JP7187152B2 - Compound, material for organic electroluminescence device, composition for organic electroluminescence device, organic electroluminescence device, and method for producing compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a compound, a material for an organic electroluminescence device, a composition for an organic electroluminescence device, an organic electroluminescence device, and a method for producing a compound.

2. Description of the Related Art In recent years, there has been active development of display devices and lighting equipment using organic electroluminescence devices, which are self-luminous light emitting devices. An organic electroluminescence device (hereinafter sometimes referred to as an organic electroluminescence device or an organic EL device) has an organic layer containing a light-emitting material. Within the organic layers of the organic EL device, recombination of electrons and holes excites the light-emitting material, causing light emission as the light-emitting material returns to its ground state.

In such an organic EL device, various materials for forming the organic layer have been developed for the purpose of improving device characteristics such as current efficiency and luminous life. For example, Patent Documents 1 to 3 disclose organic electroluminescence devices using a bicarbazole compound.

Further, in the manufacture of organic EL elements, it is common to form an organic film constituting an organic EL element by a dry film forming method such as a vapor deposition method. On the other hand, film formation by a dry film formation method such as a vapor deposition method is time-consuming and costly. The use of a wet film formation method such as a

Japanese Patent Application Laid-Open No. 2008-135498 JP 2016-111346 U.S. Publication No. 2017/0092873

However, when the organic EL element is formed by a wet film forming method such as a solution coating method, the organic EL material used in the vapor deposition is often difficult to dissolve in the coating solvent, and there is no problem with dissolution. However, the thin film produced by the wet method is more susceptible to aggregation of organic molecules than the thin film produced by the vapor deposition method. There is a possibility that energy levels such as HOMO, LUMO, S1, and T1, which are different from those in the monomolecular state, may be formed due to the aggregation of multiple organic molecules and the expansion of the molecular orbital compared to that of the monomolecular state. be. And they are highly likely to cause adverse effects such as carrier trapping and emission exciton deactivation. Therefore, the organic EL element formed by the coating method does not have sufficient current efficiency and luminous life.

An object of the present invention is to provide a compound that can be used to produce an organic electroluminescence device with excellent current efficiency and luminous life by a coating method, a method for producing the same, and an intermediate useful for synthesizing a 3,5,9-substituted carbazole. to provide.

In order to solve the above problems, one embodiment of the present invention provides a compound represented by General Formula (1) below.

（上記一般式（１）中、Ｅ及びＲ_１は、それぞれ独立して、水素原子、重水素原子、フッ素原子、シアノ基、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｅ及びＲ_１のうち少なくとも一つは、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｇは、水素原子、重水素原子、フッ素原子、シアノ基、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｒ_２は、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ａ_１～Ａ_４は、それぞれ独立して、水素原子、重水素原子、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ａ_１、Ａ_２のいずれか１つ、および／または、Ａ_３、Ａ_４のいずれか１つが置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｌは、単結合、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
ｎは、０または１の整数であり、
ｎが０のとき、Ｅは水素原子または重水素原子である。）

(In general formula (1) above, E and R ₁ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms. a cyclic group or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
At least one of E and R ₁ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms is a cyclic group;
G is a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 to 30 is an aromatic heterocyclic group,
R ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
A ₁ to A ₄ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom is an aromatic heterocyclic group having a number of 3 to 30,
Any one of A ₁ and A ₂ and/or any one of A ₃ and A ₄ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or an unsubstituted aromatic heterocyclic group having 3 to 30 ring-forming atoms,
L is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
n is an integer of 0 or 1;
When n is 0, E is a hydrogen atom or a deuterium atom. )

According to one aspect of the present invention, a compound capable of producing an organic electroluminescence device having excellent current efficiency and luminescence lifetime by a coating method, a method for producing the same, and a compound useful for synthesizing a 3,5,9-substituted carbazole Provide an intermediate.

1 is a schematic diagram showing an organic electroluminescence device according to an embodiment; FIG.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the present invention is not limited only to the following embodiments.

<Compound>
The compound according to this embodiment is a compound represented by the following general formula (1).

（上記一般式（１）中、Ｅ及びＲ_１は、それぞれ独立して、水素原子、重水素原子、フッ素原子、シアノ基、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｅ及びＲ_１のうち少なくとも一つは、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｇは、水素原子、重水素原子、フッ素原子、シアノ基、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｒ_２は、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ａ_１～Ａ_４は、それぞれ独立して、水素原子、重水素原子、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ａ_１、Ａ_２のいずれか１つ、および／または、Ａ_３、Ａ_４のいずれか１つが置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
Ｌは、単結合、置換されたもしくは無置換の炭素数６～３０の芳香族炭化水素環基、または置換されたもしくは無置換の環形成原子数３～３０の芳香族複素環基であり、
ｎは、０または１の整数であり、
ｎが０のとき、Ｅは水素原子または重水素原子である。）
本実施形態に係る化合物は、上記一般式（１）で表されるように、二つのカルバゾール環（カルバゾール骨格ともという）がｎ個のＬを介して結合されて構成されている。

(In general formula (1) above, E and R ₁ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms. a cyclic group or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
At least one of E and R ₁ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms is a cyclic group;
G is a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 to 30 is an aromatic heterocyclic group,
R ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
A ₁ to A ₄ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom is an aromatic heterocyclic group having a number of 3 to 30,
Any one of A ₁ and A ₂ and/or any one of A ₃ and A ₄ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or an unsubstituted aromatic heterocyclic group having 3 to 30 ring-forming atoms,
L is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms,
n is an integer of 0 or 1;
When n is 0, E is a hydrogen atom or a deuterium atom. )
The compound according to the present embodiment is composed of two carbazole rings (also referred to as carbazole skeletons) bonded via n Ls, as represented by the general formula (1).

In the above general formula (1), E and R ₁ each independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms. or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, more preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms.

In the present specification and claims, "X and Y are each independently" means that X and Y may be the same or different.

As used herein and in the claims, "substituted or unsubstituted" means that other substituents may be present in addition to hydrogen and deuterium atoms. Moreover, these substituents may combine with each other to form a ring.

In addition, in the present specification and claims, "hydrogen atom" is a concept including "deuterium atom" even if there is no special description of "deuterium atom". A hydrogen atom present in each group may optionally be substituted with a deuterium atom.

In addition, in the present specification and claims, "A to B" means the range from A to B including A and B.

E is bonded to one of the two carbazole rings in general formula (1).

The aromatic hydrocarbon ring group having 6 to 30 carbon atoms that can constitute E is a hydrocarbon ring having a carbocyclic ring containing one or more aromatic rings having 6 to 30 carbon atoms (aromatic hydrocarbon ring) derived from is the base. Moreover, when the aromatic hydrocarbon ring group contains two or more rings, the two or more rings may be condensed with each other. In addition, one or more hydrogen atoms present in these aromatic hydrocarbon ring groups may be substituted with a substituent.

The aromatic hydrocarbon ring constituting the aromatic hydrocarbon ring group is not particularly limited, but specific examples include benzene, pentalene, indene, naphthalene, anthracene, azulene, heptalene, acenaphthalene, phenalene, fluorene, phenanthrene, triphenylene, pyrene, chrysene, picene, perylene, pentaphene, pentacene, tetraphene, hexaphene, hexacene, rubicene, trinaphthylene, heptaphene, pyrantrene and the like.

An aromatic heterocyclic group having 3 to 30 ring-forming atoms that can constitute E is one or more heteroatoms (e.g., nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom ( S)) and is derived from a ring (aromatic heterocyclic ring) having 3 to 30 ring atoms containing one or more aromatic rings in which the remaining ring atoms are carbon atoms (C). Also, when the aromatic heterocyclic group contains two or more rings, the two or more rings may be fused together. In addition, one or more hydrogen atoms present in these aromatic heterocyclic groups may be substituted with a substituent.

Here, the number of ring-forming atoms refers to the number of atoms constituting the ring itself in a compound having a structure in which atoms are cyclically bonded (eg, single ring, condensed ring, ring assembly). Atoms that do not constitute a ring (for example, a hydrogen atom that terminates a bond of an atom that constitutes a ring), and when the ring is substituted with a substituent, the atoms contained in the substituent are not included in the number of ring-forming atoms. For example, a carbazolyl group has 13 ring atoms.

The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, but specifically,
pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline,
Quinoxaline, quinazoline, naphthyridine, acridine, phenazine, benzoquinoline, benzoisoquinoline, phenanthridine, phenanthroline, benzoquinone, coumarin, anthraquinone, fluorenone, furan, thiophene, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, pyrrole, indole, carbazole, imidazole, benzimidazole, pyrazole, indazole, oxazole, isoxazole, benzoxazole, benzisoxazole, thiazole, isothiazole, benzothiazole, benzisothiazole, imidazolinone, benzimidazolinone, imidazopyridine, imidazopyrimidine, imidazophenanthridine , benzimidazophenanthridine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene xanthone, thioxanthone and the like.

In addition, other substituents in E are not particularly limited, but examples include a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted amino group having 1 to 30 carbon atoms, cyano group, substituted or unsubstituted 6 carbon atoms to 30 aromatic hydrocarbon ring groups, or substituted or unsubstituted aromatic heterocyclic groups having 3 to 30 ring atoms.

In E, the alkyl group having 1 to 30 carbon atoms that can constitute another substituent is not particularly limited, but is, for example, a linear or branched alkyl group having 1 to 30 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4- dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2 -methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1- methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n- Heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like can be mentioned. Among these, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred.

In E, the alkoxy group having 1 to 30 carbon atoms that can constitute another substituent is not particularly limited, but is, for example, a linear or branched alkoxy group having 1 to 30 carbon atoms. Specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentyloxy group and the like. Among these, linear or branched alkoxy groups having 1 to 8 carbon atoms are preferred.

In E, the aryloxy group having 6 to 30 carbon atoms which may constitute other substituents is not particularly limited, but for example, a monocyclic or condensed polycyclic aryloxy group having 6 to 30 carbon atoms which may contain a heteroatom. is the base. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-azulenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group and the like.

In E, the amino group having 1 to 30 carbon atoms that can constitute another substituent is not particularly limited, but is, for example, a linear or branched alkylamino group having 1 to 30 carbon atoms. Specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N -tert-butylamino group, N-pentylamino group, N-alkylamino group such as N-hexylamino group, N,N-dimethylamino group, N-methyl-N-ethylamino group, N,N-diethylamino group , N,N-dipropylamino group, N,N-diisopropylamino group, N,N-dibutylamino group, N,N-diisobutylamino group, N,N-dipentylamino group, N,N-dihexylamino group, etc. of N,N-dialkylamino groups.

In E, an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 3 to 30 ring atoms that may constitute other substituents are aromatic hydrocarbon ring groups that may constitute E. , is the same definition as the aromatic heterocyclic group, so the description is omitted.

In addition, R ₁ is bonded at the ortho position to one carbazole ring in the phenyl group bonded to the nitrogen atom of one carbazole ring (the carbazole ring located on the left side of general formula (1) above). The aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute R ₁ have the same definitions as the aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute E described above. omitted.

G is a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 to 30 aromatic heterocyclic group, preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic group having 3 to 30 ring atoms It is a heterocyclic group, more preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms.

G is bonded to one carbazole ring of the two carbazole rings in general formula (1) at the ortho position to E. The substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms that can constitute G is Since the definitions are the same as those of the aromatic hydrocarbon ring group and the aromatic heterocyclic group that can constitute E, the explanation is omitted.

In general formula (1) above, R ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted It is an aromatic heterocyclic group. R ₂ is bonded to the other carbazole ring (the carbazole ring located on the right side of general formula (1) above). The aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute R ₂ have the same definitions as the aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute E described above. omitted.

In the above general formula (1), A ₁ to A ₄ each independently represent a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or It is a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms.

Among A ₁ to A ₄ , A ₁ and A ₂ are bonded to a phenyl group bonded to the nitrogen atom of one carbazole ring, and A ₃ and A ₄ are phenyl groups bonded to the nitrogen atom of the other carbazole ring. is bound to The hydrogen atom, deuterium atom, aromatic hydrocarbon ring group, and aromatic heterocyclic group that can constitute A ₁ to A ₄ are the hydrogen atom, deuterium atom, and aromatic hydrocarbon that can constitute E above. Since the definition is the same as that of the cyclic group and the aromatic heterocyclic group, the explanation is omitted.

Further, in the above general formula (1), L is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 to 30 aromatic heterocyclic groups. The aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute L have the same definitions as the aromatic hydrocarbon ring group and aromatic heterocyclic group that can constitute E described above. omitted.

Here, when L is a single bond, it indicates that two carbazole skeletons in general formula (1) are directly bonded. Further, when L is the above aromatic hydrocarbon ring group or aromatic heterocyclic group, the two carbazole skeletons in the general formula (1) are the above aromatic hydrocarbon ring groups or aromatic heterocyclic groups. indicates that it is bound via

In the general formula (1), n is an integer of 0 or 1. When n is 0, it indicates that L is a single bond (the two carbazole skeletons in general formula (1) are directly bonded). When n is 1, it means that L is the above aromatic hydrocarbon ring group or aromatic heterocyclic group.

Moreover, when n is 0, the above E is a hydrogen atom or a deuterium atom. That is, when n is 0, E is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic ring having 3 to 30 ring atoms not the base.

In the compound represented by the above general formula (1), the portion indicated by the dotted line in the following general formula (1) of the two carbazole skeletons (hereinafter referred to as bicarbazole plane) has a HOMO (Highest Occupied Molecular Orbital). part is distributed. Moreover, in the compound represented by the general formula (1), E, R ₁ and R ₂ are arranged around the bicarbazole plane. Accordingly, in the compound represented by the above general formula (1), the bicarbazole plane on which the HOMO is distributed can be inhibited from interacting with similar or different molecules present in the surroundings.

Therefore, the compound according to the present embodiment has high solubility (solubility) in solvents. In addition, the compound according to the present embodiment can suppress degradation of film quality due to aggregation of organic molecules when forming a film of an organic EL element by a wet film forming method. Specifically, the aggregation of a plurality of organic molecules expands the molecular orbital compared to that of the monomolecular state, and the energy levels such as HOMO, LUMO, S1, and T1 that are different from those of the monomolecular state are generated. may form. These energy levels are likely to cause adverse effects such as carrier trapping and exciton deactivation. Therefore, even when an organic electroluminescence device is produced by a solution coating method (hereinafter referred to as a coating method), the compound according to the present embodiment suppresses aggregation and improves the performance of the organic electroluminescence device (e.g., hole transportability). can be maintained.

Further, in the compound according to the present embodiment, in the general formula (1), any one of A ₁ and A ₂ and/or any one of A ₃ and A ₄ is substituted or unsubstituted It is an aromatic hydrocarbon ring group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms. That is, one or more substituents selected from A ₁ and A ₂ or A ₃ and A ₄ are substituted or unsubstituted aromatic hydrocarbons having 6 to 30 carbon atoms It is a cyclic group or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms.

Thus, any one of A ₁ and A ₂ and/or any one of A ₃ and A ₄ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, Or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring-forming atoms can increase the exciton stability (photochemical stability) of the compound and has an excellent emission lifetime organic electroluminescence. element can be provided.

Further, any one of A ₁ and A ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, and any one of A ₃ and A ₄ is a substituted Alternatively, an unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms is preferable in that the exciton stability (photochemical stability) of the compound can be further enhanced.

Further, in the compound according to the present embodiment, in the general formula (1), when n = 0, E is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted is not a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms. High solubility can be maintained by becoming such an aspect.

When n = 0, E is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic ring having 3 to 30 ring atoms It is considered that the reason why the solubility is lowered when it is a group is that G and _R2 interact with each other in the molecule. On the other hand, when n=1, no decrease in solubility is observed. Therefore, it is considered necessary to limit the selection of E from the viewpoint of solubility only when n=0.

Thus, when R ₁ and R ₂ are the above-mentioned aromatic hydrocarbon ring groups or aromatic heterocyclic groups, it is possible to further suppress the interaction of the same or different molecules with the bicarbazole plane on which HOMO is distributed. can. This makes it possible to improve the performance (for example, hole transport properties) of the organic electroluminescence element produced by the coating method. As a result, it is possible to provide an organic electroluminescence device that is more excellent in current efficiency and luminous life.

In addition, when G is the above-described aromatic hydrocarbon ring group or aromatic heterocyclic group, the HOMO is extended by the π conjugation effect while suppressing the decrease in the lowest excited triplet energy (also referred to as T1 energy). be done. Therefore, the hole stability of the compound represented by the general formula (1) can be increased, or the photochemical stability can be increased, and as a result, the organic electroluminescence is more excellent in luminous efficiency and luminous life. element can be provided.

Further, in the compound according to the present embodiment, L in the general formula (1) is preferably a single bond. That is, it is preferable that two carbazole rings in general formula (1) are directly bonded (n is 0 in general formula (1) above). In this case, in the compound according to this embodiment, two carbazole rings in general formula (1) can form a 3,3'-bicarbazole skeleton.

By constructing the bicarbazole plane with such a 3,3′-Bicarbazole skeleton, a stable HOMO can be constructed in the compound of the general formula (1). Therefore, it is possible to further improve the performance (for example, the hole transport property) of the organic electroluminescence device produced by the coating method. As a result, it is possible to reliably provide an organic electroluminescence device excellent in current efficiency and luminous life.

Further, in the compound according to the present embodiment, L in the general formula (1) is preferably a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms. In this case, in the compound according to this embodiment, two carbazole rings in general formula (1) are bonded at the para position via the aromatic hydrocarbon ring group.

In the compound according to the present embodiment, the structure in which such two carbazole rings are bonded to the para position via the above aromatic hydrocarbon ring group extends the π conjugation length and the bicarbazole plane on which HOMO is distributed. can be widened. This widens the HOMO region in the compound of general formula (1). Therefore, it is possible to further improve the performance (for example, the hole transport property) of the organic electroluminescence device produced by the coating method. As a result, it is possible to reliably provide an organic electroluminescence device excellent in current efficiency and luminous life.

Specific examples of the compound according to this embodiment include compounds 1 to 154 below.

According to the compounds of the present embodiment exemplified by the above general formulas (1-1) to (1-136), even when the organic electroluminescence device is produced by a coating method, the hole transport property is enhanced and the current efficiency is improved. And the light emission lifetime can be improved.

<Method for producing compound>
The method for producing the compound represented by the general formula (1) is not particularly limited, and various production methods including known synthesis methods can be used. However, from the viewpoint of reliably obtaining the compound of general formula (1), the method for producing the compound according to the present embodiment includes a compound represented by the following general formula (2) and a compound represented by the following general formula (3) Including reacting with a compound.

（上記一般式（２）中、Ｘ_１及びＸ_２は、それぞれ独立して、ハロゲン原子である。）

(In general formula (2) above, X ₁ and X ₂ are each independently a halogen atom.)

（上記一般式（３）中、Ｘ_３が、ハロゲン原子である。）

(In general formula (3) above, _X3 is a halogen atom.)

In general formula (2) above, X ₁ and X ₂ each independently represent a halogen atom, but are preferably different halogen atoms. X ₁ and X ₂ are each independently preferably selected from a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom and a bromine atom.

Moreover, in the above general formula (3), _X3 is a halogen atom. Here, a halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an astatine atom.

Preferred reaction forms using the compound represented by the general formula (2) as an intermediate include, for example, aromatic nucleophilic substitution reactions using fluorinated biphenyls (S _N Ar reaction and ipso attack reaction). (Also called), Ullmann reaction using biphenyl iodide, etc., to replace the hydrogen atom of the nitrogen of the carbazole of general formula (2) with an aromatic ring or aromatic heterocycle. .

Conventionally, when different substituents are introduced at the 3-, 5-, and 9-positions of carbazole, it is necessary to accompany the construction of the carbazole ring moiety, and the synthesis steps are long, 4 or more steps. Therefore, when trying to synthesize a compound having different substituents at the 3-, 5-, and 9-positions of carbazole, the steps from the introduction of the first substituent to the introduction of the third substituent The number was long with more than 4 stages. This is disadvantageous, for example, in terms of synthetic labor when attempting to synthesize a large number of compounds in which each of the three substituents is changed for the purpose of research or the like.

In the above general formula (2), when X ₁ = Br and X ₂ = Cl intermediates are used, different substituents are introduced stepwise and regioselectively at the 3-, 5- and 9-positions of carbazole. In this case, it is possible to suppress side reactions and synthesize with high purity or high yield, and the synthesis steps can be shortened. As a result, carbazole compounds having different substituents at the 3-, 5- and 9-positions can be easily synthesized, increased in yield, increased in purity, and reduced in cost.

The compound represented by the general formula (2) has one carbazole ring, X ₁ is bonded to the 3-position carbon atom of the carbazole ring, and X ₂ is bonded to the 5-position carbon atom. . In general formula (2) above, the hydrogen atoms bonded to the carbon atoms of the carbazole ring to which X ₁ and X ₂ are not bonded may be substituted with other substituents.

Other substituents in the compound represented by the general formula (2) are not particularly limited, but examples include a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted amino group having 1 to 30 carbon atoms, cyano group, substituted or unsubstituted aromatic hydrocarbon ring groups having 6 to 30 carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 3 to 30 ring atoms. In addition, deuterium atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, cyano groups, aromatic hydrocarbon ring groups, and aromatic heterocycles that can constitute other substituents in the compound of the general formula (2) The group has the same definition as the deuterium atom, alkyl group, alkoxy group, aryloxy group, amino group, cyano group, aromatic hydrocarbon ring group, and aromatic heterocyclic group that can constitute R ₁ . We omit the explanation here.

Moreover, the compound represented by the general formula (3) is a halogenated biphenyl. The bonding position of _X3 in the benzene ring to which _X3 of the compound represented by general formula (3) is bonded is not particularly limited. However, from the viewpoint of reliably obtaining the compound represented by the above general formula (1), the bonding position of _X3 is preferably the meta-position or para-position with respect to the phenyl group to which _X3 is not bonded. .

In the general formula (3) above, the hydrogen atoms bonded to the carbon atoms of the halogenated biphenyl to which _X3 is not bonded may be substituted with other substituents. Here, the other substituents in the compound represented by the general formula (3) have the same definition as the other substituents in the compound represented by the general formula (2), and thus the description thereof is omitted.

The method for producing a compound according to the present embodiment includes reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), thereby obtaining the general formula (1) The compound represented by can be reliably obtained. Therefore, according to the method for producing a compound according to the present embodiment, it is possible to obtain a compound that can maintain or improve current efficiency and luminous life even when an organic electroluminescence device is produced by a wet coating method.

Further, in the method for producing a compound according to the present embodiment, from the viewpoint of obtaining the compound represented by the general formula (1) more reliably, the compound represented by the following general formula (2) is the following general formula (2- A compound represented by 1) or (2-2) is preferable.

In the compound represented by the general formula (2-1) or (2-2), the halogen atoms constituting X ₁ and X ₂ are each independently a chlorine atom or a bromine atom. Specifically, in the compound represented by the general formula (2-1), X ₁ bonded to the carbon atom at the 3-position of the carbazole ring is composed of a bromine atom, and X ₂ bonded to the carbon atom at the 5-position of the carbazole ring is composed of chlorine atoms. In the compound represented by the general formula (2-2), X ₁ bonded to the carbon atom at the 3-position of the carbazole ring is composed of a chlorine atom, and X ₂ bonded to the carbon atom at the 5-position of the carbazole ring is a bromine atom. consists of

From a different point of view, the compound represented by the general formula (2) can serve as an intermediate (or precursor) for obtaining the compound represented by the general formula (1). Therefore, the compound represented by the above general formula (2) can be reliably obtained as a compound capable of maintaining or improving current efficiency and luminous life even when an organic electroluminescence device is produced by a wet coating method. It is also useful from the point of view.

<Materials for organic electroluminescence elements>
The organic electroluminescence element material (hereinafter referred to as the organic EL element material) according to the present embodiment contains the compound represented by the general formula (1). The compound represented by the general formula (1) exhibits high solubility in a solvent as described above, and suppresses aggregation of molecules to form a thin film of good quality even in a wet coating method. can do. Moreover, the compound represented by the general formula (1) has a high hole-transport property. Therefore, the organic EL device material containing the compound represented by the above general formula (1) can be used, for example, as a material for a hole injection layer, a hole transport layer and a light emitting layer.

As a result, the organic electroluminescence device using the compound represented by the general formula (1) can improve current efficiency and luminous life even when it is produced by a wet coating method. Therefore, the compound represented by the general formula (1) can be used as a material for organic EL devices.

That is, the present embodiment can provide an organic EL device material containing the compound represented by the general formula (1). Therefore, an organic electroluminescence device excellent in current efficiency and luminous life can be produced by a coating method, even from the organic EL device material containing the compound represented by the general formula (1).

<Composition for Organic Electroluminescence Device>
The composition for an organic electroluminescence device (hereinafter referred to as the composition for an organic EL device) according to this embodiment is used, for example, to form each layer of an organic EL device by a solution coating method.

The composition for an organic EL device according to this embodiment contains the compound represented by the general formula (1) and a solvent. Such a composition for an organic EL device can be configured by including the material for an organic EL device according to this embodiment and a solvent.

Although the solvent is not particularly limited, it is preferably capable of dissolving the above organic EL device materials. That is, the composition for organic EL devices is preferably a solution composition. The composition for organic electroluminescence elements of the present embodiment is an example of the composition for electroluminescence elements according to the present invention.

The solvent contained in the composition for an organic EL device is not particularly limited, but examples include toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, propylbenzene, cyclohexylbenzene, dimethylbenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, phenylacetic acid, phenyl propionic acid, methyl benzoate, ethyl benzoate and the like.

The concentration of the organic EL element material in the organic EL element composition is not particularly limited, and can be appropriately adjusted according to the application. However, from the viewpoint of ease of application, etc., the concentration of the compound represented by the general formula (1) in the composition for an organic EL device is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5 mass % to 5 mass %.

<Organic electroluminescence element>
Hereinafter, with reference to FIG. 1, the organic electroluminescence device according to this embodiment will be described in detail. FIG. 1 is a schematic diagram showing an organic electroluminescence device according to this embodiment. In this specification, "organic electroluminescence element" may be abbreviated as "organic EL element".

As shown in FIG. 1, an organic electroluminescence device (organic EL device) 100 according to the present embodiment includes a substrate 110, a first electrode 120 arranged on the substrate 110, and a A hole-injecting layer 130, a hole-transporting layer 140 disposed on the hole-injecting layer 130, a light-emitting layer 150 disposed on the hole-transporting layer 140, and an electron-transporting layer disposed on the light-emitting layer 150. 160 , an electron injection layer 170 disposed on the electron transport layer 160 , and a second electrode 180 disposed on the electron injection layer 170 .

Here, the compound represented by the general formula (1) of the present embodiment is contained in any organic layer arranged between the first electrode 120 and the second electrode 180, for example. Specifically, from the viewpoint of excellent hole transport properties, the compound represented by the general formula (1) is used for the hole injection layer 130 as the hole injection material, the hole transport layer 140 as the hole transport material, and the light emitting layer. It is preferably contained in the light-emitting layer 150 as a material (host), more preferably contained in the hole-transport layer or the light-emitting layer 150 , and still more preferably contained in the light-emitting layer 150 .

Moreover, the organic layer containing the compound represented by the general formula (1) of the present embodiment is formed by a coating method. Specifically, the organic layer containing the compound represented by the general formula (1) is formed by a spin coat method, a casting method, a micro gravure coat method, a gravure coat ) method, bar coat method, roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing A film can be formed using a solution coating method such as a method, a flexographic printing method, an offset printing method, an ink jet printing method, and the like.

Any solvent can be used in the solution coating method as long as it can dissolve the compound represented by the general formula (1). Examples of such solvents include toluene, xylene, ethylbenzene, diethylbenzene, methysilene, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, phenyl acetate, phenyl propionate, and benzoin. Examples include methyl acid and ethyl benzoate. In addition, the amount of the solvent used is not particularly limited, but from the viewpoint of ease of application, etc., the concentration of the compound represented by the general formula (1) is preferably 0.1% by mass to 10% by mass, more preferably 0.5 mass % to 5 mass %.

In addition, the method for forming layers other than the organic layer containing the compound represented by the general formula (1) is not particularly limited. Such layers other than the organic layer may be formed by, for example, a vacuum deposition method or a solution coating method.

The substrate 110 can use a substrate used in general organic EL devices. For example, the substrate 110 may be a glass substrate, a semiconductor substrate such as a silicon substrate, a plastic substrate, or the like.

A first electrode 120 is formed on the substrate 110 . Specifically, the first electrode 120 is an anode, and a metal, an alloy, a conductive compound, or the like having a large work function (minimum energy required to extract one electron from the substance) It is formed. For example, the first electrode 120 is made of indium tin oxide (In ₂ O ₃ —SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ —ZnO), tin oxide (SnO ₂ ), oxide A transmissive electrode may be formed of zinc (ZnO) or the like. Also, the first electrode 120 may be formed as a reflective electrode by laminating magnesium (Mg), aluminum (Al), or the like on the transparent conductive film.

A hole injection layer 130 is formed on the first electrode 120 . The hole injection layer 130 is a layer that facilitates injection of holes from the first electrode 120, and specifically has a thickness of about 10 nm to about 1000 nm, more specifically about 10 nm to about 100 nm. may be formed with

The hole injection layer 130 can be made of known hole injection materials. Examples of known hole injection materials that form the hole injection layer 130 include poly(ether ketone)-containing triphenylamine (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis. (Pentafluorophenyl) borate (4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate: PPBI), N,N′-diphenyl-N,N′-bis-[4-(phenyl-m-tolyl-amino) -phenyl]-biphenyl-4,4'-diamine (N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'- diamine: DNTPD), copper phthalocyanine, 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine: m -MTDATA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine: NPB), 4,4' ,4″-tris(diphenylamino)triphenylamine (4,4′,4″-tris(diphenylamino)triphenylamine: TDATA), 4,4′,4″-tris(N,N-2-naphthylphenylamino) Triphenylamine (4,4′,4″-tris(N,N-2-naphthylphenylamino) triphenylamine: 2-TNATA), polyaniline/dodecylbenzenesulphonic acid, poly(3,4-ethylenediethylene oxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS), and polyaniline/10-camphorsulfate ionic acid) and the like.

A hole transport layer 140 is formed on the hole injection layer 130 . The hole transport layer 140 is a layer having a function of transporting holes, and may be formed with a thickness of approximately 10 nm to 150 nm, for example. The hole transport layer 140 is preferably formed by a solution coating method using the compound of the present embodiment. According to this method, a compound capable of improving the current efficiency and driving life of the organic EL device 100 can be efficiently deposited over a large area.

However, if any other organic layer of the organic EL device 100 contains the compound of the present embodiment, the hole transport layer 140 may be made of a known hole transport material. Examples of known hole transport materials include 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N- Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4 ,4′-diamine (N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine: TPD), 4,4′,4″ -tris(N-carbazolyl)triphenylamine (4,4′,4″-tris(N-carbazolyl)triphenylamine: TCTA) and N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine: NPB) and the like.

A light emitting layer 150 is formed on the hole transport layer 140 . The light-emitting layer 150 is a layer that emits light by fluorescence, phosphorescence, or the like. The light-emitting layer 150 may be formed with a thickness of, for example, about 10 nm to about 60 nm. A known luminescent material can be used as the luminescent material of the luminescent layer 150 . However, the light-emitting material contained in the light-emitting layer 150 is preferably a light-emitting material capable of emitting light from triplet excitons (that is, phosphorescence). In such a case, the current efficiency and luminous life of the organic EL device 100 can be further improved.

Also, the light-emitting layer 150 can be formed by a solution coating method using the organic EL element material according to the present embodiment. In addition, in the present embodiment, the light-emitting layer 150 containing the compound represented by the general formula (1) capable of improving the current efficiency and light-emitting life of the organic EL element 100 is efficiently formed by such a solution coating method. can be deposited over a large area.

However, if any other organic layer of the organic EL element 100 contains the compound represented by the general formula (1) according to this embodiment, the light-emitting layer 150 may be made of a known material.

Among known materials constituting the light-emitting layer 150, examples of host materials include tris(8-quinolinato)aluminum (Alq3), 4,4′-bis(carbazol-9-yl). Biphenyl (4,4′-bis(carbazol-9-yl)biphenyl: CBP), poly(n-vinylcarbazole) (poly(n-vinylcarbazole): PVK), 9,10-di(naphthalen-2-yl) Anthracene (9,10-di(naphthalene)anthracene: ADN), 4,4′,4″-tris(N-carbazolyl)triphenylamine (4,4′,4″-tris(N-carbazolyl)triphenylamine: TCTA ), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene: TPBI), 3-tert-butyl -9,10-di(naphth-2-yl)anthracene (3-tert-butyl-9,10-di(naphth-2-yl)anthracene: TBADN), distyrylarylene (DSA), 4,4 '-Bis(9-carbazole)-2,2'-dimethyl-biphenyl (4,4'-bis(9-carbazole)2,2'-dimethyl-biphenyl: dmCBP) and the like may be included.

In addition, the light-emitting layer 150 includes dopant materials such as perylene and its derivatives, rubrene and its derivatives, coumarin and its derivatives, 4-dicyanomethylene-2-(p-dimethylaminostyryl), )-6-methyl-4H-pyran (4-dicyanomethylene-2-(pdimethylaminostyryl)-6-methyl-4H-pyran: DCM) and its derivatives, bis[2-(4,6-difluorophenyl)pyridinate]picolinate Iridium (III) (bis[2-(4,6-difluorophenyl)pyridinate]picolinate iridium (III): FIrpic), bis(1-phenylisoquinoline) (acetylacetonate) iridium (III) (bis(1-phenylisoquinoline) (acetylacetonate) iridium (III): Ir (piq) 2 (acac)), tris (2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III): Ir (ppy) 3), tris ( Iridium (Ir) complexes such as 2-(3-p-xyl)phenyl)pyridine iridium (III), osmium (Os) complexes, platinum complexes and the like may also be included.

Also, the light-emitting layer 150 may contain nanoparticles such as quantum dots as a light-emitting material. Quantum dots are nanoparticles composed of semiconductors of the I-VI series, the III-V series or the IV-IV series of semiconductors. Examples of such semiconductors include, but are not limited to, CdS, CdSe, CdTe, ZnSe, ZnS, PbS, PbSe, HgS, HgSe, HgTe, CdHgTe, CdSe _x Te _1-x , GaAs, InAs and InP. not something.

Also, the diameter of the nanoparticles is not particularly limited, but can be, for example, 1 to 20 nm. Nanoparticles such as quantum dots may have a single core structure, or may have a so-called core/shell structure in which the surface of a core is covered with a shell.

An electron transport layer 160 is formed on the light emitting layer 150 . The electron transport layer 160 is a layer having a function of transporting electrons. Electron transport layer 160 may be formed with a thickness of, for example, about 15 nm to about 50 nm.

Electron transport layer 160 may be formed of a known electron transport material. Known electron-transporting materials include, for example, tris(8-quinolinato)aluminum (Alq3) and compounds having a nitrogen-containing aromatic ring. Specific examples of the compound having a nitrogen-containing aromatic ring include, for example, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (1,3,5-tri[(3-pyridyl) -phen-3-yl]benzene), 2,4,6-tris(3′-(pyridin-3-yl)biphenyl-3-yl)-1,3, compounds containing a triazine ring, such as 5-triazine (2,4,6-tris(3′-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine), 2 -(4-(N-phenylbenzimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene (2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene) and a compound containing an imidazole ring.

An electron injection layer 170 is formed on the electron transport layer 160 . The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180 . The electron injection layer 170 may be formed with a thickness of about 0.3 nm to about 20 nm. The electron injection layer 170 is not particularly limited, and known materials for forming the electron injection layer 170 can be used. For example, the electron injection layer 170 may be composed of (8-quinolinato)lithium (Liq) and lithium compounds such as lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), ), lithium oxide (Li ₂ O), barium oxide (BaO), or the like.

A second electrode 180 is formed on the electron injection layer 170 . The second electrode 180 is specifically a cathode, and is formed of a metal, an alloy, a conductive compound, or the like, which has a small work function. For example, the second electrode 180 is made of metal such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca), aluminum-lithium (Al-Li), magnesium-indium (Mg-In), An alloy such as magnesium-silver (Mg--Ag) may be formed as a reflective electrode. The second electrode 180 is a transparent conductive film such as a thin film of 20 nm or less of the above metal material, indium tin oxide (In ₂ O ₃ —SnO ₂ ) and indium zinc oxide (In ₂ O ₃ —ZnO). may be formed as

Since the organic EL element 100 according to the present embodiment has an organic layer containing a compound represented by the general formula (1), an organic electroluminescence element having excellent current efficiency and luminous life can be produced by a coating method. . In addition, the compound represented by the general formula (1) can be used in an organic layer (light-emitting layer) containing a light-emitting material from the viewpoint of excellent hole-transport properties. The organic EL element 100 according to this embodiment is an example of the electroluminescence element according to the invention.

Note that the layered structure of the organic EL element 100 according to this embodiment is not limited to the above example. The organic EL element 100 according to this embodiment may be formed with another known laminated structure. For example, the organic EL device 100 may omit one or more of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170, or may additionally include other layers. may be provided. Moreover, each layer of the organic EL element 100 may be formed of a single layer, or may be formed of a plurality of layers.

For example, organic EL device 100 may further include a hole blocking layer between light-emitting layer 150 and electron-transporting layer 160 to prevent excitons or holes from diffusing into electron-transporting layer 160. good. The hole blocking layer can be formed of, for example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the like.

Hereinafter, the present invention will be described based on more detailed examples. However, the present invention is not limited to these examples. In the following, "%" is by weight unless otherwise specified. In addition, tests and evaluations were conducted in accordance with the following.

<Measurement of solubility>
A 50 mg sample solid sample was placed in a colorless and transparent sample bottle, 500 mg of a solvent was added, and ultrasonic irradiation was performed at room temperature for 5 minutes, and the presence or absence of residual sample solid was visually confirmed. At this point, if no sample solid remains and is dissolved, the solubility will be 10 wt % or more. If any sample solid remained, the solvent was added little by little and ultrasonic irradiation was repeated, and the solubility was calculated from the amount of solvent when the sample was completely dissolved. Table 1 shows the results.

<Evaluation of photochemical stability>
Photochemical stability was evaluated under the following conditions.

[Preparation of sample for measurement]
In a nitrogen atmosphere glove box with a moisture concentration of 1 ppm or less and an oxygen concentration of 1 ppm or less, the solid content ratio was evaluated by coating on a quartz substrate Host material: green phosphorescent material TEG = 100% by weight: 5% by weight, solid content ink A thin film layer having a film thickness of 50 nm was formed from a methyl benzoate solution having a concentration of 4% by weight, and was treated at 120° C. for 15 minutes at a degree of vacuum of 1×10 ⁻³ Pa. The film was transported to a vacuum deposition machine, and a circular aluminum thin film with a diameter of 2 mm and a thickness of 100 nm was formed on this film by vacuum deposition using a metal mask. This was sealed using a glass sealing tube with a desiccant and an ultraviolet curable resin to obtain a measurement sample.

[Measurement system]
The measurement system is mainly composed of the following two.

1. Photoluminescence (PL) intensity measurement system 2. UV irradiation deterioration system

1. Photoluminescence (PL) intensity measurement system Using a high-output UV-Vis fiber light source unit (Hamamatsu Photonics L10290) and an ultraviolet transmission visible absorption filter (Suruga Seiki, S76-U340), light with a wavelength of 250 nm or less and 400 nm The light from which the above light was removed was used as an excitation light source. A small fiber optical spectrometer (USB2000+UV-VIS, manufactured by Ocean Photonics) was used as a light receiver. At the time of measurement, the sample substrate was placed at an angle of 20° or more from the front of the quartz substrate so that the excitation light was accurately incident on the sample film measurement site covered with aluminum. Due to the excitation light, the sample film measurement site emits light in the hemispherical direction in front of the quartz substrate, and the light receiver is positioned within a distance that can capture this light emission and at a position that avoids specular reflection of the excitation light from the quartz substrate. installed. In order to keep the intensity of the excitation light applied to the sample constant each time the measurement was performed, the intensity of the excitation light source and the geometry of the optical system were kept constant.

2. UV irradiation deterioration system UV-LED (manufactured by CCS) with a maximum emission wavelength of 365 nm is used as a light source, and the inside of the irradiation port surface is passed through a synthetic quartz light pipe (manufactured by Edmund Optics, #65-829) with a diameter of 2 mm and a length of 75 mm. Light with a uniform intensity was used as excitation light for deterioration. The total luminous flux intensity of the excitation light was controlled using a digital power supply (PD3-10024-8-PI, manufactured by CCS) and an optical power meter (8230E, manufactured by ADCMT). The excitation light irradiation port and the quartz substrate side of the sample film were aligned and brought into close contact with each other. By irradiating the sample film with excitation light from the quartz substrate side for a certain period of time, the sample film receives an optical load and deteriorates.

[Photochemical degradation test at excitation light total flux intensity of 10 mW]
In the first stage, the above 1. photoluminescence (PL) intensity measurement system was used to measure the photoluminescence (PL) intensity of the sample thin film before deterioration. In the second step, the above 2. Using the UV irradiation deterioration system of 1. above, excitation light irradiation for deterioration is performed for 5 minutes at a total luminous flux intensity of 10 mW, and then the above 1. was used to measure the photoluminescence (PL) intensity of the sample thin film under load for 5 minutes using a photoluminescence (PL) intensity measurement system. Thereafter, by repeating the same operation as in the second step, the photoluminescence (PL) intensity of the sample thin film was measured with respect to the time when the excitation light load was applied.

[Photochemical degradation test at excitation light total flux intensity of 20 mW]
Measurement was performed in the same manner as in the photochemical degradation test at a total excitation light intensity of 10 mW, except that the excitation light total intensity was changed to 20 mW.

[Photochemical degradation test at excitation light total flux intensity of 50 mW]
Measurement was carried out in the same manner as in the deterioration test at a total excitation light intensity of 10 mW, except that the excitation light total intensity was changed to 50 mW.

[Analysis of photochemical deterioration test]
First, based on the attenuation data of the luminescence intensity obtained from the photochemical deterioration test in which the total luminous flux intensity of the excitation light is variously changed, the following correspondence is applied to adjust the acceleration coefficient a, An attenuation curve that does not depend on the total luminous flux intensity of excitation light was obtained.

Vertical axis: RI _(t) =I _(t) / _I0
Horizontal axis: X _c =E ^a ×t
RI _(t) : photoluminescence intensity ratio of sample film to initial luminance at excitation light irradiation time t t: excitation light irradiation time I _(t) : photoluminescence intensity of sample film at excitation light irradiation time t _I0 : excitation light Photoluminescence intensity of sample film before irradiation X _c : integrated intensity of corrected excitation light E: total luminous flux intensity of excitation light a: acceleration factor

From the "attenuation curve independent of the total luminous flux intensity of the excitation light" obtained by this analysis _, the corrected integrated excitation light intensity X _c 90 was taken as an index of photochemical stability. It should be noted that a larger value of X _c 90 indicates that a larger amount of energy is required for deterioration of the emission intensity and that deterioration is less likely to occur. Table 2 shows the X _c 90 results as relative values.

<Evaluation of film formability>
The film formability of the organic EL devices according to Examples and Comparative Examples was evaluated by the following method. A commercially available TBF layer was formed on a glass substrate with ITO on which indium tin oxide (ITO) was formed to a film thickness of 150 nm, and the film thickness was reduced to 30 nm from a 2% by mass methyl benzoate solution of the obtained compound. A layered film was formed by applying by a spin coating method so that The laminated film thus obtained was heated to 125° C., and the surface of the laminated film was observed with an optical microscope to evaluate the state of the film. The state of the film was evaluated according to the criteria shown below.

○: Uniform with no defects △: A few uneven points or regions can be seen, but the device can be produced ×: The continuity of the film cannot be ensured, and the device cannot be produced

<Organic EL element evaluation method>
[Evaluation of Current Efficiency and Durability (Luminous Life)]
The current efficiency and durability (luminescence life) of Examples and Comparative Examples were evaluated under the following conditions. First, the voltage and current applied to the organic EL element are measured using a DC constant voltage power supply (manufactured by KEYENCE, source meter), and the emission luminance of the organic EL element is measured using a luminance measuring device (manufactured by Topcon, SR-3 ) was used.

^Current efficiency ⁽ cd /A) was calculated. The current efficiency indicates the efficiency (conversion efficiency) of converting current into light emission energy, and the higher the current efficiency, the higher the performance of the organic EL element.

Durability (light emission life) is the time (hours) for each organic EL element to be continuously driven at a current value at which the initial luminance is 6000 cd/m ² until the light emission luminance, which decays over time, reaches 80% of the initial luminance. was designated as "LT80(h)".

<Synthesis of compound>
[Synthesis Example 1]
First, compound 14-1 was synthesized according to the following reaction scheme (4).

Specifically, 5-bromo-2-nitroaniline (122 g, 562 mmol), H ₂ SO ₄ (122 ml), and pure water (3.1 L) were mixed under a nitrogen atmosphere, cooled to 0° C., and NaNO ₂ ( 42.7 g, 619 mmol, 1.1 eq.) in water (620 ml) was added dropwise over 1 hour and stirred at room temperature for 3 hours. The reaction solution was cooled to 0° C., an aqueous solution of KI (117 g, 705 mmol, 1.25 eq.) (620 ml) was added dropwise over 1 hour, and then Cu powder (1.07 g, 16.8 mmol, 0.03 eq.) was added. The mixture was stirred at 70° C. for 3 hours. After cooling the reaction to room temperature, it was extracted with CH ₂ Cl ₂ . The organic layer was washed with 10% aqueous Na ₂ S ₂ O ₃ solution, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:CH ₂ Cl ₂ =5:1) to obtain compound 14-1 as a yellow solid. The yield of compound 14-1 was 116.1 g and the yield was 63%.

Then, compound 14-2 was synthesized according to the following reaction scheme (5).

Specifically, compound 14-1 (4-bromo-2-iodo-1-nitrobenzene) (231 g, 704 mmol) obtained in the above reaction scheme (4) and 1,4-dioxane (2. 3 L), 2-chlorophenylboronic acid (132 g, 844 mmol), 2M K ₃ PO ₄ aqueous solution (704 ml) and Pd(PPh ₃ ) ₄ (24.4 g, 21.1 mmol) were mixed and stirred at 80° C. for 8 hours. . The reaction was cooled to room temperature, H ₂ O was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:CH ₂ Cl ₂ =10:1) to obtain compound 14-2 as a yellow solid. The yield of compound 14-2 was 210 g and the yield was 95%.

Then, compound 14-3 was synthesized according to the following reaction scheme (6).

Specifically, under a nitrogen atmosphere, compound 14-2 (5-bromo-2′-chloro-2-nitro-1,1′-biphenyl) (225 g, 720 mmol) obtained in the above reaction scheme (5), o-Dichlorobenzene (2.3 L) and PPh ₃ (472 g, 1.8 mol) were mixed and stirred at 180° C. for 6 hours. After cooling to room temperature, the reaction was concentrated. This was dissolved in a mixed solvent of hexane:CH ₂ Cl ₂ =2:1, filtered three times using a silica gel pad about 15 cm long to remove the original impurities, and concentrated. This was dispersed in 500 ml of a mixed solvent of hexane:CH ₂ Cl ₂ =2:1, subjected to ultrasonic treatment for 30 minutes, and filtered to obtain compound 14-3. The yield of compound 14-3 was 67.1 g, and the yield was 33%.

Then, compound 14-4 was synthesized according to the following reaction scheme (7).

Specifically, under a nitrogen atmosphere, the compound 14-3 (3-bromo-5-chloro-9H-carbazole) (28.06 g, 100 mmol) obtained in the above reaction scheme (6), 1,4-dioxane ( 100 ml), 4-iodobiphenyl (30.81 g _, 110 mmol), K _PO (31.84 g, 150 mmol), CuI (0.95 g, 5 mmol), trans-1,2-diaminocyclohexane (1.71 g, 15 mmol). Mix and stir at 100° C. for 24 hours. The reaction liquid was cooled to room temperature, 300 ml of toluene was added, and the mixture was filtered using celite. It was then filtered using a silica gel pad and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:CH ₂ Cl ₂ =9:1) and recrystallized from hexane to obtain compound 14-4. The yield of compound 14-4 was 39.8 g and the yield was 92%.

Then, compound 14-5 was synthesized according to the following reaction scheme (8).

Specifically, under a nitrogen atmosphere, carbazole (200.7 g, 1200 mmol), 1,4-dibromo-2-fluorobenzene (335.2 g, 1320 mmol), and 480 ml of N,N-dimethylformamide were placed in a three-necked flask and mixed. NaH (62 wt % dispersion in paraffin) (NaH content: 28.8 g, 1200 mmol) was added stepwise while cooling in a bath while paying attention to the amount of hydrogen gas generated, and the mixture was stirred at 150°C for 12 hours. The mixture was diluted with 1 L of toluene, deactivated with a small amount of methanol, and then filtered using celite. This was washed three times with pure water using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:CHCl ₃ =8:2) and recrystallized from hexane to obtain compound 14-5. The yield of compound 14-5 was 341.74 g and the yield was 71%.

Then, compound 14-6 was synthesized according to the following reaction scheme (9).

Specifically, under a nitrogen atmosphere, the compound 14-5 (9-(2,5-dibromophenyl)-9H-carbazole) (20.05 g, 50 mmol) obtained in the above reaction scheme (8), phenylboronic acid ( 13.41 g, 110 mmol), 200 ml of toluene, 50 ml of ethanol, and 2 M aqueous solution of potassium carbonate (100 ml) were mixed in a three-necked flask, Pd(PPh ₃ ) ₄ (2.31 g, 2 mmol) was added, and the mixture was heated at 80° C. for 12 hours. Stirred. Toluene (500 ml) was added for dilution, cooled to room temperature, washed three times with pure water using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:CHCl ₃ =8:2) and recrystallized from hexane to obtain compound 14-6. The yield of compound 14-6 was 12.7 g and the yield was 64%.

Then, compound 14-7 was synthesized according to the following reaction scheme (10).

Specifically, the compound 1-6(9-([1,1′,4′,1″-terphenyl]-2′-yl)-9H obtained in the above reaction scheme (9) is -carbazole) (12.6 g, 32 mmol), N,N-dimethylformamide 160 ml, and CHCl ₃ (160 ml) were placed in a three-necked flask and dissolved. - Bromosuccinimide (5.70 g, 32 mmol) was added dropwise over 10 minutes, followed by stirring at room temperature for 12 hours. Toluene (500 ml was added for dilution, washed with pure water three times using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. This was subjected to silica gel chromatography (developing solvent: hexane). :CHCl ₃ =8:2), and recrystallized from hexane to obtain compound 14-7.The yield of compound 14-7 was 13.4 g, and the yield was 88%.

Then, compound 14-8 was synthesized according to the following reaction scheme (11).

Specifically, the compound 14-7(9-([1,1′,4′,1″-terphenyl]-2′-yl)-3 obtained in the above reaction scheme (10) was -bromo-9H-carbazole) (13.3 g, 28 mmol), Bis(pinacolato) diboron (7.82 g, 30.8 mmol), potassium acetate (5.50 g, 56 mmol), N,N-dimethylformamide (140 ml), After mixing in a three-necked flask, Pd(dppf)Cl ₂ (2.05 g, 2.8 mmol) was added and stirred at 80° C. for 12 hours. After diluting with 300 ml of toluene and cooling to room temperature, the mixture was filtered using celite, washed with pure water three times using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. . This was purified by silica gel chromatography (developing solvent: hexane:CH ₂ Cl ₂ =6:4) and recrystallized from hexane to obtain compound 14-8. The yield of compound 14-8 was 11.5 g and the yield was 79%.

Then, compound 14-9 was synthesized according to the following reaction scheme (12).

Specifically, the compound 14-4(9-([1,1′-biphenyl]-4-yl)-3-bromo-5-chloro-9H obtained in the above reaction scheme (11) is carried out under a nitrogen atmosphere. -carbazole) (4.33 g, 10 mmol), compound 14-8 (9-([1,1′:4′,1″-terphenyl]-2′-yl)-3-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (5.74 g, 11 mmol), toluene 100 ml, ethanol 20 ml, potassium carbonate 2M aqueous solution (10 ml) were put in a three-necked flask and mixed. (PPh ₃ ) ₄ (0.58 g, 0.5 mmol) was added, and the mixture was stirred for 8 hours at 80° C. 100 ml of pure water and 200 ml of methanol were added, and after cooling to room temperature, the precipitated solid was collected by filtration and vacuum dried. (50° C., 6 hours), the sample was dissolved by heating in toluene (500 ml), filtered through a silica gel pad, and concentrated. Recrystallization was performed twice to obtain compound 14-9, which was obtained in an amount of 4.9 g and a yield of 65%.

Then, compound 14 was synthesized according to the following reaction scheme (13).

Specifically, compound 14-9 (9-([1,1′-biphenyl]-4-yl)-9′-([1,1′ ,4′,1″-terphenyl]-2′-yl)-5-chloro-9H,9′H-3,3′-bicarbazole) (4.9 g, 6.5 mmol), 3-Biphenylboronic acid (1 .54 g, 7.8 mmol), 65 ml of toluene, ethanol (13 ml), and 2M aqueous solution of potassium carbonate (6.5 ml) were mixed in a three-necked flask, and Pd(OAc) ₂ (73 mg, 0.325 mmol), S-Phos (213 mg, 0.52 mmol) was added and stirred at 80° C. for 12 hours. The mixture was diluted with 300 ml of toluene, cooled to room temperature, washed three times with pure water using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. This was purified by silica gel chromatography (developing solvent: hexane:toluene=7:3) and recrystallized three times from a mixed solvent of hexane:ethyl acetate=1:1 to obtain compound 14. The yield of compound 14 was 3.71 g and the yield was 66%.

[Synthesis Example 2]
Compound 15-1 was obtained in the same manner as in Synthesis Example 1, except that the reaction scheme (14) below was changed and the corresponding reagents were changed.

Compound 15 was obtained in the same manner as in Synthesis Example 1, except that compound 14-4 obtained in reaction scheme (14) above was used, reaction scheme (15) below was used, and the corresponding reagents were changed.

［合成例３］

[Synthesis Example 3]

Compound 145-1 was synthesized according to the following reaction scheme (16).

具体的には、窒素雰囲気下、前述の反応スキーム（１５）で得られた化合物１５－５（９－（［１，１'－ｂｉｐｈｅｎｙｌ］－３－ｙｌ）－３－ｂｒｏｍｏ－５－ｃｈｌｏｒｏ－９Ｈ－ｃａｒｂａｚｏｌｅ）（９．５２ｇ、２２ｍｍｏｌ）、１，４－ｂｉｓ（４，４，５，５－ｔｅｔｒａｍｅｔｈｙｌ－１，３，２－ｄｉｏｘａｂｏｒｏｌａｎ－２－ｙｌ）ｂｅｎｚｅｎｅ（３．３０ｇ、１０ｍｍｏｌ）、トルエン２００ｍｌ、エタノール２０ｍｌ、炭酸カリウム２Ｍ水溶液（２０ｍｌ）を三口フラスコに入れ混合し、Ｐｄ（ＰＰｈ_３）_４（０．５８ｇ、０．５ｍｍｏｌ）を加え、８０℃で８時間撹拌した。純水１００ｍｌとメタノール２００ｍｌを加え、室温まで冷却した後に、析出固体をろ過で回収した。真空乾燥（５０℃、６時間）を行った後に、トルエン（１Ｌ）に加熱して試料を溶解させ、シリカゲルパッドを用いて濾過後、濃縮した。これを酢酸エチルで２回、分散洗浄して化合物１４５－１を得た。化合物１４５－１の収量は４．５３ｇ、収率は５８％であった。

Specifically, under a nitrogen atmosphere, the compound 15-5 (9-([1,1′-biphenyl]-3-yl)-3-bromo-5-chloro- obtained in the above reaction scheme (15) 9H-carbazole) (9.52 g, 22 mmol), 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (3.30 g, 10 mmol), toluene 200 ml, 20 ml of ethanol, and 2M aqueous potassium carbonate solution (20 ml) were placed in a three-necked flask and mixed, Pd(PPh ₃ ) ₄ (0.58 g, 0.5 mmol) was added, and the mixture was stirred at 80° C. for 8 hours. After adding 100 ml of pure water and 200 ml of methanol and cooling to room temperature, the precipitated solid was collected by filtration. After vacuum drying (50° C., 6 hours), the sample was dissolved by heating in toluene (1 L), filtered using a silica gel pad, and concentrated. This was dispersed and washed twice with ethyl acetate to obtain compound 145-1. The yield of compound 145-1 was 4.53 g and the yield was 58%.

Then, compound 145 was synthesized according to the following reaction scheme (17).

具体的には、窒素雰囲気下、上記反応スキーム（１６）で得られた化合物１４５－１（１，４－ｂｉｓ（９－（［１，１'－ｂｉｐｈｅｎｙｌ］－３－ｙｌ）－５－ｃｈｌｏｒｏ－９Ｈ－ｃａｒｂａｚｏｌ－３－ｙｌ）ｂｅｎｚｅｎｅ）（４．４７ｇ、５．７２ｍｍｏｌ）、３－Ｂｉｐｈｅｎｙｌｂｏｒｏｎｉｃ ａｃｉｄ（４．５３ｇ、２２．８８ｍｍｏｌ）、トルエン２２９ｍｌ、エタノール（２９ｍｌ）、炭酸カリウムの２Ｍ水溶液（２３ｍｌ）を三口フラスコに入れ混合し、Ｐｄ（ＯＡｃ）_２（６４ｍｇ、０．２９ｍｍｏｌ）、Ｓ－Ｐｈｏｓ（１８８ｍｇ、０．４６ｍｍｏｌ）を加え、８０℃で１２時間撹拌した。トルエン３００ｍｌを加えて希釈し、室温まで冷却した後に分液ロートを用いて純水で２回洗浄し、無水硫酸マグネシウムで乾燥し、シリカゲルパッドを用いて濾過後、濃縮した。これをシリカゲルクロマトグラフィー（展開溶媒 ヘキサン：トルエン＝６：４）で精製し、さらに酢酸エチルで分散洗浄して化合物１４５を得た。化合物１４５の収量は４．２５ｇ、収率は７３％であった。

Specifically, the compound 145-1 (1,4-bis(9-([1,1′-biphenyl]-3-yl)-5-chloro -9H-carbazol-3-yl)benzene) (4.47 g, 5.72 mmol), 3-Biphenylboronic acid (4.53 g, 22.88 mmol), toluene 229 ml, ethanol (29 ml), 2 M aqueous solution of potassium carbonate (23 ml ) were placed in a three-necked flask and mixed, Pd(OAc) ₂ (64 mg, 0.29 mmol) and S-Phos (188 mg, 0.46 mmol) were added, and the mixture was stirred at 80° C. for 12 hours. The mixture was diluted with 300 ml of toluene, cooled to room temperature, washed twice with pure water using a separating funnel, dried over anhydrous magnesium sulfate, filtered using a silica gel pad, and concentrated. This was purified by silica gel chromatography (developing solvent hexane:toluene=6:4), and dispersed and washed with ethyl acetate to obtain compound 145. The yield of compound 145 was 4.25 g, and the yield was 73%.

[Synthesis Example 4]
Compound 14-7 ((9-([1,1′,4′,1″-terphenyl]-2′-yl)-3-bromo-9H-carbazole) to compound 15-5 ((9-([ 1,1′-biphenyl]-3-yl)-3-bromo-5-chloro-9H-carbazole) was used to synthesize Comparative Example Compound 1-1 in the same manner as Compound 14-8.

Comparative Example Compound 1-1 was used in the same manner as in Synthesis Example 1, except that Comparative Example Compound 1-1 obtained in Reaction Scheme (18) was changed to the following Reaction Scheme (19) and the corresponding reagents were changed. got 2.

Comparative Example Compound 1 was prepared in the same manner as in Synthesis Example 1, except that Comparative Example Compound 1-2 obtained in Reaction Scheme (19) above was changed to the following Reaction Scheme (20) and the corresponding reagents were changed. Obtained.

[Synthesis Example 5]
Comparative Example Compound 2 was obtained in the same manner as in Synthesis Example 1, except that the reaction scheme (21) below was changed and the corresponding reagents were changed.

<Examples and Comparative Examples>
[Example 1]
First, as a first electrode (anode), a striped indium tin oxide (ITO) film with a film thickness of 150 nm is prepared on a glass substrate with ITO. On this glass substrate, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS) (Sigma - Aldrich) was applied by a spin coating method so that the dry film thickness was 30 nm to form a hole injection layer.

Next, commercially available TFB was dissolved in xylene at 1 mass % to prepare a hole transport layer coating solution. The hole transport layer coating liquid was applied onto the hole injection layer by a spin coating method so that the dry film thickness was 30 nm, and heated at 230° C. for 1 hour to form a hole transport layer.

Next, compound 14 synthesized in Synthesis Example 1 as a hole-transporting host material, compound ETH-1 as an electron-transporting host material, and tris(2-(3-p-xyl)phenyl) as a light-emitting dopant material. A methyl benzoate solution was prepared using pyridine iridium (TEG). This was applied onto the hole transport layer by a spin coating method to form a light emitting layer with a thickness of 30 nm. The mass ratios of the hole-transporting host material, the electron-transporting host material, and the light-emitting dopant material in the light-emitting layer were 90% by mass, 10% by mass, and 5% by mass, respectively, relative to the total mass of the light-emitting layer.

11-(4,6-diphenyl-1,3,5-triazin-2-yl)-12-phenyl-11,12-dihydroindolo[2,3-a]carbazole (HB-1) on the light-emitting layer ) was vapor-deposited in a vacuum vapor deposition apparatus to form a hole-blocking layer having a thickness of 10 nm. (8-quinolinolato)lithium (Liq) and KLET-03 (manufactured by Chemipro Kasei) were co-deposited on the hole-blocking layer using a vacuum deposition apparatus to form an electron-transporting layer having a thickness of 30 nm. Aluminum (Al) was vapor-deposited on the electron transport layer using a vacuum vapor deposition apparatus to form a cathode having a film thickness of 100 nm. This element was sealed in a glove box with a moisture content and an oxygen concentration of 1 ppm or less using a glass sealing tube with a desiccant and an ultraviolet curable resin, and used for evaluation of the organic EL element described later. An organic EL device was manufactured by such a method. Table 4 shows the results. Table 4 shows relative values of the current efficiency and LT80(h) of each compound when Comparative Example Compound 3 is set to 100.

The chemical formulas of ETH-1, TEG, HB-1 and Liq are shown below.

[Example 2]
An organic EL device was produced in the same manner as in Example 1, except that Compound 15 synthesized in Synthesis Example 2 was used instead of Compound 14 as the hole-transporting host material. Table 4 shows the results.

[Example 3]
An organic EL device was produced in the same manner as in Example 1, except that Compound 145 synthesized in Synthesis Example 3 was used instead of Compound 14 as the hole-transporting host material. Table 4 shows the results.

[Comparative Example 1]
An organic EL device was produced in the same manner as in Example 1, except that Comparative Example Compound 1 synthesized in Synthesis Example 4 was used instead of Compound 14 as a hole-transporting host material. Table 4 shows the results.

[Comparative Example 2]
An organic EL device was produced in the same manner as in Example 1, except that Comparative Example Compound 2 synthesized in Synthesis Example 3 was used instead of Compound 14 as the hole-transporting host material. Table 4 shows the results.

[Comparative Example 3]
An organic EL device was produced in the same manner as in Example 1, except that Comparative Example Compound 3 represented by the following chemical formula was used instead of Compound 14 as a hole-transporting host material. Table 4 shows the results.

[Comparative Example 4]
An organic EL device was produced in the same manner as in Example 1, except that Comparative Example Compound 4 represented by the following chemical formula was used instead of Compound 14 as a hole-transporting host material. Table 4 shows the results.

From Table 1, compounds 14, 15, and 145 are n = 0, and E is a phenyl group or an m-biphenyl group. It can be seen that the solubility (mass%) for is high. Therefore, it can be seen that the compound according to the present embodiment is suitable for manufacturing an organic EL device by the coating method.

Furthermore, from Table 2, it can be seen that compounds 14, 15 and 145 have higher _Xc90 and higher photochemical stability than comparative compounds 1-4. Therefore, the compound according to this embodiment can be expected to have a longer life when applied to an organic electroluminescence device (particularly, a light-emitting layer).

From Table 3, it can be seen that compounds 14, 15, and 145 have a uniform film without defects even after heating at 125° C. compared to comparative compounds 1 to 4, and exhibit good film-forming properties. . Therefore, it was found that the compound according to the present embodiment is useful as an organic EL device material for the coating method.

From Table 4, the organic EL devices of Examples 1 to 3 using compounds 14, 15, and 145 as hole-transporting host materials have current efficiencies equal to or higher than those of the organic EL devices of Comparative Examples 1 to 4. , and the emission lifetime was found to be significantly improved.

Compounds 14, 15, and 145 used in Examples 1 to 3 are preferable from the viewpoint of mass production because they can form a light-emitting layer of an organic electroluminescence device by a coating method.

As described above, the present invention has been described with reference to embodiments and examples, but the present invention is not limited to specific embodiments and examples, and various can be modified and changed.

100 organic electroluminescence element (organic EL element)
110 substrate 120 first electrode 130 hole injection layer 140 hole transport layer 150 light emitting layer 160 electron transport layer 170 electron injection layer 180 second electrode

Claims (12)

The following general formula (1):

(In the formula,
E and R ₁ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms,
at least one of E and R ₁ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms;
G is a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 to 30 is an aromatic heterocyclic group,
R ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms;
A ₁ to A ₄ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming atom is an aromatic heterocyclic group having a number of 3 to 30,
any one of A ₁ and A ₂ and/or any one of A ₃ and A ₄ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms;
L is a single bond or a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms;
n is an integer of 0 or 1;
when n is 0, E is a hydrogen atom or a deuterium atom;
The substituent of the substituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms is a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted 1 to 30 alkoxy groups, substituted or unsubstituted C6 to C30 aryloxy groups, substituted or unsubstituted C1 to C30 amino groups, cyano groups, or substituted or unsubstituted is an aromatic hydrocarbon ring group having 6 to 30 carbon atoms. )
A compound represented by E is a hydrogen atom or a deuterium atom,
The compound according to claim 1, wherein R ₁ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms. Claim 1 or wherein G is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms 2. The compound according to 2. any one of A ₁ and A ₂ is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, and any one of A ₃ and A ₄ is substituted or unsubstituted An aromatic hydrocarbon ring group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, according to any one of claims 1 to 3 compound. The compound according to any one of claims 1 to 4, wherein in the general formula (1), L is a single bond. Any one of claims 1 to 4, wherein in the general formula (1), L is a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 carbon atoms, and n is 1. The compound described in . Compounds 1-154 below:

A compound according to any one of claims 1 to 6, which is any one of A material for an organic electroluminescence device, comprising the compound according to claim 1 . A composition for an organic electroluminescence device, comprising the compound according to claim 1 and a solvent. a pair of electrodes;
and one or more organic layers arranged between the pair of electrodes,
8. An organic electroluminescence device, wherein at least one of the organic layers contains the compound according to any one of claims 1 to 7 . 11. The organic electroluminescence device according to claim 10, wherein the organic layer containing the compound further contains a light-emitting material. 12. The organic electroluminescence device according to claim 10, wherein the organic layer containing the compound is formed by a coating method.

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