JP7376892B2 - Polycyclic aromatic compounds - Google Patents

Description

The present invention relates to polycyclic aromatic compounds. The present invention also relates to organic devices using the polycyclic aromatic compound, such as organic electroluminescent elements, organic field effect transistors, and organic thin film solar cells, as well as display devices and lighting devices.

Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied in various ways because they can save power and be made thinner. ) has been actively studied because it is easy to reduce weight and increase size.

For example, three types of light-emitting materials for organic electroluminescent devices have been studied and used: fluorescent materials, phosphorescent materials, and thermally activated delayed fluorescence (TADF) materials, but fluorescent materials have low luminous efficiency and approximately It is about 25 to 62.5%. On the other hand, phosphorescent materials and TADF materials have high luminous efficiency, reaching 100% in some cases, but both have a problem of low color purity (broad emission spectrum). Display devices express a variety of colors by mixing the three primary colors of light, red, green, and blue, but if the purity of each color is low, colors that cannot be reproduced will be produced, and the image quality will suffer greatly. descend. Therefore, commercially available display devices are used after increasing the color purity (narrowing the spectrum width) by removing unnecessary colors from the emission spectrum with an optical filter. Therefore, if the original spectral width is wide, the removal rate increases, so even if the luminous efficiency of the material is high, the actual efficiency will decrease significantly. For example, the half-width of the blue emission spectrum of commercially available smartphones is approximately 20 to 25 nm, but the half-width of general fluorescent materials is approximately 40 to 60 nm, that of phosphorescent materials is approximately 60 to 90 nm, and that of TADF materials. and about 70 to 100 nm. When a fluorescent material is used, the half-width is relatively narrow, so it is sufficient to remove only a portion of the unnecessary color, but when a phosphorescent material or a TADF material is used, more than half of it needs to be removed. Against this background, there has been a desire to develop a luminescent material that has both luminous efficiency and color purity.

Patent Document 1 discloses a polycyclic aromatic compound in which aromatic rings are connected with hetero elements such as boron, phosphorus, oxygen, nitrogen, and sulfur as a new compound that dramatically improves the color purity of TADF materials. There is. Patent Document 1 reports that this polycyclic aromatic compound has a large HOMO-LUMO gap and high triplet excitation energy ( _ET ) and is therefore particularly useful as a fluorescent material for organic EL devices.

International Publication No. 2015/102118

As mentioned above, in order to further improve the luminescent properties of organic electroluminescent elements and to increase the selection of materials for organic devices such as organic electroluminescent elements, it is desired to develop compounds that were previously unknown.

As a result of intensive studies to solve the above problems, the present inventors have discovered that a compound that maintains the basic structure of the compound described in Patent Document 1 and introduces a structure that adjusts the multiple resonance effect can be used in organic EL devices, etc. The present invention was completed based on the discovery that the material has advantageous properties as a material for manufacturing organic devices.
That is, the present invention provides the following polycyclic aromatic compounds, and furthermore, an organic device material containing the following polycyclic aromatic compounds.

<1> A polycyclic aromatic compound represented by the following formula (1).

(In formula (1),
Ring A, Ring B, Ring C, Ring D, and Ring E are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen atom in these rings may be substituted,
X ¹ , X ² , X ³ and X ⁴ are each independently >O, >NR, >S or >Se, and R in >NR is optionally substituted aryl. , optionally substituted heteroaryl, or optionally substituted alkyl, and R in >NR is a linking group or single bond that connects the A ring, B ring, C ring, D ring, and /or may be bonded to the E ring,
and,
At least one hydrogen in the compound represented by formula (1) may be substituted with cyano, halogen, or deuterium. )

<2> Ring A, Ring B, Ring C, Ring D, and Ring E are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is aryl, heteroaryl, or diaryl. Amino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio, diarylboryl (two aryls are bonded via a single bond or a linking group) or trisubstituted silyl, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl; has a 5- or 6-membered ring that shares a bond with the fused 2-ring structure on the left of formula (1) consisting of B, X ¹ and X ² , and the C ring and D ring are B, X ³ and Formula (1) composed of ⁴ has a 5-membered ring or a 6-membered ring that shares a bond with the fused 2-ring structure on the right,
X ¹ , X ² , X ³ and X ⁴ are each independently >O, >NR, >S or >Se, R in >NR is aryl, heteroaryl or alkyl, At least one hydrogen in R is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or trisubstituted silyl. The above R in >N-R may be substituted by -O-, -S-, -C(-R) ₂ - or a single bond to form the above-mentioned ring A, ring B, ring C, ring D. , and/or may be bonded to the E ring, and R in the -C(-R) ₂ - is hydrogen or alkyl,
At least one hydrogen in the compound represented by formula (1) may be substituted with cyano, halogen or deuterium,
The polycyclic aromatic compound described in <1>.

<3> The polycyclic aromatic compound according to <1>, which is represented by the following formula (2).

(In formula (2),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R 12 , R ¹³ , R ¹⁴ , R ¹⁵ , and ^{R 16 are} each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthiodiarylboryl (two aryl may be bonded via a single bond or a linking group), or trisubstituted silyl, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, Adjacent groups among R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ are bonded together to form an aryl group together with ring a, ring b, ring c, or ring d, respectively. It may form a ring or a heteroaryl ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryl. may be substituted with oxy, heteroaryloxy, arylthio, heteroarylthio or trisubstituted silyl, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl;
X ¹ , X ² , X ³ and X ⁴ are each independently >O, NR, >S or >Se, and R in >NR is aryl having 6 to 12 carbon atoms, It is a heteroaryl having 2 to 15 carbon atoms or an alkyl having 1 to 6 carbon atoms, and R in the above-mentioned >N-R is -O-, -S-, -C(-R) ₂ - or a single bond. It may be bonded to the a-ring, b-ring, c-ring, d-ring, and/or e-ring, and R in the -C(-R) ₂ - is hydrogen or alkyl having 1 to 6 carbon atoms;
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. )

<4> ^{R1 , R2} , R3, ^{R4 ,} R5, ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , R11, ^R12 , ^R13 , ^R14 , ^R15 , and ^{R 16} each independently represents hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 6 carbon atoms , aryloxy having 6 to 12 carbon atoms, arylthio having 6 to 12 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, arylheteroarylamino (where aryl is aryl having 6 to 12 carbon atoms, and heteroaryl is aryl having 2 carbon atoms) -12 heteroaryl) or diheteroarylamino (heteroaryl is a heteroaryl having 2 to 12 carbon atoms), in which at least one hydrogen is an aryl having 6 to 12 carbon atoms or a diheteroarylamino (heteroaryl having 2 to 12 carbon atoms) 6 may be substituted with alkyl,
X ¹ , X ² , X ³ and X ⁴ are each independently >O or NR, and R in >NR is aryl having 6 to 10 carbon atoms or is alkyl, and R in >NR may be bonded to the a ring, b ring, c ring, d ring, and/or e ring through a single bond,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. The polycyclic aromatic compound according to <3>.

<5> R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are Each independently represents hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, carbon number Aryloxy having 6 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, arylheteroarylamino (where aryl is aryl having 6 to 10 carbon atoms, heteroaryl is heteroaryl having 2 to 12 carbon atoms), or diheteroaryl Amino (however, heteroaryl is heteroaryl having 2 to 12 carbon atoms), and at least one hydrogen in these may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms,
R ¹ is hydrogen;
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen or deuterium,
The polycyclic aromatic compound described in <4>.

<6> The polycyclic aromatic compound according to <1>, which is represented by any of the following formulas.

(In the formula, each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms, and R ¹⁰⁰ is each independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms. Aryl, carbazolyl, diarylamino (aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or aryloxy having 6 to 10 carbon atoms; may be substituted with alkyl having 1 to 6 carbon atoms, and the carbazolyl may be substituted with aryl having 6 to 10 carbon atoms or alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compounds represented by the above formulas may be substituted with cyano, halogen, or deuterium. )

<7> The polycyclic aromatic compound according to <1>, which is represented by the following formula.

<8> An organic device material containing the polycyclic aromatic compound according to any one of <1> to <7>.
<9> The organic device material according to <8>, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material.
<10> The organic device material according to <9>, wherein the organic electroluminescent element material is a light emitting layer material.
<11> A composition for forming a light-emitting layer for forming a light-emitting layer of an organic electroluminescent device by coating,
As the first component, at least one polycyclic aromatic compound according to any one of <1> to <7>;
as a second component, at least one organic solvent;
A composition for forming a light-emitting layer.
<12> An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The organic electroluminescent device, wherein the light emitting layer contains the polycyclic aromatic compound according to any one of <1> to <7>.
<13> An organic electroluminescent element comprising a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The organic electroluminescent device, wherein the light emitting layer is a layer formed from the composition for forming a light emitting layer according to <11>.

<14> An electron transport layer and/or an electron injection layer are provided between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is made of a borane derivative, a pyridine derivative, or a fluoranthene derivative. Derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, aryl nitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, quinolinol metal complexes, thiazole derivatives, benzothiazole derivatives, silole derivatives and azolines The organic electroluminescent device according to <12> or <13>, containing at least one selected from the group consisting of derivatives.
<15> The electron transport layer and/or 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, an alkaline earth Contains at least one selected from the group consisting of halides of similar metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals. , the organic electroluminescent device according to <14>.
<16> A display device comprising the organic electroluminescent element according to any one of <12> to <15>.
<17> A lighting device comprising the organic electroluminescent element according to any one of <12> to <15>.

The present invention provides a compound represented by formula (1) as a hitherto unknown polycyclic aromatic compound. The polycyclic aromatic compound represented by formula (1) can be used as an organic device material such as a material for a light emitting layer. By using the compound represented by formula (1), the light emitting characteristics of an organic electroluminescent device can be improved.

FIG. 1 is a schematic cross-sectional view showing an organic EL element according to the present embodiment. FIG. 2 is a diagram illustrating a method of manufacturing an organic EL element using an inkjet method on a substrate having banks.

In the following, the present invention will be explained in detail. Although the constituent elements described below may be explained based on typical embodiments and specific examples, the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after the "~" as lower and upper limits. Further, in this specification, "hydrogen" in the explanation of the structural formula means "hydrogen atom (H)".

In this specification, chemical structures and substituents may be expressed by the number of carbon atoms, but when a chemical structure is substituted with a substituent, or when a substituent is further substituted with a substituent, the number of carbon atoms is It refers to the number of carbon atoms in each group, and does not mean the total number of carbon atoms in the chemical structure and substituents, or the total number of carbon atoms in the substituents. For example, "substituent B having a carbon number Y substituted with a substituent A having a carbon number X" means that "substituent B having a carbon number Y" is substituted with "substituent A having a carbon number X". However, the carbon number Y is not the total carbon number of substituent A and substituent B. For example, "substituent B having carbon number Y and substituted by substituent A" means that "substituent B having carbon number Y" is substituted with "substituent A (of which the number of carbon atoms is not limited)". However, the carbon number Y is not the total carbon number of substituent A and substituent B.

1. Polycyclic Aromatic Compound The compound of the present invention is a polycyclic aromatic compound in which aromatic rings are connected with a hetero element (boron), similar to the compound described in Patent Document 1. The hetero-element-containing polycyclic aromatic compound according to the present invention has a triplet excited state (T1) because the exchange interaction between both orbitals becomes small due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). The energy difference between T1) and the singlet excited state (S1) is small, and thermally activated delayed fluorescence is exhibited.

"Thermally activated delayed fluorescence" refers to delayed fluorescence that absorbs thermal energy and causes reverse intersystem crossing from the excited triplet state to the excited singlet state, and then radiatively deactivates and emits the excited singlet state. means. In this specification, a compound capable of emitting such delayed fluorescence is sometimes referred to as a "thermally activated delayed phosphor" or "TADF material." In the present invention, when the fluorescence lifetime of a sample containing the target compound is measured at 300 K, the target compound is determined to be a "thermally activated delayed phosphor" based on the observation of a slow fluorescence component. Here, the slow fluorescence component refers to one whose fluorescence lifetime is 0.1 μsec or more. The fluorescence lifetime can be measured using, for example, a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics, C11367-01).

In normal fluorescence emission, 75% of triplet excitons generated by current excitation pass through a thermal deactivation path and cannot be extracted as fluorescence, but by using TADF material, all excitons can be used for fluorescence emission. As a result, highly efficient organic EL devices can be realized.
In general, TADF materials localize the HOMO and LUMO within the molecule using electron-donating substituents called donors and electron-accepting substituents called acceptors to achieve efficient reverse intersystem crossing. However, if a donor or acceptor is used, the structure relaxation in the excited state becomes large (for some molecules, the stable structure is different between the ground state and the excited state, so when an external stimulus crosses the ground state, (When the conversion from the excited state to the excited state occurs, the structure changes to a stable structure in the excited state), giving a broad emission spectrum with low color purity.

Therefore, Patent Document 1 (International Publication No. 2015/102118) proposes a new molecular design that dramatically improves the color purity of the TADF material. For example, in the compound (1-401) disclosed in this document, three carbons on a benzene ring consisting of six carbons are We succeeded in localizing the HOMO at (black circle) and the LUMO at the remaining three carbons (white circle). Due to this efficient reverse intersystem crossing, the luminous efficiency of the compound reaches a maximum of 100%. Furthermore, boron and nitrogen in compound (1-401) not only localize HOMO and LUMO, but also maintain a robust planar structure by condensing three benzene rings, allowing structural relaxation in the excited state. As a result, we have succeeded in obtaining an emission spectrum with high color purity and small Stokes shifts in the absorption and emission peaks. The half-width of its emission spectrum is 28 nm, indicating a level of color purity that surpasses even practically used fluorescent materials with high color purity. Furthermore, in a dimeric compound such as formula (1-422), two borons and two nitrogens are bonded to the central benzene ring, further enhancing the multiple resonance effect in the central benzene ring. As a result, it is possible to emit light with an extremely narrow emission peak width.

On the other hand, in a dimeric compound such as formula (1-422), the emission wavelength is longer due to the high planarity of the molecule and the broader resonance, which is far from the practical blue wavelength. This also caused the problem that the efficiency in light-emitting devices was not sufficiently satisfactory, probably because intermolecular stacking was induced.

As a result of intensive research, we have achieved shorter emission wavelengths and higher device efficiency by introducing a structure that adjusts the multiple resonance effect. Specifically, the polycyclic aromatic compound represented by formula (1) of the present invention does not have a bond between X ² and the C ring, so that it can reduce planarity due to steric repulsion. By shortening the emission wavelength and inhibiting intermolecular stacking, it has become possible to increase device efficiency in light-emitting devices. However, the effects of the polycyclic aromatic compound of the present invention are not limited to those based on the above principle.

The polycyclic aromatic compound of the present invention can emit light having a maximum value between 450 nm and 500 nm with high color purity, and can emit light with a half-value width of 30 nm or less, 25 nm or less, and even 20 nm or less. I can do it.

The polycyclic aromatic compound represented by formula (1) is shown below. Moreover, the polycyclic aromatic compound represented by formula (1) is preferably a polycyclic aromatic compound represented by the following formula (2).

Ring A, Ring B, Ring C, Ring D, and Ring E in formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted with a substituent. You can leave it there. This substituent includes substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and (amino group with heteroaryl), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryloxy, substituted or unsubstituted Substituted arylthio, substituted or unsubstituted heteroarylthio, substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), or substituted or unsubstituted trisubstituted silyl is preferred. When these groups have a substituent, examples of the substituent include aryl, heteroaryl, and alkyl.

In addition, the A ring and the B ring are a 5-membered ring or a 6-membered ring that shares a bond with the fused 2-ring structure on the left of formula (1) consisting of "B (boron atom)", "X ¹ " and "X ² ". A 5-membered ring that shares a bond with the fused 2-ring structure on the right of formula (1), in which ring C and ring D are composed of "B (boron atom)", "X ³ " and "X ⁴ " Alternatively, it is preferable to have a 6-membered ring.

Here, "fused two-ring structure" refers to two saturated carbon atoms containing "B (boron atom)", "X ¹ " and "X ² " shown on the left side of formula (1). It means a structure in which hydrogen rings are condensed. The same applies to the fused two-ring structure on the right side of formula (1). In addition, "a 6-membered ring that shares a bond with a fused 2-ring structure" means, for example, a ring a (benzene ring (6-membered ring)) fused to a fused 2-ring structure as shown in formula (2) above. . In addition, "the aryl ring or heteroaryl ring (which is Ring A) has this 6-membered ring" means that Ring A is formed only with this 6-membered ring, or that it contains this 6-membered ring. This means that the A ring is formed by condensing another ring with this 6-membered ring. In other words, the term "aryl ring or heteroaryl ring having a 6-membered ring (which is Ring A)" as used herein means that the 6-membered ring constituting all or part of Ring A is fused to a fused 2-ring structure. means that The same explanation applies to "B ring (b ring),""C ring (c ring),""D ring (d ring),""E ring (e ring)," and "5-membered ring."

Ring A (or ring B, ring C, ring D, ring E) in formula (1) is ring a and its substituents R ² to R ⁵ in formula (2) (or ring b and its substituents R ⁶ to R ⁹ , ring c and its substituents R ¹⁰ to R ¹³ , ring d and its substituents R ¹⁴ to R ¹⁶ , and ring e and its substituents R ¹ ). That is, formula (2) corresponds to a formula in which "rings A to D having a 6-membered ring" are selected as rings A to E in formula (1). In this sense, each ring in formula (2) is represented by a lowercase letter a to e.

R ¹ , R ² , R 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ^{15 and} R ¹⁶ is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio, diaryl boryl (the two aryls may be bonded via a single bond or a linking group), or trisubstituted silyl, in which at least one hydrogen is substituted with aryl, heteroaryl, alkyl, or cycloalkyl. You can leave it there. R ¹ , R ² , R 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ^{15 and} Preferably, R ¹⁶ is each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted diarylamino.

In formula (2), adjacent groups among R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ are bonded to each other to form ring a, ring b, and ring c, respectively. The ring and the d-ring may form an aryl ring or a heteroaryl ring. Here, the term "adjacent groups" means adjacent groups on the same ring. For example, a substituent is bonded to a benzene ring which is ring a (or ring b, or ring c or d), such as benzene ring, indole ring, pyrrole ring, benzofuran ring, benzothiophene ring, cyclohexene ring, indene ring, etc. When a ring is formed, the formed fused ring a' (fused ring b', or fused ring c', or fused ring d') is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring, or a dibenzothiophene ring, respectively. , a tetralin ring, and a fluorene ring.

In formula (2), adjacent groups among the substituents R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ in the a-ring, b-ring, c-ring and d-ring At least one hydrogen in the ring formed by bonding is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxyaryloxy, diarylboryl (two aryls are single bonds) or may be bonded via a linking group), or may be substituted with trisubstituted silyl.

Examples of the "aryl ring" which is the A ring, B ring, C ring D ring, and E ring in formula (1) include an aryl ring having 6 to 30 carbon atoms, and an aryl ring having 6 to 16 carbon atoms. is preferred, an aryl ring having 6 to 12 carbon atoms is more preferred, and an aryl ring having 6 to 10 carbon atoms is particularly preferred.

Specific "aryl rings" include a monocyclic benzene ring, a biphenyl ring, a fused bicyclic naphthalene ring, and a tricyclic terphenyl ring (m-terphenyl, o -terphenyl, p-terphenyl), fused tricyclic ring systems such as acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic ring system such as triphenylene ring, pyrene ring, naphthacene ring, and fused pentacyclic ring system. Examples include perylene ring and pentacene ring.

Examples of the "heteroaryl ring" which is ring A, ring B, ring C, ring D, and ring E in formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, and a heteroaryl ring having 2 to 25 carbon atoms. A heteroaryl ring is preferred, a heteroaryl ring having 2 to 20 carbon atoms is more preferred, a heteroaryl ring having 2 to 15 carbon atoms is even more preferred, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferred. Examples of the "heteroaryl ring" include, for example, a heterocycle containing, in addition to carbon, 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen as ring constituent atoms. In addition, this "heteroaryl ring" is defined in the below-mentioned formula (2) and is formed by combining adjacent groups of R ¹ to R ¹¹ together with ring a, ring b, or ring c. In addition, since ring a (or ring b, or ring c) is already composed of a benzene ring with 6 carbon atoms, the fused ring with a 5-membered ring fused to it has a total of 6 carbon atoms. is the lower limit carbon number.

Specific "heteroaryl rings" include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring , cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indolizine ring, Furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, thianthrene ring, indolocarbazole ring, benzindolocarbazole ring, benzobenzindrocarbazole ring, naphthobenzofuran ring, etc. can be given.

At least one hydrogen in the above "aryl ring" or "heteroaryl ring" is the first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or Unsubstituted "alkoxy", substituted or unsubstituted "aryloxy", substituted or unsubstituted "heteroaryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroarylthio", or substituted or unsubstituted "arylthio" It may be substituted with unsubstituted "diarylboryl" (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted "trisubstituted silyl", but this "Aryl" or "heteroaryl" as a substituent of 1, aryl of "diarylamino", heteroaryl of "diheteroarylamino", aryl and heteroaryl of "arylheteroarylamino", aryl of "aryloxy" , heteroaryl in "heteroaryloxy", aryl in "arylthio", heteroaryl in "heteroarylthio", aryl in "diarylboryl", "aryl" and "heteroaryl" in "trisubstituted silyl" are as mentioned above. Examples include monovalent groups of "aryl ring" or "heteroaryl ring".

Specific examples of "aryl" include phenyl, which is a monocyclic system, biphenylyl, which is a bicyclic system, naphthyl (1-naphthyl or 2-naphthyl), which is a fused bicyclic system, and terphenylyl (m-terphenylyl, which is a tricyclic system). , o-terphenylyl or p-terphenylyl), fused tricyclic ring systems such as acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, fused tetracyclic ring systems such as triphenylenyl, pyrenyl, naphthacenyl, and fused pentacyclic ring systems such as perylenyl and pentacenyl. .

Examples of the "heteroaryl" (first substituent) include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, Heteroaryl having 2 to 15 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of "heteroaryl" include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms.

Specific examples of "heteroaryl" include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H- indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxatiinyl, phenoxazinyl, phenothiazinyl, Examples include phenazinyl, indolizinyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thiophenyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, furazanyl, and thianthrenyl. Among these, carbazolyl is preferred, and 9-carbazolyl is more preferred.

Further, the "alkyl" as the first substituent may be either straight chain or branched chain, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 8 carbon atoms is preferable. (branched alkyl having 3 to 8 carbon atoms) is more preferable, alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms) is particularly preferable, and alkyl having 1 to 5 carbon atoms (branched alkyl having 3 to 5 carbon atoms) is particularly preferable. (branched 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. t-butyl, neopentyl, and t-pentyl (t-amyl) are preferred.

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.

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

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituted products having 1 to 5 carbon atoms, norbornenyl, bicyclo[1 .0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2 .1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl, etc., with adamantyl being more preferred.

Note that by introducing cycloalkyl into the compound of the present invention, a reduction in the melting point and sublimation temperature can be expected. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL elements that require high purity, thermal decomposition of the material can be avoided because purification can be performed at a relatively low temperature. means. This also applies to the vacuum evaporation process, which is an effective means for producing organic devices such as organic EL elements, and because the process can be carried out at relatively low temperatures, thermal decomposition of the material can be avoided. As a result, a high-performance organic device can be obtained. Furthermore, since the solubility in organic solvents is improved by the introduction of cycloalkyl, it can also be applied to device fabrication using a coating process. However, the present invention is not particularly limited to these principles.

Examples of "alkoxy" as the first substituent include straight chain alkoxy having 1 to 24 carbon atoms or branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (branched alkoxy having 3 to 18 carbon atoms) is preferable, alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms is preferable. Alkoxy (branched alkoxy having 3 to 6 carbon atoms) is more preferred, and alkoxy having 1 to 5 carbon atoms (branched alkoxy having 3 to 5 carbon atoms) is particularly preferred.

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

"diarylamino" (first substituent), "diheteroarylamino" (first substituent), "arylheteroarylamino" (first substituent) and "aryloxy" (first substituent), "heteroarylamino" (first substituent), "aryloxy" (first substituent), "arylthio" (first substituent), "heteroarylthio" (first substituent), "diarylboryl" (first substituent), "trisubstituted silyl" (first substituent) For details of "aryl" and "heteroaryl" in (1 substituent), the above explanation of "aryl" and "heteroaryl" can be cited.

Examples of the "trisubstituted silyl" include trialkylsilyl, triarylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, and the like.

"Trialkylsilyl" includes a group in which each of the three hydrogen atoms in silyl is independently substituted with alkyl, and this alkyl refers to the group explained as "alkyl" in the first substituent group above. I can do it. Preferred alkyls for substitution are those having 1 to 5 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, and t-amyl.

Specific trialkylsilyl includes trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-t-butylsilyl, tri-t-amylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, t-amyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethyl Silyl, t-butyldiethylsilyl, t-amyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, t-amyldipropylsilyl, Examples include methyldi-i-propylsilyl, ethyldi-i-propylsilyl, butyldi-i-propylsilyl, sec-butyldi-i-propylsilyl, t-butyldi-i-propylsilyl, t-amyldi-i-propylsilyl, trimethylsilyl, triethylsilyl, etc. , t-butyldimethylsilyl are preferred.

"Triarylsilyl" includes a group in which each of the three hydrogen atoms in silyl is independently substituted with aryl, and this aryl refers to the group explained as "aryl" in the first substituent group above. I can do it. Preferred aryls for substitution are those having 6 to 10 carbon atoms, and specific examples include phenyl, 1-naphthyl, and 2-naphthyl.

Specific examples of triarylsilyl include triphenylsilyl, diphenyl-2-naphthylsilyl, phenyl-di-2-naphthylsilyl, and tri-2-naphthylsilyl, with triphenylsilyl being preferred.

The emission wavelength can be adjusted depending on the steric hindrance, electron donating and electron withdrawing properties of the structure of the first substituent. Preferably it is a group represented by the following structural formula, more preferably methyl, t-butyl, t-amyl, t-octyl, neopentyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2,4- Xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6- Dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl, phenoxy, trimethylsilyl, t-butyldimethylsilyl and triphenylsilyl, more preferably methyl, t-butyl, t-amyl, neopentyl, Adamantyl, t-octyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, These are 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl, and triphenylsilyl. From the viewpoint of ease of synthesis, those with greater steric hindrance are preferable for selective synthesis. Specifically, t-butyl, t-amyl, neopentyl, t-octyl, adamantyl, o-tolyl, p -Tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, diphenylamino, bis(p-(t-butyl)phenyl)amino , 3,6-dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl, triphenylsilyl are preferred, t-butyl, t-amyl, neopentyl, adamantyl, diphenylamino, bis(p-(t -butyl)phenyl)amino is more preferred.

In the structural formula below, "Me" represents methyl, "tBu" represents t-butyl, "tAm" represents t-amyl, and "tOct" represents t-octyl.

The first substituent is substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", substituted or unsubstituted "aryloxy", substituted or unsubstituted "heteroaryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroarylthio", substituted or unsubstituted "diarylboryl", or substituted or unsubstituted "trisubstituted silyl" '' is described as substituted or unsubstituted, and at least one hydrogen therein may be substituted with a second substituent. Examples of this second substituent include aryl, heteroaryl, alkyl, or cycloalkyl, and specific examples thereof include the monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring", Reference may be made to the explanation of "alkyl" as the first substituent and "cycloalkyl" as the first substituent. Furthermore, in the aryl and heteroaryl as the second substituent, at least one hydrogen thereof is an aryl such as phenyl (specific examples are the groups mentioned above), or an alkyl such as methyl (specific examples are the groups mentioned above). Alternatively, structures substituted with cycloalkyl such as cyclohexyl (specific examples are the groups mentioned above) are also included in aryl and heteroaryl as the second substituent.

^R1 , ^{R2 ,} R3 ^{, R4} , R5 ^, R6, ^R7 , ^R8 , ^R9 , ^{R10 ,} R11, ^R12 , ^R13 , ^R14 , ^R15 , and aryl, heteroaryl, aryl of diarylamino, heteroaryl of diheteroarylamino, aryl and heteroaryl of arylheteroarylamino, or aryl of aryloxy, heteroaryl of heteroaryloxy, aryl of arylthio, heteroaryl in R ¹⁶ Examples of the heteroaryl of arylthio, the aryl of triarylsilyl, and the aryl of diarylboryl include "aryl" or "heteroaryl" explained in formula (1).
Also, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R 12 , R ¹³ , R ¹⁴ , R ¹⁵ , and ^{R 16} As the alkyl, cycloalkyl, alkoxy or tri-substituted silyl, the explanation of "alkyl", "cycloalkyl", "alkoxy" or "tri-substituted silyl" as the first substituent in the above explanation of formula (1) is used. can be referred to. Furthermore, the same applies to aryl, heteroaryl, alkyl, or cycloalkyl as a substituent to these groups.

In formula ( ² ), R ¹ , R ² , R 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R 12 , R ¹³ , R ¹⁴ , ^{R 15} , and R ¹⁶ are each independently hydrogen, an aryl having 6 to 30 carbon atoms, which may be substituted with an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms, and an aryl having 6 to 12 carbon atoms. or heteroaryl having 2 to 30 carbon atoms, which may be substituted with alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, or diarylamino, which may be substituted with alkyl having 1 to 6 carbon atoms (but Aryl is substituted with aryl having 6 to 12 carbon atoms), alkyl having 1 to 6 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms, aryl having 6 to 12 carbon atoms, or alkyl having 1 to 6 carbon atoms Aryloxy having 6 to 12 carbon atoms, which may be substituted with aryloxy having 6 to 12 carbon atoms, or arylthio having 6 to 12 carbon atoms, which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms, or arylthio having 6 to 12 carbon atoms, which may be substituted with Cycloalkyl having 3 to 10 carbon atoms which may be substituted with aryl or alkyl having 1 to 6 carbon atoms, arylhetero which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms Arylamino (however, aryl is aryl having 6 to 12 carbon atoms, heteroaryl which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms is heteroaryl having 2 to 12 carbon atoms), or diheteroarylamino which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms (however, heteroaryl is heteroaryl having 2 to 12 carbon atoms), hydrogen, Aryl having 6 to 10 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms; heteroaryl having 2 to 15 carbon atoms, diarylamino optionally substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms (aryl is aryl having 6 to 10 carbon atoms), carbon number Alkyl having 1 to 6 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms, aryloxy having 6 to 10 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms , cycloalkyl having 3 to 10 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms, substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms; arylheteroarylamino (where aryl is an aryl having 6 to 10 carbon atoms, and heteroaryl is a heteroaryl having 2 to 12 carbon atoms), or an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms. Diheteroarylamino (where heteroaryl is heteroaryl having 2 to 12 carbon atoms) which may be substituted with hydrogen, aryl having 6 to 12 carbon atoms, or alkyl having 1 to 6 carbon atoms is more preferable. aryl having 6 to 10 carbon atoms, which may be substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, which may be substituted with aryl having 6 to 12 carbon atoms, or alkyl having 1 to 6 carbon atoms, and aryl having 6 to 15 carbon atoms, which may be substituted with Diarylamino optionally substituted with 12 aryl or alkyl having 1 to 6 carbon atoms (aryl is aryl having 6 to 10 carbon atoms), 1 carbon atom optionally substituted with aryl having 6 to 12 carbon atoms More preferably, it is aryloxy having 6 to 10 carbon atoms which may be substituted with alkyl having 6 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, or alkyl having 1 to 6 carbon atoms.

In formula (2), R ¹ is preferably hydrogen, alkyl having 1 to 6 carbon atoms, or aryl having 6 to 12 carbon atoms, and more preferably hydrogen.
In formula (2), R ¹ , R ² , R 3 , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , ^{R 14 ,} and R ¹⁶ is each independently hydrogen or forms a ring as described below, and R ¹⁵ is substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms; Aryl having 6 to 30 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 30 carbon atoms optionally substituted with alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms Diarylamino optionally substituted with alkyl having 1 to 6 carbon atoms (aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 6 carbon atoms optionally substituted with aryl having 6 to 12 carbon atoms, carbon Aryloxy having 6 to 12 carbon atoms which may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms, or substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms. Arylthio having 6 to 12 carbon atoms is also preferred.

Aryl formed by bonding adjacent groups of R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ together with ring a, ring b, ring c, or ring d; For details of the ring or heteroaryl ring, a polycyclic structure containing a benzene ring can be cited as an unvalent ring structure in the explanation of "aryl" or "heteroaryl" of the first substituent mentioned above. Furthermore, adjacent groups among R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ are bonded together to form an aryl ring together with rings a, b, c, and d. or when forming a heteroaryl ring, substituents on these rings such as aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylaminoalkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, For details about arylthio, heteroarylthio or trisubstituted silyl and further substituents aryl, heteroaryl, alkyl or cycloalkyl, reference may be made to the explanations of the first and second substituents above. can.

In formula (1), X ¹ , X ² , X ³ , and X ⁴ are each independently >O, >NR, >S, or >Se, and R in >NR is, is an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alkyl, or an optionally substituted cycloalkyl, and R in the above >NR is a linking group or It may be bonded to ring A, ring B, ring C, ring D, and/or ring E through a single bond.

In formula (2), X ¹ , X ² , X ³ and X ⁴ are each independently >O, NR, >S or >Se, and R in >NR has 6 carbon atoms. -12 aryl, C2-15 heteroaryl, or C1-6 alkyl, and R in >N-R is -O-, -S-, -C(-R) ₂ - or may be bonded to the a-ring, b-ring, c-ring, d-ring, and/or e-ring through a single bond, and R in the -C(-R) ₂ - is hydrogen or has 1 to 6 carbon atoms. is an alkyl.

It is preferable that X ¹ , X ² , X ³ and X ⁴ are each independently >O or NR. It is more preferable that one or more of X ¹ , X ² , X ³ and X ⁴ is >O and the remainder is NR, and one of X ¹ , X ² , X ³ and X ⁴ is Or, it is more preferable that two of them are NR and the rest are >O.

R in the above >N-R is preferably an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 4 carbon atoms, and R is optionally substituted with an alkyl having 1 to 6 carbon atoms. More preferably, NR is an aryl group having 10 carbon atoms, and even more preferably NR is a phenyl group, which is optionally substituted with an alkyl group having 1 to 6 carbon atoms. Examples of phenyl which may be substituted with alkyl having 1 to 6 carbon atoms include unsubstituted phenyl, phenyl substituted at the 4-position (para-position) with alkyl having 1 to 6 carbon atoms, and mesityl.

"Aryl having 6 to 12 carbon atoms", "heteroaryl having 2 to ^{15 carbon atoms", "alkyl having 1 to 6 carbon atoms" in R of >N-R as X 1 , X 2 , X} 3 and X ⁴ or “cycloalkyl having 3 to 14 carbon atoms”, and “aryl having 6 to 12 carbon atoms”, “heteroaryl having 2 to 15 carbon atoms”, “alkyl having 1 to 6 carbon atoms”, or “ For details of "cycloalkyl having 3 to 14 carbon atoms," the above-mentioned explanations of the first substituent and the second substituent can be cited. Further, for the details of "alkyl having 1 to 6 carbon atoms" for R in "-C(-R) ₂ -", the above explanation of the first substituent can be cited. In particular, alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) is preferred.

In formula (1), R of ">N-R is -O-, -S-, -C(-R) ₂ - or a single bond to the A ring, B ring, C ring, D ring, and/or E "ring and bond", or in formula (2), ">N-R's R is -O-, -S-, -C(-R) ₂ - or a single bond to the a-ring, b-ring, c-ring, d For example, the definition "bonded with a ring and/or e-ring" can be expressed by a compound having a ring structure in which X ¹ is incorporated into a fused ring a', represented by the following formula (2-4-1). . That is, it is a compound having an a' ring formed by condensing another ring such that X ¹ is incorporated into the benzene ring which is the a ring in formula (2). Furthermore, the above definition can also be expressed in a compound having a ring structure represented by the following formula (2-4-2) in which X ⁴ is incorporated into the condensed ring c'. That is, it is a compound having a c' ring formed by condensing another ring such that X ⁴ is incorporated into the benzene ring, which is the c ring in formula (2). Furthermore, the above definition can also be expressed in a compound having a ring structure represented by the following formula (2-4-3) in which X ³ is incorporated into the condensed ring e'. That is, it is a compound having an e' ring formed by condensing another ring such that X ³ is incorporated into the benzene ring, which is the e ring in formula (2). In addition, the definition of each symbol in formula (2-4-1), formula (2-4-2), and formula (2-4-3) is the same as the definition in formula (1) or formula (2). . Similarly, compounds having a b' ring formed by condensing another ring such that X ² is incorporated into the benzene ring which is the b ring, and X ³ or X to the benzene ring which is the d ring. A compound having a d' ring formed by condensing another ring incorporating ³ , and a compound having a d' ring formed by condensing another ring by incorporating X ¹ to the e ring, which is a benzene ring. Examples include compounds that have a ring. The condensed rings a', b', c', d', and e' that are formed are, for example, a carbazole ring, a phenoxazine ring, a phenothiazine ring, or an acridine ring, with a carbazole ring being preferred.

At least one hydrogen in the polycyclic aromatic compound represented by formula (1) may be substituted with cyano, halogen, or deuterium. Furthermore, at least one hydrogen in the polycyclic aromatic compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. Here, halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.

The polycyclic aromatic compound represented by formula (1) is preferably a compound represented by any of the following structural formulas, and compounds represented by formula (1-6R) and formula (1-6-R100 ) are more preferred.

In the above formula, each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms, and R ¹⁰⁰ is each independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms. Aryl, carbazolyl, diarylamino (aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, aryloxy having 6 to 10 carbon atoms, diarylboryl (but aryl is aryl having 6 to 10 carbon atoms), trialkylsilyl (alkyl is alkyl having 1 to 6 carbon atoms), or triarylsilyl (aryl is aryl having 6 to 10 carbon atoms). The aryl may be substituted with an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 10 carbon atoms, and the carbazolyl is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 6 carbon atoms. Optionally substituted with ~10 cycloalkyl. Furthermore, at least one hydrogen in the compounds represented by the above formulas may be substituted with cyano, halogen, or deuterium.

Specific examples of the polycyclic aromatic compound represented by formula (1) include compounds represented by the following structural formula. Note that "Me" in the structural formula is methyl.

1. Method for producing polycyclic aromatic compounds Polycyclic aromatic compounds represented by formulas (1) and (2) are basically produced by producing intermediates by bonding their respective ring structures (first step). reaction), and then the final product can be produced by bonding each ring structure with a boron atom (second reaction). In the first reaction, for example, a general etherification reaction such as a nucleophilic substitution reaction or an Ullmann reaction, or a general amination reaction such as a Buchwald-Hartwig reaction, etc. 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. Note that the symbols in the structural formulas in each scheme below have the same definitions as those in formula (1) or formula (2).

The second reaction is a reaction that introduces boron atoms that bond the respective ring structures, as shown in Scheme (1) below. First, the hydrogen atoms between X ¹ and X ² and between X ³ and X ⁴ are orthometalized with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Next, boron trichloride, boron tribromide, etc. are added to perform lithium-boron metal exchange, and a Brønsted base such as N,N-diisopropylethylamine is added to cause a tandem Bora-Friedel-Crafts reaction. can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

In scheme (1), lithium was introduced into the desired position by orthometalation, but as shown in scheme (2) below, a halogen atom (Hal) was introduced in advance at the desired position to introduce lithium, and lithium was introduced by halogen-metal exchange. Lithium can also be introduced into desired positions. According to this method, the desired product can be synthesized even in cases where ortho-metalation is not possible due to the influence of substituents and is useful.

By appropriately selecting the above-mentioned synthesis method and appropriately selecting the raw materials used, it is possible to have a substituent at a desired position, and X ¹ , X ² , X ³ and X ⁴ are each independently >O, Polycyclic aromatic compounds that are >NR, >S or >Se can be synthesized.

Note that, because the location where the tandem Bora-Friedel-Crafts reaction occurs may differ due to, for example, rotation of an amino group in the intermediate, there is a possibility that by-products may be generated. In such cases, the desired polycyclic aromatic compound can be isolated from the mixture by chromatography, recrystallization, or the like.

Examples of the orthometalation reagent used in the above scheme include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, and lithium hexamethyl Examples include organic alkali compounds such as disilazide and potassium hexamethyldisilazide.

The metal-boron metal exchange reagent used in the above scheme includes boron halides such as boron trifluoride, trichloride, tribromide, and triiodide, and boron aminated halogens such as CIPN(NEt ₂ ) ₂ . Examples include boron compounds, alkoxylated boron compounds, and aryloxylated boron compounds.

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

Lewis acids used in the above scheme include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl _{3 , BBr 3 ,} GaCl 3 , GaBr ₃ , InCl ₃ , InBr _{3 ,} In(OTf) ₃ , SnCl ₄ , SnBr ₄ , AgOTf, ScCl ₃ , Sc(OTf) ₃ , ZnCl ₂ , ZnBr ₂ , Zn(OTf) ₂ , MgCl ₂ , MgBr ₂ , Mg(OTf) ₂ , LiOTf, NaOTf, KOTf, Me ₃ SiO Tf, Examples include Cu(OTf) ₂ , CuCl ₂ , YCl ₃ , Y(OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ and CoBr ₃ . Note that "Tf" represents trifluoromethylsulfonyl.

In the above scheme, a Brønsted base or a Lewis acid may be used to promote the tandem hetero Friedel-Crafts reaction. However, when using boron halides such as boron trifluoride, trichloride, tribromide, and triiodide, as the aromatic electrophilic substitution reaction progresses, hydrogen fluoride, hydrogen chloride, hydrogen bromide, Since an acid such as hydrogen iodide is generated, it is effective to use a Brønsted base to supplement the acid. On the other hand, when boron aminated halides or boron alkoxides are used, amines and alcohols are generated as the aromatic electrophilic substitution reaction progresses, so in many cases it is not necessary to use a Brønsted base. However, since the ability to eliminate amino groups and alkoxy groups is low, it is effective to use Lewis acids that promote their functions.

Furthermore, the polycyclic aromatic compounds represented by formula (1) or (2) also include compounds in which at least some hydrogen atoms are substituted with cyano, halogen, or deuterium, but such compounds etc. can be synthesized in the same manner as above by using raw materials that are cyanated, halogenated, or deuterated at desired locations.

2. Organic Device The polycyclic aromatic compound according to the present invention can be used as a material for organic devices. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, and an organic thin film solar cell.

3-1. Organic electroluminescent device <Structure of organic electroluminescent device>
FIG. 1 is a schematic cross-sectional view showing an example of an organic EL 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 a A hole transport layer 104 provided, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and a light emitting layer 105 provided on the electron transport layer 106. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

Note that the organic EL element 100 can be manufactured in the reverse order, for example, by forming a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, and an electron injection layer 107. an electron transport layer 106 provided on the electron transport layer 106; a light emitting layer 105 provided on the electron transport layer 106; a hole transport layer 104 provided on the light emitting layer 105; It is also possible to have a configuration including a hole injection layer 103 provided on the hole injection layer 103 and an anode 102 provided on the hole injection layer 103.

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

In addition to the above-mentioned configuration of "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", examples of the layers constituting the organic EL element include " "Substrate/Anode/Hole transport layer/Light emitting layer/Electron transport layer/Electron injection layer/Cathode", "Substrate/Anode/Hole injection layer/Light emitting layer/Electron transport layer/Electron injection layer/Cathode", "Substrate/ Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode", "substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode", "substrate / Anode/Emissive layer/Electron transport layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive 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" /light emitting layer/electron transport layer/cathode" or "substrate/anode/light emitting layer/electron injection layer/cathode" may be used.

<Light-emitting layer in organic electroluminescent device>
The compound of the present invention is preferably used as a material for forming one or more organic layers in an organic electroluminescent device, and more preferably used as a material for forming a light emitting layer.
The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between the electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be any compound (luminescent compound) that emits light when excited by recombination of holes and electrons, can form a stable thin film shape, and is in a solid state. It is preferable that the compound is a compound that exhibits strong luminescence (fluorescence) efficiency.
In the present invention, the compound of the present invention as a dopant material and a host material can be used as materials for the light emitting layer.

The light-emitting layer may be composed of a single layer or a plurality of layers, and each layer is formed of a material for the light-emitting layer (host material, dopant material). The host material and the dopant material may each be one type or a combination of a plurality of types. The dopant material may be contained entirely or partially in the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may also be mixed with the host material in advance and then vapor-deposited at the same time.

The amount of host material used varies depending on the type of host material, and may be determined depending on the characteristics of the host material. The amount of host material to be used is preferably 50 to 99.999% by mass, more preferably 80 to 99.95% by mass, and even more preferably 90 to 99.9% by mass of the entire material for the light emitting layer. It is.

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

Examples of the host material include carbazole derivatives that have long been known as light emitters, fused ring derivatives such as anthracene, pyrene, dibenzochrysene, or fluorene, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, Examples include cyclopentadiene derivatives. A carbazole derivative, an anthracene compound, a fluorene compound, or a dibenzochrysene compound is preferred, and a carbazole derivative or an anthracene compound is more preferred.

Examples of carbazole derivatives include compounds represented by any of the following formulas (H1), (H2), and (H3).

In formulas (H1), (H2) and (H3), L ¹ represents arylene having 6 to 24 carbon atoms, heteroarylene having 2 to 24 carbon atoms, heteroarylene arylene having 6 to 24 carbon atoms, and arylene having 6 to 24 carbon atoms. Arylene Heteroarylene Arylene, preferably arylene having 6 to 16 carbon atoms, more preferably arylene having 6 to 12 carbon atoms, particularly preferably arylene having 6 to 10 carbon atoms, specifically, benzene ring, biphenyl ring, Divalent groups such as terphenyl rings and fluorene rings may be mentioned. The heteroarylene is preferably a heteroarylene having 2 to 24 carbon atoms, more preferably a heteroarylene having 2 to 20 carbon atoms, even more preferably a heteroarylene having 2 to 15 carbon atoms, and particularly a heteroarylene having 2 to 10 carbon atoms. Preferably, specifically, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, Pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring , quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring , dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, and thianthrene ring.
At least one hydrogen in the compounds represented by the above formulas may be substituted with alkyl having 1 to 6 carbon atoms, cyano, halogen, or deuterium.

Preferred specific examples include compounds represented by any of the structural formulas listed below. In the structural formulas listed below, at least one hydrogen may be substituted with halogen, cyano, alkyl having 1 to 4 carbon atoms (eg, methyl or t-butyl), phenyl, or naphthyl.

Examples of anthracene compounds include compounds represented by the following formula (4).

In formula (4), L ² and L ³ are each independently an aryl having 6 to 30 carbon atoms or a heteroaryl having 2 to 30 carbon atoms. The aryl is preferably an aryl having 6 to 24 carbon atoms, more preferably an aryl having 6 to 16 carbon atoms, even more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms. Examples include monovalent groups 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 heteroaryl is preferably a heteroaryl having 2 to 25 carbon atoms, more preferably a heteroaryl having 2 to 20 carbon atoms, even more preferably a heteroaryl having 2 to 15 carbon atoms, and particularly a heteroaryl having 2 to 10 carbon atoms. Preferably, specifically, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, Pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring , quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring , dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, and thianthrene ring.
At least one hydrogen in the compound represented by formula (4) may be substituted with alkyl having 1 to 6 carbon atoms, cyano, halogen, or deuterium. )

As the host material, it is also preferable to use a compound represented by the following formula (5).

In formula (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, aryl, hetero aryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, trialkylsilyl or aryloxy, even if at least one hydrogen in these is substituted with aryl, heteroaryl or alkyl; Often, adjacent groups among R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with ring a, ring b, or ring c, and at least one of the formed rings two hydrogens may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, in which at least one hydrogen is substituted with aryl, heteroaryl or alkyl. may have been done,
At least one hydrogen in the compound represented by formula (2) may be substituted with halogen or deuterium.

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic EL element 100, and is usually made of quartz, glass, metal, plastic, or the like. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape depending on the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among these, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferred. If it is a glass substrate, soda lime glass or non-alkali glass may be used, and the thickness may be sufficient to maintain mechanical strength, for example, 0.2 mm or more. 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, alkali-free glass is preferable because fewer ions elute from the glass, but soda lime glass coated with a barrier coating such as SiO ₂ is also commercially available, so it is recommended to use this. can. In addition, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side of the substrate 101 in order to improve gas barrier properties. In particular, a synthetic resin plate, film, or sheet with low gas barrier properties may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 plays the role of injecting holes into the light emitting layer 105. Note that when the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these. .

Examples of materials forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide, etc.). (IZO, etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, etc. Examples of the organic compound include polythiophenes such as poly(3-methylthiophene), conductive polymers such as polypyrrole, and polyaniline. In addition, materials that are used as anodes for organic EL devices may be selected as appropriate.

The resistance of the transparent electrode is not limited as long as it can supply sufficient current for light emission of the light emitting element, but from the viewpoint of power consumption of the light emitting element, it is desirable that the resistance be low. For example, an ITO substrate with a resistance of 300 Ω/□ or less can function as an element electrode, but since it is now possible to supply substrates with a resistance of about 10 Ω/□, for example, 100 to 5 Ω/□, preferably 50 to 5 Ω. It is particularly desirable to use a low resistance product with /□. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 50 and 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescent device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one or more hole injection/transport materials, or by a mixture of a hole injection/transport material and a polymer binder. be done. Alternatively, the layer may be formed by adding an inorganic salt such as iron(III) chloride to the hole injection/transport material.

For hole injection/transport materials, it is necessary to efficiently inject and transport holes from the positive electrode between the electrodes where an electric field is applied, and the hole injection efficiency is high and the injected holes are efficiently transported. It is desirable to do so. For this purpose, it is preferable to use a substance that has a low ionization potential, high hole mobility, excellent stability, and does not easily generate trapping impurities during production and use.

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

It is also known that the conductivity of organic semiconductors is strongly influenced by their doping. Such an organic semiconductor matrix material is composed of a compound with good electron donating properties or a compound with good electron accepting properties. For doping with electron donating substances, strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known. (For example, the literature "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)" and the literature "J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by electron transfer processes in electron-donating base materials (hole-transporting materials). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. As matrix materials having hole transport properties, for example benzidine derivatives (TPD etc.) or starburst amine derivatives (TDATA etc.) or certain metal phthalocyanines (in particular zinc phthalocyanine (ZnPc) etc.) are known ( JP 2005-167175A).

The hole injection layer material and the hole transport layer material described above are a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent as a monomer, or a polymer crosslinked product thereof, or A pendant polymer compound obtained by reacting a main chain polymer with the above-mentioned reactive compound, or a pendant polymer crosslinked product thereof can also be used as a hole layer material.

<Electron injection layer and electron transport layer in organic electroluminescent device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport/injection materials, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer is a layer that is in charge of injecting electrons from the cathode and further transporting electrons, and it is desirable that the electron injection efficiency is high and that the injected electrons are efficiently transported. For this purpose, it is preferable that the material has high electron affinity, high electron mobility, excellent stability, and does not easily generate trapping impurities during production and use. However, when considering the transport balance of holes and electrons, if the role is to efficiently prevent holes from the anode from flowing to the cathode side without recombining, the electron transport capacity is not so great. Even if it is not high, it has the same effect of improving luminous efficiency as a material with high electron transport ability. Therefore, the electron injection/transport layer in this embodiment may also include the function of a layer that can efficiently block the movement of holes.

The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 may be a compound conventionally used as an electron transport compound in photoconductive materials, or a compound used in the electron injection layer and electron transport layer of an organic EL device. Any known compound may be selected and used.

Materials used for the electron transport layer or electron injection layer include compounds consisting of an aromatic ring or a heteroaromatic 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 pyrrole derivatives, fused ring derivatives thereof, and metal complexes having electron-accepting nitrogen. Specifically, fused ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, aryl nitrile derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.

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

Further, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

The above-mentioned materials can be used alone, but they can also be used in combination with different materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, aryl nitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, quinolinol metals Preferred are complexes, thiazole derivatives, benzothiazole derivatives, silole derivatives and azoline derivatives.

[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 No. 2007-27587.

In formula (ETM-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing hetero ring or cyano, and R ¹³ to R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl, X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl, and n is Each independently is an integer from 0 to 3. Further, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, and cycloalkyl.

Among the compounds represented by the formula (ETM-1), compounds represented by the following formula (ETM-1-1) and compounds represented by the following formula (ETM-1-2) are preferred.

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

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

（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 the following formulas (X-1) to (X-9).

(In each formula, R ^a is each independently alkyl, cycloalkyl, or optionally substituted phenyl, and * represents the bonding position.)

Specific examples of this borane derivative include the following compounds.

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

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

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

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

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

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

The "alkyl" in R ¹¹ to R ¹⁸ may be either straight chain or branched, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms. Preferred "alkyl" is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

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

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

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

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

As for "aryl" in R ¹¹ to R ¹⁸ , preferable aryl is aryl having 6 to 30 carbon atoms, more preferable aryl is aryl having 6 to 18 carbon atoms, and still more preferably aryl having 6 to 14 carbon atoms. Especially preferred is aryl having 6 to 12 carbon atoms.

Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, which is a monocyclic aryl, (1-,2-)naphthyl, which is a fused bicyclic aryl, and acenaphthylene-(, which is a fused tricyclic aryl). 1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2-)yl -,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylen-(1-,2-)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1- ,2-,5-)yl, fused pentacyclic aryl perylene-(1-,2-,3-)yl, pentacen-(1-,2-,5-,6-)yl, etc. .

Preferred examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl, and triphenylenyl, more preferred are phenyl, 1-naphthyl, 2-naphthyl, and phenanthryl, and particularly preferred are phenyl, 1-naphthyl, and phenanthryl. -Naphthyl or 2-naphthyl.

R ¹¹ and R ¹² in formula (ETM-2-2) may be combined to form a ring, and as a result, the five-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, and cyclohexane. , fluorene or indene may be spiro-bonded.

Specific examples of this pyridine derivative include the following compounds.

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

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 an aryl. Here, examples of the substituent when substituted include aryl, heteroarylalkyl, and cycloalkyl.

Specific examples of this fluoranthene derivative include the following compounds.

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

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

Further, adjacent groups among R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring with ring a, ring b, or ring c, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is substituted with aryl, heteroaryl, alkyl or Optionally substituted with cycloalkyl.

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

Regarding the explanation of the substituents and the form of ring formation in formula (ETM-4), the explanation of the polycyclic aromatic compound represented by formula (1) can be cited.

Specific examples of this BO derivative include the following compounds.

This BO derivative can be produced using known raw materials and known synthesis methods.

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

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

Ar can be appropriately selected independently from divalent benzene or naphthalene, and the two Ars may be different or the same, but from the viewpoint of ease of synthesis of the anthracene derivative, they are the same. It is preferable that Ar combines with pyridine to form a "site consisting of Ar and pyridine", and this site can be used, for example, as an anthracene group as a group represented by any of the following formulas (Py-1) to (Py-12). is combined with * in the formula below represents the bonding position.

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

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

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

The aryl having 6 to 20 carbon atoms in R ¹ to R ⁴ is 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 "aryl having 6 to 20 carbon atoms" include monocyclic aryl such as phenyl, (o-,m-,p-)tolyl, (2,3-,2,4-,2,5- ,2,6-,3,4-,3,5-)xylyl, mesityl (2,4,6-trimethylphenyl), (o-,m-,p-)cumenyl, bicyclic aryl (2 -,3-,4-)biphenylyl, (1-,2-)naphthyl which is a fused bicyclic aryl, and terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl. '-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p- terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused tricyclic aryl, anthracen-(1-,2-,9-)yl, acenaphthylene- (1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-, 2-,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylen-(1-,2-)yl, pyren-(1-,2-,4-)yl, tetracen-(1 -,2-,5-)yl, perylene-(1-,2-,3-)yl, which is a fused pentacyclic aryl, and the like.

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

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

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

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

R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms, and in formula (ETM-5-1), Explanations may be cited.

Specific examples of these anthracene derivatives include the following compounds.

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

[Benzofluorene derivative]
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

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

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

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

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

As for "aryl" in Ar ² , preferable aryl is aryl having 6 to 30 carbon atoms, more preferable aryl is aryl having 6 to 18 carbon atoms, still more preferably aryl having 6 to 14 carbon atoms, and especially Aryl having 6 to 12 carbon atoms is preferred.

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

Two Ar ² may be combined to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, etc. are spiro-bonded to the 5-membered ring of the fluorene skeleton. It's okay.

Specific examples of this benzofluorene derivative include the following compounds.

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

[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. 2013/079217 and International Publication No. 2013/079678.

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

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

R ¹ to R ³ may be the same or different, and include hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether (aryl ether group), arylthioether (aryl thioether group), aryl, heterocyclic group, halogen, cyano, aldehyde (aldehyde group), carbonyl, carboxyl, amino, nitro, silyl, and a fused ring formed between adjacent substituents.

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

Among these substituents, alkyl refers to a saturated aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, and may be unsubstituted or substituted. There are no particular restrictions on the substituent when substituted, and examples thereof include alkyl, aryl, and heterocyclic groups, and this point is also common to the following description. Further, the number of carbon atoms in the alkyl is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

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

Furthermore, aralkyl refers to an aromatic hydrocarbon group via an aliphatic hydrocarbon such as benzyl or phenylethyl, and both aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or substituted. do not have. The number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.

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

Further, cycloalkenyl refers to an unsaturated alicyclic hydrocarbon group containing a double bond, such as cyclopentenyl, cyclopentadienyl, and cyclohexene, and may be unsubstituted or substituted.

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

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

Furthermore, alkylthio is a group in which the oxygen atom of the ether bond of alkoxy is substituted with a sulfur atom.

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

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

Furthermore, arylthioether is a group in which the oxygen atom of the ether bond of an aryl ether is substituted with a sulfur atom.

Furthermore, aryl refers to aromatic hydrocarbon groups such as phenyl, naphthyl, biphenylyl, phenanthryl, terphenyl, and pyrenyl. Aryl may be unsubstituted or substituted. The number of carbon atoms in the aryl group 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, thiophenyl, oxazolyl, pyridyl, quinolinyl, and carbazolyl, which may be unsubstituted or substituted. The number of carbon atoms in the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

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

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

Furthermore, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted.

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

The condensed rings formed between adjacent substituents include, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar 2 and R ² , Ar ² and R ³ , R ² and R ³ , Ar ^{1 and} It is a conjugated or non-conjugated condensed ring formed between Ar ² and the like. Here, when n is 1, the two R ¹ may form a conjugated or non-conjugated condensed ring. These fused rings may contain nitrogen, oxygen, or 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 using known raw materials and known synthesis methods.

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

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

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

Specific examples of "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. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(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), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, etc.

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

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

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

Specific examples of this pyrimidine derivative include the following compounds.

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

[Arylnitrile derivative]
The aryl nitrile derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer of a plurality of compounds bonded together through 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 transport properties, and preferably has a small number of carbon atoms from the viewpoint of high T1. Specifically, Ar _ni preferably has a high T1 for use in a layer adjacent to the light-emitting layer, and is an aryl having 6 to 20 carbon atoms, preferably an aryl having 6 to 14 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms. It is an aryl having 6 to 10 carbon atoms. Further, the number n of substituted nitrile groups is preferably large from the viewpoint of high T1, and preferably small from the viewpoint of high S1. Specifically, the number n of nitrile group substitutions is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and still more preferably 1.

Each Ar is independently an optionally substituted aryl or an optionally substituted heteroaryl. From the viewpoint of high S1 and high T1, a donor heteroaryl is preferable, and since it is used as an electron transport layer, it is preferable that there is a small amount of donor heteroaryl. From the viewpoint of charge transportability, aryl or heteroaryl having a large number of carbon atoms is preferable, and it is preferable to have a large number of substituents. Specifically, the number m of substituted Ar is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 to 2.

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

Specific examples of "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. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(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), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, and the like.

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

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

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

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

Specific examples of this aryl nitrile derivative include the following compounds.

This aryl nitrile derivative can be produced using known raw materials and known synthesis methods.

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

Each Ar is independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer from 1 to 3, preferably 2 or 3.

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

Specific examples of "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. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(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), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, etc.

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

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

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

Specific examples of this triazine derivative include the following compounds.

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

[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, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4; Yes, "benzimidazole-based substituent" means that the pyridyl group in "pyridine-based substituent" in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzimidazole. At least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

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

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be cited from the explanation of formula (ETM-2-1) or formula (ETM-2-2), and each formula For R ¹¹ to R ¹⁸ in the formula, the explanation for formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, although formula (ETM-2-1) or formula (ETM-2-2) is explained in a form in which two pyridine-based substituents are bonded, when replacing these with benzimidazole-based substituents, both The pyridine-based substituent may be replaced with a benzimidazole-based substituent (i.e., n=2), or one pyridine-based substituent may be replaced with a benzimidazole-based substituent and the other pyridine-based substituent may be replaced with R ¹¹ - May be replaced by R ¹⁸ (ie n=1). Furthermore, for example, at least one of R ¹¹ to R ¹⁸ in formula (ETM-2-1) may be replaced with a benzimidazole substituent, and the "pyridine substituent" may be replaced with R ¹¹ to R ¹⁸ .

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

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

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

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

As the alkyl, cycloalkyl and aryl in R ¹¹ to R ¹⁸ , the explanation of R ¹¹ to R ¹⁸ in formula (ETM-2) can be cited. Further, in addition to the above-mentioned examples, φ may have the following structural formula, for example. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl, and * represents the bonding position.

Specific examples of this phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di(1,10- phenanthrolin-2-yl)anthracene, 2,6-di(1,10-phenanthrolin-5-yl)pyridine, 1,3,5-tri(1,10-phenanthrolin-5-yl)benzene, 9,9' -difluoro-bis(1,10-phenanthrolin-5-yl), bathocuproine, and 1,3-bis(2-phenyl-1,10-phenanthrolin-9-yl)benzene.

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

[Quinolinol metal complex]
The quinolinol metal complex is, for example, a compound represented by the following formula (ETM-13).

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

Specific examples of quinolinol metal complexes include lithium 8-quinolinol, tris(8-quinolinolate)aluminum, tris(4-methyl-8-quinolinolate)aluminum, tris(5-methyl-8-quinolinolate)aluminum, 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-methylphenolate)aluminum, bis(2-methyl-8- quinolinolate) (4-methylphenolate) aluminum, bis(2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis(2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-Methyl-8-quinolinolate)(4-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,3-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)( 2,6-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,4-dimethylphenolate)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-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(1-naphthlate)aluminum, bis(2-methyl-8-quinolinolate)(2 -naphthorate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(2-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, ,4-dimethyl-8-quinolinolate)(4-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3,5-dimethylphenolate)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-quinolinolate)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) beryllium, and the like.

This quinolinol metal complex can be produced using known raw materials and known synthesis methods.

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

[Thiazole 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).

In each formula, 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 1 to 4. "thiazole-based substituent" and "benzothiazole-based substituent" are "pyridine-based substituents" in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2). The pyridyl group in "group" is a substituent substituted for a thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with deuterium.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be cited from the explanation of formula (ETM-2-1) or formula (ETM-2-2), and each formula For R ¹¹ to R ¹⁸ in the formula, the explanation for formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, formula (ETM-2-1) or formula (ETM-2-2) is explained in a form in which two pyridine-based substituents are bonded, but these are replaced by a thiazole-based substituent (or benzothiazole-based substituent). ), both pyridine-based substituents may be replaced with a thiazole-based substituent (or benzothiazole-based substituent) (i.e., n = 2), or any one pyridine-based substituent may be replaced with a thiazole-based substituent. (or a benzothiazole-based substituent) and the other pyridine-based substituent may be replaced with R ¹¹ to R ¹⁸ (that is, n=1). Furthermore, for example, by replacing at least one of R ¹¹ to R ¹⁸ in formula (ETM-2-1) with a thiazole substituent (or benzothiazole substituent), the "pyridine substituent" is replaced with R ¹¹ to R ¹⁸ . May be replaced.

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

[Silole derivative]
The silole derivative is, for example, a compound represented by the following formula (ETM-15). Details are described in JP-A-9-194487.

X and Y are each independently alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, or heteroaryl, which may be substituted. For details of these groups, the explanations for formulas (1) and (2), as well as the explanation for formula (ETM-7-2) can be cited. Furthermore, alkenyloxy and alkynyloxy are groups in which the alkyl moiety in alkoxy is replaced with alkenyl or alkynyl, respectively, and the explanation in formula (ETM-7-2) can be cited for details of these alkenyl and alkynyl.
Furthermore, X and Y may combine to form a cycloalkyl ring (and a partially unsaturated ring), and the details of this cycloalkyl ring are shown in formula (1) and formula (2). Reference may be made to the explanation of cycloalkyl.

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

For details of halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, aryl, heteroaryl, alkenyl and alkynyl in R ¹ to R ⁴ , the explanations in formula (1) and formula (2) can be cited.

For details of alkyl, aryl and alkoxy in alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy and aryloxycarbonyloxy in R ¹ to R ⁴ , see the formula The explanations in (1) and equation (2) can be cited.

Examples of silyl include silyl and a group in which at least one of the three hydrogens of silyl is independently substituted with aryl, alkyl, or cycloalkyl, and trisubstituted silyl is preferable, triarylsilyl, trialkyl Examples include silyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, and alkyldicycloalkylsilyl. For details of aryl, alkyl, and cycloalkyl in these, the explanations in formula (1) and formula (2) can be cited.

The fused ring formed between 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 , etc. . These fused rings may contain nitrogen, oxygen, or sulfur atoms in the ring structure, or may be fused with another ring.

However, preferably when R ¹ and R ⁴ are phenyl groups, X and Y are not alkyl or phenyl. Preferably, when R ¹ and R ⁴ are thienyl groups, X and Y are alkyl, R ² and R ³ are alkyl, aryl, alkenyl, or R ² and R ³ combine to form a ring. It has a structure that does not simultaneously satisfy cycloalkyl. Preferably, when R ¹ and R ⁴ are silyl, R ² , R ³ , X and Y are each independently not hydrogen or alkyl having 1 to 6 carbon atoms. Moreover, preferably in the case of a structure in which R ¹ and R ² are fused with benzene rings, X and Y are not alkyl or phenyl.

These silole derivatives can be produced using known raw materials and known synthesis methods.

[Azoline 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 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 is a group having a valence of 1 to 40 carbon atoms. Optionally substituted with alkyl having ~6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 18 carbon atoms, or heteroaryl having 2 to 18 carbon atoms,
Y is each independently -O-, -S- or >N-Ar, 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 is may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, or heteroaryl having 2 to 12 carbon atoms, and R ¹ to R ⁵ are each independently is hydrogen, an alkyl having 1 to 4 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms, provided that Ar in >N-Ar and any one of R ¹ to R ⁵ are bonded to L. This is the part where
L is each 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 formula (L-1), X ¹ to X ⁶ are each independently =CR ⁶ - or =N-, at least two of X ¹ to X ⁶ are =CR ⁶ -, and X ¹ R ⁶ in two =CR ⁶ - of ~X ⁶ is a bonding site with φ or an azoline ring, R ⁶ in other =CR ⁶ - is hydrogen,
In formula (L-2), X ⁷ to X ¹⁴ are each independently =CR ⁶ - or =N-, at least two of X ⁷ to X ¹⁴ are =CR ⁶ -, and X ⁷ R ⁶ in two =CR ⁶ - of ~X ¹⁴ is a bonding site with φ or an azoline ring, 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 formula (ETM-16) may be substituted with deuterium.

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

In formula (ETM-16-1) and 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 is a group having a valence of 1 to 40 carbon atoms. Optionally substituted with alkyl having ~6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 18 carbon atoms, or heteroaryl having 2 to 18 carbon atoms,
In formula (ETM-16-1), Y is each independently -O-, -S- or >N-Ar, and Ar is an aryl having 6 to 12 carbon atoms or a hetero group having 2 to 12 carbon atoms. 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 formula (ETM-16-1), R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 4 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same and R ³ and R ⁴ are the same,
In formula (ETM-16-2), R ¹ to R ⁵ are each independently hydrogen, alkyl having 1 to 4 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same and R ³ and R ⁴ are the same,
In formula (ETM-16-1) and formula (ETM-16-2),
L is each 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 formula (L-1), X ¹ to X ⁶ are each independently =CR ⁶ - or =N-, at least two of X ¹ to X ⁶ are =CR ⁶ -, and X ¹ R ⁶ in two =CR ⁶ - of ~X ⁶ is a bonding site with φ or an azoline ring, R ⁶ in other =CR ⁶ - is hydrogen,
In formula (L-2), X ⁷ to X ¹⁴ are each independently =CR ⁶ - or =N-, at least two of X ⁷ to X ¹⁴ are =CR ⁶ -, and X ⁷ R ⁶ in two =CR ⁶ - of ~X ¹⁴ is a bonding site with φ or an azoline ring, 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 formula (ETM-16-1) or 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), or a divalent group represented by the following formulas (φ2-1) to (φ2-34). group, trivalent groups represented by the following formulas (φ3-1) to (φ3-3), and tetravalent groups represented by the following formulas (φ4-1) to (φ4-2). at least one hydrogen of φ is substituted with an alkyl having 1 to 6 carbons, a cycloalkyl having 3 to 14 carbons, an aryl having 6 to 18 carbons, or a heteroaryl having 2 to 18 carbons; Good too.

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

Preferably, L is a cyclic divalent group selected from the group consisting of benzene, naphthalene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, and pteridine. and at least one hydrogen in 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 is from the group consisting of phenyl, naphthyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, naphthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, and pteridinyl. At least one hydrogen of Ar in >N-Ar as Y may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms.

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

Specific examples of azoline derivatives include the following compounds. Note that "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 ring group selected from the group consisting of benzene, pyridine, pyrazine, pyrimidine, pyridazine, and triazine, and at least one hydrogen of L is an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 5 to 4 carbon atoms. Optionally substituted with cycloalkyl of 10, aryl of 6 to 10 carbon atoms, or heteroaryl of 2 to 14 carbon atoms,
Ar in >N-Ar as Y is selected from the group consisting of phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, and at least one hydrogen of the Ar is an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 5 to 4 carbon atoms. Optionally substituted with 10 cycloalkyl or aryl having 6 to 10 carbon atoms,
R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 4 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same, and R ³ and R ⁴ are the same , and all of R ¹ to R ⁴ cannot 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 azoline derivatives include the following compounds. Note that "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 explanations in formula (1) and formula (2) can be cited.

This azoline derivative can be produced using known raw materials and known synthesis methods.

[Reducing substances, others]
The electron transport layer or the electron injection layer may further contain a substance that can reduce the material forming the electron transport layer or the electron injection layer. A variety of substances can be used as this reducing substance as long as it has a certain reducing property, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, and alkali metals. 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 suitably used.

Preferred reducing substances include alkali metals such as Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), or Cs (work function: 1.95 eV), and Ca (work function: 2.3 eV). Examples include alkaline earth metals such as Sr (2.0 to 2.5 eV), Sr (2.0 to 2.5 eV), and Ba (2.52 eV), and substances with a work function of 2.9 eV or less are particularly preferred. Among these, more preferable reducing substances are alkali metals such as K, Rb, or Cs, still more preferably Rb or Cs, and most preferable is Cs. These alkali metals have 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 luminance of the organic EL element can be improved and the life of the organic EL element can be extended. Further, as a reducing substance with a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By including Cs, the reducing ability can be efficiently exhibited, and by adding it to the material forming the electron transport layer or the electron injection layer, the luminance of light emission and the longevity of the organic EL element can be improved.

The materials for the electron transport injection layer and the material for the electron transport layer described above are polymer compounds obtained by polymerizing reactive compounds substituted with reactive substituents as monomers, or crosslinked polymers thereof, or A pendant polymer compound obtained by reacting a chain polymer with the above-mentioned reactive compound, or a pendant polymer crosslinked product thereof, can also be used as an electronic layer material.

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

The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material 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 alloys, aluminum-lithium alloys such as lithium fluoride/aluminum), etc.) are preferred. In order to increase electron injection efficiency and improve device characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. In order to improve this point, a method is known in which, for example, the organic layer is doped with a trace amount of lithium, cesium, or magnesium to use a highly stable electrode. Other dopants that can also be used are inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. However, it is not limited to these.

Additionally, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys of these metals, as well as inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, and vinyl chloride, are used to protect the electrodes. A preferred example is to laminate a hydrocarbon polymer compound or the like. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

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

<Method for manufacturing organic electroluminescent device>
Each layer constituting an organic EL element is prepared using a vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method, coating method, laser heating drawing method. It can be formed by forming a thin film using a method such as (LITI). The thickness of each layer formed in this way is not particularly limited and can be set appropriately depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillation type film thickness measuring device. When forming a thin film using an evaporation method, the evaporation conditions vary depending on the type of material, the intended crystal structure and association structure of the film, and so on. Generally, the deposition conditions are: boat heating temperature +50 to +400°C, vacuum degree 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to 50 nm/sec, substrate temperature -150 to +300°C, and film thickness 2 nm to 5 μm. It is preferable to set it appropriately within a range.

When applying a direct current voltage to the organic EL element obtained in this way, it is sufficient to apply it with the anode as + polarity and the cathode as - polarity. Luminescence can be observed from the sides (anode or cathode, or both). This organic EL element also emits light when pulsed current or alternating current is applied. Note that the waveform of the applied alternating current may be arbitrary.

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

<Vapor deposition method>
After a thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, thin films of a hole injection layer and a hole transport layer are formed on this anode. On top of this, a host material and a dopant material are co-deposited to form a thin film to form a light-emitting layer, an electron transport layer and an electron injection layer are formed on this light-emitting layer, and a thin film of a cathode material is further formed by vapor deposition or the like. By forming it and using it as a cathode, the desired organic EL element can be obtained. In addition, in the production of the above-mentioned organic EL element, it is also possible to reverse the production order and produce the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode in this order. It is.

<Wet film formation method>
The wet film-forming method is carried out by preparing a liquid organic layer-forming composition containing a low-molecular compound capable of forming each organic layer of an organic EL element. If there is no suitable organic solvent to dissolve this low-molecular-weight compound, the low-molecular-weight compound is substituted with a reactive substituent and becomes a polymer together with other monomers and main chain polymers that have a solubility function. The 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 through 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 through this drying step to form a crosslinked polymer.
Depending on the difference in coating process, the method using a spin coater is the spin coating method, the method using a slit coater is the slit coating method, the method using a plate is gravure, offset, reverse offset, flexo printing method, and the method using an inkjet printer is the inkjet method. The method of spraying in a mist is called the spray method.

As an example, a method of forming a coating film on a substrate having banks using an inkjet method will be described with reference to FIG. First, a bank (200) is provided on an electrode (120) on a 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 them. By repeating this process, the next coating film (140) and further up to the light emitting layer (150) are formed, and the electron transport layer, electron injection layer and electrode are formed using the vacuum evaporation method, and the light emitting areas are separated by the bank material. Thus, an organic EL device can be manufactured.

The drying process includes methods such as air drying, heating, and reduced pressure drying. The drying step may be performed only once, or may be performed multiple times using different methods and conditions. Further, different methods may be used in combination, for example, calcination under reduced pressure.

The wet film forming method is a film forming method using a solution, and includes, for example, some printing methods (inkjet method), spin coating method, casting method, coating method, and the like. Unlike the vacuum evaporation method, the wet film formation method does not require the use of an expensive vacuum evaporation device and can form a film under atmospheric pressure. In addition, the wet film formation method allows for large-area production and continuous production, leading to reductions in manufacturing costs.

On the other hand, when compared with the vacuum evaporation method, the wet film formation method may have difficulty in laminating layers. When producing a laminated film using a wet film formation method, it is necessary to prevent the composition of the upper layer from dissolving the lower layer. solvents) are used. However, even with these techniques, it may be difficult to use a wet film formation method for coating all films.

Therefore, a method is generally adopted in which an organic EL element is fabricated using a wet film forming method for only some layers and using a vacuum evaporation method for the remaining layers.

For example, a procedure for manufacturing an organic EL element by partially applying a wet film forming method is shown below.
(Procedure 1) Film formation by vacuum evaporation of anode (Procedure 2) Film formation by wet film formation of hole injection layer forming composition containing material for hole injection layer (Procedure 3) Material for hole transport layer Forming a film by a wet film forming method of a composition for forming a hole transport layer containing a host material and a dopant material (Step 4) Forming a film by a wet film forming method of a composition for forming a light emitting layer containing a host material and a dopant material (Step 5) Electron transport layer Film formation by vacuum evaporation method (Step 6) Electron injection layer film formation by vacuum evaporation method (Step 7) Film formation by vacuum evaporation method of cathode By going through this procedure, the anode/hole injection layer/hole transport An organic EL device consisting of a layer/a light-emitting layer made of a host material and a dopant material/an electron transport layer/an electron injection layer/a cathode is obtained.
Of course, there are ways to prevent the underlying light-emitting layer from dissolving, or to form a layer containing the material for the electron transport layer and the material for the electron injection layer by using a method that forms the film from the cathode side, contrary to the above procedure. A film can be formed using a wet film forming method.

<Other film formation methods>
Laser thermal lithography (LITI) can be used to form a film from the composition for forming an organic layer. LITI is a method in which a compound attached to a base material is heated and vapor-deposited using a laser, and an organic layer-forming composition can be used as the material applied to the base material.

<Optional process>
Appropriate treatment steps, cleaning steps, and drying steps may be performed as appropriate before and after each step of film formation. Examples of the treatment steps include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment. Furthermore, a series of steps for producing banks (partition material) can also be mentioned.

Photolithography technology can be used to create the banks. As bank materials that can be used in photolithography, positive resist materials and negative resist materials can be used. Patternable printing methods such as inkjet printing, gravure offset printing, reverse offset printing, and screen printing can also be used. In this case, a permanent resist material can also be used.

Materials used for banks include polysaccharides and their derivatives, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrene, polyimides, polyamideimides, and polyetherimides. , polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth)acrylate, melamine (meth)acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin, polyvinyl chloride, chlorine Examples include fluorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene and other fluorinated polymers, fluoroolefin-hydrocarbon olefin copolymers, and fluorocarbon polymers. However, it is not limited to that.

<Organic layer forming composition used in wet film forming method>
The composition for forming an organic layer is obtained by dissolving in an organic solvent a low-molecular compound capable of forming each organic layer of an organic EL element, or a high-molecular compound obtained by polymerizing the low-molecular compound. For example, the composition for forming a light emitting layer includes the polycyclic aromatic compound of the present invention which is at least one dopant material as a first component, at least one host material as a second component, and at least one dopant material as a third component. and organic solvents. The first component functions as a dopant component of the emissive layer obtained from the composition, and the second component functions as the host component of the emissive layer. The third component functions as a solvent that dissolves the first and second components in the composition, and provides a smooth and uniform surface shape during application due to the controlled evaporation rate of the third component itself.

(1) 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 during film formation, it is possible to control and improve film formability, the presence or absence of defects in the coating, surface roughness, and smoothness. Furthermore, when forming a film using an inkjet method, it is possible to control meniscus stability in a pinhole of an inkjet head and to control and improve ejection performance. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, it is possible to improve the electrical properties, luminescence properties, efficiency, and life of an organic EL device having an organic layer obtained from the composition for forming an organic layer. I can do it.

(1-1) 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, 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 properties. Moreover, when the boiling point is lower than 300° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent, and smoothness. The organic solvent preferably contains two or more types of organic solvents from the viewpoint of good inkjet ejection properties, film formability, smoothness, and low residual solvent. On the other hand, depending on the case, the composition may be made into a solid state by removing the solvent from the organic layer forming composition in consideration of transportability and the like.

Furthermore, the organic solvent includes a good solvent (GS) and a poor solvent (PS) for at least one solute, and the boiling point (BP GS ) of the good solvent (GS) is lower than the boiling point (BP _PS ) of the poor solvent ( _PS ). Particularly preferred are configurations in which the
By adding a poor solvent with a high boiling point, the good solvent with a low boiling point evaporates first during film formation, increasing the concentration of the substances contained in the composition and the concentration of the poor solvent, thereby promoting rapid film formation. As a result, a highly smooth coating film with few defects and low surface roughness can be obtained.

The solubility difference (S _GS −S _PS ) is preferably 1% or more, more preferably 3% or more, and even 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 film formation, the organic solvent is removed from the coating film through a drying process such as vacuum, reduced pressure, or heating. When heating is performed, it is preferable to perform the heating at a temperature not higher than the glass transition temperature (Tg) of at least one of the solutes +30° C. from the viewpoint of improving coating film formation properties. Furthermore, from the viewpoint of reducing residual solvent, it is preferable to heat at least one of the solutes at a 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 can be sufficiently removed because the film is thin. Further, drying may be performed multiple times at different temperatures, and multiple drying methods may be used in combination.

(1-2) Specific examples of organic solvents Examples of organic solvents used in the organic layer-forming composition include alkylbenzene-based solvents, phenyl ether-based solvents, alkyl ether-based solvents, cyclic ketone-based solvents, aliphatic ketone-based solvents, Examples include cyclic ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents. Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2- ol, heptane-2-ol, octan-2-ol, decan-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, Propylene 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 -Fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2 -Methylanisole, phenethole, benzodioxole, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methylanisole, cymene, 1,2,3-trimethylbenzene, 1,2- Dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroberatrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decahydronaphthalene), neopentylbenzene, 2,5-dimethylanisole , 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3,4-dimethylanisole, o-tolnitrile, 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'-bitryl, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1-methyl-4-(propoxymethyl)benzene, 1-methyl -4-(Butyloxymethyl)benzene, 1-methyl-4-(pentyloxymethyl)benzene, 1-methyl-4-(hexyloxymethyl)benzene, 1-methyl-4-(heptyloxymethyl)benzene benzyl butyl ether , benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether, etc., but are not limited thereto. Moreover, a single solvent may be used or a mixture may be used.

(2) Optional components The composition for forming an organic layer may contain optional components within a range that does not impair its properties. Optional components include binders, surfactants, and the like.

(2-1) Binder The organic layer forming composition may contain a binder. The binder forms a film during film formation and also bonds 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 organic layer forming composition include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile - Styrene copolymer (AS) resins, phenolic resins, epoxy resins, melamine resins, urea resins, alkyd resins, polyurethanes, and copolymers of the above resins and polymers.

The number of binders used in the composition for forming an organic layer may be one type or a mixture of multiple types may be used.

(2-2) Surfactant The composition for forming an organic layer contains a surfactant, for example, to control the film surface uniformity, solvent affinity and liquid repellency of the film surface. You may. Surfactants are classified into ionic and nonionic based on the structure of their hydrophilic groups, and further classified into alkyl-based, silicon-based, and fluorine-based based on the structure of their hydrophobic groups. In addition, based on the structure of the molecule, it is classified into monomolecular systems with a relatively small molecular weight and a simple structure, and polymer systems with a large molecular weight and side chains and branches. Also, based on the composition, they are classified into single type and mixed type, which is a mixture of two or more types of surfactants and base materials. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.

As the surfactant, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (product name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbyk 161, Disperbyk 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbyk 180, Disperbake 181, Disperbyk Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (product name, manufactured by BYK Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 ( EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (product name, manufactured by Mitsubishi Materials Corporation), Megafac F- 470, Megafac F-471, Megafac F-475, Megafac R-08, Megafac F-477, Megafac F-479, Megafac F-553, Megafac F-554 (product name, DIC Corporation) ), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkylsulfonate, diglycerine tetrakis (fluoroalkyl polyoxyethylene ether) ), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Mention may be made of polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonates and alkyl diphenyl ether disulfonates.

Moreover, one type of surfactant may be used, or two or more types may be used in combination.

(3) Composition and physical properties of organic layer-forming composition The content of each component in the organic layer-forming composition is determined to ensure good solubility, storage stability, and film-forming properties of each component in the organic layer-forming composition. , as well as good film quality of the coating film obtained from the composition for forming an organic layer, good ejection properties when using an inkjet method, and an organic EL element having an organic layer prepared using the composition. It is determined in consideration of good electrical properties, light emitting properties, efficiency, and lifespan. For example, in the case of a composition for forming a light emitting layer, the first component is 0.0001% to 2.0% by mass based on the total mass of the composition for forming a light emitting layer, and the second component is for forming a light emitting layer. The third component is 0.0999% by mass to 8.0% by mass based on the total mass of the composition, and the third component is 90.0% by mass to 99.9% by mass based on the total mass of the composition for forming a light emitting layer. preferable.

More preferably, the first component is 0.005% by mass to 1.0% by mass based on the total mass of the composition for forming a luminescent layer, and the second component is preferably 0.005% by mass to 1.0% by mass based on the total mass of the composition for forming a luminescent layer. The amount of the third component is 0.095% by mass to 4.0% by mass, and the third component is 95.0% by mass to 99.9% by mass based on 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 based on the total mass of the composition for forming a luminescent layer, and the second component is preferably The amount of 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 based on 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 and performing stirring, mixing, heating, cooling, dissolving, dispersing, etc., the above-mentioned components using known methods. Further, after preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas substitution/enclosure treatment, etc. may be appropriately selected and carried out.

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

As for the surface tension of the composition for forming an organic layer, the lower the surface tension, the better the film formability and the coating film free of defects can be obtained. On the other hand, the higher the value, the better the inkjet ejection performance. From this, the viscosity of the organic layer forming composition is preferably such that the surface tension at 25° C. is 20 to 40 mN/m, more preferably 20 to 30 mN/m. In the present invention, surface tension is a value measured using a hanging drop method.

<Application examples of organic electroluminescent devices>
Further, the present invention can be applied to a display device equipped with an organic EL element or a lighting device equipped with an organic EL element.
A display device or a lighting device equipped with an organic EL element can be manufactured by a known method such as connecting the organic EL element according to this embodiment with a known drive device, and can be manufactured by a known method such as direct current drive, pulse drive, alternating current drive, etc. It can be driven using a known driving method as appropriate.

Examples of display devices include panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescent (EL) displays, etc. (Refer to Japanese Patent Publication No. 2004-281086, etc.). In addition, examples of display methods include matrix and/or segment methods. Note that matrix display and segment display may coexist in the same panel.

In a matrix, display pixels are arranged two-dimensionally in a grid or mosaic pattern, and characters or images are displayed as a collection of pixels. The shape and size of pixels are determined by the application. For example, rectangular pixels with sides of 300 μm or less are usually used to display images and characters on computers, monitors, and televisions, and in the case of large displays such as display panels, pixels with sides of mm order are 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 delta types and striped types. As a driving method for this matrix, either a line sequential driving method or an active matrix driving method may be used. Line sequential driving has the advantage of a simpler structure, but when considering operating characteristics, active matrix driving may be superior in some cases, so it is necessary to use it properly depending on the application.

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

Examples of lighting devices include lighting devices for indoor lighting, backlights for liquid crystal display devices, etc. etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, watches, audio devices, automobile panels, display boards, signs, and the like. In particular, considering that it is difficult to reduce the thickness of liquid crystal display devices, especially backlights for personal computers where thinning is an issue, since conventional systems consist of fluorescent lamps and light guide plates, this embodiment A backlight using a 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 in the production of organic field effect transistors, organic thin film solar cells, etc. in addition to the organic electroluminescent devices described above.

The structure of an organic field effect transistor is usually such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and a source electrode and a drain electrode are further provided in contact with the organic semiconductor active layer. A gate electrode may be provided with an insulating layer (dielectric layer) sandwiched therebetween. 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 The organic field effect transistor configured in this way is It can be applied as a pixel drive switching element for active matrix drive type liquid crystal displays and organic electroluminescent displays.

An 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 properties. 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. The organic thin film solar cell may appropriately include a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, etc. in addition to the above. For the organic thin film solar cell, known materials used for organic thin film solar cells can be appropriately selected and used in combination.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.
In addition, in the chemical formulas described in Examples, Me represents methyl and Ph represents phenyl.

Synthesis example (1)
11-Mesityl-13-phenoxy-11H-9,15,20-trioxa-11-aza-4b,19b-diborazinaphtho[3,2,1-de:3',2',1'-hi]pentacene (compound 1-34) Synthesis

Phenol (11.0 mL, 125 mmol), cesium carbonate (48.7 g, 149 mmol) and N-methyl-2-pyrrolidone (100 mL) were added with 1-bromo-3,5-difluorobenzene (5.70 mL) at room temperature under nitrogen atmosphere. , 49.9 mmol) was added thereto, and the mixture was heated and stirred at 120° C. for 18 hours. 6N hydrochloric acid (50 mL) was added to the reaction solution at 0°C, and the mixture was extracted with toluene (30 mL x 2). The obtained organic layer was washed with water (100 mL) to remove N-methyl-2-pyrrolidone. The solvent was distilled off under reduced pressure to obtain a crude product, which was then purified by silica gel column chromatography to obtain ((5-bromo-1,3-phenylene)bis(oxy))dibenzene (15. 6 g, yield 92%) was obtained.

The structure of the obtained compound was confirmed by NMR spectrum.
^1H NMR (CDCl ₃ , 400 MHz): δ=6.59 (s, 1H), 6.81 (s, 2H), 7.03 (dd, 4H), 7.16 (t, 2H), 7.36 (t, 4H).
¹³ C NMR (CDCl ₃ , 101 MHz): δ=107.5 (1C), 115.8 (2C), 119.6 (4C), 123.0 (1C), 124.3 (2C), 130.0 (4C), 155.8 (2C), 159.4 ( 2C).

2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.103g, 0.25 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.115g, 0.13 mmol), ((5- Bromo-1,3-phenylene)bis(oxy))dibenzene (4.27 g, 13 mmol), sodium-tert-butoxide (2.40 g, 25 mmol) and 2,4,6-trimethylaniline (0.700 mL, 5. O-xylene (20 mL) was added to the mixture (0 mmol) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 80° C. for 16 hours. After the reaction solution was cooled to room temperature, it was filtered using a silica gel short-pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, by purification by silica gel column chromatography and washing with hexane, N,N-bis(3,5-diphenoxyphenyl)-2,4,6-trimethylaniline (2.85 g) was obtained as a white solid. , yield 87%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (CDCl ₃ , 400 MHz): δ=2.03 (s, 6H), 2.27 (s, 3H), 6.10 (s, 2H), 6.43 (s, 4H), 6.88 (s, 2H), 6.94 ( dd, 8H), 7.03 (t, 4H), 7.26 (t, 8H).
¹³ C NMR (CDCl ₃ , 101 MHz): δ=18.4 (2C), 21.0 (1C), 102.2 (2C), 105.6 (4C), 118.6 (8C), 123.2 (4C), 129.6 (8C), 130.1 ( 2C), 137.1 (2C), 137.3 (1C), 139.1 (1C), 147.8 (2C), 156.7 (4C), 158.6 (4C).

N,N-bis(3,5-diphenoxyphenyl)-2,4,6-trimethylaniline (65.8 mg, 0.10 mmol) and boron tribromide (0.30 mL, 3.2 mmol) under nitrogen atmosphere. , 1,2,4-Trichlorobenzene (2.0 mL) was added at room temperature, and the mixture was heated and stirred at 220° C. for 6 hours. Unreacted boron tribromide was distilled off under reduced pressure at room temperature. The reaction solution was diluted with dichloromethane (10 mL), and phosphate buffer (pH=7, 5.0 mL) was added at 0°C. After separating the organic layer, the aqueous layer was extracted three times with dichloromethane (10 mL). Thereafter, the solvent was distilled off under reduced pressure to obtain a crude product. Add toluene (20 mL) and acetic acid (0.10 mL) to the crude product, heat and stir at 70°C for 30 minutes and 90°C for 30 minutes, then add acetic acid (0.40mL) and heat at 90°C for 22 hours. Stirred. The reaction solution was cooled to room temperature, saturated aqueous sodium hydrogen carbonate solution (200 mL) was added, the aqueous layer was extracted with toluene (20 mL x 3), and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, purification by silica gel column chromatography, washing with dichloromethane, and purification by GPC was performed to obtain compound (1-34) (26.9 mg, yield 40%) as a yellow solid.

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (CDCl ₃ , 400 MHz): δ=1.93 (s, 6H), 2.47 (s, 3H), 6.05 (s, 1H), 6.52 (s, 1H), 6.65 (s, 1H), 7.08 ( d, 2H), 7.18 (t, 3H), 7.35-7.50 (m, 7H), 7.64-7.69 (m, 3H), 7.74 (t, 1H), 8.71 (dd, 1H), 8.76 (dd, 1H) , 8.91 (dd, 1H).
¹³ C NMR (CDCl ₃ , 101 MHz): δ=17.4 (2C), 21.3 (1C), 95.1 (1C), 96.7 (1C), 97.5 (1C), 117.4 (1C), 117.9 (1C), 118.7 ( 1C), 120.1 (2C), 121.7 (1C), 122.9 (1C), 123.1 (1C), 124.2 (1C), 129.8 (2C), 130.6 (2C), 132.4 (1C), 133.2 (1C), 133.3 ( 1C), 134.2 (1C), 134.6 (1C), 136.1 (1C), 136.6 (2C), 137.6 (1C), 138.9 (1C), 145.4 (1C), 152.3 (1C), 155.8 (1C), 159.3 ( 1C), 160.3 (1C), 160.3 (1C), 160.4 (1C), 160.6 (1C), 162.7(1C), 163.6 (1C).

<Evaluation of basic physical properties>
Sample Preparation When evaluating the absorption and luminescence properties (fluorescence and phosphorescence) of a compound to be evaluated, the compound may be dissolved in a solvent and evaluated in a solvent, or it may be evaluated in a thin film state. Furthermore, when evaluating in a thin film state, depending on the mode of use of the compound to be evaluated in an organic EL element, there are cases where only the compound to be evaluated is made into a thin film and evaluated, and cases where the compound to be evaluated is dispersed in an appropriate matrix material. In some cases, the film may be made into a thin film for evaluation.

As the matrix material, commercially available PMMA (polymethyl methacrylate) or the like can be used. A thin film sample dispersed in PMMA can be prepared by, for example, dissolving PMMA and the compound to be evaluated in toluene, and then forming a thin film on a transparent support substrate (10 mm x 10 mm) made of quartz using a spin coating method. I can do it.

Further, a method for producing a thin film sample when the matrix material is the host material will be described below. A transparent support substrate made of quartz (10 mm x 10 mm x 1.0 mm) was fixed to a substrate holder of a commercially available evaporation apparatus (manufactured by Showa Shinku Co., Ltd.), and a molybdenum evaporation boat containing a host material and a dopant material were placed. Attach a molybdenum vapor deposition boat. Next, the pressure in the vacuum chamber is reduced to 5×10 ^-4 Pa, and the evaporation boat containing the host material and the evaporation boat containing the dopant material are simultaneously heated to achieve an appropriate film thickness and the host material is evaporated to an appropriate thickness. A mixed thin film of the material and the dopant material is formed. The deposition rate is controlled according to the set mass ratio of host material and dopant material.

Evaluation of Absorption Characteristics and Luminescent Characteristics The absorption spectrum of the sample is measured using an ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation, UV-2600). Further, the fluorescence spectrum or phosphorescence spectrum of the sample is measured using a spectrofluorophotometer (manufactured by Hitachi High-Tech Corporation, F-7000).

For measurement of fluorescence spectra, photoluminescence was measured at room temperature with excitation at an appropriate excitation wavelength. The phosphorescence spectrum was measured while the sample was immersed in liquid nitrogen (temperature 77 K) using an attached cooling unit. To observe the phosphorescence spectrum, an optical chopper was used to adjust the delay time from excitation light irradiation to the start of measurement. The sample is excited with the appropriate excitation wavelength and photoluminescence is measured.

Further, the fluorescence quantum yield is measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C9920-02G).

Evaluation of fluorescence lifetime (delayed fluorescence) Fluorescence lifetime is measured at 300K using a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C11367-01). Observe components with fast and slow fluorescence lifetimes at the maximum emission wavelength measured at an appropriate excitation wavelength. In fluorescence lifetime measurements at room temperature of general organic EL materials that emit fluorescence, slow components involving triplet components derived from phosphorescence are rarely observed due to the deactivation of triplet components due to heat. . If a slow component is observed in the compound to be evaluated, this indicates that triplet energy with a long excitation lifetime is transferred to singlet energy due to thermal activation and observed as delayed fluorescence.

Calculation of energy gap (Eg) It is calculated as Eg=1240/A from the long wavelength end A (nm) of the absorption spectrum obtained by the method described above.

Calculation of E _S , E _T and ΔEST The singlet excitation energy (E _S ) is calculated from the maximum emission wavelength B (nm) of the fluorescence spectrum as E _S =1240/B. Further, the triplet excitation energy (E _T ) is calculated from the maximum emission wavelength C (nm) of the phosphorescence spectrum as E _T =1240/C.

ΔEST is defined as the energy difference between E _S and E _T , ΔEST=E _{S −ET} . In addition, ΔEST is, for example, "Purely organic electroluminescent material realizing 100% conversion from electricity to light", H. Kaji, H. Suzuki, T. Fukushima, K. Shizu, K. Katsuaki, S. Kubo,T. Komino, It can also be calculated using the method described in H. Oiwa, F. Suzuki, A. Wakamiya, Y. Murata, C. Adachi, Nat. Commun. 2015, 6, 8476.

Evaluation of basic physical properties of compound (1-34) [absorption properties]
A thin film forming substrate (made of quartz) in which compound (1-34) is dispersed in PMMA at a concentration of 1% by mass is prepared, and an absorption spectrum is measured.

[Light emission characteristics]
This is carried out by preparing a thin film forming substrate (made of quartz) in which compound (1-34) is dispersed in PMMA at a concentration of 1% by mass, and measuring photoluminescence by exciting it at an excitation wavelength of 340 nm.

The phosphorescence spectrum is measured by preparing a thin film-forming substrate (made of quartz) in which compound (1-34) is dispersed in PMMA at a concentration of 1% by mass, and measuring photoluminescence by exciting it at an excitation wavelength of 340 nm.

The above measurements confirm that compound (1-34) is a material that can achieve high efficiency and deep blue color.

<Evaluation of organic EL elements>
The compound of the present invention has an appropriate energy gap (Eg), high triplet excitation energy ( _E It can be expected to be applied to light-emitting layers.

Evaluation items and evaluation methods Evaluation items include drive voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), maximum wavelength of emission spectrum (nm), and half-width ( nm) etc. For these evaluation items, values at appropriate emission brightness can be used.

There are two types of quantum efficiency for light-emitting devices: internal quantum efficiency and external quantum efficiency.Internal quantum efficiency is when external energy injected as electrons (or holes) into the light-emitting layer of a light-emitting device is converted purely into photons. It shows the percentage of On the other hand, external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element or continue to be reflected. Since the light is not emitted to the outside of the light emitting device, the external quantum efficiency is lower than the internal quantum efficiency.

The method for measuring spectral radiance (emission spectrum) and external quantum efficiency is as follows. The device was caused to emit light by applying a voltage using a voltage/current generator R6144 manufactured by Advantest. Spectral radiance in the visible light region was measured in the direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light-emitting surface is a completely diffusing surface, the number of photons at each wavelength is obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying it by π. Next, the number of photons was integrated over the entire observed wavelength range to obtain the total number of photons emitted from the element. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency. Further, the half-width of the emission spectrum is determined as the width between the upper and lower wavelengths at which the intensity is 50%, centering on the maximum emission wavelength.

In the present invention, by providing a novel polycyclic aromatic compound, it is possible to increase the selection of materials for organic EL devices. Moreover, by using the novel polycyclic aromatic compound as a material for an organic electroluminescent device, it is possible to provide an excellent organic EL device, a display device equipped with the same, a lighting device equipped with the same, and the like.

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 droplet

Claims (15)

A polycyclic aromatic compound represented by the following formula (2).
(In formula (2),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R 12 , R ¹³ , R ¹⁴ , R ¹⁵ , and ^{R 16 are} each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthiodiarylboryl (two aryl may be bonded via a single bond or a linking group), or trisubstituted silyl, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, Adjacent groups among R ² to R ⁵ , R ⁶ to R ⁹ , R ¹⁰ to R ¹³ and R ¹⁴ to R ¹⁶ are bonded together to form an aryl group together with ring a, ring b, ring c, or ring d, respectively. A ring or a heteroaryl ring may be formed, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryl. may be substituted with oxy, heteroaryloxy, arylthio, heteroarylthio or trisubstituted silyl, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl;
X ¹ , X ² , X ³ and X ⁴ are each independently >O, NR, >S or >Se, and R in >NR is aryl having 6 to 12 carbon atoms, It is a heteroaryl having 2 to 15 carbon atoms or an alkyl having 1 to 6 carbon atoms, and R in the above NR is -O-, -S-, -C(-R) ₂ - or a single bond. It may be bonded to the a-ring, b-ring, c-ring, d-ring, and/or e-ring, and R in the -C(-R) ₂ - is hydrogen or alkyl having 1 to 6 carbon atoms;
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. ) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R 12 , R ¹³ , R ¹⁴ , R ¹⁵ , and ^{R 16 are} Each independently represents hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 6 carbon atoms, and 6 carbon atoms. ~12 aryloxy, arylthio having 6 to 12 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, arylheteroarylamino (aryl is aryl having 6 to 12 carbon atoms, heteroaryl is heteroaryl having 2 to 12 carbon atoms) aryl), or diheteroarylamino (heteroaryl is heteroaryl having 2 to 12 carbon atoms), in which at least one hydrogen is aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms. May be replaced,
X ¹ , X ² , X ³ and X ⁴ are each independently >O or NR, and R in >NR is aryl having 6 to 10 carbon atoms or is alkyl, and R in >NR may be bonded to the a ring, b ring, c ring, d ring, and/or e ring through a single bond,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen or deuterium,
The polycyclic aromatic compound according to claim 1 . R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, and hydrogen having 6 to 10 carbon atoms. Aryloxy, cycloalkyl having 3 to 10 carbon atoms, arylheteroarylamino (where aryl is aryl having 6 to 10 carbon atoms, and heteroaryl is heteroaryl having 2 to 12 carbon atoms), or diheteroarylamino (however, Heteroaryl is a heteroaryl having 2 to 12 carbon atoms, in which at least one hydrogen may be substituted with aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms,
R ¹ is hydrogen;
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen or deuterium,
The polycyclic aromatic compound according to claim 2 . The polycyclic aromatic compound according to claim 1, which is represented by any of the following formulas.
(In the formula, each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms, and R ¹⁰⁰ is each independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms. Aryl, carbazolyl, diarylamino (aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or aryloxy having 6 to 10 carbon atoms; may be substituted with alkyl having 1 to 6 carbon atoms, and the carbazolyl may be substituted with aryl having 6 to 10 carbon atoms or alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compounds represented by the above formulas may be substituted with cyano, halogen, or deuterium. ) The polycyclic aromatic compound according to claim 1, which is represented by the following formula.
A material for an organic device, comprising the polycyclic aromatic compound according to any one of claims 1 to 5 . The organic device material according to claim 6 , wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material. The organic device material according to claim 7 , wherein the organic electroluminescent element material is a light emitting layer material. A composition for forming a light emitting layer for coating and forming a light emitting layer of an organic electroluminescent device, the composition comprising:
As the first component, at least one polycyclic aromatic compound according to any one of claims 1 to 5 ;
as a second component, at least one organic solvent;
A composition for forming a light-emitting layer. An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The organic electroluminescent device, wherein the light emitting layer contains the polycyclic aromatic compound according to any one of claims 1 to 5 . An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The organic electroluminescent device, wherein the light emitting layer is a layer formed from the composition for forming a light emitting layer according to claim 9 . It has an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is made of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO consisting of anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, aryl nitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, quinolinol metal complexes, thiazole derivatives, benzothiazole derivatives, silole derivatives and azoline derivatives The organic electroluminescent device according to claim 10 or 11 , containing at least one selected from the group. The electron transport layer and/or 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, an alkaline earth metal oxide, and an alkaline earth metal oxide. A claim containing at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes. 13. The organic electroluminescent device according to 12 . A display device comprising the organic electroluminescent element according to any one of claims 10 to 13 . A lighting device comprising the organic electroluminescent element according to any one of claims 10 to 13 .