JP2020200254A - Polycyclic aromatic compound - Google Patents

Abstract

To provide a polycyclic aromatic compound to be a material for a light emitting layer having low triplet excitation energy (ET).SOLUTION: The present invention provides a polycyclic aromatic compound represented by formula (1) (R1-R13 each denote aryl, alkyl, cycloalkyl, alkoxy or aryloxy or the like; any one of a part of R2 substituent, and R12 and R13 is substituted with a pyrenyl group substituted/unsubstituted with an alkyl group or cycloalkyl).SELECTED DRAWING: None

Description

The present invention relates to polycyclic aromatic compounds, organic electroluminescent devices using them, organic field effect transistors and organic thin film solar cells, and display devices and lighting devices.

Conventionally, display devices using light emitting elements that emit electric field light have been studied in various ways because they can save power and be thin, and further, organic electroluminescent elements made of organic materials (hereinafter, "organic EL elements" or simply "organic EL elements" or simply. (Sometimes referred to as "element") has been actively studied because it is easy to reduce the weight and size. In particular, the development of organic materials with luminescent properties such as blue, which is one of the three primary colors of light, and the combination of multiple materials with optimal luminescent properties have been actively pursued regardless of whether they are high molecular weight compounds or low molecular weight compounds. Has been studied.

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

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

In the organic EL element, holes and electrons injected from the anode and the electrode are recombined in the light emitting layer, and the energy generated at that time is extracted as light. When holes and electrons are recombined, a singlet excited state and a triplet excited state are generated at a ratio of 1: 3 based on the spin-statistics rule. When a fluorescent material is used, only the singlet excited state can be used among these excited states, so that the internal quantum efficiency is 25% at the maximum, which is an obstacle to improving the efficiency of the organic EL device.

In recent years, organic EL devices having high internal quantum efficiency have been developed by using an anthracene-based compound as a host material for a light emitting layer and using triplet-triplet-fusion (TTF). TTF is a phenomenon in which one molecule in the singlet excited state is generated from two molecules in the triplet excited state. By utilizing this, it becomes possible to create a singlet excited state from a triplet excited state generated by 75%, and the maximum value of the internal quantum efficiency is 62.5%.

Further, when the organic EL element is used in the final product, a color filter is used to extract light in a target wavelength region from the emission spectrum of the light emitting material, but if the width of the emission spectrum of the light emitting material is narrow. , The amount of light removed by the color filter is reduced, and the efficiency of extracting light from the element (external quantum efficiency) is increased.

As a group of compounds having a narrow emission spectrum, compounds in which boron and nitrogen atoms are arranged in a specific positional relationship in the molecule have been developed (International Publication No. 2015-102118). In these compounds, the spectral width is reduced by using the multiple resonance effect.

However, these compounds, the arrangement of the HOMO and LUMO of the molecule are separated by the multiple resonance effect, the triplet excitation energy (E _T) is higher. In TTF, better to use a low comparable with anthracene-based material as a host material triplet excitation energy (E _T) dopant with a becomes the high efficiency, long lifetime devices. Therefore, although these compounds satisfy the required spectral characteristics, they do not have the optimum structure as a dopant used for TTF.

International Publication No. 2004/061047 Japanese Unexamined Patent Publication No. 2001-172232 Japanese Unexamined Patent Publication No. 2005-170911 International Publication No. 2015-102118

The object of the present invention is to provide a light emitting material having a low triplet excitation energy (E _T). As described above, the narrow emission spectrum, the light emitting material satisfying low triplet excitation energy (E _T) at the same time is not known.

The present inventors have made intensive studies to solve the above problems, the polycyclic aromatic compound formed by coupling a plurality of aromatic rings with a boron atom and a nitrogen atom, lower pyrene ring having triplet excitation energy (E _T) compound obtained by introducing a is found that meets narrow emission spectrum and low triplet excitation energy (E _T) simultaneously, thereby completing the present invention.
Specifically, the present invention has the following configuration.

[1] A polycyclic aromatic compound represented by the formula (1).

(In equation (1),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these. May be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R ^{1 to} R ¹¹ are bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring or a c ring. At least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy. , At least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
R ¹² and R ¹³ are aryl, heteroaryl, alkyl or cycloalkyl, in which at least one hydrogen may be substituted with aryl, alkyl or cycloalkyl, which may be substituted with alkyl.
In the structure represented by the formula (1), any one of hydrogen, R ¹² and R ¹³ contained in R ² is replaced with pyrenyl, which may be substituted with alkyl or cycloalkyl.
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium or halogen. )
[2] Any one of R ² , R ¹² and R ¹³ is pyrenyl which may be substituted with alkyl or cycloalkyl, and at least one hydrogen in the pyrenyl is an alkyl having 1 to 6 carbon atoms or 3 carbon atoms. May be substituted with 10 to 10 cycloalkyl,
R ^{1 to} R ¹¹ are independently hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms, and at least one hydrogen in these is carbon. It may be substituted with an aryl of number 6 to 12, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 10 carbon atoms.
The polycyclic aromatic compound according to [1].
[3] The polycyclic aromatic compound according to [2] represented by the formula (2).

(In equation (2),
Any one of R ² and R ¹³ is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms.
R ⁶ and R ⁹ are independently hydrogen, aryl with 6 to 12 carbon atoms, alkyl with 1 to 10 carbon atoms or cycloalkyl with 3 to 10 carbon atoms, and at least one hydrogen in these is carbon number. It may be substituted with 6-12 aryls, 1-10 carbons alkyl or 3-10 carbons cycloalkyls.
When R ¹³ is a pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ² is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. It is a cycloalkyl, in which at least one hydrogen may be substituted with an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms or a cycloalkyl having 3 to 10 carbon atoms.
When R ² is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ¹³ is a partial structure (R-13).
R ¹²⁹ and R ¹³⁹ are independently hydrogen, an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 10 carbon atoms, an alkyl having 1 to 10 carbon atoms, or an alkyl having 3 to 10 carbon atoms. Cycloalkyl,
At least one hydrogen in the compound represented by the formula (2) may be substituted with deuterium or halogen. )
[4] R ¹³ is an unsubstituted 1-pyrenyl,
R ² , R ⁶ , R ⁹ , R ¹²⁹ , and R ¹³⁹ are independently hydrogen or alkyl having 1 to 6 carbon atoms, respectively.
The polycyclic aromatic compound according to [3].
[5] The polycyclic aromatic compound according to [4], which has a structure represented by the formula (1-1).

[6] A material for an organic device containing the polycyclic aromatic compound according to any one of [1] to [5].
[7] An organic electroluminescent device having a pair of electrodes composed of an anode and a cathode and a light emitting layer arranged between the pair of electrodes.
The light emitting layer is an organic electroluminescent device containing the polycyclic aromatic compound according to any one of [1] to [5] and the anthracene compound represented by the formula (5).

(In equation (5),
X is a group independently represented by the formula (5-X1), the formula (5-X2) or the formula (5-X3), and the naphthylene moiety in the formula (5-X1) and the formula (5-X2). May be condensed with one benzene ring, and the group represented by the formula (5-X1), the formula (5-X2) or the formula (5-X3) is bonded to the anthracene ring of the formula (5) in *. However, the two Xs cannot be the groups represented by the formula (5-X3) at the same time, and Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, and biphenylyl. , Terphenylyl, quaterphenylyl, naphthyl, phenanthril, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the formula (6), in which both Ar ¹ and Ar ³ are phenyl. Instead, at least one hydrogen in Ar ³ may be further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by formula (6).
Ar ⁴ is a silyl that is independently substituted with hydrogen, phenyl, biphenylyl, turphenyl, naphthyl, or an alkyl having 1 to 4 carbon atoms.
At least one hydrogen in the compound represented by the formula (5) may be substituted with deuterium or a group represented by the formula (6).
In formula (6), Y is -O-, -S- or> N-R ²⁹ , and R ^{21 to} R ²⁸ are independently hydrogen, optionally substituted alkyl, and optionally substituted, respectively. Aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, optionally substituted amino, halogen, It is hydroxy or cyano, and adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, and R ²⁹ may be hydrogen or substituted. Aryl, the group represented by the formula (6) is a naphthalene ring of the formula (5-X1) or the formula (5-X2) in *, a single bond of the formula (5-X3), of the formula (5-X3). It binds to Ar ³ and replaces at least one hydrogen in the compound represented by the formula (5), and binds to them at any position in the structure of the formula (6). )
[8] The naphthalene moiety in the formulas (5-X1) and (5-X2) is not condensed with one benzene ring.
Ar ⁴ is independently hydrogen, phenyl, or naphthyl,
The group represented by the formula (6) is not included other than X.
The group represented by the formula (6) is a group represented by any of the formulas (6-1) to (6-11).
The organic electroluminescent device according to [7].

(In formulas (6-1) to (6-11), Y is -O-, -S- or> N-R ²⁹ , R ²⁹ is hydrogen or aryl, and formulas (6-1) to At least one hydrogen in the group represented by the formula (6-11) is alkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, diaryl substituted amino, diheteroaryl substituted amino, aryl heteroaryl substituted amino. , Halogen, hydroxy or cyano may be substituted, and the groups represented by the formulas (6-1) to (6-11) are naphthalene of the formula (5-X1) or the formula (5-X2) in *. Ring, single bond of formula (5-X3), bond with Ar ^{3 of} formula (5-X3), and bond with these at any position in the structures of formulas (6-1) to (6-11) To do.)
[9] Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, or formulas (6-1) to formulas (6). A group represented by any of -4), and at least one hydrogen in Ar ³ is further phenyl, naphthyl, phenanthryl, fluorenyl, or any of formulas (6-1) to (6-4). May be substituted with a group represented by,
The organic electroluminescent device according to [8].
[10] It has an electron transporting layer and / or an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, or fluoranthene. Contains at least one selected from the group consisting of derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol metal complexes. The organic electric field light emitting element according to any one of [7] to [9].
[11] 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, and an alkaline soil. Contains at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. , [10] The organic electric field light emitting element.
[12] A display device including the organic electroluminescent element according to any one of [7] to [11].
[13] A lighting device provided with the organic electroluminescent element according to any one of [7] to [11].

The present invention provides novel polycyclic aromatic compounds. Polycyclic aromatic compound has a property as a light emitting material having a low triplet excitation energy (E _T), the light emitting layer of the polycyclic aromatic compound is an organic device material, especially an organic electroluminescent device of the present invention of the present invention It is useful as a material for a light emitting layer for formation. By using the compound of the present invention in a light emitting layer in combination with a specific anthracene-based material, it is possible to provide an organic EL device with high efficiency and long life.

It is the schematic sectional drawing which shows the example of the organic EL element.

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

1. 1. Polycyclic Aromatic Compound The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having an aromatic ring linked by boron and nitrogen, and has at least one pyrene ring as a partial structure. The present inventors have found that with respect to the aromatic ring linked boron and nitrogen, less by applying a pyrene ring having triplet excitation energy (E _T), the triplet excitation energy of the entire molecule (E _T) is low Found a compound. Polycyclic aromatic compounds having an aromatic ring linked by boron and nitrogen show a large HOMO-LUMO gap (bandgap Eg in a thin film) and a narrow spectral width, and are used as an excellent light emitting material in an organic electroluminescent device. In the present invention, furthermore, by employing the structure imparted with pyrene ring, lower the triplet excitation energy (E _T), the compounds useful as material for manufacturing high does not easily deteriorate organic electrolytic light-emitting device is external quantum efficiency Provided.
The polycyclic aromatic compound of the present invention is represented by the following formula (1).

In the structure represented by the formula (1), any one of hydrogen, R ¹² and R ¹³ contained in R ² is replaced with pyrenyl, which may be substituted with an alkyl group or a cycloalkyl. That is, the pyrene ring is introduced at any of hydrogen, R ¹² and R ¹³ contained in R ² . This is because R ¹² and R ¹³ do not have a directly conjugated position in the structure represented by the equation (1), and thus have no effect on the emission spectrum. Further, in the structure represented by the equation (1), R ² has only one of the frontier orbitals on it, and the spread of the orbitals is the smallest, so that the influence on light emission is small.

Pyrenyl is a monovalent group, and examples of pyrenyl include 1-pyrenyl, 2-pyrenyl, or 4-pyrenyl. Of these, 1-pyrenyl is preferred. Further, pyrenyl may be substituted with alkyl or cycloalkyl, but is preferably unsubstituted. It is particularly preferable that the pyrenyl is an unsubstituted 1-pyrenyl represented by the following formula Y.

When the hydrogen contained in R ² and pyrenyl in which any one of R ¹² and R ¹³ is substituted in the formula (1) is substituted with alkyl or cycloalkyl, the number of substitutions may be one. There may be two or more. Examples of alkyl or cycloalkyl at this time include examples described later when any one of R ^{1 to} R ¹¹ represents alkyl or cycloalkyl, respectively, and may be alkyl having 1 to 6 carbon atoms. preferable.
In formula (1), any one of R ² , R ¹² and R ¹³ is preferably pyrenyl, which may be substituted with alkyl or cycloalkyl, and any one of R ¹² and R ¹³ is More preferably, it is pyrenyl, which may be substituted with alkyl or cycloalkyl.

In formula (1), R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy. At least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl. Further, adjacent groups of R ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring. May be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl. As described above, the hydrogen contained in R ² may be pyrenyl.

Examples of the "aryl ring" that can be included in the formula (1) include a benzene ring that is a monocyclic system, a biphenyl ring that is a bicyclic system, a naphthalene ring that is a fused bicyclic system, and a terphenyl ring (m) that is a tricyclic system. -Terphenyl, o-terphenyl, p-terphenyl), fused tricyclics, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic triphenylene ring, pyrene ring, naphthalene ring, condensed Examples include the perylene ring and the pentacene ring, which are five-ring systems.
In formula (1), when adjacent groups of R ^{1 to} R ¹¹ are bonded to each other to form an aryl ring together with a ring, b ring or c ring, the a ring and b ring composed of a benzene ring are formed. , And a fused ring of each of the c rings and the above aryl ring are formed. For example, when R ¹⁰ and R ¹¹ are bonded to each other to form a benzene ring together with a b ring, a naphthalene ring is formed.

Examples of the "heteroaryl ring" that can be contained in the formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, and a heteroaryl ring having 2 to 20 carbon atoms. Aryl rings are more preferred, heteroaryl rings having 2 to 15 carbon atoms are even more preferred, and heteroaryl rings having 2 to 10 carbon atoms are particularly preferred. Examples of the "heteroaryl ring" include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of the "heteroaryl ring" include a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxazole ring, a thiazazole ring, a triazole ring, a tetrazole ring, and a pyrazole ring. Pyridin ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring , Synnoline ring, quinazoline ring, quinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysine ring, phenoxatiein ring, phenoxazine ring, phenothiazine ring, phenazine ring, indridin ring, furan ring, Examples thereof include a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a frazane ring, an oxazole ring, and a thiantolen ring.

In formula (1), when adjacent groups of R ^{1 to} R ¹¹ are bonded to each other to form a heteroaryl ring together with a ring, b ring or c ring, a ring and b are composed of a benzene ring. A fused ring is formed between each of the ring and the c ring and the heteroaryl ring described above. For example, when R ¹⁰ and R ¹¹ are bonded to each other to form a pyrrole ring together with the b ring, an indole ring is formed.

When any one of R ^{1 to} R ¹¹ represents "aryl", the "aryl" includes the monovalent group of the above-mentioned "aryl ring". The same applies to aryls in these substituents when any of R ^{1 to} R ¹¹ represents "diarylamino", "arylheteroarylamino" or "aryloxy".

When any one of R ^{1 to} R ¹¹ represents "heteroaryl", the "heteroaryl" includes the monovalent group of the "heteroaryl ring" described above. The same applies to heteroaryls in these substituents when any of R ^{1 to} R ¹¹ represents "diheteroarylamino" or "arylheteroarylamino".

When any one of R ^{1 to} R ¹¹ represents "alkyl", the "alkyl" may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms or a linear alkyl having 3 to 24 carbon atoms. Branched chain alkyl can be mentioned. An alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms is more preferable. (Branched chain alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) is particularly preferable.

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

When any one of R ^{1 to} R ¹¹ represents "cycloalkyl", the "cycloalkyl" includes a cycloalkyl having 3 to 20 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, and a cyclo having 5 to 10 carbon atoms. Examples thereof include alkyl, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.

Specific cycloalkyls include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, and methylcyclononyl. , Cyclodecanyl, methylcyclodecanyl, 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, decahydronaphthyl, decahydroazurenyl and the like.

When any one of R ^{1 to} R ¹¹ represents "alkoxy", examples of the "alkoxy" include a straight chain having 1 to 24 carbon atoms or a branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (alkoxy of branched chains having 3 to 18 carbon atoms) is preferable, and alkoxy having 1 to 12 carbon atoms (alkoxy of branched chains having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms is more preferable. Alkoxy (alkoxy of branched chains having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 4 carbon atoms (alkoxy of branched chains having 3 to 4 carbon atoms) is particularly preferable.

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

At least ^one hydrogen in hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, represented by any of R ^{1 to} R ¹¹ , is aryl, It may be substituted with heteroaryl or alkyl. Examples of aryl, heteroaryl or alkyl at this time include the above-mentioned examples when any one of R ^{1 to} R ¹¹ represents "aryl", "heteroaryl" and "alkyl", respectively.

Adjacent groups of R ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring. All of the a ring, b ring and c ring may form an aryl ring or a heteroaryl ring, and two of the a ring, the b ring and the c ring (a ring and b ring, b ring and c). Rings, or a and c rings) may form an aryl ring or a heteroaryl ring, and any one of the a ring, b ring, and c ring (a ring, b ring, or c ring). ) May form an aryl ring or a heteroaryl ring.

At least one hydrogen in the ring formed by combining adjacent groups of R ^{1 to} R ¹¹ together with the a ring, b ring or c ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroaryl. It may be substituted with one or more first substituents selected from the group consisting of amino, alkyl, cycloalkyl, alkoxy and aryloxy. Examples of aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy and aryloxy as the first substituent are any of R ^{1 to} R ¹¹ aryl, respectively. , Heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy and aryloxy.

Further, at least one hydrogen of the above first substituent may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Examples of aryl, heteroaryl, alkyl or cycloalkyl at this time include the above-mentioned examples when any one of R ^{1 to} R ¹¹ represents aryl, heteroaryl, alkyl or cycloalkyl, respectively.

In formula (1), R ¹² and R ¹³ are aryl, heteroaryl, alkyl or cycloalkyl, in which at least one hydrogen is substituted with aryl, alkyl or cycloalkyl which may be substituted with alkyl. May be good. As mentioned above, any one of hydrogen, R ¹² and R ¹³ contained in R ² is replaced with pyrenyl, which may be substituted with alkyl or cycloalkyl. When the hydrogen contained in R ² is replaced with pyrenyl, which may be substituted with alkyl or cycloalkyl, it is preferable that R ² is pyrenyl which may be substituted with alkyl or cycloalkyl. That is, it is preferable that pyrenyl is directly bonded to the a ring.

In formula (1), R ¹² and R ¹³ are aryl, heteroaryl, alkyl or cycloalkyl, or pyrenyl as described above. Examples of aryl, heteroaryl, alkyl or cycloalkyl include the above-mentioned examples when any of R ^{1 to} R ¹¹ represents aryl, heteroaryl, alkyl or cycloalkyl, respectively. Further, when R ¹² and R ¹³ are aryl, heteroaryl, alkyl or cycloalkyl, at least one hydrogen in these may be substituted with aryl, alkyl or cycloalkyl which may be substituted with alkyl. Examples of aryl, alkyl or cycloalkyl at this time include the above-mentioned examples when any of R ^{1 to} R ¹¹ represents aryl, alkyl or cycloalkyl, respectively. Further, as the "alkyl" which may be substituted with aryl, the above-mentioned example when any one of R ^{1 to} R ¹¹ represents alkyl can be given, but methyl is most preferable.

The hydrogen in the compound represented by the formula (1) may be deuterium or halogen in whole or in part. Among these, an embodiment in which all or part of hydrogen in aryl or heteroaryl is replaced with deuterium or halogen can be mentioned. The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

The polycyclic aromatic compound represented by the formula (1) is preferably a polycyclic aromatic compound represented by the formula (2).

In formula (2), any one of R ² and R ¹³ is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms.
R ⁶ and R ⁹ are independently hydrogen, aryl with 6 to 12 carbon atoms, alkyl with 1 to 10 carbon atoms or cycloalkyl with 1 to 10 carbon atoms, and at least one hydrogen in these is carbon number. It may be substituted with an alkyl having 6 to 12 aryls and 1 to 10 carbon atoms or a cycloalkyl having 1 to 10 carbon atoms.
When R ¹³ is a pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ² is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. It is a cycloalkyl, wherein at least one hydrogen thereof may be substituted with an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms.
When R ² is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ¹³ is a partial structure (R-13). R ¹²⁹ and R ¹³⁹ are independently hydrogen, an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 10 carbon atoms, an alkyl having 1 to 10 carbon atoms, or an alkyl having 3 to 10 carbon atoms. It is a cycloalkyl.

At least one hydrogen in the compound represented by the formula (2) may be substituted with deuterium or halogen.
For the description and preferred range of each substituent in formula (2), the description and preferred range of the corresponding substituent in formula (1) can be referred to. In equation (2),
It is preferred that R ¹³ is unsubstituted 1-pyrenyl and R ² , R ⁶ , R ⁹ , R ¹²⁹ and R ¹³⁹ are independently hydrogen or alkyl having 1 to 6 carbon atoms, respectively.
Specific examples of the polycyclic aromatic compound of the present invention are shown below.

2. 2. Method for Producing Polycyclic Aromatic Compounds In the polycyclic aromatic compound represented by the formula (1), basically, the a ring, the b ring and the c ring are first bonded with a bonding group (a group containing N). The intermediate can be produced (first reaction), and then the a ring, b ring and c ring can be bonded with a binding group (group containing B) to produce the final product (second reaction). reaction). In the first reaction, a general reaction such as an amination reaction such as a Buchwald-Hartwig reaction can be used. Further, in the second reaction, a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. Further, by using a pyrenyl-substituted raw material or adding a step of introducing a pyrenyl group somewhere in these reaction steps, the compound of the present invention in which the desired position is pyrenyl-substituted can be produced. Can be done. For example, a compound in which R ¹² or R ¹³ is pyrenyl can be produced by using N-pyrenylamine in the first reaction in a similar manner when introducing a binding group.

In the second reaction, first, orthometalation is performed with t-butyllithium or the like at a position between the positions where the nitrogen atom of ring a is bonded. Next, boron tribromide or the like is added, the metal of lithium-boron is exchanged, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem Bora Friedel-Crafts reaction to obtain the desired product. Can be done. Here, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

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

Further, in the above scheme, a tandem hetero-Friedel-Crafts reaction was shown by orthometalating with butyllithium or the like before adding boron trichloride or boron tribromide, but butyllithium or the like was used. It is also possible to proceed the reaction by adding boron trichloride, boron tribromide, or the like without performing the existing orthometalation.

Examples of the orthometallation reagent include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide, and potassium hexamethyl. Examples thereof include organic alkaline compounds such as disilamide.

Metal exchange reagents include boron trifluoride, boron trichloride, boron tribromide, boron halides such as boron triiodide, and boron amination halides such as CIPN (NET ₂ ) ₂ . Examples thereof include boron alkoxides and boron aryl bromides.

Bronsted bases include N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidin, 1,2,2,6,6-pentamethylpiperidin, N, N-dimethylaniline, N, N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylboran, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (Note that Ar Is an aryl such as phenyl).

Examples of the Lewis acid used in the above schemes (1) to (28) include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ and Oet ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , InBr ₃ , and so on. 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 SiOTf, Cu (OTf) ₂ , CuCl ₂ , YCl ₃ , Y (OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr _3, etc. can give.

In the above scheme, Bronsted bases or Lewis acids may be used to facilitate the tandem hetero-Friedel-Crafts reaction. However, when boron halides such as boron trifluoride, boron trichloride, boron tribromide, and boron triiodide are used, hydrogen fluoride, as the aromatic electrophobic substitution reaction progresses, Since acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced, it is effective to use a blended base that captures the acid. On the other hand, when an aminated halide of boron or an alkoxylated of boron is used, it is often necessary to use a blended base because amines and alcohols are produced as the aromatic electrophilic substitution reaction proceeds. However, since the desorption ability of amino groups and alkoxy groups is low, it is effective to use Lewis acid that promotes the desorption.

Further, the polycyclic aromatic compound of the present invention includes those in which at least some hydrogen atoms are substituted with deuterium or cyano and those in which hydrogen atoms such as fluorine and chlorine are substituted. Compounds and the like can be synthesized in the same manner as described above by using a raw material in which the desired position is deuterated, cyanated, fluorinated or chlorinated.

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

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

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

The organic EL element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107. Above the electron transport layer 106 provided on the electron transport layer 106, the light emitting layer 105 provided on the electron transport layer 106, the hole transport layer 104 provided on the light emitting layer 105, and the hole transport layer 104. The hole injection layer 103 provided in the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be provided.

Not all of the above layers are required, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Further, each of the above layers may be composed of a single layer or a plurality of layers.

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

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic EL element 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. As for the glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness may be sufficient to maintain the mechanical strength. Therefore, for example, 0.2 mm or more may be used. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. As for the material of the glass, non-alkali glass is preferable because it is better to have less elution ions from the glass, but soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so this can be used. it can. Further, in order to enhance the gas barrier property, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side, and a synthetic resin plate, film or sheet having a particularly low gas barrier property may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

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

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

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

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

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

As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a hole charge transport material, a p-type semiconductor, and a hole injection layer of an organic EL element. And any compound can be selected and used from the known compounds used 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), and triarylamine derivatives (aromatic tertiary). Polymers with amino in the main or side chains, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl-N, N'-diphenyl-4,4'-diphenyl-1,1'-diamine, N ⁴ , N ^4' -diphenyl- N ⁴ , N ^4' -bis (9-phenyl-9H-carbazole-3-yl)-[1,1'-biphenyl] -4,4'-diamine, N ⁴ , N ⁴ , N ^4' , N ^{4 '} -Tetra [1,1'-biphenyl] -4-yl)-[1,1'-biphenyl] -4,4'-diamine, 4,4', 4 "-tris (3-methylphenyl (phenyl) Triphenylamine derivatives such as amino) triphenylamine, starburstamine derivatives, etc.), stillben derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives , Kinoxalin derivatives (eg, 1,4,5,8,9,12-hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivative having the above monomer as a side chain, polyvinylcarbazole, polysilane, etc. are preferable, but a thin film necessary for producing a light emitting element can be formed and holes can be injected from the anode. Further, the compound is not particularly limited as long as it can transport holes.

It is also known that the conductivity of organic semiconductors is strongly affected by its doping. Such an organic semiconductor matrix substance is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping electron donors. (For example, reference "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (22), 3202-3204 (1998)" and reference "J. Blochwitz, M." See .Pheiffer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (6), 729-731 (1998) "). They generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number of holes and the mobility, the conductivity of the base material changes considerably. As the matrix material having hole transporting properties, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA or the like), or a specific metal phthalocyanine (particularly, zinc phthalocyanine (ZnPc) or the like) is known ( Japanese Unexamined Patent Publication No. 2005-167175).

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

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

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

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

Host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene, which have long been known as luminescent materials, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. And so on. Of these, anthracene-based compounds are particularly preferable, and anthracene-based compounds having the following specific structures are more preferable.

<Anthracene compounds>
As the anthracene-based compound, for example, a compound represented by the following formula (5) is preferably used.

In formula (5), X is a group independently represented by formula (5-X1), formula (5-X2) or formula (5-X3), respectively. The naphthalene moiety in the formula (5-X1) and the formula (5-X2) may be condensed with one benzene ring, and the formula (5-X1), the formula (5-X2) or the formula (5-X3) may be used. The group represented is bonded to the anthracene ring of formula (5) in *, and two Xs do not simultaneously become a group represented by formula (5-X3). Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl. , Or a group represented by the formula (6), and Ar ¹ and Ar ³ are not both phenyl. At least one hydrogen in Ar ³ may be further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the formula (6).
Ar ⁴ is a silyl that is independently substituted with hydrogen, phenyl, biphenylyl, turphenyl, naphthyl, or an alkyl having 1 to 4 carbon atoms. Further, at least one hydrogen in the compound represented by the formula (5) may be substituted with deuterium or a group represented by the formula (6).

The naphthalene moiety in formulas (5-X1) and (5-X2) may be condensed with one benzene ring. The structure condensed in this way is as follows.

Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl. , Or a group represented by the formula (6). However, both Ar ¹ and Ar ² are not phenyl. When Ar ¹ or Ar ² is a group represented by the formula (6), the group represented by the formula (6) is a naphthalene ring of the formula (5-X1) or the formula (5-X2) in *. , A single bond of formula (5-X3), a bond of Ar ^{3 of} formula (5-X3), and replacement with at least one hydrogen in the compound represented by formula (5) in the structure of formula (6). Combines with these at any position.

Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, or the following formulas (6-1) to (6-4). ) Is preferably the group represented by any of. At this time, at least one hydrogen in Ar ³ is further substituted with phenyl, naphthyl, phenanthryl, fluorenyl, or a group represented by any of the following formulas (6-1) to (6-4). May be good.

Further, at least one hydrogen in Ar ³ may be further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the formula (6). When the substituent contained in Ar ³ is a group represented by the formula (6), the group represented by the formula (6) is bonded to Ar ³ in the formula (5-X3) in the *.

Ar ⁴ is a silyl that is independently substituted with hydrogen, phenyl, biphenylyl, turphenyl, naphthyl, or an alkyl having 1 to 4 carbon atoms. Ar ⁴ is preferably hydrogen, phenyl, or naphthyl independently of each other.

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

Specific examples of "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, and ethyl. Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl Diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldii-propylsilyl, ethyldii-propylsilyl, Examples thereof include butyl di-propyl silyl, sec-butyl di-propyl silyl and t-butyl di-propyl silyl.

Further, at least one hydrogen in the compound represented by the formula (5) may be substituted with deuterium or a group represented by the formula (6). When substituted with a group represented by the formula (6), the group represented by the formula (6) is substituted with at least one hydrogen in the compound represented by the formula (5) in the *.

The group represented by the formula (6) is one of the substituents that the anthracene-based compound represented by the formula (5) can have.

In formula (6), Y is -O-, -S- or> N-R ²⁹ , and R ^{21 to} R ²⁸ are independently hydrogen, optionally substituted alkyl, and optionally substituted, respectively. Aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, optionally substituted amino, halogen, It is hydroxy or cyano, and adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, and R ²⁹ may be hydrogen or substituted. Aryl, the group represented by the formula (6) is a naphthalene ring of the formula (5-X1) or the formula (5-X2) in *, a single bond of the formula (5-X3), of the formula (5-X3). It binds to Ar ³ and replaces at least one hydrogen in the compound represented by the formula (5), and binds to them at any position in the structure of the formula (6). )

The "alkyl" of the "optionally substituted alkyl" in R ^{21 to} R ²⁸ may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms or a linear alkyl having 3 to 24 carbon atoms. Branched chain alkyl can be mentioned. An alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and an alkyl having 1 to 6 carbon atoms is more preferable. (Branched chain alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) is particularly preferable.

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

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

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

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

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

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

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

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

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

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

Specific "trialkylsilyl" includes trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl. Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldii-propylsilyl, ethyldii-propylsilyl, butyldii-propylsilyl, sec-butyldii Examples thereof include -propylsilyl and t-butyldii-propylsilyl.

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

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

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

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

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

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

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

Adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. Examples of the ring formed by bonding adjacent groups to each other include a cyclohexane ring in the case of a hydrocarbon ring, and "aryl" and "heteroaryl" in R ^{21 to} R ²⁸ described above as an aryl ring and a heteroaryl ring. These rings are formed so as to condense with one or two benzene rings in the following formula (6-1).

Of R ^{21 to} R ^28, the case where adjacent groups are bonded to each other and do not form a ring is a group represented by the following formula (6-1), and the case where a ring is formed is, for example, the following formula (6-2). ) ~ The groups represented by the formula (6-11) can be mentioned.

In formulas (6-1) to (6-11), Y is -O-, -S- or> N-R ²⁹ , R ²⁹ is hydrogen or aryl, and formulas (6-1) to formula (6-1) to formula. At least one hydrogen in the group represented by (6-11) is alkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, diaryl substituted amino, diheteroaryl substituted amino, aryl heteroaryl substituted amino, It may be substituted with halogen, hydroxy or cyano. The groups represented by the formulas (6-1) to (6-11) are the naphthalene rings of the formula (5-X1) or the formula (5-X2), the single bond of the formula (5-X3), and the formula (5-X3). It binds to Ar ^{3 of} 5-X3) and binds to them at any position in the structures of formulas (6-1) to (6-11). )

Examples of the group represented by the formula (6) include groups represented by any of the formulas (6-1) to (6-11), and the groups represented by the formulas (6-1) to (6-5). ) Is preferable, and the group represented by any of the formulas (6-1) to (6-4) is more preferable, and the formulas (6-1) and (6-3) are more preferable. And the group represented by any of the formula (6-4) is more preferable, and the group represented by the formula (6-1) is particularly preferable.

The group represented by the formula (6) is bonded to the naphthalene ring of the formula (5-X1) or the formula (5-X2), the single bond of the formula (5-X3), and Ar ^{3 of the} formula (5-X3) in *. And also replace with at least one hydrogen in the compound represented by the formula (5). Among these bonding forms, it was bonded to the naphthalene ring in the formula (5-X1) or the formula (5-X2), the single bond in the formula (5-X3) and / or Ar ³ in the formula (5-X3). The form is preferable.

Further, in the structure of the group represented by the formula (6), the naphthalene ring in the formula (5-X1) or the formula (5-X2), the single bond in the formula (5-X3), and the formula (5-X3). ) Ar ³ is bonded position in, also in the structure of the group represented by the formula (6), the position of replacing at least one hydrogen in the compound of formula (5) has the formula (6) It may be at any position in the structure of, for example, any of the two benzene rings in the structure of formula (6) or adjacent groups of R ^{21 to} R ^{28 in} the structure of formula (6). It can be bonded at any of the rings formed by bonding with each other or at any position in R ²⁹ in "> N-R ²⁹ " as Y in the structure of the formula (A).

Examples of the group represented by the formula (6) include the following groups. Y and * in the formula have the same definition as above.

Further, all or part of the hydrogen in the chemical structure of the anthracene compound represented by the formula (5) may be deuterium.

Specific examples of the anthracene-based compound include compounds represented by the following formulas (5-1) to (5-72).

The anthracene-based compound represented by the formula (5) includes a compound having a reactive group at a desired position in the anthracene skeleton and a compound having a reactive group in a partial structure such as the structure of X, Ar ⁴ and the formula (6). Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using the above as a starting material. Examples of the reactive group of these reactive compounds include halogen and boronic acid. As a specific manufacturing method, for example, the synthetic method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 can be referred to.

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

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

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

The material used for the electron transport layer or the electron injection layer is a compound composed of an aromatic ring or a complex aromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus. It preferably contains at least one selected from a pyrrole derivative, a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, fused ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives typified by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , Kinone derivatives such as anthraquinone and diphenoquinone, phosphoroxide derivatives, carbazole derivatives and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, flavonol metal complex and benzoquinoline metal complex. These materials may be used alone, but may be mixed with different materials.

Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, and oxadiasols. Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole, etc.), thiazazole derivatives, oxine derivative metal complexes, quinolinol-based metal complexes, quinoxalin derivatives, quinoxalin derivative polymers, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorophenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline Derivatives (2,2'-bis (benzo [h] quinoline-2-yl) -9,9'-spirobifluorene, etc.), imidazole pyridine derivatives, borane derivatives, benzoimidazole derivatives (tris (N-phenylbenzoimidazole-) 2-yl) benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as telpyridine, bipyridine derivatives, telpyridine derivatives (1,3-bis (4'-(2,2': 6'2)) "-Terpyridinyl)) benzene, etc.), naphthylidine derivatives (bis (1-naphthyl) -4- (1,8-naphthylidine-2-yl) phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indol derivatives, phosphoroxide derivatives , Bistylyl derivatives and the like.

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

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

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluorantene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol metals Derivatives are preferred.

<Borane derivative>
The borane derivative is, for example, a compound represented by the following formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.
In the above formula (ETM-1), R ¹¹ and R ¹² each independently contain hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, and optionally substituted nitrogen. At least one of the heterocycle or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, respectively. Yes, X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boron, or an optionally substituted carbazolyl, and n is an independently integer of 0 to 3. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

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

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

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

Specific examples of X ¹ include divalent groups represented by the following formulas (X-1) to (X-9).
(In each formula, ^Ra is an independently alkyl, cycloalkyl or optionally substituted phenyl.)

Specific examples of this borane derivative include the following compounds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Specific examples of this pyridine derivative include the following compounds.

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

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

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

Specific examples of this fluoranthene derivative include the following compounds.

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

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

Further, adjacent groups of R ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring. May be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.

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

As for the description of the substituent and the form of ring formation in the formula (ETM-4), the description of the polycyclic aromatic compound represented by the above formula (1) can be cited.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

R ^{1 to} R ⁴ are independently hydrogen, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 20 carbon atoms, respectively, according to the above formula (ETM-5-1). The explanation in can be quoted.

Specific examples of these anthracene derivatives include the following compounds.

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

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

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

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

The "alkyl" in Ar ² may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferred "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like can be mentioned.

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

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

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

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

Specific examples of this benzofluorene derivative include the following compounds.

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

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

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

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

R ^{1 to} R ³ may be the same or different, hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether, aryl thio ether, aryl, heterocyclic group, It is selected from fused rings formed between halogens, cyanos, aldehydes, carbonyls, carboxyls, aminos, nitros, silyls, and adjacent substituents.

Ar ¹ may be the same or different and is an array or hetero-alien. Ar ² may be the same or different and is aryl or heteroaryl. However, at least one of Ar ¹ and Ar ² has a substituent or forms a fused ring with an adjacent substituent. n is an integer from 0 to 3, and when n is 0, the unsaturated structure portion does not exist, and when n is 3, R ¹ does not exist.

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

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

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

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

Further, the cycloalkenyl indicates, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as cyclopentenyl, cyclopentadienyl, cyclohexene, etc., which may be substituted or substituted.

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

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

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

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

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

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

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

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

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

Aldehydes, carbonyls, and aminos can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

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

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

The fused rings formed between the adjacent substituents are, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , and Ar ¹ . It is a conjugated or non-conjugated fused ring formed between Ar ^{2 and the} like. Here, when n is 1, may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These fused rings may contain nitrogen, oxygen, and sulfur atoms in the ring structure, or may be condensed with another ring.

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

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

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

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

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

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

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

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

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

Specific examples of this pyrimidine derivative include the following compounds.

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

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

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

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

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

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

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

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

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

Specific examples of this carbazole derivative include the following compounds.

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

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/015601.

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

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

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

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

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

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

Specific examples of this triazine derivative include the following compounds.

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

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

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

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

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the explanation in the above formula (ETM-2-1) or the formula (ETM-2-2) can be quoted. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but when these are replaced with benzoimidazole-based substituents, both are used. The pyridine-based Substituent in the above may be replaced with a benzoimidazole-based Substituent (that is, n = 2), or any one of the pyridine-based Substituents may be replaced with a benzoimidazole-based Substituent and the other pyridine-based Substituent may be replaced with R ¹¹ It may be replaced with ~ R ¹⁸ (that is, n = 1). Further, for example, at least one of R ^{11 to} R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole-based substituent, and the “pyridine-based substituent” may be replaced with R ^{11 to} R ¹⁸ .

Specific examples of this benzoimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (10-). Naphthalene-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalene-2-yl) anthracene-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4) -(10- (Naphthalene-2-yl) anthracene-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalen-2-yl)) Anthracene-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalene-2-yl) anthracene-2-yl) phenyl) -2- Examples thereof include phenyl-1H-benzo [d] imidazole and 5- (9,10-di (naphthalene-2-yl) anthracene-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Φ of each formula is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4 The "thiazole-based substituent" and "benzothiazole-based substituent" are the "pyridine-based" in the above formulas (ETM-2), (ETM-2-1) and (ETM-2-2). The pyridyl group in the "substituent" is a substituent in which the following thiazole group or benzothiazole group is replaced, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with dehydrogen.

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

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

The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances are used as long as they have a certain reducing property. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali. From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2.95 eV). Examples thereof include alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) and Ba (2.52 eV), and a substance having a work function of 2.9 eV or less is particularly preferable. Of these, the more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more kinds of alkali metals is also preferable, and in particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be improved.

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

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

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

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

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

Next, as an example of a method for producing an organic EL device, an organic EL device composed of an anode / a hole injection layer / a hole transport layer / a light emitting layer composed of a host material and a dopant material / an electron transport layer / an electron injection layer / a cathode. The manufacturing method of the above will be described. A thin film of an anode material is formed on an appropriate substrate by a vapor deposition method or the like to prepare an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited on this to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like. By forming it into a cathode, the desired organic EL element can be obtained. In the above-mentioned production of the organic EL device, it is also possible to reverse the production order and manufacture the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. Is.

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

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

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

In the matrix, pixels for display are arranged two-dimensionally in a grid pattern or a mosaic pattern, and characters and images are displayed as a set of pixels. The shape and size of the pixels are determined by the application. For example, for displaying images and characters on a personal computer, monitor, or television, quadrangular pixels with a side of 300 μm or less are usually used, and in the case of a large display such as a display panel, pixels with a side on the order of mm should be used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. Then, as the driving method of this matrix, either a line sequential driving method or an active matrix may be used. Line sequential drive has the advantage of a simpler structure, but when considering operating characteristics, the active matrix may be superior, so it is also necessary to use it properly depending on the application.

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

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

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

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

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

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

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

Synthesis example (1)
Compound of formula (1-1): Synthesis of 5-phenyl-0- (pyrene-1-yl) -5,9-dihydro-5,9-diaza-13b-boranaft [3,2,1-de] anthracene

<Synthesis of N-Phenylpyrene-1-amine>
A flask containing aniline (3.3 g), 1-bromopyrene (10.0 g), Pd-132 (Johnson Matthey) (0.25 g), NaOtBu (5.1 g) and xylene (70 ml) under a nitrogen atmosphere. It was heated and heated at 120 ° C. for 30 minutes. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. Next, the product was purified by silica gel column chromatography (eluent: toluene) and reprecipitated with ethyl acetate and heptane to obtain 9.8 g (yield: 93%) of N-phenylpyrene-1-amine.

<Synthesis of 2-chloro-N ¹ , N ¹ , N ³ -triphenyl-N ^3- (pyrene-1-yl) benzene-1,3-diamine>
Under nitrogen atmosphere, N-phenylpyrene-1-amine (9.8 g), 2,3-dichloro-N, N-diphenylaniline (11.0 g), Pd-132 (Johnson Massey) (0.25 g), A flask containing NaOtBu (5.0 g) and xylene (80 ml) was heated and heated at 120 ° C. for 90 minutes. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. Next, the product was purified by silica gel column chromatography (eluent: toluene), reprecipitated with ethyl acetate and heptane, and 2-chloro-N ¹ , N ¹ , N ³ -triphenyl-N ^3- (pyrene-). 16.7 g (yield: 83%) of 1-yl) benzene-1,3-diamine was obtained.

<Synthesis of compound of formula (1-1)>
2-Chloro-N ¹ , N ¹ , N ³ -triphenyl-N ^3- (pyrene-1-yl) benzene-1,3-diamine (16.5 g) and t-butylbenzene (120 ml) under a nitrogen atmosphere The flask containing the above was cooled to 0 ° C., and a 1.62 M t-butyllithium hexane solution (35.7 ml) was added dropwise. After completion of the dropping, the temperature was raised to 60 ° C. and the mixture was stirred for 30 minutes. Then, the reaction solution was depressurized to distill off low boiling point components, cooled to −50 ° C., and boron tribromide (14.5 g) was added. After raising the temperature to room temperature and stirring for 0.5 hour, the mixture was cooled to 0 ° C., N-ethyl-N-isopropylpropan-2-amine (7.5 g) was added, and the mixture was heated and stirred at 100 ° C. for 1 hour. The reaction mixture was cooled to room temperature, an aqueous sodium acetate solution was added to stop the reaction, and ethyl acetate was added to separate the solutions. The organic layer was reprecipitated in a silica gel short pass column, then silica gel column chromatography (developing solution: heptane / hot toluene = 7: 3, then hot toluene only), and further in chlorobenzene, and the compound of formula (1-1) was formed. (1.13 g) was obtained.

The structure of compound (1-1) obtained by NMR measurement was confirmed.
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 9.04 (s, 2H), 8.47 (d, 1H), 8,28 (d, 1H), 8.24 (s, 2H), 8 .17 (d, 1H), 8.0s (m, 2H), 7.91 (d, 1H), 7.71 (t, 2H), 7.64 (d, 1H), 7.60 (t, 1H), 7.48 (t, 1H), 7.43 (d, 2H), 7.32 (t, 1H), 7.27 (m, 2H), 7.11 (t, 1H), 6. 81 (d, 1H), 6.52 (m, 1H), 6.14 (d, 1H), 5.89 (d, 1H).

The glass transition temperature (Tg) of the compound of the formula (1-1) was 171.9 ° C.
[Measuring equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Heating rate 10 ° C / Min.]

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

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

The organic EL devices according to Example 1 and Comparative Example 1 were produced, and the voltage (V), emission wavelength (nm), CIE chromaticity (x, y), and external quantum efficiency, which are the characteristics at the time of emitting 1000 cd / m ² , respectively. (%), The device life was measured.

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

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

When the organic EL element is driven, it deteriorates over time and the emission brightness decreases. LT97, 95, 90 represent the time required for the brightness to decrease to 97, 95, 90%, respectively, when the initial brightness is 100 (%). The larger this value is, the higher the durability of the element is and the longer the life is.

The material composition of each layer and the EL characteristic data in the produced organic EL device according to Example 1 and Comparative Example 1 are shown in Tables 1 and 2 below.

In Table 1, "HI" (hole injection layer material) is N ⁴ , N ^4' -diphenyl-N ⁴ , N ^4' -bis (9-phenyl-9H-carbazole-3-yl)-[1,1 '-Biphenyl] -4,4'-diamine, "HAT-CN" (hole injection layer material) is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, "HT -1 ”(hole transport layer material) is N- ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole-3-) Il) phenyl) -9H-fluoren-2-amine, and "HT-2" (hole transport layer material) is N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl. )-[1,1': 4', 1 "-terphenyl] -4-amine, and "ET-1" (electron transport layer material) is 4,6,8,10-tetraphenyl [1,4 ] Benoxabolinino [2,3,4-kl] phenoxabolinine, "ET-2" (electron transport layer material) is 3,3'-((2-phenylanthracene-9,10-diyl)) Bis (4,1-phenylene)) Bis (4-methylpyridine). In addition, "Host-1" is 2- (10-phenylanthracene-9-yl) naphtho [2,3-b] benzofuran, and "Dopant-1" (comparative dopant material) is 5,9-diphenyl-5. , 9-dihydro-5,9-diaza-13b-boranaft [3,2,1-de] anthracene. The chemical structure is shown below together with "Liq".

<Example 1>
<Device using compound (1-1) as a dopant>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by polishing ITO formed to a thickness of 180 nm by sputtering to 120 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI (hole injection layer material), HAT-CN (hole injection layer material) ), Molybdenum vapor deposition boat containing HT-1 (hole transport layer material), molybdenum vapor deposition boat containing HT-2 (hole transport layer material), compound ( Molybdenum vapor deposition boat containing Host-1) (host material), molybdenum vapor deposition boat containing compound (1-1) (dampron material), molybdenum containing ET-1 (electron transport layer material) Deposition boat, molybdenum vapor deposition boat containing ET-2 (electron transport layer material), aluminum nitride vapor deposition boat containing Liq, aluminum nitride boat containing LiF and aluminum nitride vapor deposition containing aluminum I installed a boat.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa, and first, a thin-film deposition boat containing HI was heated and vapor-deposited to a film thickness of 40 nm to form a hole injection layer 1. Next, the vapor deposition boat containing HAT-CN was heated and vapor-deposited to a film thickness of 5 nm to form the hole injection layer 2. Next, the vapor deposition boat containing HT-1 was heated and vapor-deposited to a film thickness of 45 nm to form the hole transport layer 1. Next, the vapor deposition boat containing HT-2 was heated and vapor-deposited to a film thickness of 10 nm to form the hole transport layer 2. Next, the vapor deposition boat containing the compound (Host-1) and the vapor deposition boat containing the compound (1-1) were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form a light emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (Host-1) to the compound (1-1) was about 98: 2. Next, the vapor deposition boat containing ET-1 was heated and vapor-deposited to a film thickness of 5 nm to form the electron transport layer 1. Next, the vapor deposition boat containing ET-2 and the vapor deposition boat containing Liq were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form an electron transport layer 2. The deposition rate was adjusted so that the weight ratio of ET-2 and Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / sec.

Then, the thin-film deposition boat containing LiF is heated to deposit at a vapor deposition rate of 0.01 to 0.1 nm / sec so that the film thickness is 1 nm, and then the thin-film deposition boat containing aluminum is heated to form a film. A cathode was formed by vapor deposition at a vapor deposition rate of 0.2 nm / sec so as to have a thickness of 100 nm to obtain an organic EL element.

A DC voltage was applied with the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of 1000 cd / m ² emission were measured. The wavelength was 458 nm, and the CIE chromaticity (x, y) = (0.137, 0.071). Blue emission was obtained. The drive voltage was 3.7 V, and the external quantum efficiency was 7.3%. The device life was 33 hours for LT97, 75 hours for LT95, and 250 hours for LT90.

<Comparative example 1>
The materials shown in Table 1 were selected as the material for each layer, and an organic EL device was obtained by a method according to Example 1. In addition, the organic EL characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2, and the life was about twice as long when the compound of the present invention was used.

The structure of the luminescent material was designed using DFT calculation. After structural optimization of the ground state was performed using the PBE0 / 6-31G (d) method, the vertical excitation energy from the ground state was calculated using the Time-dependent DFT method. All calculations were performed using the quantum chemistry calculation program Firefly (A.A. Granovsky, Firefly version 8).

The polyaromatic by connecting a plurality of aromatic rings with a boron atom and a nitrogen atom, the compounds of the present invention triplet excitation energy (E _T) is made to have a low pyrene ring, the following comparative examples (cal-Ref .) and have a low triplet excitation energy (E _T) as compared to verify that the transition energy associated with light emission (E _S) is comparable. Incidentally, E _T = 2.69 in the comparative example (cal-Ref.), Was E _S = 3.20.

<Calculation Example>
The calculation of the following structure was carried out.

<Calculation Example 1>
Compound (1-30) is, E _T = 1.98, was E _S = 3.17. Comparative Example (cal-Ref.) From E _T is lower, E _S was comparable.

<Calculation Example 2>
Compound (1-244) is, E _T = 1.99, was E _S = 3.19. Comparative Example (cal-Ref.) From E _T is lower, E _S was comparable.

The present invention provides novel polycyclic aromatic compounds. By using a light emitting layer formed by combining the polycyclic aromatic compound of the present invention and an anthracene-based compound capable of obtaining optimum light emitting characteristics in combination with the polycyclic aromatic compound, the light extraction efficiency at the time of producing a product is high and the life is long. Organic EL element can be provided.

100 Organic electroluminescent device 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims (13)

A polycyclic aromatic compound represented by the formula (1).
(In equation (1),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these. May be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R ^{1 to} R ¹¹ are bonded to each other to form an aryl ring or a heteroaryl ring together with an a ring, a b ring or a c ring. At least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy. , At least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
R ¹² and R ¹³ are aryl, heteroaryl, alkyl or cycloalkyl, in which at least one hydrogen may be substituted with aryl, alkyl or cycloalkyl, which may be substituted with alkyl.
In the structure represented by the formula (1), any one of hydrogen, R ¹² and R ¹³ contained in R ² is replaced with pyrenyl, which may be substituted with alkyl or cycloalkyl.
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium or halogen. ) Any one of R ² , R ¹² and R ¹³ is pyrenyl which may be substituted with alkyl or cycloalkyl, and at least one hydrogen in the pyrenyl is an alkyl having 1 to 6 carbon atoms or an alkyl having 3 to 10 carbon atoms. May be substituted with cycloalkyl
R ^{1 to} R ¹¹ are independently hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms, and at least one hydrogen in these is carbon. It may be substituted with an aryl of number 6 to 12, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 10 carbon atoms.
The polycyclic aromatic compound according to claim 1. The polycyclic aromatic compound according to claim 2, which is represented by the formula (2).
(In equation (2),
Any one of R ² and R ¹³ is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms.
R ⁶ and R ⁹ are independently hydrogen, aryl with 6 to 12 carbon atoms, alkyl with 1 to 10 carbon atoms or cycloalkyl with 3 to 10 carbon atoms, and at least one hydrogen in these is carbon number. It may be substituted with 6-12 aryls, 1-10 carbons alkyl or 3-10 carbons cycloalkyls.
When R ¹³ is a pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ² is hydrogen, an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. It is a cycloalkyl, in which at least one hydrogen may be substituted with an aryl having 6 to 12 carbon atoms, an alkyl having 1 to 10 carbon atoms or a cycloalkyl having 3 to 10 carbon atoms.
When R ² is pyrenyl which may be substituted with an alkyl having 1 to 10 carbon atoms, R ¹³ is a partial structure (R-13).
R ¹²⁹ and R ¹³⁹ are independently hydrogen, an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 10 carbon atoms, an alkyl having 1 to 10 carbon atoms, or an alkyl having 3 to 10 carbon atoms. Cycloalkyl,
At least one hydrogen in the compound represented by the formula (2) may be substituted with deuterium or halogen. ) R ¹³ is an unsubstituted 1-pyrenyl,
R ² , R ⁶ , R ⁹ , R ¹²⁹ , and R ¹³⁹ are independently hydrogen or alkyl having 1 to 6 carbon atoms, respectively.
The polycyclic aromatic compound according to claim 3. The polycyclic aromatic compound according to claim 4, which has a structure represented by the formula (1-1).
A material for an organic device containing the polycyclic aromatic compound according to any one of claims 1 to 5. An organic electroluminescent device having a pair of electrodes composed of an anode and a cathode and a light emitting layer arranged between the pair of electrodes.
The light emitting layer is an organic electroluminescent element containing the polycyclic aromatic compound according to any one of claims 1 to 5 and the anthracene compound represented by the formula (5).
(In equation (5),
X is a group independently represented by the formula (5-X1), the formula (5-X2) or the formula (5-X3), and the naphthylene moiety in the formula (5-X1) and the formula (5-X2). May be condensed with one benzene ring, and the group represented by the formula (5-X1), the formula (5-X2) or the formula (5-X3) is bonded to the anthracene ring of the formula (5) in *. However, the two Xs cannot be the groups represented by the formula (5-X3) at the same time, and Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, and biphenylyl. , Terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the formula (6), in which both Ar ¹ and Ar ³ are phenyl. Instead, at least one hydrogen in Ar ³ may be further substituted with phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, chrysenyl, triphenylenyl, pyrenyl, or a group represented by the above formula (6). ,
Ar ⁴ is a silyl that is independently substituted with hydrogen, phenyl, biphenylyl, turphenyl, naphthyl, or an alkyl having 1 to 4 carbon atoms.
At least one hydrogen in the compound represented by the formula (5) may be substituted with deuterium or a group represented by the formula (6).
In formula (6), Y is -O-, -S- or> N-R ²⁹ , and R ^{21 to} R ²⁸ are independently hydrogen, optionally substituted alkyl, and optionally substituted, respectively. Aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, optionally substituted amino, halogen, It is hydroxy or cyano, and adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, and R ²⁹ may be hydrogen or substituted. Aryl, the group represented by the formula (6) is a naphthalene ring of the formula (5-X1) or the formula (5-X2) in *, a single bond of the formula (5-X3), of the formula (5-X3). It binds to Ar ³ and replaces at least one hydrogen in the compound represented by the formula (5), and binds to them at any position in the structure of the formula (6). ) The naphthalene moieties in formulas (5-X1) and (5-X2) are not condensed with a single benzene ring and are not condensed.
Ar ⁴ is independently hydrogen, phenyl, or naphthyl,
The group represented by the formula (6) is not included other than X.
The organic electroluminescent device according to claim 7, wherein the group represented by the formula (6) is a group represented by any of the formulas (6-1) to (6-11).
(In formulas (6-1) to (6-11), Y is -O-, -S- or> N-R ²⁹ , R ²⁹ is hydrogen or aryl, and formulas (6-1) to At least one hydrogen in the group represented by the formula (6-11) is alkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, diaryl substituted amino, diheteroaryl substituted amino, aryl heteroaryl substituted amino. , Halogen, hydroxy or cyano may be substituted, and the groups represented by the formulas (6-1) to (6-11) are naphthalene of the formula (5-X1) or the formula (5-X2) in *. Ring, single bond of formula (5-X3), bond with Ar ^{3 of} formula (5-X3), and bond with these at any position in the structures of formulas (6-1) to (6-11) To do.) Ar ¹ , Ar ² and Ar ³ are independently hydrogen (excluding Ar ³ ), phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, fluorenyl, or formulas (6-1) to (6-4). At least one hydrogen in Ar ³ is further represented by phenyl, naphthyl, phenanthryl, fluorenyl, or any of formulas (6-1) to (6-4). May be replaced with a group
The organic electroluminescent device according to claim 8. It has an electron transporting layer and / or an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, a fluorentene derivative, or BO. Claimed to contain at least one selected from the group consisting of system derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol metal complexes. Item 2. The organic electric field light emitting element according to any one of Items 7 to 9. The electron transporting layer and / or electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, and an alkaline earth metal. Claim that it contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. 10. The organic electric field light emitting element according to 10. A display device including the organic electroluminescent device according to any one of claims 7 to 11. A lighting device including the organic electroluminescent element according to any one of claims 7 to 11.