes −X— and is bonded to the A ring, and R ^XE may be substituted. The polycyclic aromatic compound according to claim 1, which is a heteroaryl which may be substituted and has a broken line of -X- and is bonded to the C ring. The polycyclic aromatic compound according to claim 1 or 2, wherein ^{RA1 and RA4 are} bonded to each other, and ^RA2 and ^RA3 are each independently hydrogen or optionally substituted alkyl. The polycyclic aromatic compound according to claim 1 or 2, wherein ^{RA1 and RA4 are} bonded to each other to form − (CH ₂ ) _4- , and ^RA2 and ^RA3 are both methyl. The substituents when the A ring, B ring and C ring are substituted aryl rings or substituted heteroaryl rings and the aryls substituted or substituted heteroaryls R ^XD and R ^XE . When the substituents are all 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 attached via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy. , Substituted or unsubstituted aryloxy, substituted silyl and -L-Ak.
L is>N-R,> O or> S, where R in> N-R is an aryl optionally substituted, a heteroaryl optionally substituted, an alkyl optionally substituted or substituted. The cycloalkyl may be such that the> N-R R may be attached to Ak by a linking group or a single bond.
Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and at least one hydrogen in the alkyl and cycloalkyl may be substituted and at least one in the alkyl and cycloalkyl. -CH ₂ -may be substituted with -O- and -S-, and may be substituted.
Any one of claims 1 to 4, wherein the A ring, B ring, C ring, R ^XD and R ^XE are all bonded to any X and Y in a 5-membered ring or a 6-membered ring. The polycyclic aromatic compound described in. The polycyclic aromatic compound according to claim 1, which is represented by any of the following formulas (3-1-1), formula (3-1-2), and formula (3-2-1);

In Eqs. (3-1-1), Eqs. (3-1-2), Eqs. (3-2-1),
X ¹ is independently> C (-R) 2,>N-R,>O,> Si (-R) ₂ or> S, and R of> N-R has 1 carbon atom. May be substituted with an alkyl of ~ 6 or a cycloalkyl of 3-14 carbons. Even if substituted with an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms. A good heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms, and the R of> C (-R) ₂ and> Si (-R) ₂ described above are each. Independently, it is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms.
Y is B, P, P = O or P = S independently of each other.
Z is -C (-R ^Z ) = or -N = independently of each other, and two adjacent Zs are -C (-R ^Z ) _2- , -Si (-R ^Z ) _2- , It may be replaced with -N (-R ^Z )-, -O-, or -S-.
R ^Z may be independently bonded to hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be attached via a single bond or a linking group). ), Alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl or -L-Ak, wherein at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and R. Adjacent groups of ^Z may be bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a c ring, a d ring or an e ring, and at least one hydrogen in the formed ring is aryl. , Heteroaryl, Diarylamino, Diheteroarylamino, Arylheteroarylamino, Diarylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, Substituted Cyril or —L—Ak may be substituted, at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
L is>N-R,> O or> S, where R in> N-R is an aryl optionally substituted, a heteroaryl optionally substituted, an alkyl optionally substituted or substituted. The cycloalkyl may be such that the> N-R R may be attached to Ak by a linking group or a single bond.
Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and at least one hydrogen in the alkyl and cycloalkyl may be substituted and at least one in the alkyl and cycloalkyl. -CH ₂ -may be substituted with -O- and -S-, and may be substituted.
Even if at least one hydrogen in the compound represented by the formula (3-1-1), the formula (3-1-2), and the formula (3-2-1) is substituted with deuterium, cyano or halogen. good. Y is B,
Z is independently -C (-R ^Z ) = or -N =, where o- or p-position Z with respect to Y is -C (-R ^Z ) =. Item 6. The polycyclic aromatic compound according to Item 6. The polycyclic aromatic compound according to claim 7, wherein Z is -C (-R ^Z ) =. A reactive compound in which a reactive substituent is substituted on the polycyclic aromatic compound according to any one of claims 1 to 8. A polymer compound obtained by polymerizing the reactive compound according to claim 9 as a monomer, or a polymer crosslinked product obtained by further cross-linking the polymer compound. A pendant type polymer compound in which a main chain type polymer is substituted with the reactive compound according to claim 9, or a pendant type polymer crosslinked body 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 8. A material for an organic device containing the reactive compound according to claim 9. A material for an organic device containing the polymer compound or polymer crosslinked body according to claim 10. A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked body according to claim 11. The material for an organic device according to any one of claims 12 to 15, 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 16, wherein the material for an organic electroluminescent element is a material for a light emitting layer. A composition comprising the polycyclic aromatic compound according to any one of claims 1 to 8 and an organic solvent. A composition comprising the reactive compound according to claim 9 and an organic solvent. A composition comprising a main chain polymer, the reactive compound according to claim 9, and an organic solvent. A composition comprising the polymer compound or the crosslinked polymer according to claim 10 and an organic solvent. A composition comprising the pendant type polymer compound or the pendant type polymer crosslinked body according to claim 11 and an organic solvent. The polycyclic aromatic compound according to any one of claims 1 to 8, the reactive compound according to claim 9, and the reactive compound according to claim 10, which are arranged between the 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 11 or the pendant type polymer compound or pendant type polymer crosslinked body according to claim 11. The organic electroluminescent device according to claim 23, wherein the organic layer is a light emitting layer. 24. The light emitting layer comprises a host and the polycyclic aromatic compound, a reactive compound, a polymer compound, a polymer crosslinked body, a pendant type polymer compound or a pendant type polymer crosslinked body as a dopant. The organic field light emitting element according to. 25. The organic electroluminescent device according to claim 25, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzochrysene-based compound. It has at least one layer of an electron transporting layer and 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, or fluoranthene. Contains at least one selected from the group consisting of derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphinoxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives and quinolinol-based metal complexes. The organic electric field light emitting element according to any one of claims 24 to 26. At least one layer of the electron transport layer and the electron injection 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 soil. Contains at least one selected from the group consisting of 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. 27. The organic electric field light emitting element according to claim 27. 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 electric field light emitting element according to any one of claims 24 to 28, which comprises a pendant type polymer crosslinked body further crosslinked. A display device or a lighting device provided with the organic electroluminescent element according to any one of claims 23 to 29.

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